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21 CFR 524.981d - Fluocinolone acetonide, dimethyl sulfoxide solution.
... solution. 524.981d Section 524.981d Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... NEW ANIMAL DRUGS § 524.981d Fluocinolone acetonide, dimethyl sulfoxide solution. (a) Specifications. Each milliliter of solution contains 0.01 percent fluocinolone acetonide and 20 percent dimethyl...
21 CFR 524.981e - Fluocinolone acetonide, dimethyl sulfoxide otic solution.
... solution. 524.981e Section 524.981e Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... NEW ANIMAL DRUGS § 524.981e Fluocinolone acetonide, dimethyl sulfoxide otic solution. (a) Specifications. Each milliliter of solution contains 0.01 percent of fluocinolone acetonide in 60 percent...
γ-ray dosimetry using pararosaniline cyanide in dimethyl sulfoxide solutions
International Nuclear Information System (INIS)
El-Assy, N.B.; Roushdy, H.M.; Rageh, M.; McLaughlin, W.L.; Levine, H.
A chemical radiochromic dosimeter using pararosaniline cyanide in dimethyl sulfoxide can be used over a wide absorbed dose range. Experiments show that the dosimeter has a main optical absorption maximum at 554nm, which is 5nm higher than that of other polar solvents. Millimolar solutions of leucodye containing small amounts of carboxylic acid or nitrobenzene show a linear response for absorbed doses up to 11.75kGy. The yield of dye is linear with concentration up to 5mM. At that concentration the upper limit of linear response range can be extended to about 40kGy. The lower dose limit for 50mM concentration of the dye precursor hexahydroxyethyl pararosaniline (lambdasub(max)=608nm) is about 3Gy, with +-5%SD at a 95% confidence level, when using a 5cm pathlength cell. Dye formation yield varies not only with concentration of the leucocyanide, but also with type of oxidizing agent and temperature during irradiation. The latter parameter is especially critical, as dimethyl sulfoxide freezes at 17 0 C. The effect of storage temperature on the color produced after irradiation at different dose levels was also studied. (author)
Speciation in Solutions of Lithium Salts in Dimethyl Sulfoxide, Propylene Carbonate, and Dimethyl Carbonate from Raman Data: A Minireview
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M. I. Gorobets
Full Text Available Our recent Raman studies of cation and anion solvation and ion pairing in solutions of lithium salts in dimethyl sulfoxide, propylene carbonate, and dimethyl carbonate are briefly overviewed. Special attention is paid to differences in our and existing data and concepts. As follows from our results, cation solvation numbers in solutions are low (~2 and disagree with previous measurements. This discrepancy is shown to arise from correct accounting for dimerization, hydrogen bonding, and conformation equilibria in the solvents disregarded in early studies. Another disputable question touches upon the absence of free ions in solutions of lithium salts in carbonate solvents and the statement that the charge transfer in carbonate solutions is caused by SSIPs. Direct proofs of the nature of charge carriers in the solvents studied have been obtained by means of analyses of vibrational dynamics. It has been found that collision times for free anions are short and evidence weak interactions between anions and solvent molecules. In SSIPs, collision times are an order of magnitude longer thus signifying strong interactions between anions and cations. In CIPs, collision times become shorter than in SSIPs reflecting the transformation of the structure of concentrated solutions to that of molten salts.
Cryopreservation of buffy-coat-derived platelet concentrates in dimethyl sulfoxide and platelet additive solution.
Johnson, L N; Winter, K M; Reid, S; Hartkopf-Theis, T; Marks, D C
Platelets prepared in plasma can be frozen in 6% dimethyl sulfoxide (Me(2)SO) and stored for extended periods at -80°C. The aim of this study was to reduce the plasma present in the cryopreserved product, by substituting plasma with platelet additive solution (PAS; SSP+), whilst maintaining in vitro platelet quality. Buffy coat-derived pooled leukoreduced platelet concentrates were frozen in a mixture of SSP+, plasma and 6% Me(2)SO. The platelets were concentrated, to avoid post-thaw washing, and frozen at -80°C. The cryopreserved platelet units (n=9) were rapidly thawed at 37°C, reconstituted in 50% SSP+/plasma and stored at 22°C. Platelet recovery and quality were examined 1 and 24h post-thaw and compared to the pre-freeze samples. Upon thawing, platelet recovery ranged from 60% to 80%. However, there were differences between frozen and liquid-stored platelets, including a reduction in aggregation in response to ADP and collagen; increased CD62P expression; decreased viability; increased apoptosis and some loss of mitochondrial membrane integrity. Some recovery of these parameters was detected at 24h post-thaw, indicating an extended shelf-life may be possible. The data suggests that freezing platelets in 6% Me(2)SO and additive solution produces acceptable in vitro platelet quality. Copyright © 2011 Elsevier Inc. All rights reserved.
Experimental and theoretical evaluation on the microenvironmental effect of dimethyl sulfoxide on adrenaline in acid aqueous solution
Yu, Zhang-Yu; Liu, Tao; Guo, Dao-Jun; Liu, Yong-Jun; Liu, Cheng-Bu
The microenvironmental effect of dimethyl sulfoxide (DMSO) on adrenaline was studied by several approaches including the cyclic voltammetry (CV) of adrenaline at a platinum electrode in acid aqueous solution, the chemical shift of 1H nuclear magnetic resonance ( 1H NMR) of adrenaline, and the change of diffusion coefficient of adrenaline. The experimental results demonstrated that DMSO has significant microenvironmental effect on adrenaline, which was confirmed by the density functional theory (DFT) study on the hydrogen bond (H-bond) complexes of adrenaline with water and DMSO.
The effect of structural properties on rheological behaviour of starches in binary dimethyl sulfoxide-water solutions.
Directory of Open Access Journals (Sweden)
Anna Ptaszek
Full Text Available This research study analysed the rheological properties of potato amylose and potato amylopectin in binary solutions of the following water and dimethyl sulfoxide concentrations: 90% DMSO (1, 80% DMSO (2 and 50% DMSO (3, with preparation methodology involving the dissolution at the temperature of 98°C. The studies of dynamic light scattering on the biopolymer coils and the determination of main relaxation times of the solutions were carried out. For the amylose solutions, the fast relaxation phenomena are predominant. The results of the quality tests of the hysteresis loop showed, that the amylose solutions in the solvents (1 and (2 are rheologically stable and shear-thickened. The amylose solutions in solvents (3 reveal oscillatory alterations of viscosity in the time. Amylopectin solutions are characterized by 80% share of slow relaxation phenomena, very low diffusion coefficients and hydrodynamic radii in the range of 2000 nm. The amylopectin solutions are rheologically unstable.
The effect of structural properties on rheological behaviour of starches in binary dimethyl sulfoxide-water solutions
Ptaszek, Paweł; Dziubiński, Marek; Grzesik, N. Mirosław; Liszka-Skoczylas, Marta
This research study analysed the rheological properties of potato amylose and potato amylopectin in binary solutions of the following water and dimethyl sulfoxide concentrations: 90% DMSO (1), 80% DMSO (2) and 50% DMSO (3), with preparation methodology involving the dissolution at the temperature of 98°C. The studies of dynamic light scattering on the biopolymer coils and the determination of main relaxation times of the solutions were carried out. For the amylose solutions, the fast relaxation phenomena are predominant. The results of the quality tests of the hysteresis loop showed, that the amylose solutions in the solvents (1) and (2) are rheologically stable and shear-thickened. The amylose solutions in solvents (3) reveal oscillatory alterations of viscosity in the time. Amylopectin solutions are characterized by 80% share of slow relaxation phenomena, very low diffusion coefficients and hydrodynamic radii in the range of 2000 nm. The amylopectin solutions are rheologically unstable. PMID:28152071
Performance of the SMD and SM8 models for predicting solvation free energy of neutral solutes in methanol, dimethyl sulfoxide and acetonitrile.
Zanith, Caroline C; Pliego, Josefredo R
The continuum solvation models SMD and SM8 were developed using 2,346 solvation free energy values for 318 neutral molecules in 91 solvents as reference. However, no solvation data of neutral solutes in methanol was used in the parametrization, while only few solvation free energy values of solutes in dimethyl sulfoxide and acetonitrile were used. In this report, we have tested the performance of the models for these important solvents. Taking data from literature, we have generated solvation free energy, enthalpy and entropy values for 37 solutes in methanol, 21 solutes in dimethyl sulfoxide and 19 solutes in acetonitrile. Both SMD and SM8 models have presented a good performance in methanol and acetonitrile, with mean unsigned error equal or less than 0.66 and 0.55 kcal mol(-1) in methanol and acetonitrile, respectively. However, the correlation is worse in dimethyl sulfoxide, where the SMD and SM8 methods present mean unsigned error of 1.02 and 0.95 kcal mol(-1), respectively. Our results point out the SMx family of models need be improved for dimethyl sulfoxide solvent.
Performance of the SMD and SM8 models for predicting solvation free energy of neutral solutes in methanol, dimethyl sulfoxide and acetonitrile
Zanith, Caroline C.; Pliego, Josefredo R.
The continuum solvation models SMD and SM8 were developed using 2,346 solvation free energy values for 318 neutral molecules in 91 solvents as reference. However, no solvation data of neutral solutes in methanol was used in the parametrization, while only few solvation free energy values of solutes in dimethyl sulfoxide and acetonitrile were used. In this report, we have tested the performance of the models for these important solvents. Taking data from literature, we have generated solvation free energy, enthalpy and entropy values for 37 solutes in methanol, 21 solutes in dimethyl sulfoxide and 19 solutes in acetonitrile. Both SMD and SM8 models have presented a good performance in methanol and acetonitrile, with mean unsigned error equal or less than 0.66 and 0.55 kcal mol-1 in methanol and acetonitrile, respectively. However, the correlation is worse in dimethyl sulfoxide, where the SMD and SM8 methods present mean unsigned error of 1.02 and 0.95 kcal mol-1, respectively. Our results point out the SMx family of models need be improved for dimethyl sulfoxide solvent.
Effects of dimethyl sulfoxide on the hydrogen bonding structure and ...
Indian Academy of Sciences (India)
Keywords. Aqueous NMA-DMSO solution; hydrogen-bond lifetime; structural relaxation times; self- diffusion coefficients; orientational relaxation times. 1. Introduction. Dimethyl sulfoxide (DMSO) is an important organic solvent, with immense significance in chemical and biological systems.1 In addition to being an effective.
Effects of dimethyl sulfoxide on the hydrogen bonding structure
Indian Academy of Sciences (India)
Effects of dimethyl-sulfoxide (DMSO) on the hydrogen bonding structure and dynamics in aqueousN-methylacetamide (NMA) solution are investigated by classical molecular dynamics simulations. Themodifications of structure and interaction between water and NMA in presence of DMSO molecules are calculatedby ...
Radioprotection by dimethyl sulfoxide on two biological system
International Nuclear Information System (INIS)
Bernardes, D.M.L.; Villavicencio, A.L.C.H.; Del Mastro, N.L.
The effects of dimethyl sulfoxide treatment on two biological systems are examined: a) In vivo, the level of albinic mouse survive from IPEN, when irradiated with 9 Gy of 60 Co., 1 hour after the injection ip of DMSO 0,025M. b) In vivo, molecular level, when DMSO 1M, is added 10 min. before the irradiation with 25.000 Gy of 60 Co, from an aqueous solution of proteins from crystalline bovine. (C.G.C.) [pt
Regularities of thermochemical characteristics of 1-1, 2-1, 3-1 electrolyte solutions in dimethyl sulfoxide-water and propylene carbonate water mixtures
International Nuclear Information System (INIS)
Vorob'ev, A.F.; Monaenkova, A.S.; AlekseeV, G.I.
In an air-tight tilting calorimeter with an isothermal casing enthalpies of praseodymium chloride solution in water, dimethyl sulfoxide (DMSO) - water mixtures, contaning 3.86 and 18.53 mol.% DMSO, and propylene carbonate (PC) - water mixtures, containing 1.85 and 3.23 mol.% PC are measured. The enthalpies of praseodymium chloride solution in the given mixtures in case of infinite solution dilution are determined. Solvation enthalpies of praseodymium and neodymium chlorides, as well as alkali earth metal and magnesium chlorides in water and DMSO - water and PC - water mixtures are calculated. Regularities in thermochemical characteristics of solutions of the given salts in DMSO - water and PC - water mixtures are discussed
FTIR spectroscopic study of Li+ solvation in the solutions of LiBF4 in propylene carbonate, dimethyl sulfoxide, and their mixtures
Zhang, Binbin; Li, Yantao; Hou, Baorong
Ionic solvation in solutions of lithium tetrafluoroborate (LiBF4) in propylene carbonate (PC) + dimethyl sulfoxide (DMSO) mixtures has been studied using Fourier transformed infrared (FTIR) spectroscopy. Dimerization of DMSO molecules in the solutions was taken into account. The obtained results are discussed with respect to the electrolyte concentration and properties of the cations of the electrolyte. Band changes due to solvation interaction were detected in the region of the C=O stretching vibrations and ring deformation for PC, and the S=O stretching vibrations and C-S-C skeleton stretching modes for DMSO, indicating that there is a strong interaction between lithium cations and solvent molecules. In addition, Li+ was preferentially solvated by DMSO in these binary solvents as a result of the large difference in their donor number (DN) values. The structures of PC, DMSO, Li+-PC, Li+-DMSO, and Li+-PC+DMSO were given.
Obtaining tabular silver bromide crystals using double-jet method in the presence of dimethyl sulfoxide
Energy Technology Data Exchange (ETDEWEB)
Dyonizy, A.; Nowak, P. [Institute of Physical and Theoretical Chemistry, Wroclaw University of Technology, Wybrzeze St., Wyspianskiego 27, 50-370 Wroclaw (Poland)
Water-gelatine suspensions containing tabular crystals of silver bromide were obtained using the modified double-jet method, in the presence of dimethyl sulfoxide and an excess of bromide ions, used to increase silver bromide solubility. The size and morphology of crystals obtained depend mostly on the constant concentration of complexing agents in the dispersive solution, during nucleation and crystal growth. The influence of excessive bromide ions concentration and volumetric concentration of dimethyl sulfoxide in the crystallising mixture on the formation of tabular - triangular or hexagonal thin plates - of high aspect ratio has been analysed. During experiment, optimal ranges of dimethyl sulfoxide and excessive bromide ions concentrations for obtaining interesting forms of flat silver bromide crystals were determined. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)
Recommended vapor pressures for thiophene, sulfolane, and dimethyl sulfoxide
Czech Academy of Sciences Publication Activity Database
Fulem, Michal; Růžička, K.; Růžička, M.
Roč. 303, č. 2 (2011), s. 205-216 ISSN 0378-3812 Institutional research plan: CEZ:AV0Z10100521 Keywords : thiophene sulfolane * dimethyl sulfoxide * vapor pressure * heat capacity * vaporization enthalpy * recommended vapor pressure equation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.139, year: 2011
On the Origin of Microheterogeneity : A Mass Spectrometric Study of Dimethyl Sulfoxide-Water Binary Mixture
Shin, Dong Nam; Wijnen, Jan W.; Engberts, Jan B.F.N.; Wakisaka, Akihiro
We have studied the microscopic solvent structure of dimethyl sulfoxide-water mixtures and its influence on the solvation structure of solute from a clustering point of View, by means of a specially designed mass spectrometric system. It was observed that the propensity to the cluster formation is
Diapause prevention effect of Bombyx mori by dimethyl sulfoxide.
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Takayuki Yamamoto
Full Text Available HCl treatment has been, for about 80 years, the primary method for the prevention of entry into embryonic diapauses of Bombyx mori. This is because no method is as effective as the HCl treatment. In this study, we discovered that dimethyl sulfoxide (DMSO prevented entry into the diapause of the silkworm, Bombyx mori. The effect of diapause prevention was 78% as a result of treatment with 100% DMSO concentration, and the effect was comparable to that of the HCl treatment. In contrast, in the case of non-diapause eggs, hatchability was decreased by DMSO in a concentration-dependent manner. The effect of DMSO was restricted within 24 hours after oviposition of diapause eggs, and the critical period was slightly shorter than the effective period of the HCl treatment. DMSO analogs, such as dimethyl formamide (DMF and dimethyl sulfide (DMS, did little preventive effect against the diapause. Furthermore, we also investigated the permeation effects of chemical compounds by DMSO. When treated with an inhibitor of protein kinase CK2 (CK2 dissolved in DMSO, the prevention rate of the diapause was less than 40%. This means that the inhibition effect by the CK2 inhibitor was the inhibition of embryonic development after diapause prevention by DMSO. These data suggest that DMSO has the effects of preventing from entering into the diapause and permeation of chemicals into diapause eggs.
Lipase nanogel catalyzed transesterification in anhydrous dimethyl sulfoxide.
Ge, Jun; Lu, Diannan; Wang, Jun; Liu, Zheng
The present work showed that Candida rugosa lipase, which is inactive in anhydrous dimethyl sulfoxide (DMSO), has been granted its original catalytic activity and greatly enhanced stability when encapsulated into a polyacrylamide nanogel. The molecular simulation and structural analysis suggested that the polyacrylamide nanogel shielded the extraction of essential water and maintained the native configuration of encapsulated lipase in anhydrous DMSO at an elevated temperature. The electron and fluorescence microscopy showed that the lipase nanogel would be well dispersed in anhydrous DMSO where its native counterpart aggregated. The encapsulated lipase behaved as a stable catalyst for transesterification between dextran and vinyl decanoate in anhydrous DMSO at 60 degrees C for 240 h and yielded a dextran-based polymeric surfactant with regioselectivity toward the C-2 hydroxyl group in the glucopyranosyl unit of dextran. All these indicated a high potential of enzyme nanogel for nonaqueous biocatalysis.
Membrane permeability of the human granulocyte to water, dimethyl sulfoxide, glycerol, propylene glycol and ethylene glycol.
Vian, Alex M; Higgins, Adam Z
Granulocytes are currently transfused as soon as possible after collection because they rapidly deteriorate after being removed from the body. This short shelf life complicates the logistics of granulocyte collection, banking, and safety testing. Cryopreservation has the potential to significantly increase shelf life; however, cryopreservation of granulocytes has proven to be difficult. In this study, we investigate the membrane permeability properties of human granulocytes, with the ultimate goal of using membrane transport modeling to facilitate development of improved cryopreservation methods. We first measured the equilibrium volume of human granulocytes in a range of hypo- and hypertonic solutions and fit the resulting data using a Boyle-van't Hoff model. This yielded an isotonic cell volume of 378 μm(3) and an osmotically inactive volume of 165 μm(3). To determine the permeability of the granulocyte membrane to water and cryoprotectant (CPA), cells were injected into well-mixed CPA solution while collecting volume measurements using a Coulter Counter. These experiments were performed at temperatures ranging from 4 to 37°C for exposure to dimethyl sulfoxide, glycerol, ethylene glycol, and propylene glycol. The best-fit water permeability was similar in the presence of all of the CPAs, with an average value at 21°C of 0.18 μmatm(-1)min(-1). The activation energy for water transport ranged from 41 to 61 kJ/mol. The CPA permeability at 21°C was 6.4, 1.0, 8.4, and 4.0 μm/min for dimethyl sulfoxide, glycerol, ethylene glycol, and propylene glycol, respectively, and the activation energy for CPA transport ranged between 59 and 68 kJ/mol. Copyright © 2013 Elsevier Inc. All rights reserved.
Antioxidant properties of dimethyl sulfoxide and its viability as a solvent in the evaluation of neuroprotective antioxidants.
Sanmartín-Suárez, Carolina; Soto-Otero, Ramón; Sánchez-Sellero, Inés; Méndez-Álvarez, Estefanía
Dimethyl sulfoxide is an amphiphilic compound whose miscibility with water and its ability to dissolve lipophilic compounds make it an appreciated solvent in biomedical research. However, its reported antioxidant properties raise doubts about its use as a solvent in evaluating new antioxidants. The goal of this investigation was to evaluate its antioxidant properties and carry out a comparative study on the antioxidant properties of some known neuroprotective antioxidants in the presence and absence of dimethyl sulfoxide. The antioxidant properties of dimethyl sulfoxide were studied in rat brain homogenates by determining its ability to reduce both lipid peroxidation (TBARS formation) and protein oxidation (increase in protein carbonyl content and decrease in free thiol content) induced by ferrous chloride/hydrogen peroxide. Its ability to reduce the production of hydroxyl radicals by 6-hydroxydopamine autoxidation was also estimated. The same study was also performed with three known antioxidants (α-phenyl-N-tert-butylnitrone; 2-methyl-2-nitrosopropane; 5,5-dimethyl-1-pyrroline N-oxide) in the presence and absence of dimethyl sulfoxide. Our results showed that dimethyl sulfoxide is able to reduce both lipid peroxidation and protein carbonyl formation induced by ferrous chloride/hydrogen peroxide in rat brain homogenates. It can also reduce the production of hydroxyl radicals during 6-hydroxydopamine autoxidation. However, it increases the oxidation of protein thiol groups caused by ferrous chloride/hydrogen peroxide in rat brain homogenate. Despite the here reported antioxidant and pro-oxidant properties of dimethyl sulfoxide, the results obtained with α-phenyl-N-tert-butylnitrone, 2-methyl-2-nitrosopropane, and 5,5-dimethyl-1-pyrroline N-oxide corroborate the antioxidant properties attributed to these compounds and support the potential use of dimethyl sulfoxide as a solvent in the study of the antioxidant properties of lipophilic compounds. Dimethyl sulfoxide
Onychomycosis treated with a dilute povidone–iodine/dimethyl sulfoxide preparation
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Capriotti K
Full Text Available Kara Capriotti,1,2,* Joseph A Capriotti1,3,*1ALC Therapeutics, LLC, Springhouse, PA, 2Bryn Mawr Skin and Cancer Institute, Rosemont, PA, 3Plessen Ophthalmology Consultants, Christiansted, VI, USA*These authors are related through marriage Background: Povidone–iodine (PVP-I 10% aqueous solution is a well-known, nontoxic, commonly used topical antiseptic with no reported incidence of fungal resistance. We have been using a low-dose formulation of 1% PVP-I (w/w in a solution containing dimethyl sulfoxide (DMSO in our clinical practice for a variety of indications. Presented here is our clinical experience with this novel formulation in a severe case of onychomycosis that was resistant to any other treatment. Findings: A 49-year-old woman who had been suffering from severe onychomycosis for years presented after failing to find any remedy including over the counter (OTC, topical, and systemic oral prescribed therapies. Conclusion: The topical povidone–iodine/DMSO system was very effective in this case at alleviating the signs and symptoms of onychomycosis. This novel combination warrants further investigation in randomized, controlled trials to further elucidate its clinical utility. Keywords: onychomycosis, povidone–iodine, fungus, nail
Dimethyl sulfoxide and sodium bicarbonate in the treatment of refractory cancer pain.
Hoang, Ba X; Tran, Dao M; Tran, Hung Q; Nguyen, Phuong T M; Pham, Tuan D; Dang, Hong V T; Ha, Trung V; Tran, Hau D; Hoang, Cuong; Luong, Khue N; Shaw, D Graeme
Pain is a major concern of cancer patients and a significant problem for therapy. Pain can become a predominant symptom in advanced cancers. In this open-label clinical study, the authors have treated 26 cancer patients who have been declared as terminal without the option of conventional treatment. These patients suffered from high levels of pain that was poorly managed by all available interventional approaches recommended by World Health Organization (WHO) guideline. The results indicate that intravenous infusion of dimethyl sulfoxide (DMSO) and sodium bicarbonate (SB) solution can be a viable, effective, and safe treatment for refractory pain in cancer patients. These patients had pain due to the disease progression and complication of chemotherapy and radiation. Moreover, the preliminary clinical outcome of 96-day follow-up suggests that the application of DMSO and SB solution intravenously could lead to better quality of life for patients with nontreatable terminal cancers. The data of this clinical observation indicates that further research and application of the DMSO and SB combination may help the development of an effective, safe, and inexpensive therapy to manage cancer pain.
Trimesic acid dimethyl sulfoxide solvate: space group revision
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Sylvain Bernès
Full Text Available The structure of the title solvate, C9H6O6·C2H6OS, was determined 30 years ago [Herbstein, Kapon & Wasserman (1978. Acta Cryst. B34, 1613–1617], with data collected at room temperature, and refined in the space group P21. The present redetermination, based on high-resolution diffraction data, shows that the actual space group is more likely to be P21/m. The crystal structure contains layers of trimesic acid molecules lying on mirror planes. A mirror plane also passes through the S and O atoms of the solvent molecule. The molecules in each layer are interconnected through strong O—H...O hydrogen bonds, forming a two-dimensional supramolecular network within each layer. The donor groups are the hydroxyls of the trimesic acid molecules, while the acceptors are the carbonyl or the sulfoxide O atoms.
Crystal structure of hexakis(dimethyl sulfoxide-κOmanganese(II diiodide
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Mathias Glatz
Full Text Available The asymmetric unit of the title salt, [Mn(C2H6OS6]I2, consists of one MnII ion, six O-bound dimethyl sulfoxide (DMSO ligands and two I− counter-anions. The isolated complex cations have an octahedral configuration and are grouped in hexagonally arranged rows extending parallel to [100]. The two I− anions are located between the rows and are linked to the cations through two weak C—H...I interactions.
A model to predict the permeation kinetics of dimethyl sulfoxide in articular cartilage.
Yu, Xiaoyi; Chen, Guangming; Zhang, Shaozhi
Cryopreservation of articular cartilage (AC) has excited great interest due to the practical surgical importance of this tissue. Characterization of permeation kinetics of cryoprotective agents (CPA) in AC is important for designing optimal CPA addition/removal protocols to achieve successful cryopreservation. Permeation is predominantly a mass diffusion process. Since the diffusivity is a function of temperature and concentration, analysis of the permeation problem would be greatly facilitated if a predictive method were available. This article describes, a model that was developed to predict the permeation kinetics of dimethyl sulfoxide (DMSO) in AC. The cartilage was assumed as a porous medium, and the effect(s) of composition and thermodynamic nonideality of the DMSO solution were considered in model development. The diffusion coefficient was correlated to the infinite dilution coefficients through a binary diffusion thermodynamic model. The UNIFAC model was used to evaluate the activity coefficient, the Vignes equation was employed to estimate the composition dependence of the diffusion coefficient, and the Siddiqi-Lucas correlation was applied to determine the diffusion coefficients at infinite dilution. Comparisons of the predicted overall DMSO uptake by AC with the experimental data over wide temperature and concentration ranges [1~37°C, 10~47% (w/w)] show that the model can accurately describe the permeation kinetics of DMSO in AC [coefficient of determination (R(2)): 0.961~0.996, mean relative error (MRE): 2.2~9.1%].
Thermodynamic parameters of the complexation of uranyl(VI) by diethylenetriamine in dimethyl sulfoxide
International Nuclear Information System (INIS)
Cassol, A.; Bernardo, P. di; Portanova, R.; Tolazzi, M.; Tomat, G.; Zanonato, P.L.
The changes in free energy, enthalpy, and entropy for the complex formation reactions between uranyl(VI) ion and diethylenetriamine (dien) in dimethyl sulfoxide have been determined by potentiometric and calorimetric measurements at 25 C in a medium of ionic strength 0.1 mol dm -3 . The amine forms a very stable 1:1 complex which results stabilized only by the highly favourable enthalpy change. Entropy change is negative and opposes the reaction. The comparison of the thermodynamic data concerning complexation of uranyl(VI) by charged and uncharged ligands reveals that in this case (uncharged ligand) the enthalpy contribution is mainly related to the formation of the metal-ligand bonds while the entropy term might be associated with the decrease in the translational and conformational entropy occurring in the complexation of the ligand. FTIR and calorimetric measurements have been carried out to study the effect of traces of water on the equilibria in solution. It has been found that water can interfere in the complexation reaction giving rise to the formation of a dinuclear hydroxo complex in which probably two μ 2 -OH bridges link two monomer moieties. (orig.)
Potentiometric investigation of acid dissociation and anionic homoconjugation equilibria of substituted phenols in dimethyl sulfoxide[Substituted phenols; Acid-base equilibria; Dimethyl sulfoxide (DMSO); Potentiometry
Energy Technology Data Exchange (ETDEWEB)
Czaja, Malgorzata; Kozak, Anna; Makowski, Mariusz; Chmurzynski, Lech. E-mail: firstname.lastname@example.com
Standard acidity constants, K{sub a}{sup DMSO} (HA), expressed as pK{sub a}{sup DMSO} (HA) values, and anionic homoconjugation constants, K{sup DMSO}{sub AHA{sup -}}, (in the form of lg K{sup DMSO}{sub AHA{sup -}} values) have been determined for 11 substituted phenol-phenolate systems a polar protophilic aprotic solvent, dimethyl sulfoxide (DMSO) with a potentiometric titration. A linear relationship has been determined between lg K{sup DMSO}{sub AHA{sup -}} and pK{sub a}{sup DMSO} (HA). The tendency towards anionic homoconjugation in these systems increases with increasing pK{sub a}{sup DMSO} (HA) that is with declining phenol acidity. The pK{sub a}{sup DMSO} (HA) are correlated with both pK{sub a}{sup W} (HA) water and other polar non-aqeous solvents.
Three-body dissociations: The photodissociation of dimethyl sulfoxide at 193 nm
Energy Technology Data Exchange (ETDEWEB)
Blank, D.A.; North, S.W.; Stranges, D. [Lawrence Berkeley National Lab., CA (United States)] [and others
When a molecule with two equivalent chemical bonds is excited above the threshold for dissociation of both bonds, how the rupture of the two bonds is temporally coupled becomes a salient question. Following absorption at 193 nm dimethyl sulfoxide (CH{sub 3}SOCH{sub 3}) contains enough energy to rupture both C-S bonds. This can happen in a stepwise (reaction 1) or concerted (reaction 2) fashion where the authors use rotation of the SOCH{sub 3} intermediate prior to dissociation to define a stepwise dissociation: (1) CH{sub 3}SOCH{sub 3} {r_arrow} 2CH{sub 3} + SO; (2a) CH{sub 3}SOCH{sub 3} {r_arrow} CH{sub 3} + SOCH{sub 3}; and (2b) SOCH{sub 3} {r_arrow} SO + CH{sub 3}. Recently, the dissociation of dimethyl sulfoxide following absorption at 193 nm was suggested to involve simultaneous cleavage of both C-S bonds on an excited electronic surface. This conclusion was inferred from laser induced fluorescence (LIF) and resonant multiphoton ionization (2+1 REMPI) measurements of the internal energy content in the CH{sub 3} and SO photoproducts and a near unity quantum yield measured for SO. Since this type of concerted three body dissociation is very interesting and a rather rare event in photodissociation dynamics, the authors chose to investigate this system using the technique of photofragment translational spectroscopy at beamline 22.214.171.124. The soft photoionization provided by the VUV undulator radiation allowed the authors to probe the SOCH{sub 3} intermediate which had not been previously observed and provided good evidence that the dissociation of dimethyl sulfoxide primarily proceeds via a two step dissociation, reaction 2.
Potentiometric investigations of molecular heteroconjugation equilibria of substituted phenol+n-butylamine systems in dimethyl sulfoxide
International Nuclear Information System (INIS)
Czaja, MaIgorzata; Baginska, Katarzyna; Kozak, Anna; Makowski, Mariusz; Chmurzynski, Lech
Molecular heteroconjugation constants, K BHA DMSO and K AHB DMSO , expressed as their logarithms, have been determined by potentiometric titration for eleven substituted phenol+n-butylamine systems in a polar protophilic aprotic solvent, dimethyl sulfoxide (DMSO). An increasing tendency towards molecular heteroconjugation in these systems without proton transfer has been found with increasing pK a DMSO (HA), i.e., with decreasing phenol acidity. Moreover, a linear correlation has been established between the determined lgK BHA DMSO values and pK a DMSO (HA). Furthermore, overall stability constants, lgK o DMSO , could be correlated linearly with pK a DMSO (HA) values
Radioprotective effects of dimethyl sulfoxide in two biological systems
International Nuclear Information System (INIS)
Mastro, N.L. del; Bernardes, D.M.L.; Villavicencio, A.L.C.
The present study was conducted: a) to confirm data from others describing a radioprotective capacity of DMSO in mice; b) to establish whether this protective behavior could be evidenced in an in vitro chemical system utilizing bovine crystalline protein as target. Heterozigous female albino mice were used for the 30-day-survival studies after 9 Gy sup(60)Co gamma irradiation (dose rate: 4.5 Gy/min) injected 1 h prior with 2000 mg/kg DMSO intraperitoneally. Total body weight curves during the same period were also analysed. For the molecular level studies 1 M DMSO was added to a series of aqueous protein solutions from bovine lens and 10 min later irradiated with 5 different doses from 5,000 to 25,000 Gy sup(60)Co (average dose rate 14 Gy/min). After irradiation, spectrophotometric reading at 600 nm and free thiol group determinations were performed in order to evaluate the radiation-induced modifications. (author)
A New Look at the Stability of Dimethyl Sulfoxide and Acetonitrile in Li-O2 Batteries
DEFF Research Database (Denmark)
Younesi, Reza; Norby, Poul; Vegge, Tejs
Dimethyl sulfoxide (DMSO) and acetonitrile (MeCN) have recently been highlighted as promising electrolyte solvents for Li-O2 batteries. Possible reactions between these two solvents and Li2O2 are here discussed using X-ray photoelectron spectroscopy to analyze surface of the Li2O2 powder after...
Chemiluminescence of curcumin and quenching effect of dimethyl sulfoxide on its peroxyoxalate system
Energy Technology Data Exchange (ETDEWEB)
Yari, Abdollah, E-mail: email@example.com [Lorestan University, Department of Chemistry, Flakalaflak Street, 68178-17133 Khorramabad (Iran, Islamic Republic of); Saidikhah, Marzieh [Lorestan University, Department of Chemistry, Flakalaflak Street, 68178-17133 Khorramabad (Iran, Islamic Republic of)
The chemiluminescence behavior of the reaction between bis(2,4,6-trichlorophenyl)oxalate (TCPO) and hydrogen peroxide, in the presence of curcumin as fluorophore, has been investigated. Experimental factors such as TCPO, sodium salicylate (SS), hydrogen peroxide and curcumin concentration were optimized. The chemiluminescence signal showed a linear decay while dimethyl sulfoxide (DMSO) was added to the peroxyoxalate (PO-CL) system. The reaction resulted in a Stern-Volmer plot with a K{sub q} value of 7.3x10{sup 4}. The evaluated lower and upper detection limits of measurable concentrations of DMSO are 3.50x10{sup -5} and 1.53x10{sup -4} M, respectively. The PO-CL parameters were estimated by computer fitting of the experimental CL intensity to proper models.
Dimethyl Sulfoxide Enhances Effectiveness of Skin Antiseptics and Reduces Contamination Rates of Blood Cultures
LaSala, Paul R.; Han, Xiang-Yang; Rolston, Kenneth V.; Kontoyiannis, Dimitrios P.
Effective skin antisepsis is of central importance in the prevention of wound infections, colonization of medical devices, and nosocomial transmission of microorganisms. Current antiseptics have a suboptimal efficacy resulting in substantial infectious morbidity, mortality, and increased health care costs. Here, we introduce an in vitro method for antiseptic testing and a novel alcohol-based antiseptic containing 4 to 5% of the polar aprotic solvent dimethyl sulfoxide (DMSO). The DMSO-containing antiseptic resulted in a 1- to 2-log enhanced killing of Staphylococcus epidermidis and other microbes in vitro compared to the same antiseptic without DMSO. In a prospective clinical validation, blood culture contamination rates were reduced from 3.04% for 70% isopropanol–1% iodine (control antiseptic) to 1.04% for 70% isopropanol–1% iodine–5% DMSO (P antiseptics containing strongly polarized but nonionizing (polar aprotic) solvents. PMID:22378911
Crystal structure of hexakis(dimethyl sulfoxide-κO)manganese(II) tetraiodide
Haque, Mohammed
The title salt, [Mn(C2H6OS)6]I4, is made up from discrete [Mn(DMSO)6]2+ (DMSO is dimethyl sulfoxide) units connected through non-classical hydrogen bonds to linear I4 2- tetraiodide anions. The MnII ion in the cation, situated on a position with site symmetry -3., is octahedrally coordinated by O atoms of the DMSO molecule with an Mn - O distance of 2.1808(12)Å. The I4 2- anion contains a neutral I2 molecule weakly coordinated by two iodide ions, forming a linear centrosymmetric tetraiodide anion. The title compound is isotypic with the Co, Ni, Cu, and Zn analogues.
Potentiometric investigation of acid dissociation and anionic homoconjugation equilibria of substituted phenols in dimethyl sulfoxide
International Nuclear Information System (INIS)
Czaja, Malgorzata; Kozak, Anna; Makowski, Mariusz; Chmurzynski, Lech.
Standard acidity constants, K a DMSO (HA), expressed as pK a DMSO (HA) values, and anionic homoconjugation constants, K DMSO AHA - , (in the form of lg K DMSO AHA - values) have been determined for 11 substituted phenol-phenolate systems a polar protophilic aprotic solvent, dimethyl sulfoxide (DMSO) with a potentiometric titration. A linear relationship has been determined between lg K DMSO AHA - and pK a DMSO (HA). The tendency towards anionic homoconjugation in these systems increases with increasing pK a DMSO (HA) that is with declining phenol acidity. The pK a DMSO (HA) are correlated with both pK a W (HA) water and other polar non-aqeous solvents
Lack of effect of deferoxamine, dimethyl sulfoxide, and catalase on monocrotaline pyrrole pulmonary injury
Energy Technology Data Exchange (ETDEWEB)
Bruner, L.H.; Johnson, K.; Carpenter, L.J.; Roth, R.A.
Monocrotaline pyrrole (MCTP) is a reactive metabolite of the pyrrolizidine alkaloid monocrotaline. MCTP given intravenously to rats causes pulmonary hypertension and right ventricular hypertrophy. Lesions in lungs after MCTP treatment contain macrophages and neutrophils, which may contribute to the damage by generation of reactive oxygen metabolites. Rats were treated with MCTP and agents known to protect against oxygen radical-mediated damage in acute models of neutrophil-dependent lung injury. Rats received MCTP and deferoxamine mesylate (DF), dimethyl sulfoxide (DMSO), or polyethylene glycol-coupled catalase (PEG-CAT). MCTP/vehicle-treated controls developed lung injury manifested as increased lung weight, release of lactate dehydrogenase into the airway, and sequestration of SVI-labeled bovine serum albumin in the lungs. Cotreatment of rats with DF, DMSO, or PEG-CAT did not protect against the injury due to MCTP. These results suggest that toxic oxygen metabolites do not play an important role in the pathogenesis of MCTP-induced pulmonary injury.
Potentiometric investigations of molecular heteroconjugation equilibria of substituted phenol+n-butylamine systems in dimethyl sulfoxide
Energy Technology Data Exchange (ETDEWEB)
Czaja, MaIgorzata [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Baginska, Katarzyna [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Kozak, Anna [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Makowski, Mariusz [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Chmurzynski, Lech [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland)]. E-mail: firstname.lastname@example.com
Molecular heteroconjugation constants, K{sub BHA}{sup DMSO} and K{sub AHB}{sup DMSO}, expressed as their logarithms, have been determined by potentiometric titration for eleven substituted phenol+n-butylamine systems in a polar protophilic aprotic solvent, dimethyl sulfoxide (DMSO). An increasing tendency towards molecular heteroconjugation in these systems without proton transfer has been found with increasing pK{sub a}{sup DMSO} (HA), i.e., with decreasing phenol acidity. Moreover, a linear correlation has been established between the determined lgK{sub BHA}{sup DMSO} values and pK{sub a}{sup DMSO} (HA). Furthermore, overall stability constants, lgK{sub o}{sup DMSO}, could be correlated linearly with pK{sub a}{sup DMSO} (HA) values.
Vapor pressure, density, viscosity and refractive index of dimethyl sulfoxide + 1,4-dimethylbenzene system
Directory of Open Access Journals (Sweden)
Full Text Available This paper reports the experimental results of isothermal vapor–liquid equilibrium data between 303.15 and 333.15 K, and densities, viscosities, refractive indices from 298.15 to 323.15 K of the dimethyl sulfoxide + 1,4-dimethylbenzene system over the entire range of mixture composition. The obtained PTX data were correlated by the Wilson and NRTL models and estimated by the UNIFAC model. The excess Gibbs energy and activity coefficients were calculated and compared with others excess properties. Excess molar volumes, viscosity deviations and deviations in refractivity were calculated from the experimental data; all the computed quantities were fitted to the Redlich–Kister equation. The resulting excess functions were interpreted in terms of structure and interactions.
cis-Dichlorido(dimethyl sulfoxide-κS(N,N,N′,N′-tetramethylguanidine-κN′′platinum(II
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Ivan I. Eliseev
Full Text Available In the title compound, cis-[PtCl2(C5H13N3(C2H6OS], the four-coordinate PtII atom is bonded to one N atom of the N,N,N′,N′-tetramethylguanidine ligand, one dimethyl sulfoxide S atom and two chloride ligands, forming a cis-square-planar geometry. The bond lengths and angles of the N—Pt—Cl functionality are typical for imine dichloridoplatinum(II complexes. The H atom of the imino group is oriented towards the O atom of the sulfoxide group of a neighboring molecule and forms an N—H...O hydrogen bond.
Effect of Calcium Chloride on the Permeation of the Cryoprotectant Dimethyl Sulfoxide to Japanese Whiting Sillago japonica Embryos
Rahman, Sk. Mustafizur; Majhi, Sullip Kumar; Suzuki, Toru; Strussmann, Carlos Augusto; Watanabe, Manabu
Cryopreservation of fish eggs and embryos is a highly desired tool to promote aquaculture production and fisheries resource management, but it is still not technically feasible. The failure to develop successful cryopreservation protocols for fish embryos is largely attributed to poor cryoprotectant permeability. The purpose of this study was to test the effectiveness of CaCl2 to enhance cryoprotectant uptake by fish embryos. In this study, embryos (somites and tail elongation stages) of Japanese whiting Sillago japonica were exposed to 10 and 15% dimethyl sulfoxide (DMSO) in artificial sea water (ASW) or a solution of 0.125M CaCl2 in distilled water for 20 min at 24°C. The toxicity of all solutions was estimated from the hatching rates of the embryos and High Performance Liquid Chromatography was used to determine the amount of DMSO taken up during impregnation. The results showed that DMSO incorporation into the embryos was greatly (›50%) enhanced in the presence of CaCl2 compared to ASW. CaCl2 itself was not toxic to the embryos but, probably as a result of the enhanced DMSO uptake, caused decreases in survival of about 14-44% relative to ASW. Somites stage embryos were more tolerant than tail elongation ones to DMSO both as ASW and CaCl2 solutions. The use of CaCl2 as a vehicle for DMSO impregnation could be a promising aid for the successful cryopreservation of fish embryos.
trans-Chlorido(dimethyl sulfoxide-κS(pyridine-2-carboxylato-κ2N,Oplatinum(II
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Kwang Ha
Full Text Available In the title complex, [Pt(C6H4NO2Cl(C2H6OS], the PtII ion is in a distorted square-planar environment defined by the N and O atoms from the chelating pyridine-2-carboxylate (pic anionic ligand, one S atom of the dimethyl sulfoxide molecule and one Cl ion. The complex is disposed about a crystallographic mirror plane parallel to the ac plane passing through all the atoms of the complex except the methyl atoms of the dimethyl sulfoxide. The molecules are stacked in columns along the b axis with a Pt...Pt distance of 4.9508 (5 Å. Within the column, intermolecular C—H...O hydrogen bonds and weak π–π interactions between adjacent pyridine rings are present, the shortest centroid–centroid distance being 5.153 (4 Å.
Historical perspectives and the future of adverse reactions associated with haemopoietic stem cells cryopreserved with dimethyl sulfoxide
DEFF Research Database (Denmark)
Cox, Michael A; Kastrup, Jens; Hrubiško, Mikulas
A retrospective review of the published literature identified several hundred adverse reactions (e.g. nausea, chills, cardiac arrhythmias, neurological symptoms and respiratory arrest) associated with the transplantation of stem cells cryopreserved with dimethyl sulfoxide. The occurrences...... of these are generally accepted as commonplace, as the majority of reactions are transient, whilst a few patients may require clinical treatment. This exploratory study is a collation of the historical data and the expectations for the notification of serious adverse reactions. Outline information is presented...
Variation of Spectral Characteristics of Coelenteramide-Containing Fluorescent Protein from Obelia Longissima Exposed to Dimethyl Sulfoxide
Petrova, A. S.; Alieva, R. R.; Belogurova, N. V.; Tirranen, L. S.; Kudryasheva, N. S.
Effect of dimethyl sulfoxide (DMSO), a widespread biomedical agent, on spectral-luminescent characteristics of coelenteramide-containing fluorescent protein - discharged obelin - is investigated. Contributions of violet and blue-green spectral components to fluorescence of discharged obelin are elucidated and characterized at different photoexcitation energies. Dependences of these contributions on the DMSO concentration are presented. Spectral changes are related to the destructive effect of DMSO on fluorescent protein and decreasing efficiency of proton transfer to electronically excited states of fluorophore.
Intravesical Dimethyl Sulfoxide Inhibits Acute and Chronic Bladder Inflammation in Transgenic Experimental Autoimmune Cystitis Models
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Ronald Kim
Full Text Available New animal models are greatly needed in interstitial cystitis/painful bladder syndrome (IC/PBS research. We recently developed a novel transgenic cystitis model (URO-OVA mice that mimics certain key aspects of IC/PBS pathophysiology. This paper aimed to determine whether URO-OVA cystitis model was responsive to intravesical dimethyl sulfoxide (DMSO and if so identify the mechanisms of DMSO action. URO-OVA mice developed acute cystitis upon adoptive transfer of OVA-specific OT-I splenocytes. Compared to PBS-treated bladders, the bladders treated with 50% DMSO exhibited markedly reduced bladder histopathology and expression of various inflammatory factor mRNAs. Intravesical DMSO treatment also effectively inhibited bladder inflammation in a spontaneous chronic cystitis model (URO-OVA/OT-I mice. Studies further revealed that DMSO could impair effector T cells in a dose-dependent manner in vitro. Taken together, our results suggest that intravesical DMSO improves the bladder histopathology of IC/PBS patients because of its ability to interfere with multiple inflammatory and bladder cell types.
Dimethyl sulfoxide (DMSO) as intravesical therapy for interstitial cystitis/bladder pain syndrome: A review.
Rawls, William F; Cox, Lindsey; Rovner, Eric S
The purpose of this review is to update the current understanding of dimethyl sulfoxide (DMSO) and its role in the treatment of interstitial cystitis (IC). A systematic review was conducted using the PRIMSA checklist to identify published articles involving intravesical DMSO for the treatment of IC. Thirteen cohort studies and three randomized-controlled trials were identified. Response rates relying on subjective measurement scores range from 61 to 95%. No increased efficacy was found with "cocktail" DMSO therapy. Great variation existed in diagnostic criteria, DMSO instillation protocols and response measurements. The current evidence backing DMSO is a constellation of cohort studies and a single randomized-controlled trial versus placebo. The optimal dose, dwell time, type of IC most likely to respond to DMSO, definitions of success/failure and the number of treatments are not universally agreed upon. Improvements in study design, phenotyping patients based on symptoms, as well as the emergence of reliable biomarkers of the disease may better guide the use of DMSO in the future. © 2017 Wiley Periodicals, Inc.
Shaping Gold Nanocrystals in Dimethyl Sulfoxide: Toward Trapezohedral and Bipyramidal Nanocrystals Enclosed by {311} Facets.
Niu, Wenxin; Duan, Yukun; Qing, Zikun; Huang, Hejin; Lu, Xianmao
The remarkable synthetically tunable structural, electronic, and optical properties of gold nanocrystals have attracted increasing interest and enabled multidisciplinary applications. Over the past decades, nearly all the possible fundamental shapes of faceted Au nanocrystals have been synthesized, except for only one missing-the trapezohedron enclosed by {hkk} facets. In this report, the unprecedented synthesis of trapezohedral Au nanocrystals with {311} crystal facets was realized. Dimethyl sulfoxide (DMSO) was discovered as a solvent for shaping Au nanocrystals with {311} crystal facets for the first time. Mechanistic studies, together with previous DFT and STM studies, attribute the unique role of DMSO to its ambidentate nature, where both sulfur and oxygen of DMSO can coordinate to gold surface, endowing its unique role in stabilizing high-index {311} facets through a "two center bonding" mode. The DMSO-based synthesis provides a new synthetic tool toward the synthesis of a series of unreported Au nanocrystals with new structures. In particular, a new type of gold bipyramids, the octagonal bipyramids, was first synthesized with additional plasmonic tunability while simultaneously retaining their {311} facets. The application of these new Au nanocrystals in surface-enhanced Raman scattering spectroscopy was investigated, and their shape-dependent performances were demonstrated. These results highlight the tremendous potential of using ambidentate molecules as shape- and surface-directing agents for metal nanocrystals and offer the promise of enabling new synthetic tools toward atomically precise control of surface structures of metal nanocrystals.
Dimethyl sulfoxide alterations of macromolecular synthesis by chick limb mesenchymal cells in vitro
International Nuclear Information System (INIS)
Major, F.W.; Parker, C.L.; Patterson, R.M.
Earlier the authors reported that dimethyl sulfoxide (DMSO) inhibited the chondrogenesis of chick limb cells in vitro at concentrations of 30 mg/ml or greater. The present study was undertaken to determine if inhibition by DMSO might be due to an alteration in protein and/or DNA synthesis by the treated cells. Micromass cultures were prepared from stage 23-25 chick limb mesenchyme. The cells were treated with either 30 or 40 mg of DMSO/ml of culture medium for 24, 48, and 72 hr. After each treatment, protein and DNA synthesis were analyzed by the incorporation of [ 3 H]-leucine and [ 3 H]-thymidine, respectively. Cell cultures exposed to 40 mg DMSO/ml for 24 hr showed a significant decrease in protein synthesis, while there was no decrease in protein synthesis for cells treated with 30 mg DMSO/ml. At both 48 and 72 hr treatment with 30 mg of DMSO, there was a decrease in [ 3 H]-leucine incorporation. The thymidine studies indicated that there was a significant decrease in DNA synthesis as early as 24 hr for both DMSO concentrations. These findings suggest that the inhibition of chondrogenesis following DMSO treatment may be related to alterations in macromolecular synthesis possibly including extracellular cartilage matrix production
Study on calcination of bi-layered films produced by anodizing iron in dimethyl sulfoxide electrolyte
International Nuclear Information System (INIS)
Jagminas, Arūnas; Klimas, Vaclovas; Mažeika, Kęstutis; Mickevičius, Sigitas; Balakauskas, Saulius
Research on well adherent, thick and nanoporous oxide film formation onto the metal substrates underwent a major burst throughout the last decade. In the current study, thick bi-layered films produced onto a pure iron surface by anodizing way in dimethyl sulfoxide (DMSO) electrolyte containing silica hexafluoride acid have been investigated upon the annealing in air. Compositional, phase and structural transformations of the film material to hematite, α-Fe 2 O 3 , were studied using Mössbauer spectroscopy at room to cryogenic temperatures, thermogravimetry (TG), differential thermal analysis (DTA), photoemission spectroscopy, scanning electron microscopy (SEM), and wave dispersive X-ray spectroscopy (WDX). Experimental findings indicated that much longer heating in air is required for these films to be fully transformed to hematite. This effect is linked here with the complex nature of DMSO films. Based on the combined WDX, photoemission and Mössbauer spectroscopy results, the transformations taken place during calcination of such amorphous films by heat-treatment in air to crystalline hematite have been determined. Investigations on the calcination effects of thick iron anodic films reported here offer opportunities for both fundamental research and practical applications.
Dimethyl sulfoxide alterations of macromolecular synthesis by chick limb mesenchymal cells in vitro
Energy Technology Data Exchange (ETDEWEB)
Major, F.W.; Parker, C.L.; Patterson, R.M.
Earlier the authors reported that dimethyl sulfoxide (DMSO) inhibited the chondrogenesis of chick limb cells in vitro at concentrations of 30 mg/ml or greater. The present study was undertaken to determine if inhibition by DMSO might be due to an alteration in protein and/or DNA synthesis by the treated cells. Micromass cultures were prepared from stage 23-25 chick limb mesenchyme. The cells were treated with either 30 or 40 mg of DMSO/ml of culture medium for 24, 48, and 72 hr. After each treatment, protein and DNA synthesis were analyzed by the incorporation of (/sup 3/H)-leucine and (/sup 3/H)-thymidine, respectively. Cell cultures exposed to 40 mg DMSO/ml for 24 hr showed a significant decrease in protein synthesis, while there was no decrease in protein synthesis for cells treated with 30 mg DMSO/ml. At both 48 and 72 hr treatment with 30 mg of DMSO, there was a decrease in (/sup 3/H)-leucine incorporation. The thymidine studies indicated that there was a significant decrease in DNA synthesis as early as 24 hr for both DMSO concentrations. These findings suggest that the inhibition of chondrogenesis following DMSO treatment may be related to alterations in macromolecular synthesis possibly including extracellular cartilage matrix production.
Lack of effect of deferoxamine, dimethyl sulfoxide, and catalase on monocrotaline pyrrole pulmonary injury
International Nuclear Information System (INIS)
Bruner, L.H.; Johnson, K.; Carpenter, L.J.; Roth, R.A.
Monocrotaline pyrrole (MCTP) is a reactive metabolite of the pyrrolizidine alkaloid monocrotaline. MCTP given intravenously to rats causes pulmonary hypertension and right ventricular hypertrophy. Lesions in lungs after MCTP treatment contain macrophages and neutrophils, which may contribute to the damage by generation of reactive oxygen metabolites. Rats were treated with MCTP and agents known to protect against oxygen radical-mediated damage in acute models of neutrophil-dependent lung injury. Rats received MCTP and deferoxamine mesylate (DF), dimethyl sulfoxide (DMSO), or polyethylene glycol-coupled catalase (PEG-CAT). MCTP/vehicle-treated controls developed lung injury manifested as increased lung weight, release of lactate dehydrogenase into the airway, and sequestration of 125 I-labeled bovine serum albumin in the lungs. Cotreatment of rats with DF, DMSO, or PEG-CAT did not protect against the injury due to MCTP. These results suggest that toxic oxygen metabolites do not play an important role in the pathogenesis of MCTP-induced pulmonary injury
Nucleophilic Substitution Reactions of N-Methyl α-Bromoacetanilides with Benzylamines in Dimethyl Sulfoxide
International Nuclear Information System (INIS)
Adhikary, Keshab Kumar; Lee, Hai Whang
Kinetic studies of the reactions of N-methyl-Y-α-bromoacetanilides with substituted X-benzylamines have been carried out in dimethyl sulfoxide at 25.0 .deg. C. The Hammett plots for substituent X variations in the nucleophiles (log k N vs σ X ) are slightly biphasic concave upwards/downwards, while the Bronsted plots (log k N vs pK a ) are biphasic concave downwards with breakpoints at X = H. The Hammett plots for substituent Y variations in the substrates (log k N vs σ Y ) are biphasic concave upwards/downwards with breakpoints at Y = H. The cross-interaction constant ρ XY values are all negative: ρ XY = -0.32 for X = Y = electron-donating: -0.22 for X = electron-withdrawing and Y = electron-donating: -1.80 for X = electron-donating and Y = electronwithdrawing: -1.43 for X = Y = electron-withdrawing substituents. Deuterated kinetic isotope effects are primary normal (k H /k D > 1) for Y = electron-donating, while secondary inverse (k H /k D < 1) for Y = electronwithdrawing substituent. The proposed mechanisms of the benzylaminolyses of N-methyl-Y-α-bromoacetanilides are a concerted mechanism with a five membered ring TS involving hydrogen bonding between hydrogen (deuterium) atom in N-H(D) and oxygen atom in C = O for Y = electron-donating, while a concerted mechanism with an enolate-like TS in which the nucleophile attacks the α-carbon for Y = electronwithdrawing substituents
Dimethyl sulfoxide damages mitochondrial integrity and membrane potential in cultured astrocytes.
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Chan Yuan
Full Text Available Dimethyl sulfoxide (DMSO is a polar organic solvent that is used to dissolve neuroprotective or neurotoxic agents in neuroscience research. However, DMSO itself also has pharmacological and pathological effects on the nervous system. Astrocytes play a central role in maintaining brain homeostasis, but the effect and mechanism of DMSO on astrocytes has not been studied. The present study showed that exposure of astrocyte cultures to 1% DMSO for 24 h did not significantly affect cell survival, but decreased cell viability and glial glutamate transporter expression, and caused mitochondrial swelling, membrane potential impairment and reactive oxygen species production, and subsequent cytochrome c release and caspase-3 activation. DMSO at concentrations of 5% significantly inhibited cell variability and promoted apoptosis of astrocytes, accompanied with more severe mitochondrial damage. These results suggest that mitochondrial impairment is a primary event in DMSO-induced astrocyte toxicity. The potential cytotoxic effects on astrocytes need to be carefully considered during investigating neuroprotective or neurotoxic effects of hydrophobic agents dissolved by DMSO.
Dissolution of brominated epoxy resins by dimethyl sulfoxide to separate waste printed circuit boards.
Zhu, Ping; Chen, Yan; Wang, Liangyou; Qian, Guangren; Zhang, Wei Jie; Zhou, Ming; Zhou, Jin
Improved methods are required for the recycling of waste printed circuit boards (WPCBs). In this study, WPCBs (1-1.5 cm(2)) were separated into their components using dimethyl sulfoxide (DMSO) at 60 °C for 45 min and a metallographic microscope was used to verify their delamination. An increased incubation time of 210 min yielded a complete separation of WPCBs into their components, and copper foils and glass fibers were obtained. The separation time decreased with increasing temperature. When the WPCB size was increased to 2-3 cm(2), the temperature required for complete separation increased to 90 °C. When the temperature was increased to 135 °C, liquid photo solder resists could be removed from the copper foil surfaces. The DMSO was regenerated by rotary decompression evaporation, and residues were obtained. Fourier transform infrared spectroscopy (FT-IR), thermal analysis, nuclear magnetic resonance, scanning electron microscopy, and energy-dispersive X-ray spectroscopy were used to verify that these residues were brominated epoxy resins. From FT-IR analysis after the dissolution of brominated epoxy resins in DMSO it was deduced that hydrogen bonding may play an important role in the dissolution mechanism. This novel technology offers a method for separating valuable materials and preventing environmental pollution from WPCBs.
Homogeneous graft copolymerization of styrene onto cellulose in a sulfur dioxide-diethylamine-dimethyl sulfoxide cellulose solvent
International Nuclear Information System (INIS)
Tsuzuki, M.; Hagiwara, I.; Shiraishi, N.; Yokota, T.
Graft copolymerization of styrene onto cellulose was studied in a homogeneous system [SO 2 (liquid)- diethylamine (DEA)-dimethyl sulfoxide (DMSO) medium)] by γ-ray mutual irradiation technique. At the same time, homopolymerization of styrene was also examined separately in DMSO, SO 2 -DMSO, DEA-DMSO, and SO 2 -DEA-DMSO media by the same technique. Polymerization of styrene hardly occurs on concentrations above 10 mole SO 2 -DEA complex per mole glucose unit. Maximum percent grafting was obtained in concentrations of 4 mole, after which it decreased rapidly. Total conversion and percent grafting increased with the irradiation time. The value (=0.55) of the slope of the total conversion rate plotted against the dose was only a little higher than the 1/2 which was expected from normal kinetics. No retardation in homopolymerization of styrene in DMSO, SO 2 -DMSO, and DEA-DMSO was evident, while the retardation of homopolymerization in the SO 2 -DEA-DMSO medium was measurable. Sulfur atoms were detected in the polymers obtained in both of SO 2 -DMSO and SO 2 -DEA-DMSO solutions. All of the molecular weights of polymers obtained in the present experiment were very low
Dimethyl sulfoxide-induced dehydration of the intermembrane space of dipalmitoylphosphatidylcholine multilamellar vesicles: Neutron and synchrotron diffraction study
Kiselev, M. A.; Zemlyanaya, E. V.
Small-angle neutron scattering spectra of a polydispersed population of dipalmitoylphosphatidylcholine (DPPC) unilamellar vesicles in heavy water in the presence of dimethyl sulfoxide (DMSO) are analyzed by means of the separated form-factor method. An increase in the mole fraction of DMSO in water from 0 to 15% was shown to lead to an increase in the thickness of the bilayer to the characteristics repeat distances of DPPC multilamellar membranes. This fact is indicative of dehydration of the intermembrane space and a steric contact between adjacent DPPC bilayers at 15% mole fraction of DMSO.
Concentrations of trimethoprim and sulfamethoxazole in cerebrospinal fluid and serum in mares with and without a dimethyl sulfoxide pretreatment.
Green, S L; Mayhew, I G; Brown, M P; Gronwall, R R; Montieth, G
Each of seven mares was given an intravenous (IV) injection of 40% dimethyl sulfoxide (DMSO) at a dosage of 1 g/kg, over 35 min, immediately followed by a single IV injection of a trimethoprim (TMP) and sulfamethoxazole (SMZ) combination (SMZ 83%, TMP 17%) at a combined dosage of 44 mg/kg (7.48 mg/kg TMP; 36.52 mg/kg SMZ). Each horse served as its own control and was alternately treated with an identical dose of TMP-SMZ treatment alone at least seven days following or preceding the DMSO and T...
Freezing of Apheresis Platelet Concentrates in 6% Dimethyl Sulfoxide: The First Preliminary Study in Turkey
Yılmaz, Soner; Çetinkaya, Rıza Aytaç; Eker, İbrahim; Ünlü, Aytekin; Uyanık, Metin; Tapan, Serkan; Pekoğlu, Ahmet; Pekel, Aysel; Erkmen, Birgül; Muşabak, Uğur; Yılmaz, Sebahattin; Avcı, İsmail Yaşar; Avcu, Ferit; Kürekçi, Emin; Eyigün, Can Polat
Objective: Transfusion of platelet suspensions is an essential part of patient care for certain clinical indications. In this pioneering study in Turkey, we aimed to assess the in vitro hemostatic functions of platelets after cryopreservation. Materials and Methods: Seven units of platelet concentrates were obtained by apheresis. Each apheresis platelet concentrate (APC) was divided into 2 equal volumes and frozen with 6% dimethyl sulfoxide (DMSO). The 14 frozen units of APCs were kept at -80 °C for 1 day. APCs were thawed at 37 °C and diluted either with autologous plasma or 0.9% NaCl. The volume and residual numbers of leukocytes and platelets were tested in both before-freezing and post-thawing periods. Aggregation and thrombin generation tests were used to analyze the in vitro hemostatic functions of platelets. Flow-cytometric analysis was used to assess the presence of frozen treated platelets and their viability. Results: The residual number of leukocytes in both dilution groups was <1x106. The mean platelet recovery rate in the plasma-diluted group (88.1±9.5%) was higher than that in the 0.9% NaCl-diluted group (63±10%). These results were compatible with the European Directorate for the Quality of Medicines quality criteria. Expectedly, there was no aggregation response to platelet aggregation test. The mean thrombin generation potential of post-thaw APCs was higher in the plasma-diluted group (2411 nmol/L per minute) when compared to both the 0.9% NaCl-diluted group (1913 nmol/L per minute) and the before-freezing period (1681 nmol/L per minute). The flow-cytometric analysis results for the viability of APCs after cryopreservation were 94.9% and 96.6% in the plasma and 0.9% NaCl groups, respectively. Conclusion: Cryopreservation of platelets with 6% DMSO and storage at -80 °C increases their shelf life from 7 days to 2 years. Besides the increase in hemostatic functions of platelets, the cryopreservation process also does not affect their viability
Freezing of Apheresis Platelet Concentrates in 6% Dimethyl Sulfoxide: The First Preliminary Study in Turkey
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Soner Yılmaz
Full Text Available Objective: Transfusion of platelet suspensions is an essential part of patient care for certain clinical indications. In this pioneering study in Turkey, we aimed to assess the in vitro hemostatic functions of platelets after cryopreservation. Materials and Methods: Seven units of platelet concentrates were obtained by apheresis. Each apheresis platelet concentrate (APC was divided into 2 equal volumes and frozen with 6% dimethyl sulfoxide (DMSO. The 14 frozen units of APCs were kept at -80 °C for 1 day. APCs were thawed at 37 °C and diluted either with autologous plasma or 0.9% NaCl. The volume and residual numbers of leukocytes and platelets were tested in both before-freezing and post-thawing periods. Aggregation and thrombin generation tests were used to analyze the in vitro hemostatic functions of platelets. Flow-cytometric analysis was used to assess the presence of frozen treated platelets and their viability. Results: The residual number of leukocytes in both dilution groups was <1x106. The mean platelet recovery rate in the plasma-diluted group (88.1±9.5% was higher than that in the 0.9% NaCl-diluted group (63±10%. These results were compatible with the European Directorate for the Quality of Medicines quality criteria. Expectedly, there was no aggregation response to platelet aggregation test. The mean thrombin generation potential of postthaw APCs was higher in the plasma-diluted group (2411 nmol/L per minute when compared to both the 0.9% NaCl-diluted group (1913 nmol/L per minute and the before-freezing period (1681 nmol/L per minute. The flowcytometric analysis results for the viability of APCs after cryopreservation were 94.9% and 96.6% in the plasma and 0.9% NaCl groups, respectively. Conclusion: Cryopreservation of platelets with 6% DMSO and storage at -80 °C increases their shelf life from 7 days to 2 years. Besides the increase in hemostatic functions of platelets, the cryopreservation process also does not affect their
21 CFR 524.660a - Dimethyl sulfoxide solution.
...) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS OPHTHALMIC AND TOPICAL DOSAGE FORM NEW ANIMAL DRUGS § 524.660a... per day. Total duration of therapy should not exceed 30 days. (ii) In dogs administered 3 or 4 times daily in an amount not to exceed 20 milliliters per day. Total duration of therapy should not exceed 14...
FT-IR spectra were obtained of 0.5% volumetric solutions of propyl sulfide, propyl sulfoxide, and propyl sulfone in hexane, CCl4, CS2, and CHCl3 to assist in the assignment of FT-IR-PAS spectra of propyl sulfoxide sorbed within the structure of several peats and onto cellulose. T...
Risk factors that affect the treatment of interstitial cystitis using intravesical therapy with a dimethyl sulfoxide cocktail.
Hung, Man-Jung; Chen, Yi-Ting; Shen, Pao-Sheng; Hsu, Shih-Tien; Chen, Gin-Den; Ho, Esther Shih-Chu
Dimethyl sulfoxide (DMSO) bladder instillation is a standard therapy for interstitial cystitis (IC); however, there are varying degrees of success. We hypothesize that first-line intravesical therapy with a DMSO cocktail will optimize treatment outcome. Ninety women with newly diagnosed IC were enrolled consecutively for the treatment. The IC symptom and problem index was used as an outcome measure. Six (6.7%) patients dropped out of the treatment due to intolerable bladder irritation. Fifty-five (65.5%) of the remaining 84 patients, who completed the treatment, experienced ≧50% symptomatic improvement. After a regression analysis, three clinical variables were found to affect treatment adversely, i.e., the presence of advanced cystoscopic glomerulations, microscopic hematuria, and urodynamic detrusor underactivity, respectively. Our results suggest bladder instillation with a DMSO cocktail may well be considered as first-line therapy for IC patients. However, there exists a subgroup of nonresponders who may have severe disease.
Cryopreservation of Peruvian Paso horse spermatozoa: dimethylacetamide preserved an optimal sperm function compared to dimethyl sulfoxide, ethylene glycol and glycerol.
Santiani, A; Evangelista-Vargas, S; Vargas, S; Gallo, S; Ruiz, L; Orozco, V; Rosemberg, M
The objective was to evaluate the effect of different cryoprotectant agents in the cryopreservation of Peruvian Paso horse semen. Twenty semen samples were collected from five Peruvian Paso horse stallions. Each sample was divided into 12 parts to form the groups: dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), ethylene glycol (EG) and glycerol (GLY), at 3%, 4% and 5%. Samples were frozen using a rate-controlled freezer. Sperm parameters evaluated were motility and viability/acrosomal status. After thawing, progressive motility in DMA group was higher (p < .05) than in DMSO, EG and GLY groups. Similarly, viable acrosome-intact spermatozoa were higher (p < .05) using DMA in comparison with DMSO. No differences were found when comparing concentrations for any of the cryoprotectant agents. In conclusion, DMA seems to be a good cryoprotectant agent for the cryopreservation of Peruvian Paso horse stallion semen. © 2016 Blackwell Verlag GmbH.
Octakis(dimethyl sulfoxide-κOcerium(III μ6-oxido-dodeca-μ2-oxido-hexaoxidohexamolybdate(VI dimethyl sulfoxide tetrasolvate
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Arbia Ben Khélifa
Full Text Available The title complex, [Ce(C2H6OS8]2[Mo6O19]3·4C2H6OS, was obtained as a byproduct of the reaction of [(C4H94N]2[Mo6O19] with Ce(NO33·6H2O and phthalic acid in dimethylsulfoxide solution. The asymmetric unit consists of a complex [Ce(C2H6OS8]3+ cation, one and a half of the Lindqvist-type [Mo6O19]2− polyanions and two dimethylsulfoxide solvent molecules; the half polyanion lies on an inversion center. The Ce3+ ion is coordinated by eight dimethylsulfoxide ligands through the O atoms in the form of a distorted square antiprism. The Ce—O bond lengths range from 2.429 (6 to 2.550 (5 Å. The cohesion of the structure is ensured by S...O [3.115 (6, 3.242 (10 and 3.12 (3 Å], O...O [3.037 (10 Å] and C—H...O interactions between cations and anions. The S and C atoms of a dmso ligand are disordered over three sites in a 0.45:0.30:0.25 ratio. The dimethylsulfoxide solvent molecules are highly disordered and could not be modelled successfully; their contribution was therefore removed from the refinement using the SQUEEZE routine in PLATON [Spek (2009. Acta Cryst. D65, 148–155]. Potential solvent-accessible voids of 500.0 Å3 occur in the crystal structure.
Dimethyl sulfoxide (DMSO) waste residues and municipal waste water odor by dimethyl sulfide (DMS): the north-east WPCP plant of Philadelphia.
Glindemann, Dietmar; Novak, John; Witherspoon, Jay
This study shows for the first time that overlooked mg/L concentrations of industrial dimethyl sulfoxide (DMSO) waste residues in sewage can cause "rotten cabbage" odor problems bydimethyl sulfide (DMS) in conventional municipal wastewater treatment. In laboratory studies, incubation of activated sludge with 1-10 mg/L DMSO in bottles produced dimethyl sulfide (DMS) at concentrations that exceeded the odor threshold by approximately 4 orders of magnitude in the headspace gas. Aeration at a rate of 6 m3 air/m3 sludge resulted in emission of the DMS into the exhaust air in a manner analogous to that of an activated sludge aeration tank. A field study atthe NEWPCP sewage treatment plant in Philadelphia found DMSO levels intermittently peaking as high as 2400 mg/L in sewage near an industrial discharger. After 3 h, the DMSO concentration in the influent to the aeration tank rose from a baseline level of less than 0.01 mg/L to a level of 5.6 mg/L and the DMS concentration in the mixed liquor rose from less than 0.01 to 0.2 mg/L. Finding this link between the intermittent occurrence of DMSO residues in influent of the treatment plant and the odorant DMS in the aeration tank was the keyto understanding and eliminating the intermittent "canned corn" or "rotten cabbage" odor emissions from the aeration tank that had randomly plagued this plant and its city neighborhood for two decades. Sewage authorities should consider having wastewater samples analyzed for DMSO and DMS to check for this possible odor problem and to determine whether DMSO emission thresholds should be established to limit odor generation at sewage treatment plants.
Gamma-radiolysis of dimethyl sulfoxide. II. Radiolysis yields and possible mechanisms
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Gutierrez, M. C.; Barrera, R.
As result of quantitative studies on gamma-radiolysis of DMSO at a dose range of 90-850 Mrads, constant G values have been obtained for the following radiolysis compounds: G(-DMSO) - 6.7 ±0.2; G(dimethyl sulphide) - 3.4 ±0.3; G(methane) - 0,75 ± 0.04; G(dimethyl disulphide) -0.33 ±0,03; G(tri methylsulphonium methanesulphonate) - 0.26 ± 0,01; G(methyl methanethiosulphonate) - 0,25 ±0.02; G(dimethyl sulphona)-0.21±0.02; G(H 2 )-0.18±0.02; and G(propane)--0.0092±0.0007. Initial G values have been obtained for other identified compounds: Gi(ethane)-0,46; Gi(CO)-0.052; and Gi(CO 2 )-0.030. Possible mechanisms on the radiolysis process are proposed. (Author) 17 refs
Poly[μ3-chlorido-μ2-chloridodichlorido(μ-dimethyl sulfoxide-κ2O:S(dimethyl sulfoxide-κO(μ-pyrimidine-κ2N:N′ruthenium(IIIsodium
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Skylar Ferrara
Full Text Available The title complex, [NaRuCl4(C4H4N2(C2H6OS2]n, is the sodium salt of monoanionic octahedral [RuIIICl4(pyrimidine(DMSO]− in which the sulfur-bound dimethyl sulfoxide (DMSO and pyrimidine ligand are oriented trans to one another on the RuIII atom. The average of the four Ru—Cl bond lengths is 2.355 (15 Å, and the Ru—S and Ru—N bond lengths are 2.2853 (3 and 2.1165 (11 Å, respectively. The complex forms a chain, with a six-coordinate sodium ion bridging the ruthenium(III units. The sodium cation is coordinated by cis-chloride ligands on ruthenium [Na—Cl = 2.9576 (7 and 2.6988 (7 Å], chloride and DMSO ligands from the ruthenium complexes related by inversion [Na—Cl and Na—O = 2.8888 (7 and 2.2623 (12 Å, respectively], a nitrogen ligand from the pyrimidine of the tetrachloridoruthenium(III complex related by the twofold rotation axis [Na—N = 2.5224 (14 Å] and an oxygen-bound DMSO [Na—O = 2.3165 (12 Å].
Genomic Analysis of Anaerobic Respiration in the Archaeon Halobacterium sp. Strain NRC-1: Dimethyl Sulfoxide and Trimethylamine N-Oxide as Terminal Electron Acceptors†
Müller, Jochen A.; DasSarma, Shiladitya
We have investigated anaerobic respiration of the archaeal model organism Halobacterium sp. strain NRC-1 by using phenotypic and genetic analysis, bioinformatics, and transcriptome analysis. NRC-1 was found to grow on either dimethyl sulfoxide (DMSO) or trimethylamine N-oxide (TMAO) as the sole terminal electron acceptor, with a doubling time of 1 day. An operon, dmsREABCD, encoding a putative regulatory protein, DmsR, a molybdopterin oxidoreductase of the DMSO reductase family (DmsEABC), and...
Fullerenol C60(OH)24 nanoparticles decrease relaxing effects of dimethyl sulfoxide on rat uterus spontaneous contraction
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Slavic, Marija; Djordjevic, Aleksandar; Radojicic, Ratko; Milovanovic, Slobodan; Orescanin-Dusic, Zorana; Rakocevic, Zlatko; Spasic, Mihajlo B.; Blagojevic, Dusko
Dimethyl sulfoxide (DMSO) is a widely used solvent and cryoprotectant that can cause impaired blood flow, reduction in intracranial pressure, tissue edema, inflammatory reactions, inhibition of vascular smooth muscle cell migration and proliferation, processes which can lead to atherosclerosis of the coronary, peripheral and cerebral circulation. Although the adverse effects are rare when DMSO is administered in clinically established concentrations, there is no safe antagonist for an overdose. In this work, we treated isolated spontaneous and calcium-induced contractile active rat uteri (Wistar, virgo intacta), with DMSO and fullerenol C 60 (OH) 24 nanoparticle (FNP) in DMSO. FNP is a water-soluble derivative of fullerene C 60 . Its size is a 1.1 nm in diameter and is a very promising candidate for a drug carrier in nanomedicine. FNP also displays free radical scavenging activity. DMSO decreased both spontaneous and calcium-induced contractions. In contrast, FNP only decreased spontaneous contraction. FNP decreased copper–zinc superoxide dismutase activity and prevented the DMSO-induced increase in glutathione reductase activity. Atomic force microscopy detected that FNP aggregated with calcium ions. Our results indicate that FNP has properties that make it a good candidate to be a modulator of DMSO activity which could minimize side effects of the latter.
Dimethyl Sulfoxide Induced Destabilization and Disassembly of Various Structural Variants of Insulin Fibrils Monitored by Vibrational Circular Dichroism.
Zhang, Ge; Babenko, Viktoria; Dzwolak, Wojciech; Keiderling, Timothy A
Dimethyl sulfoxide (DMSO) induced destabilization of insulin fibrils has been previously studied by Fourier transform infrared spectroscopy and interpreted in terms of secondary structural changes. The variation of this process for fibrils with different types of higher-order morphological structures remained unclear. Here, we utilize vibrational circular dichroism (VCD), which has been reported to provide a useful biophysical probe of the supramolecular chirality of amyloid fibrils, to characterize changes in the macroscopic chirality following DMSO-induced disassembly for two types of insulin fibrils formed under different conditions, at different reduced pH values with and without added salt and agitation. We confirm that very high concentrations of DMSO can disaggregate both types of insulin fibrils, which initially maintained a β-sheet conformation and eventually changed their secondary structure to a disordered form. The two types responded to varying concentrations of DMSO, and disaggregation followed different mechanisms. Interconversion of specific insulin fibril morphological types also occurred during the destabilization process as monitored by VCD. With transmission electron microscopy, we were able to correlate the changes in VCD sign patterns to alteration of morphology of the insulin fibrils.
Palliative treatment for advanced biliary adenocarcinomas with combination dimethyl sulfoxide-sodium bicarbonate infusion and S-adenosyl-L-methionine.
Hoang, Ba X; Tran, Hung Q; Vu, Ut V; Pham, Quynh T; Shaw, D Graeme
Adenocarcinoma of the gallbladder and cholangiocarcinoma account for 4% and 3%, respectively, of all gastrointestinal cancers. Advanced biliary tract carcinoma has a very poor prognosis with all current available modalities of treatment. In this pilot open-label study, the authors investigated the efficacy and safety of a combination of dimethyl sulfoxide-sodium bicarbonate (DMSO-SB) infusion and S-adenosyl-L-methionine (ademetionine) oral supplementation as palliative pharmacotherapy in nine patients with advanced nonresectable biliary tract carcinomas (ABTCs). Patients with evidence of biliary obstruction with a total serum bilirubin ≤300 μmol/L were allowed to join the study. The results of this 6-month study and follow-up of all nine patients with ABTC indicated that the investigated combination treatment improved pain control, blood biochemical parameters, and quality of life for the patients. Moreover, this method of treatment has led to a 6-month progression-free survival for all investigated patients. The treatment was well tolerated for all patients without major adverse reactions. Given that ABTC is a highly fatal malignancy with poor response to chemotherapy and targeted drugs, the authors consider that the combination of DMSO-SB and ademetionine deserves further research and application as a palliative care and survival-enhancing treatment for this group of patients.
Dimethyl sulfoxide-sodium bicarbonate infusion for palliative care and pain relief in patients with metastatic prostate cancer.
Hoang, Ba X; Le, Bao T; Tran, Hau D; Hoang, Cuong; Tran, Hung Q; Tran, Dao M; Pham, Cu Q; Pham, Tuan D; Ha, Trung V; Bui, Nga T; Shaw, D Graeme
Prostate cancer (adenocarcinoma of the prostate) is the most widespread cancer in men. It causes significant suffering and mortality due to metastatic disease. The main therapy for metastatic prostate cancer (MPC) includes androgen manipulation, chemotherapy, and radiotherapy and/or radioisotopes. However, these therapeutic approaches are considered palliative at this stage, and their significant side effects can cause further decline in patients' quality of life and increase non-cancer-related morbidity/mortality. In this study, the authors have used the infusion of dimethyl sulfoxide-sodium bicarbonate (DMSO-SB) to treat 18 patients with MPC. The 90-day follow-up of the patients having undergone the proposed therapeutic regimen showed significant improvement in clinical symptoms, blood and biochemistry tests, and quality of life. There were no major side effects from the treatment. In searching for new and better methods for palliative treatment and pain relief, this study strongly suggested therapy with DMSO-SB infusions could provide a rational alternative to conventional treatment for patients with MPC.
Chlorpromazine and dimethyl sulfoxide modulate the catalytic activity of the plasma membrane Ca2+-ATPase from human erythrocyte.
Plenge-Tellechea, Fernando; Domínguez-Solís, Carlos A; Díaz-Sánchez, Ángel G; Meléndez-Martínez, David; Vargas-Medrano, Javier; Sierra-Fonseca, Jorge A
The plasma membrane Ca 2+ -ATPase (PMCA) removes Ca 2+ from the cytosol into the extracellular space. Its catalytic activity can be stimulated by calmodulin (CaM) or by limited proteolysis. We evaluated the effect of chlorpromazine (CPZ) and dimethyl sulfoxide (DMSO) over the hydrolytic activity of PMCA. Activity was monitored in three different forms: native, CaM-activated and proteolyzed by trypsin. CPZ appears to inhibit PMCA without directly interfering with the C-terminal site, since it is affected by CaM and proteolysis. Although the treatment of PMCA with trypsin and CaM produces an activation, it also produces an enzymatic form that is more sensitive to inhibition by CPZ. The same case was observed in the DMSO inhibition experiments. In the absence of CPZ, DMSO produces a progressive loss of activity, but in the presence of CPZ the profile of activity against DMSO changes and produces a recovery of activity, indicating a possible partition of CPZ by the solvent. Increasing Ca 2+ concentrations indicated that CPZ interacts with PMCA rather than with CaM. This observation is supported by docking analysis that suggests that the CPZ-PMCA interaction is non-competitive. We propose that CPZ interacts with the state of lower affinity for Ca 2 + .
Crystal structure of μ-oxalato-κ2O1:O2-bis[(dimethyl sulfoxide-κOtriphenyltin(IV
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Serigne Fallou Pouye
Full Text Available In the previously reported [C2O4(SnPh32] complex [Diop et al. (2003. Appl. Organomet. Chem. 17, 881–882.], the SnIV atoms are able to formally complete their coordination by addition of dimethyl sulfoxide (DMSO molecules provided by the reaction medium, affording the title complex, [Sn2(C6H56(C2O4(C2H6OS2]. The SnIV atoms are then pentacoordinated, with a common trans trigonal–bipyramidal arrangement. The asymmetric unit contains one half-molecule, which is completed by inversion symmetry in space group type C2/c. The inversion centre is placed at the mid-point of the central bis-monodentate oxalate dianion, C2O42−, which bridges the [(SnPh3(DMSO] moieties. The molecule crystallizes as a disordered system, with two phenyl rings disordered by rotation about their Sn—C bonds, while the DMSO molecule is split over two positions due to a tetrahedral inversion at the S atom. All disordered parts were refined with occupancies fixed of 0.5.
Fullerenol C60(OH)24 nanoparticles decrease relaxing effects of dimethyl sulfoxide on rat uterus spontaneous contraction
Slavic, Marija; Djordjevic, Aleksandar; Radojicic, Ratko; Milovanovic, Slobodan; Orescanin-Dusic, Zorana; Rakocevic, Zlatko; Spasic, Mihajlo B.; Blagojevic, Dusko
Dimethyl sulfoxide (DMSO) is a widely used solvent and cryoprotectant that can cause impaired blood flow, reduction in intracranial pressure, tissue edema, inflammatory reactions, inhibition of vascular smooth muscle cell migration and proliferation, processes which can lead to atherosclerosis of the coronary, peripheral and cerebral circulation. Although the adverse effects are rare when DMSO is administered in clinically established concentrations, there is no safe antagonist for an overdose. In this work, we treated isolated spontaneous and calcium-induced contractile active rat uteri (Wistar, virgo intacta), with DMSO and fullerenol C60(OH)24 nanoparticle (FNP) in DMSO. FNP is a water-soluble derivative of fullerene C60. Its size is a 1.1 nm in diameter and is a very promising candidate for a drug carrier in nanomedicine. FNP also displays free radical scavenging activity. DMSO decreased both spontaneous and calcium-induced contractions. In contrast, FNP only decreased spontaneous contraction. FNP decreased copper-zinc superoxide dismutase activity and prevented the DMSO-induced increase in glutathione reductase activity. Atomic force microscopy detected that FNP aggregated with calcium ions. Our results indicate that FNP has properties that make it a good candidate to be a modulator of DMSO activity which could minimize side effects of the latter.
Acid-base equilibrium dynamics in methanol and dimethyl sulfoxide probed by two-dimensional infrared spectroscopy.
Lee, Chiho; Son, Hyewon; Park, Sungnam
Two-dimensional infrared (2DIR) spectroscopy, which has been proven to be an excellent experimental method for studying thermally-driven chemical processes, was successfully used to investigate the acid dissociation equilibrium of HN3 in methanol (CH3OH) and dimethyl sulfoxide (DMSO) for the first time. Our 2DIR experimental results indicate that the acid-base equilibrium occurs on picosecond timescales in CH3OH but that it occurs on much longer timescales in DMSO. Our results imply that the different timescales of the acid-base equilibrium originate from different proton transfer mechanisms between the acidic (HN3) and basic (N3(-)) species in CH3OH and DMSO. In CH3OH, the acid-base equilibrium is assisted by the surrounding CH3OH molecules which can directly donate H(+) to N3(-) and accept H(+) from HN3 and the proton migrates through the hydrogen-bonded chain of CH3OH. On the other hand, the acid-base equilibrium in DMSO occurs through the mutual diffusion of HN3 and N3(-) or direct proton transfer. Our 2DIR experimental results corroborate different proton transfer mechanisms in the acid-base equilibrium in protic (CH3OH) and aprotic (DMSO) solvents.
Dimethyl sulfoxide is a potent modulator of estrogen receptor isoforms and xenoestrogen biomarker responses in primary culture of salmon hepatocytes
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Mortensen, Anne S.; Arukwe, Augustine
Dimethyl sulfoxide (DMSO) has been frequently used as carrier solvent in toxicological experiments where the most compelling DMSO attributes are its exceptionally low toxicity and environmental impact. We were inspired by recent and consistent observations that ethanol and DMSO modulate endocrine-disruptor biomarker responses in both in vitro and in vivo studies in our laboratory, to take a critical evaluation of these effects. Quantitative (real-time) polymerase chain reaction (PCR) method with specific primer pairs was used in this study to measure DMSO-induced time-dependent modulation of estrogen receptor (ER) isoforms, vitellogenin (Vtg) and zona radiata-protein (Zr-protein) gene expression patterns in primary culture of salmon hepatocytes. In addition, immunochemical analysis, using indirect enzyme linked immunosorbent assay (ELISA) with monoclonal (Vtg) and polyclonal (Zr-proteins) antibodies was used to detect and measure Vtg and Zr-proteins secreted in culture media. Salmon hepatocytes were isolated by a two-step collagenase perfusion method and exposed to 0.1% or 10 μL/L of DMSO after 48 h pre-culture. Cells were harvested at 12, 24, 48 and 72 h after exposure and analysed for ERα, ERβ, Vtg and Zr-protein gene expression using real-time PCR method. Media samples were collected at similar time-intervals for protein analysis. Our data show that DMSO-induced significant increase in ERα, ERβ, Vtg and Zr-protein genes in a time-dependent manner. Indirect ELISA analysis showed a time-specific effect of DMSO. The use of DMSO as carrier solvent in fish endocrine disruption studies should be re-evaluated. We recommend more investigation, using other endocrine-disruptor biomarkers in order to validate the suitability of common carrier solvents used in toxicology with the aim of setting new maximum allowable concentrations. In particular, given the high sensitivity of genomic approaches in toxicology, these results may have serious consequences for the
[The dimethyl sulfoxide under general anesthesia: An alternative after failure without anesthesia in the painful bladder syndrome/interstitial cystitis?
Gaullier, M; Tricard, T; Mouracade, P; Saussine, C
The intravesical instillation of dimethyl sulfoxide (iDMSO), performed without anesthestic, is a therapeutic option for the painful bladder syndrome/interstial cystitis (PBS/IC). Some patients are against those iDMSO because of bad tolerance. Our study evaluates the tolerance and the outcome of the iDMSO under general anesthetic (GA) after the failure of the iDMSO without anesthetic. From May 2013 to April 2016, 11 patients with a PBS, 9 women (81.8 %), have been treated by iDMSO without anesthetic, without improvement because of bad tolerance and no possibility to have a one hour contact between the bladder and the DMSO. The 11 patients were evaluated by mictional calendar and Sant O'Leary score. All the patients had a hydrodistension and a per os treatment without improvement. Six new iDMSO were performed under general anesthetic in ambulatory surgery with good tolerance for the 11 patients. The frequency and the nocturia before iDMSO without anesthetic and after iDMSO under general anesthetic were 32.2minutes [15; 60] and 6.3 per night [3; 10] and 126.9minutes [25; 240] and 3 per night [2; 6], so a variation respectively of 96.4minutes [0; 180] and of 3.75 per night [2; 6]. The symptom score and the problem index were 17.5 [13; 20] and 15.5 [13; 16] before and 13.5 [4; 20] and 12 [1; 16] after iDMSO under general anesthetic; a variation of 3.2 [0; 9] and 4 [0; 12]. The iDMSO under general anesthetic seems to improve objectively and subjectively the patients who are not improved by the instillations without anesthetic because of bad tolerance. 4. Copyright © 2018 Elsevier Masson SAS. All rights reserved.
Urinary glycosaminoglycans excretion and the effect of dimethyl sulfoxide in an experimental model of non-bacterial cystitis
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Roberto Soler
Full Text Available PURPOSE: We reproduced a non-bacterial experimental model to assess bladder inflammation and urinary glycosaminoglycans (GAG excretion and examined the effect of dimethyl sulfoxide (DMSO. MATERIALS AND METHODS: Female rats were instilled with either protamine sulfate (PS groups or sterile saline (control groups. At different days after the procedure, 24 h urine and bladder samples were obtained. Urinary levels of hyaluronic acid (HA and sulfated glycosaminoglycans (S-GAG were determined. Also to evaluate the effect of DMSO animals were instilled with either 50% DMSO or saline 6 hours after PS instillation. To evaluate the effect of DMSO in healthy bladders, rats were instilled with 50% DMSO and controls with saline. RESULTS: In the PS groups, bladder inflammation was observed, with polymorphonuclear cells during the first days and lymphomononuclear in the last days. HA and S-GAG had 2 peaks of urinary excretion, at the 1st and 7th day after PS injection. DMSO significantly reduced bladder inflammation. In contrast, in healthy bladders, DMSO produced mild inflammation and an increase in urinary HA levels after 1 and 7 days and an increase of S-GAG level in 7 days. Animals instilled with PS and treated with DMSO had significantly reduced levels of urinary HA only at the 1st day. Urinary S-GAG/Cr levels were similar in all groups. CONCLUSIONS: Increased urinary levels of GAG were associated with bladder inflammation in a PS-induced cystitis model. DMSO significantly reduced the inflammatory process after urothelial injury. Conversely, this drug provoked mild inflammation in normal mucosa. DMSO treatment was shown to influence urinary HA excretion.
Cluster-continuum quasichemical theory calculation of the lithium ion solvation in water, acetonitrile and dimethyl sulfoxide: an absolute single-ion solvation free energy scale.
Carvalho, Nathalia F; Pliego, Josefredo R
Absolute single-ion solvation free energy is a very useful property for understanding solution phase chemistry. The real solvation free energy of an ion depends on its interaction with the solvent molecules and on the net potential inside the solute cavity. The tetraphenyl arsonium-tetraphenyl borate (TATB) assumption as well as the cluster-continuum quasichemical theory (CC-QCT) approach for Li(+) solvation allows access to a solvation scale excluding the net potential. We have determined this free energy scale investigating the solvation of the lithium ion in water (H2O), acetonitrile (CH3CN) and dimethyl sulfoxide (DMSO) solvents via the CC-QCT approach. Our calculations at the MP2 and MP4 levels with basis sets up to the QZVPP+diff quality, and including solvation of the clusters and solvent molecules by the dielectric continuum SMD method, predict the solvation free energy of Li(+) as -116.1, -120.6 and -123.6 kcal mol(-1) in H2O, CH3CN and DMSO solvents, respectively (1 mol L(-1) standard state). These values are compatible with the solvation free energy of the proton of -253.4, -253.2 and -261.1 kcal mol(-1) in H2O, CH3CN and DMSO solvents, respectively. Deviations from the experimental TATB scale are only 1.3 kcal mol(-1) in H2O and 1.8 kcal mol(-1) in DMSO solvents. However, in the case of CH3CN, the deviation reaches a value of 9.2 kcal mol(-1). The present study suggests that the experimental TATB scale is inconsistent for CH3CN. A total of 125 values of the solvation free energy of ions in these three solvents were obtained. These new data should be useful for the development of theoretical solvation models.
Characteristics of the formation of enzyme-bound ATP from medium inorganic phosphate by mitochondrial F1 adenosinetriphosphatase in the presence of dimethyl sulfoxide
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Kandpal, R.P.; Stempel, K.E.; Boyer, P.D.
Addition of dimethyl sulfoxide promotes the formation of enzyme-bound ATP from medium P/sub i/ by mitochondrial F 1 adenosinetriphosphatase that has tightly bound ADP present. Measurements are reported of medium P/sub i/ ↔ H 18 OH exchange and of the dependence of formation of enzyme-bound ATP on P/sub i/ concentration. Attainment of an apparent equilibrium between medium P/sub i/ and bound ATP requires longer than 30 min, even though the rates of P/sub i/ binding and release after apparent equilibrium is reached would suffice for a faster approach to equilibrium. Slow protein conformational changes or other unknown modulating factors may be responsible for the slow rate of bound ATP formation. After apparent equilibrium is reached, each P/sub i/ that binds to the enzyme reversibly forms ATP about 50 times before being released to the medium. The rate of interconversion of bound ATP to bound ADP and P/sub i/ is much slower than that in the absence of dimethyl sulfoxide as measured with sufficient low ATP concentrations so that single-site catalysis is favored. Although the interconversion rate is slowed, the equilibrium constant for bound ATP formation from bound ADP and P/sub i/ is not far from unity. Dimethyl sulfoxide favors the formation of enzyme-bound ATP by promoting the competent binding of P/sub i/ to enzyme with ADP bound at a catalytic site rather than by promoting formation of bound ATP from bound ADP and P/sub i/
(4-Hydr-oxy-2-oxidobenzaldehyde thio-semicarbazonato-κO,N,S)(1,10-phenanthroline-κN,N')zinc(II) dimethyl sulfoxide disolvate monohydrate.
Tan, Kong Wai; Ng, Chew Hee; Maah, Mohd Jamil; Ng, Seik Weng
The Zn(II) atom in the title compound, [Zn(C(8)H(7)N(3)O(2)S)(C(12)H(8)N(2))]·2C(2)H(6)OS·H(2)O, is N,N'-chelated by the N-heterocycle and N,O,S-chelated by the deprotonated Schiff base in a distorted square-pyramidal enviroment. Hydrogen bonds link the mononuclear mol-ecule, the water and the dimethyl sulfoxide (DMSO) mol-ecules into a linear chain motif. One DMSO mol-ecule is disordered over two positions in respect of the S atom in an approximate 1:1 ratio.
Extraction of 14C-labeled photosynthate from aquatic plants with dimethyl sulfoxide (DMSO)
International Nuclear Information System (INIS)
Filbin, G.J.; Hough, R.A.
DMSO was tested as a solvent to extract 14 C-labeled photosynthate from three species of aquatic plants in photosynthesis measurements and compared with the dry oxidation method for plant radioassay. Extraction of ca. 300 mg of fresh or rehydrated dry plant tissue samples in 10 ml of reagent-grade DMSO for 8h at 65 0 C resulted in a stable, nonviscous solution with excellent liquid scintillation counting characteristics. Extraction efficiency was in the range of 96-99% of fixed 14 C, and precision was comparable to, or better than, that obtained with dry oxidation. The method is simple and inexpensive, and for fresh tissue the same sample extracts can be used for chlorophyll analyses
Long-term outcomes of intravesical dimethyl sulfoxide/heparin/hydrocortisone therapy for interstitial cystitis/bladder pain syndrome.
Lim, Yik N; Dwyer, Peter; Murray, Christine; Karmakar, Debjyoti; Rosamilia, Anna; Thomas, Elizabeth
For decades, intravesical dimethyl sulfoxide (DMSO) cocktail therapy has been used for the treatment of interstitial cystitis/bladder pain syndrome (IC/BPS), but little is known about its long-term efficacy. We aimed to assess the long-term efficacy of intravesical DMSO/heparin/hydrocortisone/bupivacaine therapy in patients with IC/BPS. Patients with IC/BPS from our institutions who underwent this therapy with >2 years follow-up were surveyed with O'Leary-Sant interstitial cystitis symptom and problem index questionnaires before and after therapy. Chart reviews and telephone surveys were then conducted to determine their posttherapy course. Of 68 eligible women, 55 (80.0%) with a median follow-up of 60 months (range 24-142) were surveyed. Their mean age at therapy onset was 44.8 years and their mean body mass index was 26.2 kg/m 2 . There were statistically significant improvements in O'Leary-Sant and pain scores of 23-47% at both 6 weeks and the end of the follow-up period. At the end of the follow-up period, 19 of the 55 women (34.5%) were cured (requiring no further treatment) and 12 (21.8%) were significantly improved (requiring only ongoing oral medication). Univariate and multivariate analyses showed that DMSO treatment failure was more likely in patients with pretreatment day-time urinary frequency more than 15 episodes per day (OR 1.41), nocturia more than two episodes per night (OR 2.47), maximum bladder diary voided volume <200 ml (OR 1.39) and bladder capacity under anaesthesia <500 ml (OR 1.6). At a median follow-up of 60 months, intravesical DMSO cocktail therapy appeared moderately effective for the treatment of IC/BPS. Treatment failure was more frequent in patients with pretreatment symptoms of reduced bladder capacity.
Dimethyl sulfoxide is a potent modulator of estrogen receptor isoforms and xenoestrogen biomarker responses in primary culture of salmon hepatocytes
Energy Technology Data Exchange (ETDEWEB)
Mortensen, Anne S. [Department of Biology, Norwegian University of Science and Technology (NTNU), Hogskoleringen 5, 7491 Trondheim (Norway); Arukwe, Augustine [Department of Biology, Norwegian University of Science and Technology (NTNU), Hogskoleringen 5, 7491 Trondheim (Norway)]. E-mail: email@example.com
Dimethyl sulfoxide (DMSO) has been frequently used as carrier solvent in toxicological experiments where the most compelling DMSO attributes are its exceptionally low toxicity and environmental impact. We were inspired by recent and consistent observations that ethanol and DMSO modulate endocrine-disruptor biomarker responses in both in vitro and in vivo studies in our laboratory, to take a critical evaluation of these effects. Quantitative (real-time) polymerase chain reaction (PCR) method with specific primer pairs was used in this study to measure DMSO-induced time-dependent modulation of estrogen receptor (ER) isoforms, vitellogenin (Vtg) and zona radiata-protein (Zr-protein) gene expression patterns in primary culture of salmon hepatocytes. In addition, immunochemical analysis, using indirect enzyme linked immunosorbent assay (ELISA) with monoclonal (Vtg) and polyclonal (Zr-proteins) antibodies was used to detect and measure Vtg and Zr-proteins secreted in culture media. Salmon hepatocytes were isolated by a two-step collagenase perfusion method and exposed to 0.1% or 10 {mu}L/L of DMSO after 48 h pre-culture. Cells were harvested at 12, 24, 48 and 72 h after exposure and analysed for ER{alpha}, ER{beta}, Vtg and Zr-protein gene expression using real-time PCR method. Media samples were collected at similar time-intervals for protein analysis. Our data show that DMSO-induced significant increase in ER{alpha}, ER{beta}, Vtg and Zr-protein genes in a time-dependent manner. Indirect ELISA analysis showed a time-specific effect of DMSO. The use of DMSO as carrier solvent in fish endocrine disruption studies should be re-evaluated. We recommend more investigation, using other endocrine-disruptor biomarkers in order to validate the suitability of common carrier solvents used in toxicology with the aim of setting new maximum allowable concentrations. In particular, given the high sensitivity of genomic approaches in toxicology, these results may have serious
Viscosity Coefficients of KCl, NaCl, NaI, KNO3, LiNO3, NaBPh4 and Bu4NI in Water - Dimethyl Sulfoxide Binary Mixtures With a Low Organic Solvent Content
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Adam Bald
Full Text Available In this work the viscosities of KCl, NaCl, NaI, KNO3, LiNO3, NaBPh4 and Bu4NI solutions (from ~0.01 mol dm–3 to ~0.05 mol dm–3 in water (1 + dimethyl sulfoxide (DMSO (2 binary mixtures with mole fractions of DMSO, x2 = 0.01, 0.02, 0.05, 0.075, 0.10 and 0.15, were determined at 298. 15 K. The viscosities measured were used to evaluate the viscosity B-coefficients by means of Jones-Dole's equation. The results obtained allowed us to determine the values of B± coefficients for individual ions using the assumption about the equality B(Bu4N+ = B(BPh4–. All the results have been discussed in terms of ion-solvent interactions.
Directory of Open Access Journals (Sweden)
M. Hayyan
Full Text Available Abstract The long-term stability of superoxide ion (O2•− with four ionic liquids (ILs, namely 1-(2-methoxyethyl-1-methylpiperidinium tris(pentafluoroethyltrifluorophosphate [MOEMPip][TPTP], 1-(3-methoxypropyl-1-methylpiperidinium bis(trifluoromethylsulfonylimide [MOPMPip][TFSI], N-ethyl-N,N-dimethyl-2-methoxyethylammonium bis(trifluoromethylsulfonylimide [N112,1O2][TFSI], and ethyl-dimethyl-propylammonium bis(trifluoromethylsulfonylimide [EDMPAmm][TFSI], was studied for up to 24 h using two-second intervals. This was achieved by chemical generation of O2•− by dissolution of potassium superoxide salt in dimethyl sulfoxide and the subsequent addition of the IL. The decrease in the concentration of O2•− after the introduction of the IL was monitored using a UV-vis spectrophotometer. The ammonium-based ILs were found to be more stable than piperidinium-based ILs. To the best of our knowledge, this was the first time that O2•− stability with ILs has been monitored continuously for up to 24 h. This should provide a better insight into the stability and kinetics of O2•− for industrial applications and its role in energy-storage devices. The most appropriate IL as a medium was [EDMPAmm][TFSI], and O2•− generated in this IL was used to destroy nearly 90% of thiophene.
Influence of hydroxyapatite nanoparticles on the viscosity of dimethyl sulfoxide-H2O-NaCl and glycerol-H2O-NaCl ternary systems at subzero temperatures.
Yi, Jingru; Tang, Heyu; Zhao, Gang
The viscosity, at subzero temperatures, of ternary solutions commonly used in cryopreservation is tremendously important for understanding ice formation and molecular diffusion in biopreservation. However, this information is scarce in the literature. In addition, to the best of our knowledge, the effect of nanoparticles on the viscosity of these solutions has not previously been reported. The objectives of this study were thus: (i) to systematically measure the subzero viscosity of two such systems, dimethyl sulfoxide (Me2SO)-H2O-NaCl and glycerol-H2O-NaCl; (ii) to explore the effect of hydroxyapatite (HA) nanoparticles on the viscosity; and (iii) to provide models that precisely predict viscosity at multiple concentrations of cryoprotective agent (CPA) in saline solutions at subzero temperatures. Our experiments were performed in two parts. We first measured the viscosity at multiple CPA concentrations [0.3-0.75 (w/w)] in saline solution with and without nanoparticles at subzero temperatures (0 to -30°C). The data exhibited a good fit to the Williams-Landel-Ferry (WLF) equation. We then measured the viscosity of residual unfrozen ternary solutions with and without nanoparticles during equilibrium freezing. HA nanoparticles made the solution more viscous, suggesting applications for these nanoparticles in preventing cell dehydration, ice nucleation, and ice growth during freezing and thawing in cryopreservation. Copyright © 2014 Elsevier Inc. All rights reserved.
Comparison of vibration spectra and of valence force fields of the dimethyl sulfoxide and of its addition compounds with boron trifluoride and bivalent palladium halides
International Nuclear Information System (INIS)
Tranquille, Michel
In its first part, this research thesis addresses vibration spectra and valence force fields of the dimethyl sulfoxide (DMSO) molecule: report of published results obtained by various techniques (microwave, X ray, NMR, slow neutron or vibration spectroscopy), discussion and analysis of vibration spectra, determination of thermodynamic values, determination of normal vibration modes. The second part addresses the study of vibration spectra of coordination compounds of DMSO: influence of water on DMSO vibration spectra, DMSO coordination compounds with boron trifluoride or with palladium halides. The third part addresses the study of valence force fields and of normal modes of vibration of DMSO coordination compounds (same compounds as above), and the fourth part reports the comparison of some DMSO properties in function of the complexing site
Use of sulfoxides as novel synergists in the solvent extraction of uranium (VI) by various substituted diketones
International Nuclear Information System (INIS)
Shukla, J.P.; Kedari, C.S.
The role of symmetric long chain dialkyl sulfoxides as synergists in the solvent extraction of uranyl ion into toluene with heptafluoro dimethyl octanedione (HFOD) from nitric acid solutions has been investigated. The synergistic reactivity of different sulfoxides follows the order : DPSO < DBSO < DISO < DHSO < BESO. Five β-diketones namely HTFA, HTTA, HFOD, HPMBP, HPMTFP are studied in combination with bis(2-ethylhexyl)sulfoxide (BESO) to reveal their extraction ability. (author). 4 refs., 2 tabs
Unscrambling micro-solvation of -COOH and -NH groups in neat dimethyl sulfoxide: insights from1H-NMR spectroscopy and computational studies.
Takis, Panteleimon G; Papavasileiou, Konstantinos D; Peristeras, Loukas D; Boulougouris, Georgios C; Melissas, Vasilios S; Troganis, Anastassios N
Dimethyl sulfoxide (DMSO) has a significant, multi-faceted role in medicine, pharmacy, and biology as well as in biophysical chemistry and catalysis. Its physical properties and impact on biomolecular structures still attract major scientific interest, especially the interactions of DMSO with biomolecular functional groups. In the present study, we shed light on the "isolated" carboxylic (-COOH) and amide (-NH) interactions in neat DMSO via 1 H NMR studies along with extensive theoretical approaches, i.e. molecular dynamics (MD) simulations, density functional theory (DFT), and ab initio calculations, applied on model compounds (i.e. acetic and benzoic acid, ethyl acetamidocyanoacetate). Both experimental and theoretical results show excellent agreement, thereby permitting the calculation of the association constants between the studied compounds and DMSO molecules. Our coupled MD simulations, DFT and ab initio calculations, and NMR spectroscopy results indicated that complex formation is entropically driven and DMSO molecules undergo multiple strong interactions with the studied molecules, particularly with the -COOH groups. The combined experimental and theoretical techniques unraveled the interactions of DMSO with the most abundant functional groups of peptides (i.e. peptide bonds, side chain and terminal carboxyl groups) in high detail, providing significant insights on the underlying thermodynamics driving these interactions. Moreover, the developed methodology for the analysis of the simulation results could serve as a template for future thermodynamic and kinetic studies of similar systems.
A potentiometric study of (acid+base) equilibria in substituted 4-nitropyridine N-oxide systems in methanol and dimethyl sulfoxide
International Nuclear Information System (INIS)
Gurzynski, Lukasz; Puszko, Aniela; Makowski, Mariusz; Chmurzynski, Lech
The acid dissociation constants for cationic acids conjugated with 4-nitropyridine N-oxides have been determined using potentiometric titration method. The measurements in the systems of thirteen 4-nitropyridine N-oxide derivatives were carried out in the polar amphiprotic methanol (MeOH) and in the aprotic protophilic dimethyl sulfoxide (DMSO). Likewise as in the polar aprotic protophobic solvents (acetonitrile, acetone) it was found that in MeOH for all N-oxides studied the pK a values were readily determinable, whereas in DMSO the pK a values were hardly determinable or indeterminable by using the potentiometric method. In addition, just like in our previous investigations it was revealed that the sequence of the pK a values of the cationic acids in methanol is the same as in the water and the values are lower than those determined in acetonitrile and acetone. Also, it was found that the phenomenon of cationic homoconjugation equilibria was not present in the systems involving 4-nitropyridine N-oxide derivatives in both solvents used. Furthermore, protonation energies, ΔE prot , and Gibbs free enthalpies, ΔG prot , in vacuo have been compared with acid dissociation constants (expressed as pK a MeOH values) of the protonated N-oxides determined by potentiometric titration in methanol to establish a correlation between these magnitudes
Second-harmonic generation microscopy used to evaluate the effect of the dimethyl sulfoxide in the cryopreservation process in collagen fibers of differentiated chondrocytes
Andreoli-Risso, M. F.; Duarte, A. S. S.; Ribeiro, T. B.; Bordeaux-Rego, P.; Luzo, A.; Baratti, M. O.; Adur, J.; de Thomaz, A. A.; Pelegati, V. B.; Carvalho, H. F.; Cesar, C. L.; Kharmadayan, P.; Costa, F. F.; Olalla-Saad, S. T.
Cartilaginous lesions are a significant public health problem and the use of adult stem cells represents a promising therapy for this condition. Cryopreservation confers many advantages for practitioners engaged in cell-based therapies. However, conventional slow freezing has always been associated with damage and mortality due to intracellular ice formation, cryoprotectant toxicity, and dehydration. The aim of this work is to observe the effect of the usual Dimethyl Sulfoxide (DMSO) cryopreservation process on the architecture of the collagen fiber network of chondrogenic cells from mesenchymal stem cells by Second Harmonic Generation (SHG) microscopy. To perform this study we used Mesenchymal Stem Cells (MSC) derived from adipose tissue which presents the capacity to differentiate into other lineages such as osteogenic, adipogenic and chondrogenic lineages. Mesenchymal stem cells obtained after liposuction were isolated digested by collagenase type I and characterization was carried out by differentiation of mesodermic lineages, and flow cytometry using specific markers. The isolated MSCs were cryopreserved by the DMSO technique and the chondrogenic differentiation was carried out using the micromass technique. We then compared the cryopreserved vs non-cryopreserved collagen fibers which are naturally formed during the differentiation process. We observed that noncryopreserved MSCs presented a directional trend in the collagen fibers formed which was absent in the cryopreserved MSCs. We confirmed this trend quantitatively by the aspect ratio obtained by Fast Fourier Transform which was 0.76 for cryopreserved and 0.52 for non-cryopreserved MSCs, a statistical significant difference.
A Novel QSPR Model for Prediction of Gas to Dimethyl Sulfoxide Solvation Enthalpy of Organic Compounds Based on Support Vector Machine.
Golmohammadi, Hassan; Dashtbozorgi, Zahra; Acree, William E
In this study, a quantitative structureproperty relationship (QSPR) study is developed for the prediction of gas to dimethyl sulfoxide solvation enthalpy (ΔHSolv ) of organic compounds based on molecular descriptors calculated solely from molecular structure considerations. Diverse types of molecular descriptors were calculated to represent the molecular structures of the various compounds studied. Multiple linear regression (MLR) was employed to select an optimal subset of descriptors that have significant contributions to the ΔHSolv overall property. Our investigation revealed that the dependence of physicochemical properties on solvation enthalpy is a nonlinear observable fact and that MLR method is unable to model the solvation enthalpy accurately. It has been observed that support vector machine (SVM) and artificial neural network (ANN) demonstrates better performance compared with MLR. The standard error value of the test set for SVM is 1.731 kJ mol(-1) , while it is 2.303 kJ mol(-1) and 5.146 kJ mol(-1) for ANN and MLR, respectively. The results showed that the calculated ΔHSolv values by SVM were in good agreement with the experimental data, and the performance of the SVM model was superior to those of MLR and ANN ones. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Maintenance of the response to dimethyl sulfoxide treatment using hyperbaric oxygen in interstitial cystitis/painful bladder syndrome: a prospective, randomized, comparative study.
Gallego-Vilar, Daniel; García-Fadrique, Gonzalo; Povo-Martin, Ivan; Salvador-Marin, Manuel; Gallego-Gomez, Juan
Interstitial cystitis (IC)/painful bladder syndrome (PBS) is a difficult disease to manage and creates critical limitations in patients' daily lives. Our objective was to determine the efficacy of hyperbaric oxygen (HBO) therapy in the maintenance of response after the administration of intravesical dimethyl sulfoxide (DMSO). We conducted an open, prospective, randomized, comparative pilot study with women diagnosed with IC/PBS according to the European Society for the Study of Interstitial Cystitis criteria. In the first phase, DMSO was given to all patients. In the second phase, we used 1:1 randomization and administered HBO to 10 women. The evaluated variables were pain (through a visual analog scale), frequency and urgency of voids, nocturia, and quality of life using the O'Leary-Sant Interstitial Cystitis Score/Problem Index and the King's Health Questionnaire. In the second phase, we measured the length of time that clinical improvement was maintained. The mean age was 47.6 years (SD 18.4). Out of 20 patients, 14 experienced clinical improvement after DMSO in all of the evaluated symptoms (p < 0.05; 95% CI). After the second phase, all patients who received HBO had a more substantive and prolonged maintenance of the effects of DMSO. In this study, HBO improved the maintenance of the beneficial effects of DMSO among women with IC/PBS. Copyright © 2013 S. Karger AG, Basel.
Fullerenol C{sub 60}(OH){sub 24} nanoparticles decrease relaxing effects of dimethyl sulfoxide on rat uterus spontaneous contraction
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Slavic, Marija, E-mail: firstname.lastname@example.com [University of Belgrade, Department for Physiology, Institute for Biological Research ' Sinisa Stankovic' (IBISS) (Serbia); Djordjevic, Aleksandar [University of Novi Sad, Department of Chemistry, Biochemistry and the Environment, Faculty of Sciences (Serbia); Radojicic, Ratko [University of Belgrade, Faculty of Biology (Serbia); Milovanovic, Slobodan [University of East Sarajevo, Department of Pharmacology, Faculty of Medicine at Foca (Bosnia and Herzegowina); Orescanin-Dusic, Zorana [University of Belgrade, Department for Physiology, Institute for Biological Research ' Sinisa Stankovic' (IBISS) (Serbia); Rakocevic, Zlatko [University of Belgrade, Institute for Nuclear Sciences ' Vinca' (Serbia); Spasic, Mihajlo B.; Blagojevic, Dusko [University of Belgrade, Department for Physiology, Institute for Biological Research ' Sinisa Stankovic' (IBISS) (Serbia)
Dimethyl sulfoxide (DMSO) is a widely used solvent and cryoprotectant that can cause impaired blood flow, reduction in intracranial pressure, tissue edema, inflammatory reactions, inhibition of vascular smooth muscle cell migration and proliferation, processes which can lead to atherosclerosis of the coronary, peripheral and cerebral circulation. Although the adverse effects are rare when DMSO is administered in clinically established concentrations, there is no safe antagonist for an overdose. In this work, we treated isolated spontaneous and calcium-induced contractile active rat uteri (Wistar, virgo intacta), with DMSO and fullerenol C{sub 60}(OH){sub 24} nanoparticle (FNP) in DMSO. FNP is a water-soluble derivative of fullerene C{sub 60}. Its size is a 1.1 nm in diameter and is a very promising candidate for a drug carrier in nanomedicine. FNP also displays free radical scavenging activity. DMSO decreased both spontaneous and calcium-induced contractions. In contrast, FNP only decreased spontaneous contraction. FNP decreased copper-zinc superoxide dismutase activity and prevented the DMSO-induced increase in glutathione reductase activity. Atomic force microscopy detected that FNP aggregated with calcium ions. Our results indicate that FNP has properties that make it a good candidate to be a modulator of DMSO activity which could minimize side effects of the latter.
Complex formation reactions of uranyl(VI) with neutral N-donors in dimethyl sulfoxide. Influence of small amounts of water
International Nuclear Information System (INIS)
Cassol, A.; Di Bernardo, P.; Zanonato, P.; Portanova, R.; Tolazzi, M.
Quantitative information about the existence and thermodynamic stability of uranyl(VI) ion complexes based solely upon nitrogen coordination has been obtained in the solvent dimethyl sulfoxide. Calorimetric, potentiometric, and FT-IR investigations, under controlled anhydrous conditions, show that the uranyl(VI) ion can form both mono and bis chelates with the ethylenediamine ligand and only a mono chelate of rather low stability with propylenediamine. With the monodentate ligand n-butylamine only a very weak metal-ligand interaction has been detected. The stability constants and the enthalpy and entropy changes have been calculated for the identified coordinated species. All data refer to 25.0 degree C and a tetraethylammonium perchlorate medium of ionic strength 0.1 M. All the complexes are enthalpy stabilized whereas the entropy contributions oppose the complex formation. Calorimetric and FT-IR measurements carried out to investigate the effects of small amounts of water present show that a very low water concentration, comparable to that of the coordinating metal ion, can give rise to hydrolysis reactions that may compete with complex formation. This is due to the combined action of different factors that are discussed. 39 refs., 6 figs., 1 tab
A potentiometric study of (acid+base) equilibria in substituted 4-nitropyridine N-oxide systems in methanol and dimethyl sulfoxide
Energy Technology Data Exchange (ETDEWEB)
Gurzynski, Lukasz [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Puszko, Aniela [Department of Organic Chemistry, School of Economics, Wroclaw (Poland); Makowski, Mariusz [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Chmurzynski, Lech [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland)]. E-mail: email@example.com
The acid dissociation constants for cationic acids conjugated with 4-nitropyridine N-oxides have been determined using potentiometric titration method. The measurements in the systems of thirteen 4-nitropyridine N-oxide derivatives were carried out in the polar amphiprotic methanol (MeOH) and in the aprotic protophilic dimethyl sulfoxide (DMSO). Likewise as in the polar aprotic protophobic solvents (acetonitrile, acetone) it was found that in MeOH for all N-oxides studied the pK{sub a} values were readily determinable, whereas in DMSO the pK{sub a} values were hardly determinable or indeterminable by using the potentiometric method. In addition, just like in our previous investigations it was revealed that the sequence of the pK{sub a} values of the cationic acids in methanol is the same as in the water and the values are lower than those determined in acetonitrile and acetone. Also, it was found that the phenomenon of cationic homoconjugation equilibria was not present in the systems involving 4-nitropyridine N-oxide derivatives in both solvents used. Furthermore, protonation energies, {delta}E{sub prot}, and Gibbs free enthalpies, {delta}G{sub prot}, in vacuo have been compared with acid dissociation constants (expressed as pK{sub a}{sup MeOH} values) of the protonated N-oxides determined by potentiometric titration in methanol to establish a correlation between these magnitudes.
A contribution to the controversy over dimethyl sulfoxide toxicity: anesthesia monitoring results in patients treated with Onyx embolization for intracranial aneurysms
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Pamuk, A.G.; Aypar, U. [Hacettepe University Hospital, Department of Anesthesia, Sihhiye, Ankara (Turkey); Saatci, I.; Cekirge, H.S. [Hacettepe University Hospital, Department of Radiology, Ankara (Turkey)
Onyx injection is a new technique for embolization of cerebral aneurysms that is involved in a controversy about the 'toxicity' of its solvent, dimethyl sulfoxide (DMSO). We retrospectively studied 38 patients treated for aneurysms with the liquid polymer, Onyx. Induction was with propofol, fentanyl and vecuronium, and anesthesia was maintained with isoflurane in O{sub 2} and N{sub 2}O. The patients were given 500 ml of fluid after induction, and bradycardia was prevented in order to keep patients hyperdynamic. Electrocardiography (ECG), non-invasive blood pressure (NIBP), pulse oximetry, core temperatures, invasive blood pressure (BP), etCO{sub 2}, and urine output were monitored throughout the intervention. Heart rate and BP changes in response to balloon inflation, DMSO injection, Onyx injection and balloon deflation were recorded. The patients were followed with serial neurological examinations, computerized tomography and/or magnetic resonance imaging postoperatively for evidence of any neurological injury. Cumulative DMSO doses were always well under previously implicated doses for systemic toxicity. No changes implicating toxic reactions were observed during DMSO and Onyx injections. Balloon-induced changes returned to baseline within 1 min of balloon deflation. Technique-related permanent morbidity occurred in two patients (worsening of cranial nerve palsies in one and monocular blindness in another) and intracranial hemorrhage with resulting death in one patient. All patients showed a tendency to oxygen desaturation, but this finding did not cause any clinical consequence. Anesthesiologists need to be vigilant in monitoring patients treated with techniques that are new or are being developed. We have seen no evidence of toxicity or any anesthetic complications in our group of patients, our only clinical concern being a tendency to oxygen desaturation, which may be explained by the inhalational elimination of DMSO. (orig.)
A contribution to the controversy over dimethyl sulfoxide toxicity: anesthesia monitoring results in patients treated with Onyx embolization for intracranial aneurysms
International Nuclear Information System (INIS)
Pamuk, A.G.; Aypar, U.; Saatci, I.; Cekirge, H.S.
Onyx injection is a new technique for embolization of cerebral aneurysms that is involved in a controversy about the 'toxicity' of its solvent, dimethyl sulfoxide (DMSO). We retrospectively studied 38 patients treated for aneurysms with the liquid polymer, Onyx. Induction was with propofol, fentanyl and vecuronium, and anesthesia was maintained with isoflurane in O 2 and N 2 O. The patients were given 500 ml of fluid after induction, and bradycardia was prevented in order to keep patients hyperdynamic. Electrocardiography (ECG), non-invasive blood pressure (NIBP), pulse oximetry, core temperatures, invasive blood pressure (BP), etCO 2 , and urine output were monitored throughout the intervention. Heart rate and BP changes in response to balloon inflation, DMSO injection, Onyx injection and balloon deflation were recorded. The patients were followed with serial neurological examinations, computerized tomography and/or magnetic resonance imaging postoperatively for evidence of any neurological injury. Cumulative DMSO doses were always well under previously implicated doses for systemic toxicity. No changes implicating toxic reactions were observed during DMSO and Onyx injections. Balloon-induced changes returned to baseline within 1 min of balloon deflation. Technique-related permanent morbidity occurred in two patients (worsening of cranial nerve palsies in one and monocular blindness in another) and intracranial hemorrhage with resulting death in one patient. All patients showed a tendency to oxygen desaturation, but this finding did not cause any clinical consequence. Anesthesiologists need to be vigilant in monitoring patients treated with techniques that are new or are being developed. We have seen no evidence of toxicity or any anesthetic complications in our group of patients, our only clinical concern being a tendency to oxygen desaturation, which may be explained by the inhalational elimination of DMSO. (orig.)
Dimethyl sulfoxide-caused changes in pro- and anti-angiogenic factor levels could contribute to an anti-angiogenic response in HeLa cells.
Şimşek, Ece; Aydemir, Esra Arslan; İmir, Nilüfer; Koçak, Orhan; Kuruoğlu, Aykut; Fışkın, Kayahan
Dimethyl sulfoxide (DMSO) is widely used in biological research as a general solvent. While it has been previously demonstrated that DMSO possesses a wide range of pharmacological effects, there is no published work regarding the effects of DMSO on pro-angiogenic factor levels. This study was designed to investigate the possible effects of DMSO on the levels of three pro-angiogenic factors released from HeLa cells in vitro. Cells were treated with two different and previously determined concentrations of DMSO. The cytotoxic effects of DMSO concentrations on HeLa cells were determined via MTT. Survival rates of DMSO-treated cells were determined by Invitrogen live/dead viability/cytotoxicity kit and trypan blue exclusion assay. Changes in the pro-angiogenic levels in media were evaluated by Cayman's Substance P Enzyme Immunoassay ELISA kit. Vascular endothelial growth factor ELISA kit and interferon gamma ELISA kit for substance P, VEGF and IFNγ respectively. Changes in substance P levels were corrected by standard western blotting. Changes in VEGF and IFNγ levels were corrected both by western blot and real time PCR. Treatment with 1.4 μM DMSO caused a time-dependent inhibition of cell proliferation at 24, 48 and 72 h. 1.4 μM DMSO caused a significant reduction in VEGF levels at 72 h of incubation and sharp increases in IFNγ levels at both 48 and 72 h of incubation. According to real time PCR analyses, DMSO (1.4 μM) exhibited an inhibitory effect on VEGF but acted as an augmenter of IFNγ release on HeLa cells in vitro. This is the first report showing that the general solvent DMSO suppressed HeLa cell proliferation, decreased the levels of two pro-angiogenic factors (substance P and VEGF) and increased the release of an anti-angiogenic factor IFNγ in vitro. Copyright © 2015 Elsevier Ltd. All rights reserved.
Dimethyl sulfoxide inhibits spontaneous diabetes and autoimmune recurrence in non-obese diabetic mice by inducing differentiation of regulatory T cells
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Lin, Gu-Jiun [Department of Biology and Anatomy, National Defense Medical Center, Taipei, Taiwan, ROC (China); Sytwu, Huey-Kang [Department of Microbiology and Immunology, National Defense Medical Center, Taipei, Taiwan, ROC (China); Yu, Jyh-Cherng [Department of General Surgery, Tri-Service General Hospital, National Defense Medical Center, Taipei, Taiwan, ROC (China); Chen, Yuan-Wu [School of Dentistry, National Defense Medical Center, Taipei, Taiwan, ROC (China); Department of Oral and Maxillofacial Surgery, Tri-Service General Hospital, National Defense Medical Center, Taipei, Taiwan, ROC (China); Kuo, Yu-Liang [Department of Medical Imaging, Chung Shan Medical University Hospital, Taichung, Taiwan, ROC (China); School of Medical Imaging and Radiological Sciences, Chung Shan Medical University, Taichung, Taiwan, ROC (China); Yu, Chiao-Chi [Department of Biology and Anatomy, National Defense Medical Center, Taipei, Taiwan, ROC (China); Department of General Surgery, Tri-Service General Hospital, National Defense Medical Center, Taipei, Taiwan, ROC (China); Chang, Hao-Ming; Chan, De-Chuan [Department of General Surgery, Tri-Service General Hospital, National Defense Medical Center, Taipei, Taiwan, ROC (China); Huang, Shing-Hwa, E-mail: firstname.lastname@example.com [Department of Biology and Anatomy, National Defense Medical Center, Taipei, Taiwan, ROC (China); Department of General Surgery, Tri-Service General Hospital, National Defense Medical Center, Taipei, Taiwan, ROC (China)
Type 1 diabetes mellitus (T1D) is caused by the destruction of insulin-producing β cells in pancreatic islets by autoimmune T cells. Islet transplantation has been established as an effective therapeutic strategy for T1D. However, the survival of islet grafts can be disrupted by recurrent autoimmunity. Dimethyl sulfoxide (DMSO) is a solvent for organic and inorganic substances and an organ-conserving agent used in solid organ transplantations. DMSO also exerts anti-inflammatory, reactive oxygen species scavenger and immunomodulatory effects and therefore exhibits therapeutic potential for the treatment of several human inflammatory diseases. In this study, we investigated the therapeutic potential of DMSO in the inhibition of autoimmunity. We treated an animal model of islet transplantation (NOD mice) with DMSO. The survival of the syngeneic islet grafts was significantly prolonged. The population numbers of CD8, DC and Th1 cells were decreased, and regulatory T (Treg) cell numbers were increased in recipients. The expression levels of IFN-γ and proliferation of T cells were also reduced following DMSO treatment. Furthermore, the differentiation of Treg cells from naive CD4 T cells was significantly increased in the in vitro study. Our results demonstrate for the first time that in vivo DMSO treatment suppresses spontaneous diabetes and autoimmune recurrence in NOD mice by inhibiting the Th1 immune response and inducing the differentiation of Treg cells. - Highlights: • We report a therapeutic potential of DMSO in autoimmune diabetes. • DMSO exhibits an immune modulatory effect. • DMSO treatment increases regulatory T cell differentiation. • The increase in STAT5 signaling pathway explains the effect of DMSO in Tregs.
Effective extraction method for dioxin analysis from lipid-rich biological matrices using a combination of pressurized liquid extraction and dimethyl sulfoxide/acetonitrile/hexane partitioning
Energy Technology Data Exchange (ETDEWEB)
Kitamura, Kimiyoshi; Takazawa, Yoshikatsu; Hashimoto, Shunji; Choi, Jae-Won; Ito, Hiroyasu; Morita, Masatoshi
For the analysis of dioxins (i.e. PCDDs/Fs, polychlorinated dibenzo-p-dioxins/dibenzofurans, and Co-PCBs, coplanar polychlorinated biphenyls) in lipid-rich biological matrices, we examined the potential of a novel extraction method, consisting of a combination of pressurized liquid extraction (PLE) using 1:9 (v/v) dimethyl sulfoxide (DMSO)/acetonitrile (1:9, v/v) as solvent and DMSO/acetonitrile/hexane partitioning. This method could potentially reduce the large amount of lipids typically generated in the extraction of dioxins. Our cleanup procedure, using tandem multilayer silica gel-activated carbon (MLS-AC) column chromatography, a simplification of the conventional method, was capable of separating mono-ortho-PCBs from non-ortho-PCBs/PCDDs/Fs in half the time required for the conventional method. The optimal conditions for PLE common to all solvents used in this investigation were 2000 psi and {>=}180 degree sign C. The amount of lipid extracted was approximately 1/100 of that extracted using acetone/hexane (1:1, v/v), making sulfuric acid treatment unnecessary. In both meat and fecal matrices, dioxin congener levels extracted by this method were almost identical to those obtained by conventional solvent extraction methods, such as those employing acetone/hexane or toluene. Moreover, the R.S.D.s of dioxins extracted by this method were <15%, as well as those obtained by conventional techniques. Our new method was advantageous in shortening removing lipid procedure to 2-3 h.
Dimethyl sulfoxyde diethyl fumarate solution for high dose dosimetry
International Nuclear Information System (INIS)
Al-Kassiri, H.; Kattan, M.; Daher, Y.
Dosimetric characterization of diethyl fumarate DEF in dimethyl sulfoxyde DMSO solution has been studied spectrophotometrically for possible application at high dose radiation dosimetry in the range (0-225 kGy). The absorption spectra of irradiated solution showed broad absorption bands between (325-400 nm) with a shoulder at 332 nm. The absorption increases as the dose is increased. Absorbance at 332 nm were measured and plotted against absorbed dose. Linear relationship and good response were found between absorbed dose and absorbance of 20% DEF concentration in the range (0-225 kGy) at the wave length, and linearity up to 250 kGy of absorbance at 332 nm .Good dose rate independence was observed in the range (14-33 kGy/h). The effect of post irradiation storage in darkness and indirect daylight conditions were not found to influence the absorption up to 700 h after irradiation. The effect of irradiation temperature within the range (0 to 60 centigrade degree) on the dosimetry performance was discussed.(author)
Dimethyl sulfoxyde diethyl fumarate solution for high dose dosimetry
International Nuclear Information System (INIS)
Al-Kassiri, H.; Kattan, M.; Daher, Y.
Dosimetric characterization of diethyl fumarate DEF in dimethyl sulfoxyde DMSO solution has been studied spectrophotometrically for possible application at high dose radiation dosimetry in the range (0-225 kGy). The absorption spectra of irradiated solution showed broad absorption bands between (325-400 nm) with a shoulder at 332 nm. The absorption increases as the dose is increased. Absorbance at 332 nm were measured and plotted against absorbed dose. Linear relationship and good response were found between absorbed dose and absorbance of 20% DEF concentration in the range (0-225 kGy) at the wave length, and linearity up to 250 kGy of absorbance at 332 nm .Good dose rate independence was observed in the range (14-33 kGy/h). The effect of post irradiation storage in darkness and indirect daylight conditions were not found to influence the absorption up to 700 h after irradiation. The effect of irradiation temperature within the range (0 to 60 centigrade degree) on the dosimetry performance was discussed. (author)
Photochemical induced growth and aggregation of metal nanoparticles in diode-array spectrophotometer via excited dimethyl-sulfoxide.
Zidki, Tomer; Cohen, Haim; Meyerstein, Dan
Ag(0) and Au(0) nanoparticles suspended in dilute aqueous solutions containing (CH(3))(2)SO are photochemically unstable. The light source of a diode-array spectrophotometer induces, within less than a minute, particle growth and aggregation. The results indicate that this process is triggered by UV light absorption by the (CH(3))(2)SO.
Experimental densities and excess volumes for binary mixtures of (dimethyl sulfoxide+an aromatic hydrocarbon) at temperatures from (293.15 to 353.15) K at atmospheric pressure
International Nuclear Information System (INIS)
Wang Haijun; Liu Wei
Experimental data on density of (dimethyl sulfoxide+benzene, or toluene, or ethylbenzene, or styrene) were obtained at temperatures (293.15, 303.15, 313.15, 323.15, 333.15, 343.15, 353.15) K and atmospheric pressure by means of a vibrating-tube densimeter. From these data, excess molar volume has been calculated. The computed quantities have been fitted to the fourth-order Redlich-Kister equation to derive the coefficients and estimate the standard error values. It was found that the VmE in the systems studied increases with rising temperature
Effects of intratesticular administration of zinc gluconate and dimethyl sulfoxide on clinical, endocrinological, and reproductive parameters in dogs.
Vannucchi, C I; Angrimani, D S R; Eyherabide, A R; Mazzei, C P; Lucio, C F; Maiorka, P C; Silva, L C G; Nichi, M
Nonsurgical sterilization methods are considered alternative tools for the worldwide challenge represented by canine overpopulation control. Intratesticular injection of zinc gluconate associated with DMSO arises as an option because of the effortless diffusion throughout the testicular parenchyma. This study aimed to verify the effectiveness of a double testicular injection of zinc gluconate associated with DMSO as a chemical contraceptive for male dogs. The study was conducted with 22 dogs treated with two intratesticular injections of the chemical solution (treated group; n = 15) or 0.9% NaCl solution (control group; n = 7) on a monthly interval. All animals were submitted to clinical examination, breeding soundness evaluation including morphologic and sonographic examination of the testes, assessment of libido, volume of the sperm-rich fraction, sperm motility, total sperm count, plasma membrane integrity, sperm morphologic abnormalities, and the total number of morphologically normal and motile sperm in the ejaculate. Blood samples were collected for serum testosterone analysis, and testicular tissue was morphologically and histologically evaluated. No clinical alterations and signs of pain or local sensitivity along the experimental period were noticed. However, the injection of zinc gluconate and DMSO significantly reduced libido and testosterone concentrations (even beyond the reference range for intact male dogs). Impairment of sperm quality-related variables was observed 15 days after the first intratesticular administration of zinc gluconate and DMSO (i.e., decrease in sperm count and sperm motility and an increase in major sperm defects and by this a decrease in the total number of morphologically normal and motile sperm). Testicular ultrasonographic analysis revealed reduction of testicular volume and changes of testicular echotexture in treated animals, compatible with tissue degeneration, fibrosis, and calcification of testicular parenchyma on
Evaluation of human platelet lysate and dimethyl sulfoxide as cryoprotectants for the cryopreservation of human adipose-derived stem cells.
Wang, Chuan; Xiao, Ran; Cao, Yi-Lin; Yin, Hong-Yu
Cryopreservation provides an effective technique to maintain the functional properties of human adipose-derived stem cells (ASCs). Dimethylsulfoxide (DMSO) and fetal bovine serum (FBS) are frequently used as cryoprotectants for this purpose. However, the use of DMSO can result in adverse effects and toxic reactions and FBS can introduce risks of viral, prion, zoonose contaminations and evoke immune responses after injection. It is therefore crucial to reduce DMSO concentrations and use serum-free solution in the cryopreservation process. Human platelet lysate (PL) is a promising candidate for use as an alternative to DMSO and FBS. Therefore, in this study, with an aim to identify a cryoprotective agent for ASC cryopreservation, we determined the viability, proliferation potential, phenotype, and differentiation potential of fresh ASCs and ASCs cryopreserved using different combinations of three cryoprotective agents: fetal bovine serum (FBS), dimethylsulfoxide (DMSO), and human platelet lysate (PL). The viability of the ASCs cryopreserved with 90% FBS and 10% DMSO, 95% FBS and 5% DMSO, and 97% PL and 3% DMSO was >80%, and the proliferation potentials, cell phenotypes, and differentiation potentials of these groups were similar to those of fresh ASCs. Together, our findings suggest that a combination of 97% PL and 3% DMSO is an ideal cryoprotective agent for the efficient cryopreservation of human ASCs. Copyright © 2017 Elsevier Inc. All rights reserved.
Crystal structure of a one-dimensional helical-type silver(I coordination polymer: catena-poly[[silver(I-μ-N-(pyridin-4-ylmethylpyridine-3-amine-κ2N:N′] nitrate dimethyl sulfoxide disolvate
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Bokhee Moon
Full Text Available The asymmetric unit of the title compound, {[Ag(C11H11N3]NO3·2(CH32SO}n, comprises one AgI atom, one N-(pyridine-4-ylmethylpyridine-3-amine ligand, one nitrate anion and two dimethyl sulfoxide molecules. The AgI atoms are bridged by two pyridine N atoms from two symmetry-related ligands, forming a helical chain and adopting a slightly distorted linear coordination geometry [N—Ag—N = 175.37 (8°]. The helical chain, with a pitch length of 16.7871 (8 Å, propagates along the b-axis direction. In the crystal, symmetry-related right- and left-handed helical chains are alternately arranged via Ag...Ag interactions [3.4145 (4 Å] and π–π stacking interactions [centroid–centroid distance = 3.650 (2 Å], resulting in the formation of a two-dimensional supramolecular network extending parallel to (100. Weak Ag...O [2.775 (2, 3.169 (4 and 2.690 (2 Å] interactions, as well as several N—H...O and C—H...O hydrogen-bonding interactions, contribute to the stabilization of the crystal structure. Parts of the dimethyl sulfoxide solvent molecule are disordered over two sets of sites in a 0.937 (3:0.063 (3 ratio.
Crystal structure of diaquabis(7-diethylamino-3-formyl-2-oxo-2H-chromen-4-olato-κ2O3,O4zinc(II dimethyl sulfoxide disolvate
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Aaron B. Davis
Full Text Available The structure of the title coordination complex, [Zn(C14H14NO42(H2O2]·2C2H6OS, shows that the ZnII cation adopts an octahedral geometry and lies on an inversion center. Two organic ligands occupy the equatorial positions of the coordination sphere, forming a chelate ring motif via the O atom on the formyl group and another O atom of the carbonyl group (a pseudo-β-diketone motif. Two water molecules occupy the remaining coordination sites of the ZnII cation in the axial positions. The water molecules are each hydrogen bonded to a single dimethyl sulfoxide molecule that has been entrapped in the crystal lattice.
Trans-ligand-dependent arrangement (bent or linear) of Pt II-bound dialkylcyanamide ligands: Molecular structure of trans-dichloro(dimethylcyanamide)(dimethyl sulfoxide)platinum(II)
Anisimova, Tatyana B.; Bokach, Nadezhda A.; Fritsky, Igor O.; Haukka, Matti
The title compound, trans-[PtCl 2(NCNMe 2)(Me 2SO)], is the first example of the structurally characterized Pt II species having the nitrile and the sulfoxide ligands in the trans-position to each other. The most significant feature of this structure is the non-linear arrangement of the Pt sbnd N1 sbnd C1 fragment providing the rare case of the bent form of the dialkylcyanamide ligand.
Gamma-radiolysis of dimethyl sulfoxide. II. Radiolysis yields and possible mechanisms; Gamma-Radiolisis del dimetilsulfoxido II. Rendimientos radioloticos y posibles mecanismos
Energy Technology Data Exchange (ETDEWEB)
Gutierrez, M. C.; Barrera, R.
As result of quantitative studies on gamma-radiolysis of DMSO at a dose range of 90-850 Mrads, constant G values have been obtained for the following radiolysis compounds: G(-DMSO) - 6.7 {+-}0.2; G(dimethyl sulphide) - 3.4 {+-}0.3; G(methane) - 0,75 {+-} 0.04; G(dimethyl disulphide) -0.33 {+-}0,03; G(tri methylsulphonium methanesulphonate) - 0.26 {+-} 0,01; G(methyl methanethiosulphonate) - 0,25 {+-}0.02; G(dimethyl sulphona)-0.21{+-}0.02; G(H{sub 2})-0.18{+-}0.02; and G(propane)--0.0092{+-}0.0007. Initial G values have been obtained for other identified compounds: Gi(ethane)-0,46; Gi(CO)-0.052; and Gi(CO{sub 2})-0.030. Possible mechanisms on the radiolysis process are proposed. (Author) 17 refs.
Interomolecular interactions in diluted solutions of potassium iodocuprates (1) in dimethyl ether of diethylene glycol
International Nuclear Information System (INIS)
Gorodinskaya, Eh.Ya.; Mel'nikova, N.B.; Yurin, K.V.
The role of donor solvent in the formation of potassium mononuclear iodocuprates (1) in the system CuI-KI-dimethyl ether of diethylene glycol has been considerd. The calculated values of enthalpy, free energy and entropy of viscous flow activation in the range of temperatures 298-318 K for the solutions testify to decomposition of the solvent structure. Negative deviations of mole volumes from the additivity rule characterized strong molecular interaction
Co-cultures of human coronary smooth muscle cells and dimethyl sulfoxide-differentiated HL60 cells upregulate ProMMP9 activity and promote mobility-modulation by reactive oxygen species.
Bernard, Yohann; Melchior, Chantal; Tschirhart, Eric; Bueb, Jean-Luc
Vascular cells and leukocytes, involved in the development of atherosclerosis, produce cytokines and/or reactive oxygen species (ROS) and matrix metalloproteinases (MMPs) implicated in cell mobility. We investigated by co-culture experiments the effects of human coronary smooth muscle cells (HCSMC) on MMPs characteristics and mobility of neutrophil-like dimethyl sulfoxide-differentiated HL60 cells (not equal HL60). The effects of superoxide dismutase (SOD) and catalase were also analyzed. All the studied MMP2 characteristics remained unchanged. HCSMC stimulated MMP9 protein level, activity and mobility of not equal HL60 cells and expressed and secreted a variety of cytokines implicated in atherosclerosis. SOD and catalase increased MMP9 expression, protein level and activity of not equal HL60, but migration of not equal HL60 cells was only decreased by catalase, demonstrating that ROS are more efficient in modulating MMP9 activity of not equal HL60 than their mobility. Finally, HCSMC being able to stimulate not equal HL60, their co-cultures may represent an in vitro approach to study cellular interactions occurring in vivo during atherosclerosis.
Red/blue shifting hydrogen bonds in acetonitrile-dimethyl sulphoxide solutions: FTIR and theoretical studies
Kannan, P. P.; Karthick, N. K.; Mahendraprabu, A.; Shanmugam, R.; Elangovan, A.; Arivazhagan, G.
FTIR spectra of neat acetonitrile (AN), dimethyl sulphoxide (DMSO) and their binary solutions at various mole fractions have been recorded at room temperature. Theoretical calculations have also been carried out on acetonitrile (monomer, dimer), dimethyl sulphoxide (monomer, dimer) and AN - DMSO complex molecules. 1:2 (AN:DMSO) and 2:1 complexation through the red shifting (AN) C - H ⋯ O = S(DMSO) and blue shifting (DMSO) C - H ⋯ N ≡ C(AN) hydrogen bonds has been identified. The experimental and theoretical studies favour the presence of both the monomer and dimer in liquid AN, but only closed dimers in DMSO. The dipole-dipole interactions existed in AN and DMSO dimers disappear in the complex molecules. Partial π bond between S and O atoms, and three lone pair of electrons on oxygen atom of DMSO have been noticed theoretically.
Optimization of the freezing process for hematopoietic progenitor cells: effect of precooling, initial dimethyl sulfoxide concentration, freezing program, and storage in vapor-phase or liquid nitrogen on in vitro white blood cell quality.
Dijkstra-Tiekstra, Margriet J; Setroikromo, Airies C; Kraan, Marcha; Gkoumassi, Effimia; de Wildt-Eggen, Janny
Adding dimethyl sulfoxide (DMSO) to hematopoietic progenitor cells (HPCs) causes an exothermic reaction, potentially affecting their viability. The freezing method might also influence this. The aim was to investigate the effect of 1) precooling of DMSO and plasma (D/P) and white blood cell (WBC)-enriched product, 2) DMSO concentration of D/P, 3) freezing program, and 4) storage method on WBC quality. WBC-enriched product without CD34+ cells was used instead of HPCs. This was divided into six or eight portions. D/P (20 or 50%; precooled or room temperature [RT]) was added to the WBC-enriched product (precooled or RT), resulting in 10% DMSO, while monitoring temperature. The product was frozen using controlled-rate freezing ("fast-rate" or "slow-rate") and placed in vapor-phase or liquid nitrogen. After thawing, WBC recovery and viability were determined. Temperature increased most for precooled D/P to precooled WBC-enriched product, without influence of 20 or 50% D/P, but remained for all variations below 30°C. WBC recovery for both freezing programs was more than 95%. Recovery of WBC viability was higher for slow-rate freezing compared to fast-rate freezing (74% vs. 61%; p Effect of precooling D/P or WBC-enriched product and of storage in vapor-phase or liquid nitrogen was marginal. Based on these results, precooling is not necessary. Fifty percent D/P is preferred over 20% D/P. Slow-rate freezing is preferred over fast-rate freezing. For safety reasons storage in vapor-phase nitrogen is preferred over storage in liquid nitrogen. Additional testing using real HPCs might be necessary. © 2014 AABB.
Bis[N-(2-aminoethylethane-1,2-diamine-κ3N,N′,N′′]copper(II tris[diamminetetrakis(thiocyanato-κNchromate(III] thiocyanate dimethyl sulfoxide tetradecasolvate monohydrate
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Vitalina M. Nikitina
Full Text Available The ionic title complex, [Cu(C4H13N32]2[Cr(NCS4(NH32]3(NCS·14C2H6OS·H2O, consists of complex [Cu(dien2]2+ cations [dien is N-(2-aminoethylethane-1,2-diamine], complex [Cr(NCS4(NH32]− anions, an NCS− counter-anion and uncoordinated dimethyl sulfoxide (DMSO and water solvent molecules. One of the Cr atoms lies on an inversion center, while the second Cr atom and the Cu atom lie in general positions. The thiocyanate counter-anion and water molecule are disordered over two positions close to an inversion center. There are several types of hydrogen-bond interactions present in the title compound, which connect the complex cations and anions into bulky [Cu2Cr3] polynuclear species. The four NH3 groups of the complex anions and six bridging DMSO O atoms link the three complex anions via hydrogen bonding into the anionic polynuclear species [Cr(NCS4(NH32]3·6DMSO. The last one is connected by four bridging DMSO O atoms with the two complex copper cations through N—H... O hydrogen bonds between the terminal NH3 groups of the anionic polynuclear species and the NH and NH2 groups of the dien ligand. One additional DMSO molecule is connected via hydrogen bonding to one of the terminal NH3 groups of the anionic polynuclear species. Another DMSO molecule is connected via hydrogen bonding to each Cu(dien2]2+ cation.
On the Origin of Microheterogeneity : Mass Spectrometric Studies of Acetonitrile-Water and Dimethyl Sulfoxide-Water Binary Mixtures (Part 2)
Shin, Dong Nam; Wijnen, Jan W.; Engberts, Jan B.F.N.; Wakisaka, Akihiro
The microscopic structures of acetonitrile-water and DMSO-water binary mixed solvents and their influence on the solvation for solutes (some alcohols and phenol) have been studied on the basis of the cluster structures observed through a specially designed mass spectrometer. In acetonitrile-water
Preparation of cellulose diacetate/cellulose hybrid fiber by dry-jet wet spinning in tetrabutylammonium acetate/dimethyl sulfoxide solvent
Yu, Yongqi; Zhang, Wentao; Gao, Xin; Jiang, Zeming; Miao, Jiaojiao; Zhang, Liping
Cellulose diacetate (CDA)/cellulose hybrid fibers with nice properties were prepared by dry-jet wet spinning using a tetrabutylammonium acetate/dimethylsulfoxide system as a solvent at 50 °C. Scanning electron microscopy (SEM) images exhibited the hybrid fibers with circular cross section and smooth surface. In addition, SEM and Fourier transform infrared spectroscopy analysis indicated the nice compatibility of CDA and cellulose. The hybrid fibers with the addition of CDA showed higher thermal stability and a wider range of degradation than pure cellulose material. It was found that the elongation at break of the fibers increased from 4.87 to 13.22% with increasing CDA/cellulose ratio from 0 to 4:6, which was comparable with CDA fiber spun from 1-butyl-3-methylimidazolium chloride. The 1095.5/cm Raman characteristic band of the hybrid fibers with lower intensity was observed, while it did not towards a higher wave number compared to that of fibers containing less CDA. In addition, the shear viscosity of the solutions exhibited a character of typical shear-thinning behaviour with variation of shear rates.
A randomized, open-label, multicenter study of the efficacy and safety of intravesical hyaluronic acid and chondroitin sulfate versus dimethyl sulfoxide in women with bladder pain syndrome/interstitial cystitis.
Cervigni, Mauro; Sommariva, Monica; Tenaglia, Raffaele; Porru, Daniele; Ostardo, Edoardo; Giammò, Alessandro; Trevisan, Silvia; Frangione, Valeria; Ciani, Oriana; Tarricone, Rosanna; Pappagallo, Giovanni L
Intravesical instillation of hyaluronic acid (HA) plus chondroitin sulfate (CS) in women with bladder pain syndrome/interstitial cystitis (BPS/IC) has shown promising results. This study compared the efficacy, safety, and costs of intravesical HA/CS (Ialuril ® , IBSA) to dimethyl sulfoxide (DMSO). Randomized, open-label, multicenter study involving 110 women with BPS/IC. The allocation ratio (HA/CS:DMSO) was 2:1. Thirteen weekly instillations of HA (1.6%)/CS (2.0%) or 50% DMSO were given. Patients were evaluated at 3 (end-of-treatment) and 6 months. Primary endpoint was reduction in pain intensity at 6 months by visual analogue scale (VAS) versus baseline. Secondary efficacy measurements were quality of life and economic analyses. A significant reduction in pain intensity was observed at 6 months in both treatment groups versus baseline (P < 0.0001) in the intention-to-treat population. Treatment with HA/CS resulted in a greater reduction in pain intensity at 6 months compared with DMSO for the per-protocol population (mean VAS reduction 44.77 ± 25.07 vs. 28.89 ± 31.14, respectively; P = 0.0186). There were no significant differences between treatment groups in secondary outcomes. At least one adverse event was reported in 14.86% and 30.56% of patients in the HA/CS and DMSO groups, respectively. There were significantly fewer treatment-related adverse events for HA/CS versus DMSO (1.35% vs. 22.22%; P = 0.001). Considering direct healthcare costs, the incremental cost-effectiveness ratio of HA/CS versus DMSO fell between 3735€/quality-adjusted life years (QALY) and 8003€/QALY. Treatment with HA/CS appears to be as effective as DMSO with a potentially more favorable safety profile. Both treatments increased health-related quality of life, while HA/CS showed a more acceptable cost-effectiveness profile. © 2016 Wiley Periodicals, Inc.
Adsorption of dimethyl trisulfide from aqueous solution on a low-cost adsorbent: thermally activated pinecone
Shang, Jingge; He, Wei; Fan, Chengxin
Thermally activated pinecone (TAP) was used for the adsorption of dimethyl trisulfide (DMTS) from aqueous solutions, which was proved to be the main odorous in algae-caused black bloom. The effects of adsorbent dosage, adsorbate concentration and contact time on DMTS biosorption were studied. The TAP produced at 600°C exhibited a relatively high surface area (519.69 m2/g) and excellent adsorption capacity. The results show that the adsorption of DMTS was initially fast and that the equilibrium time was 6 h. Higher initial DMTS concentrations led to lower removal percentages but higher adsorption capacity. The removal percentage of DMTS increased and the adsorption capacity of TAP decreased with an increase in adsorbent dosage. The adsorption process conforms well to a pseudo-second-order kinetics model. The adsorption of DMTS is more appropriately described by the Freundlich isotherm ( R 2 =0.996 1) than by the Langmuir isotherm ( R 2 =0.916 9). The results demonstrate that TAP could be an attractive low-cost adsorbent for removing DMTS from water.
Influence of the nature of organic diluents on the extraction of uranium(VI) by bis(2-ethylhexyl) sulfoxide from nitric acid solutions
International Nuclear Information System (INIS)
Shukla, J.P.; Kedari, C.S.
The extraction of uranium(VI) from nitric acid solutions by bis(2-ethylhexyl) sulfoxide (BESO) has been examined using sixteen inert organic diluents in order establish the correlation between its distribution coefficient and some physico-chemical properties of the diluents. The extracted solvated species is shown to be UO 2 (NO 3 ) 2 x 2BESO, irrespective of their nature. The extraction rate is lower in halogen substituted hydrocarbons as compared to the other diluents used. Among benzene derivatives, extraction is found to decrease with number of substituted methyl groups. Extraction efficiency decreases as the organic solvent is varied in the order: benzene > nitromethane > toulene > nitrobenzene > cyclohexane > p-xylene > monochlorobenzene > dodecane > o-dichlorobenzene > hexane > decalin > 1,2-dichloroethane > 1,1,1-trichloroethane > carbon tetrachloride > tetrachloroethane > chloroform. Among the properties showing good correlations with distribution coefficient are Hansen's three-dimensional solubility parameters and Dimroth's empirical solvent polarity parameters [E T(30) ]. Polarizability indices are most satisfactorily applicable to a wide variety of solvents. (author). 24 refs., 5 figs., 2 tabs
A new monoclinic polymorph of dichloridotetrakis(dimethyl sulfoxideruthenium(II
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Galina Gencheva
Full Text Available The title compound, cis,fac-dichloridotetrakis(dimethyl sulfoxide-κ3S,κO-ruthenium(II, [RuCl2(C2H6OS4], was obtained from newly synthesized ruthenium complexes of 3-amino-2-chloropyridine. The Ru atom has a distorted octahedral coordination with two cis-oriented chloride ligands and four dimethyl sulfoxide ligands. Three of the sulfoxide ligands are S-bonded in a fac configuration, while the fourth is O-bonded. The title compound represents a new, and fourth, polymorph of the complex. Two other monoclinic forms and an orthorhombic modification have been reported previously.
Effects of dimethyl sulfoxide on the hydrogen bonding structure and ...
Indian Academy of Sciences (India)
a least-square fit of the long-time region of MSD as obtained from simulations. The diffusion coefficients calculated using these two different routes have been found to be quite close to each other and we have taken the average of the values obtained from these two routes for a given type of species. Our calculated self- ...
21 CFR 524.660b - Dimethyl sulfoxide gel.
... Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... use—(1) Indications for use. For use on horses and dogs as a topical application to reduce acute... grams per day. Total duration of therapy should not exceed 30 days. (ii) Dogs. Administer 3 or 4 times...
Hexakis(dimethyl sulfoxide-κOchromium(III trichloride
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Turganbay S. Iskenderov
Full Text Available In the title compound, [Cr(C2H6OS6]Cl3, each CrIII ion is located on a three-fold inversion axis and is coordinated by six dimethylsulfoxide ligands [Cr—O = 1.970 (2–1.972 (2 Å; O—Cr—O = 88.19 (9 and 91.81 (9°] in a slightly distorted octahedral geometry. The Cl− anions take part in the formation of weak C—H...Cl hydrogen bonds, which contribute to the crystal packing stabilization.
Gamma irradiation of coumarin in aqueous solution
International Nuclear Information System (INIS)
Gopakumar, K.; Kini, U.R.; Ashawa, S.C.; Bhandari, N.S.; Krishnan, G.U.; Krishnan, D.
Aqueous solutions of coumarin become fluorescent on gamma irradiation. The main fluorescent product formed, 7-hydroxy coumarin, shows a dependence on oxygen. The yield in the presence of oxygen is three times that in the nitrogen saturated condition. The effect of cysteine, dimethyl sulfoxide, thymine and sodium nitrite on the gamma response of coumarin suggests the involvement of hydroxyl radicals in the formation of the fluorescent product. The hydroxyl rate constant for coumarin was determined using isopropanol as the co-competitor. The G (-coumarin) in the aerated and nitrogen saturated conditions was also determined. (author)
Thermodynamic and kinetic behavior of hydrogen electrode in a solution of 0.5 M KClO4 in dimethyl sulphoxide
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Full Text Available The hydrogen electrode on an interface platinum/dimethyl sulphoxide + 0.5 M KClO4 solution was examined from both the thermodynamic and kinetic aspect, using HCl as a proton source. The equilibrium potential was shown to obey a Nernstian dependence on concentration. The voltammograms recorded using a rotating platinum disc electrode evidenced that the cathodic evolution of hydrogen proceeds under mixed, activationdiffusion control. The diffusion coefficient of the proton was determined to amount to 4.5×10-6 cm2 s-1. In the region of activation control, a Tafel slope of about 0.110 V dec-1 was estimated, which indicates that the Volmer reaction is the rate determining step.
How do glycerol and dimethyl sulphoxide affect local tetrahedral structure of water around a nonpolar solute at low temperature? Importance of preferential interaction
Daschakraborty, Snehasis
Glycerol and dimethyl sulphoxide (DMSO) have vital roles in cryoprotection of living cells, tissues, etc. The above action has been directly linked with disruption of hydrogen (H-) bond structure and dynamics of water by these cosolvents at bulk region and around various complex units, such as peptide, amino acid, protein, and lipid membrane. However, the disruption of the local structure of the water solvent around a purely hydrophobic solute is still not studied extensively. The latter is also important in the context of stabilization of protein from cold denaturation. Through all-atom molecular dynamics simulation, we have investigated the comparative effect of glycerol and DMSO on the orientational order of water around a nonpolar solute at -5 °C. A steady reduction of the tetrahedral order of water is observed at bulk (>10 Å distance from the solute) and solute interface (determines whether the involvement of the cosolvent molecules in H-bonding with solvent water in the interface is akin to the bulk region or not.
Extraction of plutonium(IV) by bis(2-ethylhexyl) sulfoxide: a novel branched-chain extractant (Preprint No. ST.23)
International Nuclear Information System (INIS)
Shukla, J.P.; Kedari, C.S.
Di-n-alkyl sulfoxides offer certain distint advantages over other common extractants for use in actinides separation particularly in the presence of high radiation fields. Despite widespread interest in these extractants, practical applications of such sulfoxides in nuclear fuel reprocessing have been seriously hampered owing to their poor solubility in common aliphatic hydrocarbon diluents. Recently a promising new branched-chain sulfoxide extractant, bis( 2-ethylhexyl) sulfoxide (BESO) has been introduced as a novel extracting agent for uranium. It possesses almost all the advantages of other sulfoxides, but excels the rest in terms of its complete miscibility with dodecane and the highest Ksub(H) value reported for any sulfoxide. As a part of comprehensive program to explore its analytical usefulness, data concerning preliminary studies on the extraction of plutonium with BESO form nitric acid solutions are reported. (author)
Crystal structures of hibiscus acid and hibiscus acid dimethyl ester isolated from Hibiscus sabdariffa (Malvaceae)
Zheoat, Ahmed M.; Gray, Alexander I.; Igoli, John O.; Kennedy, Alan R.; Ferro, Valerie A.
The biologically active title compounds have been isolated from Hibiscus sabdariffa plants, hibiscus acid as a dimethyl sulfoxide monosolvate [systematic name: (2S,3R)-3-hy?droxy-5-oxo-2,3,4,5-tetra?hydro?furan-2,3-di?carb?oxy?lic acid dimethyl sulfoxide monosolvate], C6H6O7?C2H6OS, (I), and hibiscus acid dimethyl ester [systematic name: dimethyl (2S,3R)-3-hy?droxy-5-oxo-2,3,4,5-tetra?hydro?furan-2,3-di?carboxyl?ate], C8H10O7, (II). Compound (I) forms a layered structure with alternating laye...
Application of lanthanide complexes for the purification of di-isobutyl-sulfoxide
International Nuclear Information System (INIS)
Osorio, V.K.L.; Martinez, S.A.Q.; Silva, R.M.X. da
A new procedure for the purification of sulfoxides based on the selective precipitation of their complexes with class (a) metallic ions is reported. A commercial sample of di-isobutylsulfoxide containing about 5 - 10% of the corresponding sulfone was purified by precipitation with lanthanide perchlorates from alcoholic solutions. The recovery of the sulfoxide from the solid complex was accomplished by dissolving the complex in water and extracting the sulfoxide with chloroform. Alternatively the aqueous solution of the complex was passed successively through columns containing strongly acidic cation-exchanger resin in the H-cycle and strongly basic anionic-exchanger in the OH-cycle. T.L.C. homogeneous sulfoxide was obtained simply by evaporation of the solvent at reduced pressure. (Author) [pt
Solution blow spinning: parameters optimization and effects on the properties of nanofibers from poly(lactic) acid/dimethyl carbonate solutions
Solution blow spinning (SBS) is a process to produce non-woven fiber sheets with high porosity and an extremely large amount of surface area. In this study, a Box-Behnken experimental design (BBD) was used to optimize the processing parameters for the production of nanofibers from polymer solutions ...
Oxygen atom transfer reactions from Mimoun complexes to sulfides and sulfoxides. A bonding evolution theory analysis.
González-Navarrete, Patricio; Sensato, Fabricio R; Andrés, Juan; Longo, Elson
In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change.
Viscosity of crystalline proteins in solution, when irradiated with 60 Co
International Nuclear Information System (INIS)
Bernardes, D.M.L.; Mastro, N.L. del
In order to study 60 Co radiation effects on proteins, an aqueous solution of bovine crystalline was irradiated with doses from O to 25,000 Gy. Changes in viscosity were followed whether in the presence or absence of radiation response modifiers: glutathione (GSH), amino ethyl isothiourea (AET), mercapto ethyl alanine (MEA) e dimethyl sulfoxide (DMSO). Viscosity data at different temperature revealed that aggregate formation was the predominant process induced by radiation. The results showed also that in presence of those substances the radiation effects was diminished. (author)
Phase separation phenomena in solutions of poly(2,6-dimethyl-1,4-phenyleneoxide) in mixtures of trichloroethylene, 1-octanol, and methanol: Relationship to membrane formation
Wijmans, J.G.; Rutten, H.J.J.; Smolders, C.A.
The phase boundaries in the quaternary system consisting of the polymer poly(2,6-dimethyl-1,4-phenyleneoxide) (PPO[Note ][PPO is a registered trademark of the General Electric Company.]), the solvent trichloroethylene (TCE), and the nonsolvents 1-octanol (OcOH) and methanol (MeOH) are determined.
Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions
Energy Technology Data Exchange (ETDEWEB)
Dou, Benjia [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Wheeler, Lance M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Christians, Jeffrey A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Moore, David [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Harvey, Steven P [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Berry, Joseph J [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Van Hest, Marinus F [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Barnes, Frank S. [University of Colorado; Shaheen, Sean E. [University of Colorado
Whereas the promise of metal halide perovskite (MHP) photovoltaics (PV) is that they can combine high efficiency with solution-processability, the chemistry occurring in precursor inks is largely unexplored. Herein, we investigate the degradation of MHP solutions based on the most widely used solvents, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). For the MHP inks studied, which contain formamidinium (FA+), methylammonium (MA+), cesium (Cs+), lead (Pb2+), bromide (Br-), and iodide (I-), dramatic compositional changes are observed following storage of the inks in nitrogen in the dark. We show that hydrolysis of DMF in the precursor solution forms dimethylammonium formate, which subsequently incorporates into the MHP film to compromise the ability of Cs+ and MA+ to stabilize FA+-based MHP. The changes in solution chemistry lead to a modification of the perovskite film stoichiometry, band gap, and structure. The solid precursor salts are stable when ball-milled into a powder, allowing for the storage of large quantities of stoichiometric precursor materials.
Cysteine sulfoxide derivatives in Petiveria alliacea.
Kubec, R; Musah, R A
Two diastereomers of S-benzyl-L-cysteine sulfoxide have been isolated from fresh roots of Petiveria alliacea. Their structures and absolute configurations have been determined by NMR, MALDI-HRMS, IR and CD spectroscopy and confirmed by comparison with authentic compounds. Both the R(S) and S(S) diastereomers of the sulfoxide are present in all parts of the plant (root, stem, and leaves) with the latter diastereomer being predominant. Their total content greatly varied in different parts of the plant between 0.07 and 2.97 mg g(-1) fr. wt, being by far the highest in the root. S-Benzylcysteine has also been detected in trace amounts (<10 microg g(-1) fr. wt) in all parts of the plant. This represents the first report of the presence of S-benzylcysteine derivatives in nature.
Crystal structures of hibiscus acid and hibiscus acid dimethyl ester isolated from Hibiscus sabdariffa (Malvaceae).
Zheoat, Ahmed M; Gray, Alexander I; Igoli, John O; Kennedy, Alan R; Ferro, Valerie A
The biologically active title compounds have been isolated from Hibiscus sabdariffa plants, hibiscus acid as a dimethyl sulfoxide monosolvate [systematic name: (2 S ,3 R )-3-hy-droxy-5-oxo-2,3,4,5-tetra-hydro-furan-2,3-di-carb-oxy-lic acid dimethyl sulfoxide monosolvate], C 6 H 6 O 7 ·C 2 H 6 OS, (I), and hibiscus acid dimethyl ester [systematic name: dimethyl (2 S ,3 R )-3-hy-droxy-5-oxo-2,3,4,5-tetra-hydro-furan-2,3-di-carboxyl-ate], C 8 H 10 O 7 , (II). Compound (I) forms a layered structure with alternating layers of lactone and solvent mol-ecules, that include a two-dimensional hydrogen-bonding construct. Compound (II) has two crystallographically independent and conformationally similar mol-ecules per asymmetric unit and forms a one-dimensional hydrogen-bonding construct. The known absolute configuration for both compounds has been confirmed.
Methionine Sulfoxide Reductase A (MsrA and Its Function in Ubiquitin-Like Protein Modification in Archaea
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Xian Fu
Full Text Available Methionine sulfoxide reductase A (MsrA is an antioxidant enzyme found in all domains of life that catalyzes the reduction of methionine-S-sulfoxide (MSO to methionine in proteins and free amino acids. We demonstrate that archaeal MsrA has a ubiquitin-like (Ubl protein modification activity that is distinct from its stereospecific reduction of MSO residues. MsrA catalyzes this Ubl modification activity, with the Ubl-activating E1 UbaA, in the presence of the mild oxidant dimethyl sulfoxide (DMSO and in the absence of reductant. In contrast, the MSO reductase activity of MsrA is inhibited by DMSO and requires reductant. Liquid chromatography-tandem mass spectrometry (LC-MS/MS analysis reveals that MsrA-dependent Ubl conjugates are associated with DNA replication, protein remodeling, and oxidative stress and include the Ubl-modified MsrA, Orc3 (Orc1/Cdc6, and Cdc48d (Cdc48/p97 AAA+ ATPase. Overall, we found archaeal MsrA to have opposing MSO reductase and Ubl modifying activities that are associated with oxidative stress responses and controlled by exposure to mild oxidant.
Kerstholt, René P V; Engberts, Jan B F N; Blandamer, Michael J
Rate constants are reported for the hydrolysis of 1-benzoyl-3-phenyl-1,2,4-triazole and p-methoxyphenyl dichloroethanoate in aqueous solutions containing formamide, acetamide, propionamide, isobutyramide, N-methylformamide, N,N-dimethylformamide, n-butyramide, N-methylacetamide,
Potassium hydroxide/dimethyl sulfoxide promoted intramolecular cyclization for the synthesis of benzimidazol-2-ones.
Beyer, Astrid; Reucher, Christine M M; Bolm, Carsten
A new protocol for intramolecular N-arylations of ureas to form benzimidazol-2-ones has been developed. The cyclization reaction occurs in the presence of KOH and DMSO at close to ambient temperature. Under these conditions the yields are high and a wide range of functional groups are tolerated.
CCDC 1515632: Experimental Crystal Structure Determination : hexakis(dimethyl sulfoxide)-manganese(ii) tetraiodide
Haque, M.A.
An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Early ontogeny, growth and mortality of common carp (Cyprinus carpio) at low concentrations of dimethyl sulfoxide
Czech Academy of Sciences Publication Activity Database
Máchová, J.; Prokeš, Miroslav; Kroupová, H.; Svobodová, Z.; Mácová, S.; Doleželová, P.; Velíšek, J.
Roč. 78, č. 3 (2009), s. 505-512 ISSN 0001-7213 R&D Projects: GA MZe QH71305 Grant - others:GA MZe(CZ) QH82117 Institutional research plan: CEZ:AV0Z60930519 Keywords : auxiliary substance * toxicity * fish embryos * larvae Subject RIV: GL - Fishing Impact factor: 0.403, year: 2009
Conference on Biological Actions and Medical Applications of Dimethyl Sulfoxide (DMSO), 15-17 September 1982.
normal by both clinical and scintigraphic examination. At that moment it was decided to perform a total hip arthroplasty and DMSO was gradually replaced...FDA to satisfy a vocal but radical minority. It would be reasonable, two decades after enacting (with some haste) the 1962 drug law revisions , to... total body concentration as yet but suspect that MSM is banked in some of the organs, other than the adrenals. Based on radiolabel I'S studies, the
Micro volume voltammetric determination of 4-nitrophenol in dimethyl sulfoxide at a glassy carbon electrode
Czech Academy of Sciences Publication Activity Database
Gajdar, J.; Barek, J.; Fojta, Miroslav; Fischer, J.
Roč. 148, č. 9 (2017), s. 1639-1644 ISSN 0026-9247 Institutional support: RVO:68081707 Keywords : square-wave voltammetry * nitrobenzene Subject RIV: CE - Biochemistry OBOR OECD: Biochemistry and molecular biology Impact factor: 1.282, year: 2016
Health Effects Research on Munition Contaminated Dimethyl Sulfoxide Recrystallization Process Solvent. Phase I Studies.
except in the treatment of interstitial cystitis . However, with increasing data supporting the conten- tion that it is therapeutically effective without...significant toxic side effects, it may soon be licensed by the U.S. Food and Drug Administration for use in the treatment of scleroderma and muscle
Cryopreservation with dimethyl sulfoxide prevents accurate analysis of skinned skeletal muscle fibers mitochondrial respiration.
Meyer, Alain; Charles, Anne-Laure; Zoll, Joffrey; Guillot, Max; Lejay, Anne; Singh, François; Schlagowski, Anna-Isabel; Isner-Horobeti, Marie-Eve; Pistea, Cristina; Charloux, Anne; Geny, Bernard
Impact of cryopreservation protocols on skeletal muscle mitochondrial respiration remains controversial. We showed that oxygen consumption with main mitochondrial substrates in rat skeletal muscles was higher in fresh samples than in cryopreserved samples and that this difference was not fixed but grow significantly with respiration rates with wide fluctuations around the mean difference. Very close results were observed whatever the muscle type and the substrate used. Importantly, the deleterious effects of ischemia-reperfusion observed on fresh samples vanished when cryopreserved samples were studied. These data demonstrate that this technic should probably be performed only extemporaneously. Copyright © 2014 Elsevier Masson SAS. All rights reserved.
Diaquabis(dimethyl sulfoxide-κObis(saccharinato-κNcobalt(II
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Fezile S. W. Potwana
Full Text Available The title complex, [Co(C7H4NO3S2(C2H6OS2(H2O2], contains a Co2+ cation in an octahedral coordination environment. The metal atom is surrounded by two different neutral ligands, namely dimethylsulfoxide (DMSO and water, each coordinating through the O atom. The anionic saccharinate (sac; 1,1,3-trioxo-2,3-dihydro-1λ6,2-benzothiazol-2-ide ligand coordinates through the N atom. Each of the three similar ligand pairs is in a trans configuration with respect to each other. The Co atom lies on a crystallographic center of symmetry and the octahedral geometry is not significantly distorted. A short O—H...O hydrogen bond is present between a water H atom and the ketone O atom; two longer hydrogen bonds (intra- and intermolecular are also present between a water H and a sulfonic O atom, forming a supramolecular assembly through head-to-tail aggregation between adjacent complexes.
Antiviral activity of platinum (II) and palladium (II) complexes of dimethyl sulfoxide (DMSO) in vitro
International Nuclear Information System (INIS)
Al-Allaf, T.; Rashan, L
The antiviral activity of complexes cis-[Pt(DMSO) 2 CI 2 ] and trans-[Pd(DMSO) 2 CI 2 ] against the reverse transcriptase enzyme, herpes and influenza viruses have been studied in vitro. Both complexes demonstrated some activity against the reverse transcriptase enzyme in which the inhibition concentration (IC 5 0) of the cis-Pt and the trans-Pd complexes were shown to be 37.6 and 35.5 μ g/ml respectively. This activity was compared with that of the standard reference; the phosphonoformate (PFA). On the other hand, both complexes have no antiviral activity against herpes and influenza viruses No cytotoxic effects on the three cell lines, Raji, K562 and Mrc-5 were demonstrated by these complexes at the concentrations studied in vitro. (authors). 16 refs., 1 tab., 2 figs
The effect of Dimethyl Sulfoxide on hepatogenic differentiation of Mesenchymal Stem Cells
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Effat Alizadeh
The results demonstrate that DMSO speeds up hepatic differentiation of AT-MSCs characterized by rapid changes in morphology, higher expression of hepatic marker gene (AFP in both mRNA and protein level (P
Formation and stability of calcium complexes of dimethyl sulfoxide in water
Czech Academy of Sciences Publication Activity Database
Jakl, M.; Straka, Michal; Jaklová Dytrtová, Jana; Roithová, J.
Roč. 360, č. 1 (2014), s. 8-14 ISSN 1387-3806 R&D Projects: GA ČR GP13-21409P Grant - others:GA ČR(CZ) GAP206/12/0539 Institutional support: RVO:61388963 Keywords : bonding energies * DFT * ESI-MS * complexation * speciation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.972, year: 2014
Efficient conversion of cellulose into biofuel precursor 5-hydroxymethylfurfural in dimethyl sulfoxide-ionic liquid mixtures.
Xiao, Shaohua; Liu, Bing; Wang, Yimei; Fang, Zhongfeng; Zhang, Zehui
In recent years, cellulose has received increasing attention as a potential material for the production of biofuels and bio-based chemicals. In this study, a new process for the efficient conversion of cellulose into 5-hydroxymethylfurfural (HMF) was developed by the use of AlCl3 as the catalyst in DMSO-ionic liquid ([BMIM]Cl) mixtures. Various reaction parameters such as reaction time, reaction temperature, solvent and catalyst dosage were investigated in detail. A high HMF yield of 54.9% was obtained from cellulose at 150°C after 9h in a mixed solvent of DMSO-[BMIM]Cl (10 wt.%). More importantly, the catalytic system could be reused for several times despite of the slight loss of its catalytic activity. Copyright © 2013 Elsevier Ltd. All rights reserved.
Acidity constants of sparingly water-soluble drugs from potentiometric determinations in aqueous dimethyl sulfoxide.
Fini, A; De Maria, P; Guarnieri, A; Varoli, L
A brief analysis of the acid-base equilibria in pure organic solvents and/or in their aqueous mixtures is reported with the aim of determining dissociation constants of acidic drugs that are sparingly soluble in water. Among aqueous organic mixtures, aqueous Me2SO (80% w/w) presents properties particularly suitable for acid-base studies, and thermodynamically meaningful acidity constants can be obtained by a potentiometric technique, provided that the glass electrode is properly calibrated. Thermodynamic acidity constants of more than 100 acids have been potentiometrically determined at 25 degrees C in this mixed solvent, and the selected series of acids has been divided into four classes according to the nature of the acidic group (COOH, OH, SH) and the structure of the acid (aliphatic, aromatic, heterocyclic). A linear relationship between the experimental pKa values in water and pKa values in aqueous Me2SO (80% w/w) has been found within the single classes and a group of equations has been derived (the asterisk denotes pKa values in which infinite dilution in the mixed solvent is taken as a standard state). For the carboxylic acid class, the following "common" equation has been found: pKa(H2O) = -0.80 + 0.67 pKa (Me2SO; 80% w/w). As an application, pKa values in water are reported for a representative number of sparingly soluble acids. These values have been calculated by means of the "common" equation, using pKa values experimentally determined in aqueous Me2SO (80% w/w). The calculated values are in good agreement with those expected from the acid structures.
Cardiac mitochondrial oxidative capacity is partly preserved after cryopreservation with dimethyl sulfoxide.
Meyer, A; Charles, A L; Singh, F; Zoll, J; Talha, S; Enache, I; Chaarloux, A; Inser-Horobeti, M E; Geny, B
Cardiac muscle cryopreservation is a challenge for both diagnostic procedure requiring viable tissues and therapeutic advance in regenerative medicine. Mitochondria are targets of both direct and indirect damages, secondary to congelation per se and/or to cryoprotectant's toxic effects, which participate to diminution of viability and/or functioning of cells after freezing. At the cardiac muscle level, only one study had investigated mitochondrial respiration after cryopreservation. To determine the effect of cryopreservation on mitochondrial respiration of cardiac muscle. We recorded mitochondrial respiration through complexes I, II, III and IV along with mitochondrial coupling in fresh and cryopreserved rat left ventricles samples and assessed difference of the means, correlation and agreement between the measures in all samples. Mitochondrial respiration was partly maintained up to 70% in cryopreserved samples whatever the substrate. A significant correlation was observed between fresh and cryopreserved samples (r = 0.71, p cryopreservation (- 1.44 ± 0.15; p cryopreservation. Further, the fluctuations around the mean difference were wide (-14.06, +5.08 µmol/min/g), increasing with respiration rates (p cryopreservation using DMSO partly protect cardiac mitochondrial respiration and coupling. These data support the interest to further refine cryopreservation methods.
Petroleum sulfides, sulfoxides, and sulfones used as extragents
International Nuclear Information System (INIS)
Nikitin, Yu.E.; Lyapina, N.K.; Murinov, Yu.I.
Possibilities of using petroleum sulfides, sulfoxides and sulfones for extraction and separation of wide range of elements are considered. It is shown that petroleum sulfides appear to be effective and selective extractants in extraction and separation of noble metals (Ru, Au, Pt, etc.). Petroleum sulfoxides are promising for solvent extraction of transition metals, actinides, rare earths etc
Temperature-dependent thermochemical properties of the Mebicaret (2,4-dimethyl-6,8-diethylglycoluril) solutions in H{sub 2}O and D{sub 2}O at the ambient pressure
Energy Technology Data Exchange (ETDEWEB)
Ivanov, Evgeniy V., E-mail: email@example.com [Laboratory of Thermodynamics of Solutions of Non-electrolytes and Biologically Active Substances, G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, 1 Akademicheskaya Str., 153045 Ivanovo (Russian Federation); Batov, Dmitriy V. [Incorporated Physicochemical Center of Solution Researches, G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, 1 Akademicheskaya Str., 153045 Ivanovo (Russian Federation); Department of Inorganic Chemistry, Ivanovo's State University of Chemistry and Technology, 7 Sheremetevsky Ave., 153000 Ivanovo (Russian Federation); Baranov, Vladimir V.; Kravchenko, Angelina N. [Laboratory of Nitrogen-containing Compounds, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Ave., 199119 Moscow (Russian Federation)
Highlights: • Enthalpies of solution of Mebicaret in H{sub 2}O and D{sub 2}O were measured calorimetrically. • Enthalpy-isotopic effect was found to be negative and decreasing with temperature. • Standard molar heat capacities of solution are positive and higher in heavy water. • Enthalpic coefficients for pair 2-2-interactions are more negative in heavy water. • The prevailingly hydrophilic hydration of Mebicaret is weakened with temperature. - Abstract: The enthalpies of solution of Mebicaret or 2,4-dimethyl-6,8-diethyl-2,4,6,8-tatraazabicyclo[3.3.0]octane-3,7-dione in ordinary (H{sub 2}O) and heavy (D{sub 2}O) water at (278.15, 279.15, 288.15, 298.15, 308.15, and 313.15) K as well as the enthalpies of dilution of its H/D isotopically distinguishable aqueous solutions at 298.15 K were measured calorimetrically. The standard (at infinite dilution) molar enthalpies and heat capacities of solution, and the enthalpic coefficients for pair (h{sub 22}) and triplet (h{sub 222}) interactions between hydrated solute molecules along with D{sub 2}O−H{sub 2}O solvent isotope effects (IEs) on the studied quantities were computed. The enthalpic effects of Mebicaret dissolution in H{sub 2}O and D{sub 2}O experience a negative-to-positive sign inversion nearby 303 K and 304 K, respectively, whereas the corresponding IEs were found to be wholly negative (by sign) and decreasing in magnitude with increasing temperature. The h{sub 22} values as well as IEs on them were found to be negative, too. On the contrary, the values of h{sub 222} are positive and comparable in magnitude with h{sub 22} ones. These facts indicate that the Mebicaret hydration, being enhanced in the D{sub 2}O medium, is dualistic by the nature with the prevailing hydrophilic mechanism.
Methionine Sulfoxide Reductase A (MsrA) and Its Function in Ubiquitin-Like Protein Modification inArchaea.
Fu, Xian; Adams, Zachary; Liu, Rui; Hepowit, Nathaniel L; Wu, Yifei; Bowmann, Connor F; Moskovitz, Jackob; Maupin-Furlow, Julie A
Methionine sulfoxide reductase A (MsrA) is an antioxidant enzyme found in all domains of life that catalyzes the reduction of methionine- S -sulfoxide (MSO) to methionine in proteins and free amino acids. We demonstrate that archaeal MsrA has a ubiquitin-like (Ubl) protein modification activity that is distinct from its stereospecific reduction of MSO residues. MsrA catalyzes this Ubl modification activity, with the Ubl-activating E1 UbaA, in the presence of the mild oxidant dimethyl sulfoxide (DMSO) and in the absence of reductant. In contrast, the MSO reductase activity of MsrA is inhibited by DMSO and requires reductant. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis reveals that MsrA-dependent Ubl conjugates are associated with DNA replication, protein remodeling, and oxidative stress and include the Ubl-modified MsrA, Orc3 (Orc1/Cdc6), and Cdc48d (Cdc48/p97 AAA+ ATPase). Overall, we found archaeal MsrA to have opposing MSO reductase and Ubl modifying activities that are associated with oxidative stress responses and controlled by exposure to mild oxidant. IMPORTANCE Proteins that are damaged by oxidative stress are often targeted for proteolysis by the ubiquitin-proteasome system (UPS). The mechanisms that control this response are poorly understood, especially under conditions of mild oxidative stress when protein damage is modest. Here, we discovered a novel function of archaeal MsrA in guiding the Ubl modification of target proteins in the presence of mild oxidant. This newly reported activity of MsrA is distinct from its stereospecific reduction of methionine- S -sulfoxide to methionine residues. Our results are significant steps forward, first, in elucidating a protein factor that guides Ubl modification in archaea, and second, in providing an insight into oxidative stress responses that can trigger Ubl modification in a cell. Copyright © 2017 Fu et al.
Mechanistic Study on the Solution-Phase n-Doping of 1,3-Dimethyl-2-aryl-2,3-dihydro-1H-benzoimidazole Derivatives
Naab, Benjamin D.; Guo, Song; Olthof, Selina; Evans, Eric G. B.; Wei, Peng; Millhauser, Glenn L.; Kahn, Antoine; Barlow, Stephen; Marder, Seth R.; Bao, Zhenan
The discovery of air-stable n-dopants for organic semiconductor materials has been hindered by the necessity of high-energy HOMOs and the air sensitivity of compounds that satisfy this requirement. One strategy for circumventing this problem is to utilize stable precursor molecules that form the active doping complex in situ during the doping process or in a postdeposition thermal- or photo-activation step. Some of us have reported on the use of 1H-benzimidazole (DMBI) and benzimidazolium (DMBI-I) salts as solution- and vacuum-processable n-type dopant precursors, respectively. It was initially suggested that DMBI dopants function as single-electron radical donors wherein the active doping species, the imidazoline radical, is generated in a postdeposition thermal annealing step. Herein we report the results of extensive mechanistic studies on DMBI-doped fullerenes, the results of which suggest a more complicated doping mechanism is operative. Specifically, a reaction between the dopant and host that begins with either hydride or hydrogen atom transfer and which ultimately leads to the formation of host radical anions is responsible for the doping effect. The results of this research will be useful for identifying applications of current organic n-doping technology and will drive the design of next-generation n-type dopants that are air stable and capable of doping low-electron-affinity host materials in organic devices. PMID:24011269
Differential solubility of curcuminoids in serum and albumin solutions: implications for analytical and therapeutic applications
Directory of Open Access Journals (Sweden)
Quitschke Wolfgang W
Full Text Available Abstract Background Commercially available curcumin preparations contain a mixture of related polyphenols, collectively referred to as curcuminoids. These encompass the primary component curcumin along with its co-purified derivatives demethoxycurcumin and bisdemethoxycurcumin. Curcuminoids have numerous biological activities, including inhibition of cancer related cell proliferation and reduction of amyloid plaque formation associated with Alzheimer disease. Unfortunately, the solubility of curcuminoids in aqueous solutions is exceedingly low. This restricts their systemic availability in orally administered formulations and limits their therapeutic potential. Results Methods are described that achieve high concentrations of soluble curcuminoids in serum. Solid curcuminoids were either mixed directly with serum, or they were predissolved in dimethyl sulfoxide and added as aliquots to serum. Both methods resulted in high levels of curcuminoid-solubility in mammalian sera from different species. However, adding aliquots of dimethyl sulfoxide-dissolved curcuminoids to serum proved to be more efficient, producing soluble curcuminoid concentrations of at least 3 mM in human serum. The methods also resulted in the differential solubility of individual curcuminoids in serum. The addition of dimethyl sulfoxide-dissolved curcuminoids to serum preferentially solubilized curcumin, whereas adding solid curcuminoids predominantly solubilized bisdemethoxycurcumin. Either method of solubilization was equally effective in inhibiting dose-dependent HeLa cell proliferation in culture. The maximum concentration of curcuminoids achieved in serum was at least 100-fold higher than that required for inhibiting cell proliferation in culture and 1000-fold higher than the concentration that has been reported to prevent amyloid plaque formation associated with Alzheimer disease. Curcuminoids were also highly soluble in solutions of purified albumin, a major component of
Measurement of Thermal Conductivities of Two Cryoprotective Agent Solutions for Vitreous Cryopreservation of Organs at the Temperature Range of 77 K-300 K Using a Thermal Sensor Made of Microscale Enamel Copper Wire.
Li, Yufang; Zhao, Gang; Hossain, S M Chapal; Panhwar, Fazil; Sun, Wenyu; Kong, Fei; Zang, Chuanbao; Jiang, Zhendong
Biobanking of organs by cryopreservation is an enabling technology for organ transplantation. Compared with the conventional slow freezing method, vitreous cryopreservation has been regarded to be a more promising approach for long-term storage of organs. The major challenges to vitrification are devitrification and recrystallization during the warming process, and high concentrations of cryoprotective agents (CPAs) induced metabolic and osmotic injuries. For a theoretical model based optimization of vitrification, thermal properties of CPA solutions are indispensable. In this study, the thermal conductivities of M22 and vitrification solution containing ethylene glycol and dimethyl sulfoxide (two commonly used vitrification solutions) were measured using a self-made microscaled hot probe with enameled copper wire at the temperature range of 77 K-300 K. The data obtained by this study will further enrich knowledge of the thermal properties for CPA solutions at low temperatures, as is of primary importance for optimization of vitrification.
Identification of biotin sulfone, bisnorbiotin methyl ketone, and tetranorbiotin-l-sulfoxide in human urine.
Zempleni, J; McCormick, D B; Mock, D M
In previous studies using the HPLC and avidin-binding assay, five unidentified avidin-binding substances were observed in human urine. The present study investigated the identity of these substances. Urine was collected before and after intravenous administration of 18.5 mumol biotin to healthy adults. Unknown substances 1 and 3 were initially identified as biotin sulfone and bisnorbiotin methyl ketone, respectively, by coelution with authentic standards on HPLC. Identities were confirmed by thin-layer chromatography and by derivatization with p-dimethyl-aminocinnamaldehyde. As expected for biotin metabolites, the urinary excretion of biotin sulfone and bisnorbiotin methyl ketone increased with biotin administration. The urinary excretion of biotin sulfone increased 21-fold from 0.2 nmol/h before to 4.2 nmol/h after administration; the excretion of bisnorbiotin methyl ketone increased 130-fold from 0.4 to 51.8 nmol/h. At presumed steady state in free-living subjects (n = 6), biotin sulfone and bisnorbiotin methyl ketone accounted for 3.6% and 7.9% of total biotin excretion, respectively. Traces of tetranorbiotin-l-sulfoxide were also identified by using thin-layer chromatography and derivatization with p-dimethylaminocinnamaldehyde. However, tetranorbiotin-l-sulfoxide was not detectable in urine by the HPLC and avidin-binding assay because this metabolite has weak avidin-binding affinity. We conclude that biotin sulfone and bisnorbiotin methyl ketone are present in measurable quantities in human urine; their quantitation should allow more accurate studies on human biotin metabolism and turnover.
Alcohol-based solutions for bovine testicular tissue fixation.
Cabrera, Nelson C; Espinoza, Jorge R; Vargas-Jentzsch, Paul; Sandoval, Patricio; Ramos, Luis A; Aponte, Pedro M
Tissue fixation, a central element in histotechnology, is currently performed with chemical compounds potentially harmful for human health and the environment. Therefore, alternative fixatives are being developed, including alcohol-based solutions. We evaluated several ethanol-based mixtures with additives to study fixative penetration rate, tissue volume changes, and morphologic effects in the bovine testis. Fixatives used were Bouin solution, 4% formaldehyde (F4), 70% ethanol (E70), E70 with 1.5% glycerol (E70G), E70 with 5% acetic acid (E70A), E70 with 1.5% glycerol and 5% acetic acid (E70AG), and E70 with 1.5% glycerol, 5% acetic acid, and 1% dimethyl sulfoxide (DMSO; E70AGD). Five-millimeter bovine testicular tissue cubes could be completely penetrated by ethanol-based fixatives and Bouin solution in 2-3 h, whereas F4 required 21 h. Bouin solution produced general tissue shrinkage, whereas the other fixatives (alcohol-based and F4) caused tissue volume expansion. Although Bouin solution is an excellent fixative for testicular tissue, ethanol-based fixatives showed good penetration rates, low tissue shrinkage, and preserved sufficient morphology to allow identification of the stages of the seminiferous epithelium cycle, therefore representing a valid alternative for histotechnology laboratories. Common additives such as acetic acid, glycerol, and DMSO offered marginal benefits for the process of fixation; E70AG showed the best preservation of morphology with excellent nuclear detail, close to that of Bouin solution.
Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization
Directory of Open Access Journals (Sweden)
Barry M. Trost
Full Text Available A full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enynes. This complex was used to synthesize a broad array of [3.1.0] and [4.1.0] bicycles. Sulfonamide- and phosphoramidate-containing products could be deprotected under reducing conditions. Catalysis performed with enantiomerically enriched propargyl alcohols revealed a matched/mismatched effect that was strongly dependent on the nature of the solvent.
Excited state dynamics and isomerization in ruthenium sulfoxide complexes.
King, Albert W; Wang, Lei; Rack, Jeffrey J
Molecular photochromic compounds are those that interconvert between two isomeric forms with light. The two isomeric forms display distinct electronic and molecular structures and must not be in equilibrium with one another. These light-activated molecular switch compounds have found wide application in areas of study ranging from chemical biology to materials science, where conversion from one isomeric form to another by light prompts a response in the environment (e.g., protein or polymeric material). Certain ruthenium and osmium polypyridine sulfoxide complexes are photochromic. The mode of action is a phototriggered isomerization of the sulfoxide from S- to O-bonded. The change in ligation drastically alters both the spectroscopic and electrochemical properties of the metal complex. Our laboratory has pioneered the preparation and study of these complexes. In particular, we have applied femtosecond pump-probe spectroscopy to reveal excited state details of the isomerization mechanism. The data from numerous complexes allowed us to predict that the isomerization was nonadiabatic in nature, defined as occurring from a S-bonded triplet excited state (primarily metal-to-ligand charge transfer in character) to an O-bonded singlet ground state potential energy surface. This prediction was corroborated by high-level density functional theory calculations. An intriguing aspect of this reactivity is the coupling of nuclear motion to the electronic wave function and how this coupling affects motions productive for isomerization. In an effort to learn more about this coupling, we designed a project to examine phototriggered isomerization in bis-sulfoxide complexes. The goal of these studies was to determine whether certain complexes could be designed in which a single photon excitation event would prompt two sulfoxide isomerizations. We employed chelating sulfoxides in this study and found that both the nature of the chelate ring and the R group on the sulfoxide affect
Palladium(II)-catalyzed ortho-olefination of arenes applying sulfoxides as remote directing groups.
Wang, Binjie; Shen, Chuang; Yao, Jinzhong; Yin, Hong; Zhang, Yuhong
A novel palladium-catalyzed ortho-C(sp(2))-H olefination protocol has been developed by the use of sulfoxide as the directing group. Importantly, relatively remote coordination can be accessed to achieve the ortho olefination of benzyl, 2-arylethyl, and 3-arylpropenyl sulfoxide substrates, and the olefinated sulfoxide can be easily transformed to other functionalities.
Alloxazine-cyclodextrin conjugates for organocatalytic enantioselective sulfoxidations
Czech Academy of Sciences Publication Activity Database
Mojr, V.; Buděšínský, Miloš; Cibulka, R.; Kraus, Tomáš
Roč. 9, č. 21 (2011), s. 7318-7326 ISSN 1477-0520 R&D Projects: GA ČR(CZ) GA203/07/1246; GA ČR GA203/09/1919 Institutional research plan: CEZ:AV0Z40550506 Keywords : cyclodextrin s * alloxazines * sulfoxidations Subject RIV: CC - Organic Chemistry Impact factor: 3.696, year: 2011
Now at the Met: fine art of reversible sulfoxidation.
Ilani, Tal; Fass, Deborah
In this issue, Lee et al. (2013) exhibit methionine sulfoxidation in a new light. By bringing together two antagonistic enzymes affecting methionine redox state, the authors demonstrate that methionine oxidation constitutes a reversible, posttranslational regulatory mechanism, akin to protein phosphorylation. Copyright © 2013 Elsevier Inc. All rights reserved.
Evidence for the dimerization-mediated catalysis of methionine sulfoxide reductase A from Clostridium oremlandii.
Lee, Eun Hye; Lee, Kitaik; Kwak, Geun-Hee; Park, Yeon Seung; Lee, Kong-Joo; Hwang, Kwang Yeon; Kim, Hwa-Young
Clostridium oremlandii MsrA (CoMsrA) is a natively selenocysteine-containing methionine-S-sulfoxide reductase and classified into a 1-Cys type MsrA. CoMsrA exists as a monomer in solution. Herein, we report evidence that CoMsrA can undergo homodimerization during catalysis. The monomeric CoMsrA dimerizes in the presence of its substrate methionine sulfoxide via an intermolecular disulfide bond between catalytic Cys16 residues. The dimeric CoMsrA is resolved by the reductant glutaredoxin, suggesting the relevance of dimerization in catalysis. The dimerization reaction occurs in a concentration- and time-dependent manner. In addition, the occurrence of homodimer formation in the native selenoprotein CoMsrA is confirmed. We also determine the crystal structure of the dimeric CoMsrA, having the dimer interface around the two catalytic Cys16 residues. A central cone-shaped hole is present in the surface model of dimeric structure, and the two Cys16 residues constitute the base of the hole. Collectively, our biochemical and structural analyses suggest a novel dimerization-mediated mechanism for CoMsrA catalysis that is additionally involved in CoMsrA regeneration by glutaredoxin.
Synthesis, crystal structure, and spectra of 3,3- dimethyl-1-N-(1'-phenyl-2',3'-dimethyl-5'-oxo-3'- pyrazolin-4'-yl)imino-1,2,3,4-tetrahydroisoquinoline
International Nuclear Information System (INIS)
Sokol, V.I.; Ryabov, M.A.; Merkur'eva, N.Yu.; Davydov, V.V.; Zaitsev, B.E.; Shklyaev, Yu.V.; Sergienko, V.S.; Zaitsev, B.E.
The synthesis and the crystal and molecular structure of 3,3-dimethyl-1-N-(1'-phenyl-2',3'- dimethyl-5'-oxo-3'-pyrazolin-4'-yl)imino-1,2,3,4-tetrahydroisoquinoline are reported. As is evidenced by the 1H NMR, IR, and electron spectra, the tautomeric form of the compounds observed in the crystal is also retained in solutions
Functional integrity of Colossoma macropomum (Cuvier, 1816 sperm cryopreserved with enriched extender solutions
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Raycon Roberto Freitas Garcia
Full Text Available Cryoprotectant solutions are used to protect the sperm from alterations caused by the low temperature in the cryopreservation process. We evaluated the quality of Colossoma macropomum semen after freezing, using dimethyl sulfoxide (DMSO as a cryoprotectant, combined with two extender solutions (T1 - Solution 1: Glucose 90.0 g/L, Sodium Citrate 6.0 g/L, EDTA 1.5 g/L, Sodium Bicarbonate 1.5 g/L, Potassium Chloride 0.8 g/L, Gentamycin Sulphate 0.2 g/L, and T2 - Solution 2: Glucose 90.0 g/L, ACP(r-104 10.0 g/L. Motility rate and motility time did not differ between T1 and T2 and were lower than fresh semen. The number of normal sperm was significantly different in treatments T1 (15.1% and T2 (21.9%, and both showed a reduction in the percentage of normal sperm compared to fresh semen (57.4%. The values found for the rates of fertilization and hatching, mitochondrial functionality and sperm DNA, did not differ between the treatments (T1 and T2. Regarding membrane integrity, there was a higher percentage of spermatozoa with intact membranes in T1 (53.4% than T2 (43.7%. The extender solutions, combined with 10% DMSO, maintained the sperm DNA intact in almost all the C. macropomum sperm cells, however there was a loss in their functionality.
Dymethyl sulfoxide complexes of rare earth perrhenates
International Nuclear Information System (INIS)
Osorio, V.K.L.; Kawano, Y.; Kuya, M.K.; Perrier, M.
The complexes Ln(ReO 4 ) 3 .8dmso (Ln = La-Lu, Y) and La(ReO 4 ) 3 .8dmso-d 6 have been prepared and characterized by conductance, infrared and Raman measurements. All the complexes have structures involving complex cation and non-coordinated anions in the solid state. The conductance values in nitromethane solution indicate a behavior near to a 1:1 electrolyte type. A comparative study with the data accumulated on the literature shows that perrhenate anion has higher coordinating capacity than perchlorate and hexafluorophosphate ones. (Author) [pt
Enhanced fluorescence of Tb(III), Dy(III) perchlorate by salicylic acid in bis(benzoylmethyl) sulfoxide complexes and luminescence mechanism
International Nuclear Information System (INIS)
Li Wenxian; Zheng Yushan; Sun Xiaojun; Chai Wenjuan; Ren Tie; Shi Xiaoyan
Two novel ternary rare earth perchlorate complexes had been synthesized by using bis(benzoylmethyl) sulfoxide as first ligand (L=C 6 H 5 COCH 2 SOCH 2 COC 6 H 5 ), salicylic acid as second ligand (L ' =C 6 H 4 OHCOO - ). The compounds were characterized by elemental analysis, TG-DSC and molar conductivities in DMF solution. The composition was suggested as [REL 5 L'](ClO 4 ) 2 .nH 2 O (RE=Tb, Dy; n=6, 8 ). Based on IR, 1 HNMR and UV spectra, it showed that the first ligand, bis(benzoylmethyl) sulfoxide (L), bonded with Tb(III), Dy(III) ions by the oxygen atom of sulfinyl group. The second ligand, salicylic acid group (L'), not only bonded with RE(III) ions by one oxygen atom of carboxyl group but also bonded with RE(III) ions by oxygen atom of phenolic hydroxyl group. In bis(benzoylmethyl) sulfoxide system, fluorescent spectra of the complexes showed that the luminescence of Tb(III), Dy(III) ions was enhanced by the second ligand salicylic acid. The ternary complexes had stronger fluorescence than the binary ones where only bis(benzoylmethyl) sulfoxide acted as ligand. Phosphorescent spectra of the two ligands indicated that the coordination of salicylic acid resulted in the matching extent increasing between the triplet state of ligand and excited state of the rare earths. The relationship between fluorescence lifetime and fluorescence intensity was also discussed.
Effects of L-cysteine and N-acetyl-L-cysteine on 4-hydroxy-2, 5-dimethyl-3(2H)-furanone (furaneol), 5-(hydroxymethyl)furfural, and 5-methylfurfural formation and browning in buffer solutions containing either rhamnose or glucose and arginine.
Haleva-Toledo, E; Naim, M; Zehavi, U; Rouseff, R L
Solutions of L-cysteine (Cys) and N-acetyl-L-cysteine (AcCys), containing glucose or rhamnose, with or without arginine, were buffered to pH 3, 5, and 7 and incubated at 70 degrees C for 48 h. Cys and AcCys inhibited the formation of (hydroxymethyl)furfural (HMF) from glucose and methylfurfural (MF) from rhamnose under acidic conditions. AcCys inhibited the accumulation of 4-hydroxy-2, 5-dimethyl- 3(2H)-furanone (DMHF, Furaneol) from rhamnose, but Cys, under our experimental conditions, enhanced Furaneol accumulation from rhamnose. Cys and AcCys reacted directly with Furaneol but not with HMF or MF. Both Cys and AcCys inhibited nonenzymatic browning at pH 7. At pH 3, however, Cys reacted with both glucose and rhamnose to produce unidentified compounds that increased the visible absorbency.
The Effect of Diazoxide and Dimethyl Sulfoxide on Behavioral Outcomes and Markers of Pathology Following Controlled Cortical Impact
Immunol, vol. 30, no. 11, pp. 547-556, 2009. 59. M. Gaetz, "The neurophysiology ofbrain injury," Clin Neurophysiol, vol. 115, no. 1' pp. 4-18, 2004. 60...systemically administered dimethylsulfoxide in the rat: a neurophysiological and pathological study. Toxicology letters 118, 103-107. Chauhan, N.B., Gatto, R...Gram, D.X., and Sherwin, R.S. (2005). Activation of ATP-sensitive K +channels in the ventromedial hypothalamus amplifies counterregu1atory hormone
α-chymotrypsin in water-acetone and water-dimethyl sulfoxide mixtures: Effect of preferential solvation and hydration.
Sirotkin, Vladimir A; Kuchierskaya, Alexandra A
We investigated water/organic solvent sorption and residual enzyme activity to simultaneously monitor preferential solvation/hydration of protein macromolecules in the entire range of water content at 25°C. We applied this approach to estimate protein destabilization/stabilization due to the preferential interactions of bovine pancreatic α-chymotrypsin with water-acetone (moderate-strength H-bond acceptor) and water-DMSO (strong H-bond acceptor) mixtures. There are three concentration regimes for the dried α-chymotrypsin. α-Chymotrypsin is preferentially hydrated at high water content. The residual enzyme activity values are close to 100%. At intermediate water content, the dehydrated α-chymotrypsin has a higher affinity for acetone/DMSO than for water. Residual enzyme activity is minimal in this concentration range. The acetone/DMSO molecules are preferentially excluded from the protein surface at the lowest water content, resulting in preferential hydration. The residual catalytic activity in the water-poor acetone is ∼80%, compared with that observed after incubation in pure water. This effect is very small for the water-poor DMSO. Two different schemes are operative for the hydrated enzyme. At high and intermediate water content, α-chymotrypsin exhibits preferential hydration. However, at intermediate water content, in contrast to the dried enzyme, the initially hydrated α-chymotrypsin possesses increased preferential hydration parameters. At low water content, no residual enzyme activity was observed. Preferential binding of DMSO/acetone to α-chymotrypsin was detected. Our data clearly demonstrate that the hydrogen bond accepting ability of organic solvents and the protein hydration level constitute key factors in determining the stability of protein-water-organic solvent systems. © 2017 Wiley Periodicals, Inc.
The use of dimethyl sulfoxide in contact lens disinfectants is a potential preventative strategy against contracting Acanthamoeba keratitis.
Siddiqui, Ruqaiyyah; Aqeel, Yousuf; Khan, Naveed Ahmed
Acanthamoeba castellanii is the causative agent of blinding keratitis. Though reported in non-contact lens wearers, it is most frequently associated with improper use of contact lens. For contact lens wearers, amoebae attachment to the lens is a critical first step, followed by amoebae binding to the corneal epithelial cells during extended lens wear. Acanthamoeba attachment to surfaces (biological or inert) and migration is an active process and occurs during the trophozoite stage. Thus retaining amoebae in the cyst stage (dormant form) offers an added preventative measure in impeding parasite traversal from the contact lens onto the cornea. Here, we showed that as low as 3% DMSO, abolished A. castellanii excystation. Based on the findings, it is proposed that DMSO should be included in the contact lens disinfectants as an added preventative strategy against contracting Acanthamoeba keratitis. Copyright © 2016 British Contact Lens Association. Published by Elsevier Ltd. All rights reserved.
Primary Eye Irritation Potential of the Holston Compounds: Virgin DMSO (Dimethyl Sulfoxide), DMSO Recycle Solvent, and DMSO Evaporator Sludge.
slight deepening of the rugae or light hyperemia of circumeorneal blood vessels), or obvious swelling of the eyelids accompanied by severe...I Markedly deepened rugae , congestion, swelling, moderate circumcorneal hyperemia or injection, any of these or any combination thereof, iris still
Photoisomerization Mechanism of Ruthenium Sulfoxide Complexes: Role of the Metal-Centered Excited State in the Bond Rupture and Bond Construction Processes.
Li, Huifang; Zhang, Lisheng; Zheng, Lvyin; Li, Xun; Fan, Xiaolin; Zhao, Yi
Phototriggered intramolecular isomerization in a series of ruthenium sulfoxide complexes, [Ru(L)(tpy)(DMSO)](n+) (where tpy=2,2':6',2''-terpyridine; DMSO=dimethyl sulfoxide; L=2,2'-bipyridine (bpy), n=2; N,N,N',N'-tetramethylethylenediamine (tmen) n=2; picolinate (pic), n=1; acetylacetonate (acac), n=1; oxalate (ox), n=0; malonate (mal), n=0), was investigated theoretically. It is observed that the metal-centered ligand field ((3) MC) state plays an important role in the excited state S→O isomerization of the coordinated DMSO ligand. If the population of (3) MCS state is thermally accessible and no (3) MCO can be populated from this state, photoisomerization will be turned off because the (3) MCS excited state is expected to lead to fast radiationless decay back to the original (1) GSS ground state or photodecomposition along the Ru(2+) -S stretching coordinate. On the contrary, if the population of (3) MCS (or (3) MCO ) state is inaccessible, photoinduced S→O isomerization can proceed adiabatically on the potential energy surface of the metal-to-ligand charge transfer excited states ((3) MLCTS →(3) MLCTO ). It is hoped that these results can provide valuable information for the excited state isomerization in photochromic d(6) transition-metal complexes, which is both experimentally and intellectually challenging as a field of study. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
21 CFR 172.133 - Dimethyl dicarbonate.
... following titration method: principles of method Dimethyl dicarbonate (DMDC) is mixed with excess...) Stirrer Device for potentiometric titration Reference electrode Glass electrode reagents Acetone...,000 ppm (0.2 percent) dimethyl carbonate as determined by a method entitled "Gas Chromatography Method...
Asymmetric Sulfoxidation Catalyzed by a Vanadium-Containing Bromoperoxidase.
Andersson, Malin; Willetts, Andrew; Allenmark, Stig
A vanadium-containing bromoperoxidase (VBrPO) from the alga Corallina officinalis has been shown to catalyze the stereoselective oxidation of some aromatic bicyclic sulfides to the corresponding (S)-sulfoxides in high (up to 91%) ee. Hydrogen peroxide was found to have a large effect on the catalyzed reaction, most likely due to an inhibition of VBrPO. High optical and chemical yields were found to be favored by a continuous slow addition of hydrogen peroxide to keep a low excess. The reaction gives no overoxidation to sulfone, and its stereochemistry is the opposite as compared to that previously found with the heme-containing chloroperoxidase (CPO) from Caldariomyces fumago.
International Nuclear Information System (INIS)
Long, E.C.
A liquid scintillation solution is described which includes (1) a scintillation solvent (toluene and xylene), (2) a primary scintillation solute (PPO and Butyl PBD), (3) a secondary scintillation solute (POPOP and Dimethyl POPOP), (4) a plurality of substantially different surfactants and (5) a filter dissolving and/or transparentizing agent. 8 claims
Stereoselective analysis of thioridazine-2-sulfoxide and thioridazine-5-sulfoxide: an investigation of rac-thioridazine biotransformation by some endophytic fungi.
Borges, Keyller Bastos; De Souza Borges, Warley; Pupo, Mônica Tallarico; Bonato, Pierina Sueli
The purpose of this study was to develop a method for the stereoselective analysis of thioridazine-2-sulfoxide (THD-2-SO) and thioridazine-5-sulfoxide (THD-5-SO) in culture medium and to study the biotransformation of rac-thioridazine (THD) by some endophytic fungi. The simultaneous resolution of THD-2-SO and THD-5-SO diastereoisomers was performed on a CHIRALPAK AS column using a mobile phase of hexane:ethanol:methanol (92:6:2, v/v/v)+0.5% diethylamine; UV detection was carried out at 262 nm. Diethyl ether was used as extractor solvent. The validated method was used to evaluate the biotransformation of THD by 12 endophytic fungi isolated from Tithonia diversifolia, Viguiera arenaria and Viguiera robusta. Among the 12 fungi evaluated, 4 of them deserve prominence for presenting an evidenced stereoselective biotransformation potential: Phomopsis sp. (TD2) presented greater mono-2-sulfoxidation to the form (S)-(SE) (12.1%); Glomerella cingulata (VA1) presented greater mono-5-sulfoxidation to the forms (S)-(SE)+(R)-(FE) (10.5%); Diaporthe phaseolorum (VR4) presented greater mono-2-sulfoxidation to the forms (S)-(SE) and (R)-(FE) (84.4% and 82.5%, respectively) and Aspergillus fumigatus (VR12) presented greater mono-2-sulfoxidation to the forms (S)-(SE) and (R)-(SE) (31.5% and 34.4%, respectively).
Small-scale cookoff bomb (SSCB) tests on solutions of DMSO/LX-10-1 and DMSO/PBX-9404
Energy Technology Data Exchange (ETDEWEB)
Helm, F.; Hoffman, D.M.
The small-scale cookoff bomb test was developed by the Navy at China Lake as a method for evaluation of the violence of thermal decomposition of explosives and propellants. The UN {open_quotes}Recommendations on the Transport of Dangerous Goods - Tests and Criteria{close_quotes} (ST/SG/AC.10/11) have accepted the small-scale cookoff bomb test as a test for classification of a substance as an explosive (class 1 substance) for storage and shipment. The US Departments of Transportation and Defense have agreed to use the UN tests as US criteria for storage and shipment. The UN scheme is designed to assess the relative hazard of explosives so that an appropriate classification for transport can be made by the competent authority (DOT). Three thermal tests have been approved: the Koenen test, the internal ignition test and the small-scale cookoff bomb (SSCB) test. Lawrence Livermore National Laboratory has designed a dissolution work station for removal of the plastic bonded explosives (PBXs) LX-10-1 and PBX-9404 from two artillery fired atomic projectiles (AFAPs) using dimethyl sulfoxide (DMSO) as the solvent. The DOE Explosives Safety Manual allows up to 33% solutions of explosives to be handled as non-explosive in the laboratory and 25% solutions to be stored as non-explosives unless the explosive precipitates out. In order to ship solutions of LX-10-1 or PBX-9404 in DMSO on US highways for waste or recycling as non-explosives, these solutions must be approved for shipping by the DOT based on the results of UN test series 1. The compositions of LX-10-1 and PBX-9404 are given in Table 1. The shock sensitivity of solutions of these two plastic bonded explosives in dimethyl sulfoxide (DMSO) has been evaluated using the UN series 1 gap test for liquids as described in a previous report. The purpose of this paper is to present the results of the SSCB tests on pure DMSO and 25% PBX solutions in DMSO to assist in the classification of these solutions.
Protein Conformation and Supercharging with DMSO from Aqueous Solution
Sterling, Harry J.; Prell, James S.; Cassou, Catherine A.; Williams, Evan R.
The efficacy of dimethyl sulfoxide (DMSO) as a supercharging reagent for protein ions formed by electrospray ionization from aqueous solution and the mechanism for supercharging were investigated. Addition of small amounts of DMSO to aqueous solutions containing hen egg white lysozyme or equine myoglobin results in a lowering of charge, whereas a significant increase in charge occurs at higher concentrations. Results from both near-UV circular dichroism spectroscopy and solution-phase hydrogen/deuterium exchange mass spectrometry indicate that DMSO causes a compaction of the native structure of these proteins at low concentration, but significant unfolding occurs at ~63% and ~43% DMSO for lysozyme and myoglobin, respectively. The DMSO concentrations required to denature these two proteins in bulk solution are ~3-5 times higher than the concentrations required for the onset of supercharging, consistent with a significantly increased concentration of this high boiling point supercharging reagent in the ESI droplet as preferential evaporation of water occurs. DMSO is slightly more basic than m-nitrobenzyl alcohol and sulfolane, two other supercharging reagents, based on calculated proton affinity and gas-phase basicity values both at the B3LYP and MP2 levels of theory, and all three of these supercharging reagents are significantly more basic than water. These results provide additional evidence that the origin of supercharging from aqueous solution is the result of chemical and/or thermal denaturation that occurs in the ESI droplet as the concentration of these supercharging reagents increases, and that proton transfer reactivity does not play a significant role in the charge enhancement observed.
Conversion of dimethyl ether--boron trifluoride complex to potassium fluoborate
Eberle, A.R.
A method of preparing KBF/sub 4/ from the dimethyl ether complex of BF/sub 3/ is given. This may be accomplished by introducing the dimethyl ether complex of BF/sub 3/ into an aqueous solution of KF and alcohol, expelling the ether liberated from the complex by heating or stirring and recovering the KBF/sub 4/ so formed. The KBF/sub 4/ is then filtered from the alcohol-water solution, which may be recycled, to reduce the loss of KBF/sub 4/ which is not recovered by filtration.
Chamber simulation of photooxidation of dimethyl sulfide and isoprene in the presence of NOx
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M. Jang
Full Text Available To improve the model prediction for the formation of H2SO4 and methanesulfonic acid (MSA, aerosol-phase reactions of gaseous dimethyl sulfide (DMS oxidation products [e.g., dimethyl sulfoxide (DMSO] in aerosol have been included in the DMS kinetic model with the recently reported gas-phase reactions and their rate constants. To determine the rate constants of aerosol-phase reactions of both DMSO and its major gaseous products [e.g., dimethyl sulfone (DMSO2 and methanesulfinic acid (MSIA], DMSO was photooxidized in the presence of NOx using a 2 m3 Teflon film chamber. The rate constants tested in the DMSO kinetic mechanisms were then incorporated into the DMS photooxidation mechanism. The model simulation using the newly constructed DMS oxidation mechanims was compared to chamber data obtained from the phototoxiation of DMS in the presence of NOx. Within 120-min simulation, the predicted concentrations of MSA increase by 200–400% and those of H2SO4, by 50–200% due to aerosol-phase chemistry. This was well substantiated with experimental data. To study the effect of coexisting volatile organic compounds, the photooxidation of DMS in the presence of isoprene and NOx has been simulated using the newly constructed DMS kinetic model integrated with the Master Chemical Mechanism (MCM for isoprene oxidation, and compared to chamber data. With the high concentrations of DMS (250 ppb and isoprene (560–2248 ppb, both the model simulation and experimental data showed an increase in the yields of MSA and H2SO4 as the isoprene concentration increased.
Atmospherically Relevant Radicals Derived from the Oxidation of Dimethyl Sulfide.
Mardyukov, Artur; Schreiner, Peter R
The large number and amounts of volatile organosulfur compounds emitted to the atmosphere and the enormous variety of their reactions in various oxidation states make experimental measurements of even a small fraction of them a daunting task. Dimethyl sulfide (DMS) is a product of biological processes involving marine phytoplankton, and it is estimated to account for approximately 60% of the total natural sulfur gases released to the atmosphere. Ocean-emitted DMS has been suggested to play a role in atmospheric aerosol formation and thereby cloud formation. The reaction of ·OH with DMS is known to proceed by two independent channels: abstraction and addition. The oxidation of DMS is believed to be initiated by the reaction with ·OH and NO 3 · radicals, which eventually leads to the formation of sulfuric acid (H 2 SO 4 ) and methanesulfonic acid (CH 3 SO 3 H). The reaction of DMS with NO 3 · appears to proceed exclusively by hydrogen abstraction. The oxidation of DMS consists of a complex sequence of reactions. Depending on the time of the day or altitude, it may take a variety of pathways. In general, however, the oxidation proceeds via chains of radical reactions. Dimethyl sulfoxide (DMSO) has been reported to be a major product of the addition channel. Dimethyl sulfone (DMSO 2 ), SO 2 , CH 3 SO 3 H, and methanesulfinic acid (CH 3 S(O)OH) have been observed as products of further oxidation of DMSO. Understanding the details of DMS oxidation requires in-depth knowledge of the elementary steps of this seemingly simple transformation, which in turn requires a combination of experimental and theoretical methods. The methylthiyl (CH 3 S·), methylsulfinyl (CH 3 SO·), methylsulfonyl (CH 3 SO 2 ·), and methylsulfonyloxyl (CH 3 SO 3 ·) radicals have been postulated as intermediates in the oxidation of DMS. Therefore, studying the chemistry of sulfur-containing free radicals in the laboratory also is the basis for understanding the mechanism of DMS oxidation in the
Effect of cotton pectin content and bioscouring on alkyl-dimethyl-benzyl-ammonium chloride adsorption
Our previous research has shown both the rate and the total amount of alkyl-dimethyl-benzyl-ammonium chloride (ADBAC) exhausted from a bulk solution of ADBAC are significantly greater for greige cotton nonwovens than cotton nonwovens that have been both scoured and bleached. The presence of pectin ...
Directory of Open Access Journals (Sweden)
Maria de Hoyos Guajardo, Ph.D. Candidate, M.Sc., B.Eng.
Full Text Available The theory that is presented below aims to conceptualise how a group of undergraduate students tackle non-routine mathematical problems during a problem-solving course. The aim of the course is to allow students to experience mathematics as a creative process and to reflect on their own experience. During the course, students are required to produce a written 'rubric' of their work, i.e., to document their thoughts as they occur as well as their emotionsduring the process. These 'rubrics' were used as the main source of data.Students' problem-solving processes can be explained as a three-stage process that has been called 'solutioning'. This process is presented in the six sections below. The first three refer to a common area of concern that can be called'generating knowledge'. In this way, generating knowledge also includes issues related to 'key ideas' and 'gaining understanding'. The third and the fourth sections refer to 'generating' and 'validating a solution', respectively. Finally, once solutions are generated and validated, students usually try to improve them further before presenting them as final results. Thus, the last section deals with'improving a solution'. Although not all students go through all of the stages, it may be said that 'solutioning' considers students' main concerns as they tackle non-routine mathematical problems.
Hydrogenation of sulfoxides to sulfides under mild conditions using ruthenium nanoparticle catalysts.
Mitsudome, Takato; Takahashi, Yusuke; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi
The first demonstration of the hydrogenation of sulfoxides under atmospheric H2 pressure is reported. The highly efficient reaction is facilitated by a heterogeneous Ru nanoparticle catalyst. The mild reaction conditions enable the selective hydrogenation of a wide range of functionalized sulfoxides to the corresponding sulfides. The high redox ability of RuO(x) nanoparticles plays a key role in the hydrogenation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Evidence for participation of the methionine sulfoxide reductase repair system in plant seed longevity
Châtelain, Emilie; Satour, Pascale; Laugier, Edith; Ly Vu, Benoit; Payet, Nicole; Rey, Pascal; Montrichard, Françoise
Seeds are in a natural oxidative context leading to protein oxidation. Although inevitable for proper progression from maturation to germination, protein oxidation at high levels is detrimental and associated with seed aging. Oxidation of methionine to methionine sulfoxide is a common form of damage observed during aging in all organisms. This damage is reversible through the action of methionine sulfoxide reductases (MSRs), which play key roles in lifespan control in yeast and animal cells. ...
Fluorescent signaling based on sulfoxide profluorophores: application to the visual detection of the explosive TATP.
Malashikhin, Sergey; Finney, Nathaniel S
The first visual fluorescence-based assay for the peroxide explosive triacetone triperoxide (TATP) is described. The assay is based on a conceptually new fluorescence signaling mechanism, in which nonemissive pyrenyl sulfoxide profluorophores are oxidized to visibly emissive pyrenyl sulfones. Although not without limitations, these first-generation fluorescent probes can provide a visual response to ca. 100 nmol of TATP. In addition, the success of this assay suggests the potential for broader application of aryl sulfoxides in fluorescent chemosensing.
The discovery of methionine sulfoxide reductase enzymes: An historical account and future perspectives.
Achilli, Cesare; Ciana, Annarita; Minetti, Giampaolo
L-Methionine (L-Met) is the only sulphur-containing proteinogenic amino acid together with cysteine. Its importance is highlighted by it being the initiator amino acid for protein synthesis in all known living organisms. L-Met, free or inserted into proteins, is sensitive to oxidation of its sulfide moiety, with formation of L-Met sulfoxide. The sulfoxide could not be inserted into proteins, and the oxidation of L-Met in proteins often leads to the loss of biological activity of the affected molecule. Key discoveries revealed the existence, in rats, of a metabolic pathway for the reduction of free L-Met sulfoxide and, later, in Escherichia coli, of the enzymatic reduction of L-Met sulfoxide inserted in proteins. Upon oxidation, the sulphur atom becomes a new stereogenic center, and two stable diastereoisomers of L-Met sulfoxide exist. A fundamental discovery revealed the existence of two unrelated families of enzymes, MsrA and MsrB, whose members display opposite stereospecificity of reduction for the two sulfoxides. The importance of Msrs is additionally emphasized by the discovery that one of the only 25 selenoproteins expressed in humans is a Msr. The milestones on the road that led to the discovery and characterization of this group of antioxidant enzymes are recounted in this review. © 2015 International Union of Biochemistry and Molecular Biology.
Bis(2-ethylhexyl)sulfoxide as an extractant for americium(III) from aqueous nitrate media
International Nuclear Information System (INIS)
Shukla, J.P.; Kedari, C.S.
Solvent extraction separation of Am(III) from dilute aqueous nitrate media into n-dodecane by bis(2-ethylhexyl)sulfoxide (BESO) has been investigated over a wide range of experimental conditions. Very poor extractability of Am(III) necessitated the use of calcium nitrate as the salting-out agent. Effects of certain variables such as acidity, extractant concentration, salting-out agent concentration, organic diluents on the metal extraction by BESO have been examined in detail. By increasing the concentration of BESO in organic phase or calcium nitrate in aqueous phase, nearly quantitative extraction of americium even from moderate acidity is accomplished. Slope analyses applied to Am(III) distribution experiments from acidic nitrate solutions indicate predominant formation of the trisolvated organic phase complex, Am(NO 3 ) 3 *3BESO for which equilibrium constant is found to be, log K x = 1.99. Extraction behavior of Am(III) has also been evaluated in the presence of several water-miscible polar organic solvents to study their possible synergistic effects on its extraction. Extractability of americium increased 5 to 10-fold with increasing concentration of some of these additives, with maximum enhancement being observed in the presence of acetone or acetonitrile. Recovery of BESO from loaded americium is easily obtained using dilute nitric acid as the strippant. (author) 30 refs.; 2 figs.; 5 tabs
Expression of Four Methionine Sulfoxide Reductases in Staphylococcus aureus
Directory of Open Access Journals (Sweden)
Kuldeep Singh
Full Text Available Staphylococcus aureus possesses three MsrA enzymes (MsrA1, MsrA2, MsrA3 that reduce the S-epimer of methionine sulfoxide (MetO and an MsrB enzyme that reduces R-MetO. The four msr genes are expressed from three different promoters. The msrA1/msrB genes are coexpressed. To determine the expression pattern of msr genes, three independent reporter strains were constructed where msr promoter was cloned in front of a promoterless lacZ and the resulting construct was integrated in the chromosome. Using these strains, it was determined that the msrA1/B expression is significantly higher in S. aureus compared to msrA2 or msrA3. Expression of msrA1/B was highest during stationary phase growth, but the expression of msrA2 and msrA3 was highest during the early to midexponential growth phase. Expression of msrA1/B was induced by oxacillin and the expression of msrA3 was upregulated by salt. Expression of msrA2 remained unchanged under all tested conditions.
Cysteine Sulfoxidation Increases the Photostability of Red Fluorescent Proteins.
Ren, Haiyan; Yang, Bing; Ma, Cheng; Hu, Ying S; Wang, Peng George; Wang, Lei
Photobleaching of fluorescent proteins (FPs) is a major limitation to their use in advanced microscopy, and improving photostability remains highly challenging due to limited understanding of its molecular mechanism. Here we discovered a new mechanism to increase FP photostability. Cysteine oxidation, implicated in only photobleaching before, was found to drastically enhance FP photostability to the contrary. We generated a far-red FP mStable by introducing a cysteine proximal to the chromophore. Upon illumination, this cysteine was oxidized to sulfinic and sulfonic acids, enabling mStable more photostable than its ancestor mKate2 by 12-fold and surpassing other far-red FPs. mStable outperformed in laser scanning confocal imaging and super-resolution structured illumination microscopy. Moreover, photosensitization to oxidize a cysteine similarly introduced in another FP mPlum also increased its photostability by 23-fold. This postfolding cysteine sulfoxidation cannot be simply substituted by the isosteric aspartic acid, representing a unique mechanism valuable for engineering better photostability into FPs.
Triethylammonium salt of dimethyl diphenyldithiophosphates: Single ...
Indian Academy of Sciences (India)
Triethylammonium salt of dimethyl diphenyldithiophosphates: Single crystal X-ray and DFT analysis. SANDEEP KUMAR RUCHI KHAJURIA MANDEEP KOUR RAKESH KUMAR LOVE KARAN RANA GEETA HUNDAL VIVEK K GUPTA RAJNI KANT SUSHIL K PANDEY. Regular Article Volume 128 Issue 6 June 2016 pp ...
Optical clearing: impact of optical and dielectric properties of clearing solutions on pulmonary tissue mechanics.
Schwenninger, David; Priebe, Hans-Joachim; Schneider, Matthias; Runck, Hanna; Guttmann, Josef
Optical clearing allows tissue visualization under preservation of organ integrity. Optical clearing of organs with a physiological change in three-dimensional geometry (such as the lung) would additionally allow visualization of macroscopic and microscopic tissue geometry. A prerequisite, however, is the preservation of the native tissue mechanics of the optically cleared lung tissue. We investigated the impact of optical and dielectric properties of clearing solutions on biomechanics and clearing potency in porcine tissue strips of healthy lungs. After fixation, bleaching, and rehydration, four methods of optical clearing were investigated using eight different protocols. The mechanical and optical properties of the cleared lung tissue strips were investigated by uniaxial tensile testing and by analyzing optical transparency and translucency for red, green, and blue light before, during, and after the biochemical optical clearing process. Fresh tissue strips were used as controls. Best balance between efficient clearing and preserved mechanics was found for clearing with a 1:1 mixture of dimethyl sulfoxide (DMSO) and aniline. Our findings show that 1 ) the degree of tissue transparency and translucency correlated with the refractive index of the clearing solution index ( r = 0.976, P = 0.0004; and r = 0.91, P = 0.0046, respectively), 2 ) tissue mechanics were affected by dehydration and the type of clearing solution, and 3 ) tissue biomechanics and geometry correlated with the dielectric constant of the clearing solution ( r = -0.98, P mechanics, our results help to compose optimal clearing solutions. In addition, the results allow conclusions on the molecular interaction of solvents with collagen fibers in tissue, thereby consolidating existing theories about the functionality of collagen. Copyright © 2017 the American Physiological Society.
International Nuclear Information System (INIS)
Long, E.C.
The invention deals with a liquid scintillation solution which contains 1) a scintillation solvent (toluol), 2) a primary scintillation solute (PPO), 3) a secondary scintillation solute (dimethyl POPOP), 4) several surfactants (iso-octyl-phenol polyethoxy-ethanol and sodium di-hexyl sulfosuccinate) essentially different from one another and 5) a filter resolution and/or transparent-making agent (cyclic ether, especially tetrahydrofuran). (HP) [de
Synthesis of Sulfoximine Carbamates by Rhodium-Catalyzed Nitrene Transfer of Carbamates to Sulfoxides.
Zenzola, Marina; Doran, Robert; Luisi, Renzo; Bull, James A
Sulfoximines are of considerable interest for incorporation into medicinal compounds. A convenient synthesis of N-protected sulfoximines is achieved, under mild conditions, by rhodium-catalyzed transfer of carbamates to sulfoxides. The first examples of 4-membered thietane-oximines are prepared. Sulfoximines bearing Boc and Cbz groups are stable to further cross coupling reactions, and readily deprotected. This method may facilitate the preparation of NH-sulfoximines providing improved (global) deprotection strategies, which is illustrated in the synthesis of methionine sulfoxide (MSO).
Proton dynamics investigation for dimethyl ammonium cation
International Nuclear Information System (INIS)
Pislewski, N.; Tritt-Goc, J.; Jakubas, R.
Proton dynamics in dimethyl ammonium cation has been investigated by means of NMR and spin echo methods in polycrystalline salts [NH 2 (CH 3 ) 2 ] + Bi 2 J 9 - and [NH 2 (CH 3 ) 2 ] + SbJ 9 - . Spin-lattice relaxation time as well as second moment of NMR line have been measured for influence study of crystal structure changes on proton dynamics
Studies on the influence of tris(pentafluorophenyl)borane on the properties of ethylene carbonate, dimethyl carbonate and poly(ethylene oxide) dimethyl ether lithium trifluoromethanesulfonate electrolytes
Energy Technology Data Exchange (ETDEWEB)
Zukowska, Grazyna Z.; Marcinek, Marek; Drzewiecki, Stanislaw; Kryczka, Jolanta; Syzdek, Jaroslaw; Adamczyk-Wozniak, Agnieszka; Wieczorek, Wladyslaw; Sporzynski, Andrzej [Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw (Poland)
In this paper we present our studies on the properties of battery electrolyte based on EC/DMC (ethylene carbonate/dimethyl carbonate, w/w ratio 2:5) and PEODME (poly(ethylene oxide) dimethyl ether) (M{sub w} = 500) doped with LiCF{sub 3}SO{sub 3}-lithium trifluoromethanesulfonate (LiTf) and modified with TPFPB (tris(pentafluorophenyl)borane) as a potential anion trapping agent. We were particularly interested how this compound behaves in different solvents, e.g. battery mixture EC/DMC and model polymeric matrix PEODME. We also verified stability of the proposed solutions by means of DSC and FTIR, determined influence on conductivity and lithium transference numbers by impedance spectroscopy, and finally attempted to define mechanism of influence of boron addition on different systems. (author)
Unraveling the structural components of soil humin by use of solution-state nuclear magnetic resonance spectroscopy.
Simpson, Andre J; Song, Guixue; Smith, Emma; Lam, Buuan; Novotny, Etelvino H; Hayes, Michael H B
Humin is the most recalcitrant and least understood fraction of soil organic matter. By definition, humin is that fraction not extracted by traditional aqueous alkaline soil extractants. Here we show that > or = 70% of the traditional humin fraction is solubilized when 0.1 M NaOH + 6 M urea and dimethyl sulfoxide (DMSO) + 6% H2SO4 are used in series after conventional extraction. Multidimensional solution-state NMR is applied in this study to gain an understanding of the major constituents present in these "solubilized humin fractions". The spectra indicated strong contributions from five main categories of components, namely, peptides, aliphatic species, carbohydrates, peptidoglycan, and lignin. Diffusion edited spectroscopy indicated that all species are present as macromolecules (or stable aggregate species). Although the distribution of the components is generally similar, peptidoglycan is present at significant levels supporting a higher microbial contribution to humin than to humic and fulvic fractions. The abundance of plant- and microbial-derived materials found does not exclude "humic" materials (e.g., oxidized lignin) or the presence of novel compounds at lower concentrations but suggests that a large proportion of humin is formed from classes of known compounds and parent biopolymers.
A Click Chemistry Approach towards Flavin-Cyclodextrin Conjugates-Bioinspired Sulfoxidation Catalysts
Czech Academy of Sciences Publication Activity Database
Tomanová, P.; Šturala, J.; Buděšínský, Miloš; Cibulka, R.
Roč. 20, č. 11 (2015), s. 19837-19848 ISSN 1420-3049 Institutional support: RVO:61388963 Keywords : click chemistry * cyclodextrin * flavin * monooxygenase * oxidation * sulfoxides * green chemistry Subject RIV: CC - Organic Chemistry Impact factor: 2.465, year: 2015 http://www.mdpi.com/1420-3049/20/11/19667/htm
Flavin-cyclodextrin conjugates as catalysts of enantioselective sulfoxidations with hydrogen peroxide in aqueous media
Czech Academy of Sciences Publication Activity Database
Mojr, V.; Herzig, V.; Buděšínský, Miloš; Cibulka, R.; Kraus, Tomáš
Roč. 46, č. 40 (2010), s. 7599-7601 ISSN 1359-7345 R&D Projects: GA ČR(CZ) GA203/07/1246 Institutional research plan: CEZ:AV0Z40550506 Keywords : cyclodextrin s * sulfoxidation * flavins Subject RIV: CC - Organic Chemistry Impact factor: 5.787, year: 2010
Polycyclic Ketone Monooxygenase (PockeMO): A Robust Biocatalyst for the Synthesis of Optically Active Sulfoxides
de Gonzalo, Gonzalo; Fürst, Maximilian; Fraaije, Marco
A recently discovered, moderately thermostable Baeyer-Villiger monooxygenase, polycyclic ketone monooxygenase (PockeMO), from Thermothelomyces thermophila has been employed as a biocatalyst in a set of asymmetric sulfoxidations. The enzyme was able to catalyze the oxidation of various alkyl aryl
The determination of sulfoxide configuration in six-membered rings using NMR specroscopy and DFT calculations
Czech Academy of Sciences Publication Activity Database
Dračínský, Martin; Pohl, Radek; Slavětínská, Lenka; Janků, J.; Buděšínský, Miloš
Roč. 22, č. 3 (2011), s. 356-366 ISSN 0957-4166 R&D Projects: GA ČR GA203/09/1919 Institutional research plan: CEZ:AV0Z40550506 Keywords : NMR * calculation of NMR parameters * sulfoxides * configuration Subject RIV: CC - Organic Chemistry Impact factor: 2.652, year: 2011
Solution-state NMR spectroscopy of famotidine revisited: spectral assignment, protonation sites, and their structural consequences.
Marosi, Attila; Szalay, Zsófia; Béni, Szabolcs; Szakács, Zoltán; Gáti, Tamás; Rácz, Ákos; Noszál, Béla; Demeter, Ádám
Multinuclear one (1D-) and two-dimensional (2D) nuclear magnetic resonance (NMR) spectroscopic investigations of famotidine, the most potent and widely used histamine H(2)-receptor antagonist, were carried out in dimethyl sulfoxide-d(6) (DMSO-d(6)) and water. Previous NMR assignments were either incomplete or full assignment was based only on 1D spectra and quantum-chemical calculations. Our work revealed several literature misassignments of the (1)H, (13)C, and (15)N NMR signals and clarified the acid-base properties of the compound at the site-specific level. The erroneous assignment of Baranska et al. (J. Mol. Struct. 2001, 563) probably originates from an incorrect hypothesis about the major conformation of famotidine in DMSO-d(6). A folded conformation similar to that observed in the solid-state was also assumed in solution, stabilized by an intramolecular hydrogen bond involving one of the sulphonamide NH(2) protons and the thiazole nitrogen. Our detailed 1D and 2D NMR experiments enabled complete ab initio (1)H, (13)C, and (15)N assignments and disproved the existence of the sulphonamide NH hydrogen bond in the major conformer. Rather, the molecule is predominantly present in an extended conformation in DMSO-d(6). The aqueous acid-base properties of famotidine were studied by 1D (1)H- and 2D (1)H/(13)C heteronuclear multiple-bond correlation (HMBC) NMR-pH titrations. The experiments identified its basic centers including a new protonation step at highly acidic conditions, which was also confirmed by titrations and quantum-chemical calculations on a model compound, 2-[4-(sulfanylmethyl)-1,3-thiazol-2-yl]guanidine. Famotidine is now proved to have four protonation steps in the following basicity order: the sulfonamidate anion protonates at pH = 11.3, followed by the protonation of the guanidine group at pH = 6.8, whereas, in strong acidic solutions, two overlapping protonation processes occur involving the amidine and thiazole moieties.
Determination of dimethyl selenide and dimethyl sulphide compounds causing off-flavours in bottled mineral waters.
Guadayol, Marta; Cortina, Montserrat; Guadayol, Josep M; Caixach, Josep
Sales of bottled drinking water have shown a large growth during the last two decades due to the general belief that this kind of water is healthier, its flavour is better and its consumption risk is lower than that of tap water. Due to the previous points, consumers are more demanding with bottled mineral water, especially when dealing with its organoleptic properties, like taste and odour. This work studies the compounds that can generate obnoxious smells, and that consumers have described like swampy, rotten eggs, sulphurous, cooked vegetable or cabbage. Closed loop stripping analysis (CLSA) has been used as a pre-concentration method for the analysis of off-flavour compounds in water followed by identification and quantification by means of GC-MS. Several bottled water with the aforementioned smells showed the presence of volatile dimethyl selenides and dimethyl sulphides, whose concentrations ranged, respectively, from 4 to 20 ng/L and from 1 to 63 ng/L. The low odour threshold concentrations (OTCs) of both organic selenide and sulphide derivatives prove that several objectionable odours in bottled waters arise from them. Microbial loads inherent to water sources, along with some critical conditions in water processing, could contribute to the formation of these compounds. There are few studies about volatile organic compounds in bottled drinking water and, at the best of our knowledge, this is the first study reporting the presence of dimethyl selenides and dimethyl sulphides causing odour problems in bottled waters. Copyright © 2016 Elsevier Ltd. All rights reserved.
Footwear contact dermatitis from dimethyl fumarate.
Švecová, Danka; Šimaljakova, Maria; Doležalová, Anna
Dimethyl fumarate (DMF) is an effective inhibitor of mold growth. In very low concentrations, DMF is a potent sensitizer that can cause severe allergic contact dermatitis (ACD). It has been identified as the agent responsible for furniture contact dermatitis in Europe. The aim of this study was to evaluate patients in Slovakia with footwear ACD associated with DMF, with regard to clinical manifestations, patch test results, and results of chemical analysis of their footwear. Nine patients with suspected footwear contact dermatitis underwent patch testing with the following allergens: samples of their own footwear, commercial DMF, the European baseline, shoe screening, textile and leather dye screening, and industrial biocides series. The results were recorded according to international guidelines. The content of DMF in footwear and anti-mold sachets was analyzed using gas chromatography and mass spectrometry. Acute ACD was observed in nine Caucasian female patients. All patients developed delayed sensitization, as demonstrated by positive patch testing using textile footwear lining. Seven patients were patch tested with 0.1% DMF, and all seven were positive. Chemical analysis of available footwear showed that DMF was present in very high concentrations (25-80 mg/Kg). Dimethyl fumarate is a new footwear allergen and was responsible for severe ACD in our patients. To avoid an increase in the number of cases, the already approved European preventive measures should be accepted and commonly employed. © 2013 The International Society of Dermatology.
Dimethyl carbonate as a modern green reagent and solvent
International Nuclear Information System (INIS)
Arico, F; Tundo, Pietro
Published data on dimethyl carbonate as a safe reagent and solvent in organic synthesis are generalized and analyzed. The methods of dimethyl carbonate preparation and its use as methylating and carboxymethylating reagent are considered. The attention is focused on the environmentally safe processes corresponding to the green chemistry principles.
Carbon Nanotube Dispersion in Solvents and Polymer Solutions: Mechanisms, Assembly, and Preferences.
Pramanik, Chandrani; Gissinger, Jacob R; Kumar, Satish; Heinz, Hendrik
Debundling and dispersion of carbon nanotubes (CNTs) in polymer solutions play a major role in the preparation of carbon nanofibers due to early effects on interfacial ordering and mechanical properties. A roadblock toward ultrastrong fibers is the difficulty to achieve homogeneous dispersions of CNTs in polyacrylonitrile (PAN) and poly(methyl methacrylate) (PMMA) precursor solutions in solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF). In this contribution, molecular dynamics simulations with accurate interatomic potentials for graphitic materials that include virtual π electrons are reported to analyze the interaction of pristine single wall CNTs with the solvents and polymer solutions at 25 °C. The results explain the barriers toward dispersion of SWCNTs and quantify CNT-solvent, polymer-solvent, as well as CNT-polymer interactions in atomic detail. Debundling of CNTs is overall endothermic and unfavorable with dispersion energies of +20 to +30 mJ/m 2 in the pure solvents, + 20 to +40 mJ/m 2 in PAN solutions, and +20 to +60 mJ/m 2 in PMMA solutions. Differences arise due to molecular geometry, polar, van der Waals, and CH-π interactions. Among the pure solvents, DMF restricts CNT dispersion less due to the planar geometry and stronger van der Waals interactions. PAN and PMMA interact favorably with the pure solvents with dissolution energies of -0.7 to -1.1 kcal per mole monomer and -1.5 to -2.2 kcal per mole monomer, respectively. Adsorption of PMMA onto CNTs is stronger than that of PAN in all solvents as the molecular geometry enables more van der Waals contacts between alkyl groups and the CNT surface. Polar side groups in both polymers prefer interactions with the polar solvents. Higher polymer concentrations in solution lead to polymer aggregation via alkyl groups and reduce adsorption onto CNTs. PAN and PMMA solutions in DMSO and dilute solutions in DMF support CNT dispersion more than other
Some dilute solution properties of highly isotactic polyacrylonitrile in aq. nitric acid
International Nuclear Information System (INIS)
Yamazaki, Hitoshi; Miyazaki, Yukio; Saito, Masatoshi; Kamide, Kenji
An attempt was made to investigate the dilute solution properties of highly isotactic polyacrylonitrile (PAN) dissolved in aq. nitric acid and to estimate the molecular parameters, such as the unperturbed chain dimension A and the characteristic ratio C ∞ . For this purpose a highly isotactic polymer with isotactic triad content of 73.4% was synthesized by irradiating γ-ray on acrylonitrile-urea canal complex at -78degC and was subjected to successive precipitation fractionation, using dimethyl sulfoxide as solvent and toluene as precipitant, into 7 fractions. Among them 2 fractions with isotactic triad of 71.0 and 77.9%, respectively were employed for further study. The weight-average molecular weight M w and the second virial coefficient A 2 of these fractions in 70wt% aq. nitric acid soln. were measured by the light scattering method. The 70wt% aq. nitric acid soln. was predicted to be able to dissolve perfectly-isotactic PAN with M w of 1.5-2.6 x 10 5 at room temperature. The Mark-Houwink-Sakurada equations in aq. nitric acid solutions differ significantly depending on the stereoregularity of PAN employed, even if highly concentrated acids are used. A 57.5wt% aq. nitric acid soln. is determined, by the dependence of A 2 on the nitric acid concentration, to be a Flory's theta solvent for PAN with isotactic triad of 71.0% at 25degC. A of PAN increases rapidly with isotactic triad content, especially in the range higher than 50%. C ∞ of PAN is always far larger than the calculated value of non-polar Monte Carlo chain for polypropyrene [P. J. Flory et al., J. Am. Chem. Soc., 88, 639 (1966)] over the whole range higher than 50% isotactic diad. (author)
Dimethyl Sulfoxide (DMSO) Decreases Cell Proliferation and TNF-α, IFN-γ, and IL-2 Cytokines Production in Cultures of Peripheral Blood Lymphocytes.
de Abreu Costa, Lucas; Henrique Fernandes Ottoni, Marcelo; Dos Santos, Michaelle Geralda; Meireles, Agnes Batista; Gomes de Almeida, Valéria; de Fátima Pereira, Wagner; Alves de Avelar-Freitas, Bethânia; Eustáquio Alvim Brito-Melo, Gustavo
Dimethylsulfoxide (DMSO) is an amphipathic molecule composed of a polar domain characterized by the sulfinyl and two nonpolar methyl groups, for this reason it is able to solubilize polar and nonpolar substances and transpose hydrophobic barriers. DMSO is widely used to solubilize drugs of therapeutic applications and studies indicated that 10% v/v concentration did not modify culture viability when used to treat human peripheral blood mononuclear cells (PBMC). However, some DMSO concentrations could influence lymphocyte activation and present anti-inflammatory effects. Therefore, the objective of this study was to evaluate the effect of DMSO on lymphocyte activation parameters. Cell viability analysis, proliferation, and cytokine production were performed on PBMC from six healthy subjects by flow cytometry. The results indicated that 2.5% v/v DMSO concentrations did not modify lymphocytes viability. DMSO at 1% and 2% v/v concentrations reduced the relative proliferation index of lymphocytes and at 5% and 10% v/v concentrations reduced the percentage of total lymphocytes, cluster of differentiation 4⁺ (CD4⁺) T lymphocytes and CD8⁺ T lymphocytes interferon-γ (IFN-γ), tumor necrosis factor-α (TNF-α) and interleukin-2 (IL-2) producers. Thus, it was concluded that DMSO has an in vitro anti-inflammatory effect by reducing lymphocyte activation demonstrated with proliferation reduction and the decrease of cytokine production.
Dimethyl Sulfoxide (DMSO Decreases Cell Proliferation and TNF-α, IFN-γ, and IL-2 Cytokines Production in Cultures of Peripheral Blood Lymphocytes
Directory of Open Access Journals (Sweden)
Lucas de Abreu Costa
Full Text Available Dimethylsulfoxide (DMSO is an amphipathic molecule composed of a polar domain characterized by the sulfinyl and two nonpolar methyl groups, for this reason it is able to solubilize polar and nonpolar substances and transpose hydrophobic barriers. DMSO is widely used to solubilize drugs of therapeutic applications and studies indicated that 10% v/v concentration did not modify culture viability when used to treat human peripheral blood mononuclear cells (PBMC. However, some DMSO concentrations could influence lymphocyte activation and present anti-inflammatory effects. Therefore, the objective of this study was to evaluate the effect of DMSO on lymphocyte activation parameters. Cell viability analysis, proliferation, and cytokine production were performed on PBMC from six healthy subjects by flow cytometry. The results indicated that 2.5% v/v DMSO concentrations did not modify lymphocytes viability. DMSO at 1% and 2% v/v concentrations reduced the relative proliferation index of lymphocytes and at 5% and 10% v/v concentrations reduced the percentage of total lymphocytes, cluster of differentiation 4+ (CD4+ T lymphocytes and CD8+ T lymphocytes interferon-γ (IFN-γ, tumor necrosis factor-α (TNF-α and interleukin-2 (IL-2 producers. Thus, it was concluded that DMSO has an in vitro anti-inflammatory effect by reducing lymphocyte activation demonstrated with proliferation reduction and the decrease of cytokine production.
Low-molecular-weight carbohydrate Pentaisomaltose may replace dimethyl sulfoxide as a safer cryoprotectant for cryopreservation of peripheral blood stem cells
DEFF Research Database (Denmark)
Svalgaard, Jesper Dyrendom; Haastrup, Eva Kannik; Reckzeh, Kristian
-related side effects, there is an increasing demand for DMSO-free alternatives. We therefore investigated whether Pentaisomaltose (PIM), a low-molecular-weight carbohydrate (1 kDa), can be used for cryopreservation of peripheral blood stem cells, more specifically hematopoietic progenitor cell apheresis (HPC......(A)) product. STUDY DESIGN AND METHODS: We cryopreserved patient or donor HPC(A) products using 10% DMSO or 16% PIM and quantified the recovery of CD34+ cells and CD34+ subpopulations by multicolor flow cytometry. In addition, we compared the frequency of HPCs after DMSO and PIM cryopreservation using...... and therefore may have the potential to be used for cryopreservation of peripheral blood stem cells....
Genotoxic effects of three selected black toner powders and their dimethyl sulfoxide extracts in cultured human epithelial A549 lung cells in vitro.
Gminski, Richard; Decker, Katharina; Heinz, Christina; Seidel, Albrecht; Könczöl, Mathias; Goldenberg, Ella; Grobéty, Bernard; Ebner, Winfried; Gieré, Reto; Mersch-Sundermann, Volker
Until now, the adverse effects of toner powders on humans have been considered to be minimal. However, several recent reports have suggested possible significant adverse health effects from toner dust inhalation. The aim of this study was to evaluate the genotoxic potential of black toner powders in vitro. For the study of DNA damage, A549 cells were exposed to toner-powder suspensions and to their DMSO extracts, and then subjected to the comet assay and to the in-vitro cytokinesis block micronucleus test (CB-MNvit). Cytotoxic effects of the toner samples were assessed by the erythrosin B assay. Furthermore, size, shape, and composition of the toner powders were investigated. None of the three toner powders or their DMSO extracts reduced cell viability; however, they did induce DNA damage and formed micronuclei at concentrations from 80 to 400 μg cm(-2) , although to a varying extent. All toner powders contain considerable amounts of the pigments carbon black and magnetite (Fe(3) O(4) ) as well as small amounts of polycyclic aromatic hydrocarbons (PAHs). The overall results of our in-vitro study suggest that the investigated toner-powder samples are not cytotoxic but genotoxic. From the results of the physical and chemical characterization, we conclude that metals and metalloids as components of magnetite, or PAHs as components of the carbon-bearing material, are responsible for the genotoxic effects. Further research is necessary to determine the relevance of these in-vitro observations for private and occupational toner powder exposure. Copyright © 2010 Wiley-Liss, Inc.
Structural parameters of dimethyl sulfoxide, DMSO, at 100 K, based on a redetermination by use of high-quality single-crystal X-ray data.
Reuter, Hans
The title compound, C 2 H 6 OS, is a high melting, polar and aprotic solvent widely used in organic and inorganic chemistry. It serves as a H-atom acceptor in hydrogen bonding and is used as an ambidentate ligand in coordination chemistry. The evaluation of the influence of inter-molecular inter-actions on the inter-nal structural parameters of the chemically bonded DMSO mol-ecules affords precise structural data of the free mol-ecule as a point of reference. So far, valid data have been obtained only by use of neutron powder diffraction [Ibberson (2005 ▸). Acta Cryst. C 61 , o571-o573]. In the present redetermination, structural data have been obtained from a single-crystal X-ray diffraction experiment at 100 K, revealing a better comparison with DMSO mol-ecules in other crystal structures. In the solid state, the pyramidal mol-ecule exhibits a nearly perfect C s symmetry [including H atoms, which are eclipsed with respect to the C⋯C axis], with a C-S-C bond angle of 97.73 (7)° and an S-O bond length of 1.5040 (10) Å, corresponding very well with an S=O double bond, and with almost equal S-C bond lengths [mean value = 1.783 (4) Å] and O-S-C bond angles [mean value = 106.57 (4)°]. The crystal packing is influenced by C-H⋯O inter-actions (2.42-2.47 Å) between all three H atoms of only one methyl group with the O atoms of three neighbouring DMSO mol-ecules. The inter-actions of the O atom with H atoms (or Lewis acids, or hydrogen-donor groups) of adjacent mol-ecules in relation to the orientation of the complete DMSO mol-ecule are described in terms of the angle ω and the distance d norm ; ω is the angle between the pseudo-mirror plane of the mol-ecule and the plane defined through the S=O bond and the inter-acting atom, and d norm is the distance of the inter-acting atom from the plane perpendicular to the S=O bond.
Structural parameters of dimethyl sulfoxide, DMSO, at 100 K, based on a redetermination by use of high-quality single-crystal X-ray data
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Hans Reuter
Full Text Available The title compound, C2H6OS, is a high melting, polar and aprotic solvent widely used in organic and inorganic chemistry. It serves as a H-atom acceptor in hydrogen bonding and is used as an ambidentate ligand in coordination chemistry. The evaluation of the influence of intermolecular interactions on the internal structural parameters of the chemically bonded DMSO molecules affords precise structural data of the free molecule as a point of reference. So far, valid data have been obtained only by use of neutron powder diffraction [Ibberson (2005. Acta Cryst. C61, o571–o573]. In the present redetermination, structural data have been obtained from a single-crystal X-ray diffraction experiment at 100 K, revealing a better comparison with DMSO molecules in other crystal structures. In the solid state, the pyramidal molecule exhibits a nearly perfect Cs symmetry [including H atoms, which are eclipsed with respect to the C...C axis], with a C—S—C bond angle of 97.73 (7° and an S—O bond length of 1.5040 (10 Å, corresponding very well with an S=O double bond, and with almost equal S—C bond lengths [mean value = 1.783 (4 Å] and O—S—C bond angles [mean value = 106.57 (4°]. The crystal packing is influenced by C—H...O interactions (2.42–2.47 Å between all three H atoms of only one methyl group with the O atoms of three neighbouring DMSO molecules. The interactions of the O atom with H atoms (or Lewis acids, or hydrogen-donor groups of adjacent molecules in relation to the orientation of the complete DMSO molecule are described in terms of the angle ω and the distance dnorm; ω is the angle between the pseudo-mirror plane of the molecule and the plane defined through the S=O bond and the interacting atom, and dnorm is the distance of the interacting atom from the plane perpendicular to the S=O bond.
Radioprotective effects of dimethyl sulfoxide in golden hamster embryo cells exposed to gamma rays at 77 K. I. Radical formation as studied by electron spin resonance
International Nuclear Information System (INIS)
Miyazaki, T.; Hayakawa, Y.; Suzuki, K.; Suzuki, M.; Watanabe, M.
Formation of free radicals in golden hamster embryo (GHE) cells in the frozen living state by gamma irradiation has been studied by electron spin resonance spectroscopy at 4.2 and 77 K. The relative yields of H atoms, OH radicals, and organic radicals trapped in the irradiated GHE cells are 12, 72, and 16%, respectively, of total radical yields. When dimethylsulfoxide (DMSO) is added to GHE cells at 77 K, a large quantity of CH2SOCH3 radicals (DMSO radicals) are formed after gamma irradiation. The yields of OH radicals are not affected by the addition of DMSO. When the GHE cell-DMSO mixtures are irradiated with gamma rays at 77 K and then warmed to 111 K, the OH radicals decay, whereas the DMSO radicals do not increase complementarily. Moreover, the decay rates of the OH radicals at 111 K do not depend upon the concentration of DMSO. Thus OH radicals do not react with DMSO during warming of the irradiated sample. When H atoms are produced by gamma irradiation of acid ice at 60 K, the decay rates of the H atoms at 77 K increase with increasing DMSO concentration, indicating that DMSO reacts with H atoms (CH3SOCH3 + H----.CH2SOCH3 + H2) at 77 K by quantum-mechanical tunneling. When the GHE cell-DMSO mixture is irradiated with gamma rays at 77 or 4.2 K in the dark, DMSO ions are produced in addition to DMSO radicals. Therefore it is concluded that DMSO does not scavenge OH radicals, but does capture H atoms, holes and/or electrons in the gamma-irradiated cells, resulting in the remarkable formation of DMSO radicals. This scavenger effect of DMSO may be related to the radioprotection of DMSO against cell killing
CCDC 977701: Experimental Crystal Structure Determination : (2-(bis(2-Methoxyphenyl)phosphino)-N-(2-(trifluoromethyl)phenyl)benzenesulfonamidato)-(dimethyl sulfoxide)-methyl-palladium
Jian, Zhongbao
An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Use of Two-Dimensional Fluorescence Spectroscopy for Monitoring of the Effect of Dimethyl Sulfoxide in the Growth and Viability of Immobilized Plant Cells
Czech Academy of Sciences Publication Activity Database
Vaňková, Radomíra; Kuncová, Gabriela; Podrazký, Ondřej; Gaudinová, Alena; Vaněk, Tomáš
Roč. 57, č. 12 (2003), s. 632-635 ISSN 0354-7531 R&D Projects: GA MŠk OC 840.10; GA MŠk OC 843.10 Institutional research plan: CEZ:AV0Z4072921; CEZ:AV0Z5038910 Keywords : Two-Dimensional Fluorescence Spectroscopy * Immobilized Plant Cells * Tobacco Subject RIV: CE - Biochemistry
Theoretical and experimental study of the antifreeze protein AFP752, trehalose and dimethyl sulfoxide cryoprotection mechanism: correlation with cryopreserved cell viability
Czech Academy of Sciences Publication Activity Database
Kratochvílová, Irena; Golan, Martin; Pomeisl, Karel; Richter, Jan; Sedláková, Silvia; Šebera, Jakub; Mičová, Júlia; Falk, Martin; Falková, Iva; Řeha, David; Elliott, J.R.; Varga, K.; Follett, S.E.; Šimek, Daniel
Roč. 7, č. 1 (2017), s. 352-360 ISSN 2046-2069 R&D Projects: GA ČR(CZ) GA15-05095S; GA MŠk LO1409; GA ČR(CZ) GA14-10279S; GA ČR(CZ) GA16-12454S; GA ČR GBP302/12/G157; GA MZd NV16-29835A Grant - others:FUNBIO(XE) CZ.2.16/3.1.00/21568 Institutional support: RVO:68378271 ; RVO:61388971 ; RVO:68081707 Keywords : X-ray diffraction * DFT * Raman spectroscopy * DSC * cryoprotectants Subject RIV: BO - Biophysics; EE - Microbiology, Virology (MBU-M) OBOR OECD: Biophysics Impact factor: 3.108, year: 2016
Bis{μ-2-(1H-indol-3-yl-N′-[1-(5-methyl-2-oxidophenylethylidene]acetohydrazidato}bis[aquazinc(II] dimethyl sulfoxide tetrasolvate
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Hapipah M. Ali
Full Text Available The dinuclear title compound, [Zn2(C19H17N3O22(H2O2]·4C2H6OS, lies about a center of inversion. The deprotonated monoanion O,N,O-chelates the Zn atom; the hydroxy O atom also engages in bonding to the symmetry-related Zn atom so that one N and three O atoms form a square around the metal. The coordination geometry is square-pyramidal, with the apical site occupied by a water molecule. Hydrogen bonds, with the water molecule serving as donor atom, lead to the formation of a linear chain motif. There is an N—H...O hydrogen bond between the complex molecule and solvent O atom.
Dimethyl sulfoxide potentiates death receptor-mediated apoptosis in the human myeloid leukemia U937 cell line through enhancement of mitochondrial membrane depolarization
Czech Academy of Sciences Publication Activity Database
Vondráček, Jan; Souček, Karel; Sheard, M. A.; Chramostová, Kateřina; Andrysík, Zdeněk; Hofmanová, Jiřina; Kozubík, Alois
Roč. 30, č. 1 (2006), s. 81-89 ISSN 0145-2126 R&D Projects: GA ČR(CZ) GA524/03/0766 Institutional research plan: CEZ:AV0Z50040507 Keywords : human myeloid leukemia * DMSO * apoptosis Subject RIV: BO - Biophysics Impact factor: 2.483, year: 2006
CCDC 860713: Experimental Crystal Structure Determination : catena-[dimethylammonium (mu-5,5'-ethyne-1,2-diyldiisophthalato)-indium N,N-dimethylformamide dimethyl sulfoxide solvate monohydrate
Zheng, Bing
An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Crystal structure of μ-oxalodihydroxamato-bis[(2,2′-bipyridyl(dimethyl sulfoxide-κOcopper(II] bis(perchlorate
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Irina A. Odarich
Full Text Available The centrosymmetric binuclear complex, [Cu2(C2H2N2O4(C10H8N22(C2H6OS2](ClO42, contains two copper(II ions, connected through an N-deprotonated oxalodihydroxamic acid dianion, two terminal 2,2′-bipyridine ligands, and two apically coordinating dimethylsulfoxide molecules. Two non-coordinating perchlorate anions assure electrical neutrality. The copper(II ions in the complex dication [Cu2(C10H8N22(μ-C2H2N2O4(C2H6SO2]2+ are in an O2N3 square-pyramidal donor environment, the Cu–Cu separation being 5.2949 (4 Å. Two hydroxamate groups in the deprotonated oxalodihydroxamic acid are located trans to one each other. In the crystal, O—H...O and C—H...O hydrogen bonds link the complex cations to the perchlorate anions. Further C—H...O hydrogen bonds combine with π–π contacts with a centroid-to-centroid separation of 3.6371 (12 Å to stack the molecules along the a-axis direction.
Studies on the toxicity of dimethyl sulfoxide, ethylene glycol, methanol and glycerol to loach (Misgurnus fossilis) sperm and the effect on subsequent embryo development.
Kopeika, J; Kopeika, E; Zhang, T; Rawson, D M
The process of sperm cryopreservation consists of several steps: equilibration of sperm in cryoprotectant medium, freezing of sperm to subzero temperatures, low temperature storage and thawing of the sperm suspension. It has been shown that cryopreservation can cause some damage to the genetic material of cells although the mechanism and significance of these changes are still unknown. The aim of this work was to study the effect of cryoprotectant equilibration process on genetic damage of Loach (Misgurnus fossilis) sperm, using embryo survival as an indicator. Decrease in embryo survival after the 20th stage is generally believed to result from the failure in the genome function of embryos. In the first set of the experiments, Loach sperm were equilibrated in cryoprotectants Me2SO, ethylene glycol, methanol and glycerol (0.6, 1.2, 2.5 M) for 60 min at 10 degree C. The effect of cryoprotectant equilibration on sperm was evaluated based on the survival of embryos derived from cryoprotectant treated sperm. Embryo survival was evaluated at the following stages: 7th, 14th, 17th, 20th, 23rd, 26th, 31st, 34th, 35th, 36th and 37th. Cryoprotectants at concentrations greater than 1.2 M had significant effect on the survival of the embryos after the 20th stage. The effect of glycerol was the most significant with 64.8 +/- 2.4% of embryos survival compared to 77.0 +/- 2.4% for control. Me2SO treatment also effects embryo survival significantly. Possible mechanisms of the genetic instability of cryoprotectants are discussed.
Stable Overexpression of the Constitutive Androstane Receptor Reduces the Requirement for Culture with Dimethyl Sulfoxide for High Drug Metabolism in HepaRG Cells.
van der Mark, Vincent A; Rudi de Waart, D; Shevchenko, Valery; Elferink, Ronald P J Oude; Chamuleau, Robert A F M; Hoekstra, Ruurdtje
Dimethylsulfoxide (DMSO) induces cellular differentiation and expression of drug metabolic enzymes in the human liver cell line HepaRG; however, DMSO also induces cell death and interferes with cellular activities. The aim of this study was to examine whether overexpression of the constitutive androstane receptor (CAR, NR1I3), the nuclear receptor controlling various drug metabolism genes, would sufficiently promote differentiation and drug metabolism in HepaRG cells, optionally without using DMSO. By stable lentiviral overexpression of CAR, HepaRG cultures were less affected by DMSO in total protein content and obtained increased resistance to acetaminophen- and amiodarone-induced cell death. Transcript levels of CAR target genes were significantly increased in HepaRG-CAR cultures without DMSO, resulting in increased activities of cytochrome P450 (P450) enzymes and bilirubin conjugation to levels equal or surpassing those of HepaRG cells cultured with DMSO. Unexpectedly, CAR overexpression also increased the activities of non-CAR target P450s, as well as albumin production. In combination with DMSO treatment, CAR overexpression further increased transcript levels and activities of CAR targets. Induction of CYP1A2 and CYP2B6 remained unchanged, whereas CYP3A4 was reduced. Moreover, the metabolism of low-clearance compounds warfarin and prednisolone was increased. In conclusion, CAR overexpression creates a more physiologically relevant environment for studies on hepatic (drug) metabolism and differentiation in HepaRG cells without the utilization of DMSO. DMSO still may be applied to accomplish higher drug metabolism, required for sensitive assays, such as low-clearance studies and identification of (rare) metabolites, whereas reduced total protein content after DMSO culture is diminished by CAR overexpression. Copyright © 2016 by The American Society for Pharmacology and Experimental Therapeutics.
Transition-Metal-Free Highly Efficient Aerobic Oxidation of Sulfides to Sulfoxides under Mild Conditions
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Hua Zhang
Full Text Available A highly efficient transition-metal-free catalytic system Br2/NaNO2/H2O has been developed for a robust and economic acid-free aerobic oxidation of sulfides. It is noteworthy that the sulfide function reacts under mild conditions without over-oxidation to sulfone. The role of NaNO2as an efficient NO equivalent for the activation of molecular oxygen was identified. Under the optimal conditions, a broad range of sulfide substrates were converted into their corresponding sulfoxides in high yields by molecular oxygen. The present catalytic system utilizes cheap and readily available agents as the catalysts, exhibits high selectivity for sulfoxide products and releases only innocuous water as the by-products.
Determination of the impurities in drug products containing montelukast and in silico/in vitro genotoxicological assessments of sulfoxide impurity.
Emerce, Esra; Cok, Ismet; Degim, I Tuncer
Impurities affecting safety, efficacy, and quality of pharmaceuticals are of increasing concern for regulatory agencies and pharmaceutical industries, since genotoxic impurities are understood to play important role in carcinogenesis. The study aimed to analyse impurities of montelukast chronically used in asthma theraphy and perform genotoxicological assessment considering regulatory approaches. Impurities (sulfoxide, cis-isomer, Michael adducts-I&II, methylketone, methylstyrene) were quantified using RP-HPLC analysis on commercial products available in Turkish market. For sulfoxide impurity, having no toxicity data and found to be above the qualification limit, in silico mutagenicity prediction analysis, miniaturized bacterial gene mutation test, mitotic index determination and in vitro chromosomal aberration test w/wo metabolic activation system were conducted. In the analysis of different batches of 20 commercial drug products from 11 companies, only sulfoxide impurity exceeded qualification limit in pediatric tablets from 2 companies and in adult tablets from 7 companies. Leadscope and ToxTree programs predicted sulfoxide impurity as nonmutagenic. It was also found to be nonmutagenic in Ames MPF Penta I assay. Sulfoxide impurity was dose-dependent cytotoxic in human peripheral lymphocytes, however, it was found to be nongenotoxic. It was concluded that sulfoxide impurity should be considered as nonmutagenic and can be classified as ordinary impurity according to guidelines. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.
Study on the synthesis of dimethyl 1,4-cyclohexanedicarboxylate by catalytic hydrogenation of dimethyl terephthalate
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LI Yuanhua
Full Text Available In the field of polymer industry,1,4-cyclohexanedimethanol (CHDM occupies an important position especially for the synthesis of highly valued polyester products.In industry,CHDM is prepared from dimethyl terephthalate (DMT through a two-step hydrogenation process Palladium supported on magnesium oxide (Pd/MgO was prepared by animpregnation method and was characterized by x-ray diffraction (XRD,transmission electron microscope (TEM and scan electron microscope (SEM.During the hydrogenation of DMT to synthesize dimethyl 1,4-cyclohexanedicarboxylate (DMCD,the as-prepared Pd/MgO was used as the catalyst with methyl acetate as the solvent.Under optimized reaction conditions (reaction temperature:180 ℃,reaction pressure:4.5 MPa,the conversion of DMT was 100% and the selectivity of DMCD was 99%.Such a catalyst shows a good potential in industrial applications.
Enantioselective synthesis of the novel chiral sulfoxide derivative as a glycogen synthase kinase 3beta inhibitor.
Saitoh, Morihisa; Kunitomo, Jun; Kimura, Eiji; Yamano, Toru; Itoh, Fumio; Kori, Masakuni
Glycogen synthase kinase 3beta (GSK-3beta) inhibitors are expected to be attractive therapeutic agents for the treatment of Alzheimer's disease (AD). Recently we discovered sulfoxides (S)-1 as a novel GSK-3beta inhibitor having in vivo efficacy. We investigated practical asymmetric preparation methods for the scale-up synthesis of (S)-1. The highly enantioselective synthesis of (S)-1 (94% ee) was achieved by titanium-mediated oxidation with D-(-)-diethyl tartrate on gram scale.
Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation
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Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.; Yang, Yuan; Seifert, Soenke; Yan, Yushan; Mark Maupin, C.; Liberatore, Matthew W.; Herring, Andrew M.
A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXS revealed a cation scattering peak with a d-spacing from 7 to 15 A. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 degrees C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. This is particularly true for the film cast from ethyl lactate.
Studies of a novel cysteine sulfoxide lyase from Petiveria alliacea: the first heteromeric alliinase.
Musah, Rabi A; He, Quan; Kubec, Roman; Jadhav, Abhijit
A novel alliinase (EC 22.214.171.124) was detected and purified from the roots of the Amazonian medicinal plant Petiveria alliacea. The isolated enzyme is a heteropentameric glycoprotein composed of two alpha-subunits (68.1 kD each), one beta-subunit (56.0 kD), one gamma-subunit (24.8 kD), and one delta-subunit (13.9 kD). The two alpha-subunits are connected by a disulfide bridge, and both alpha- and beta-subunits are glycosylated. The enzyme has an isoelectric point of 4.78 and pH and temperature optima of 8.0 and approximately 52 degrees C, respectively. Its activation energy with its natural substrate S-benzyl-l-cysteine sulfoxide is 64.6 kJ mol(-1). Kinetic studies showed that both K(m) and V(max) vary as a function of substrate structure, with the most preferred substrates being the naturally occurring P. alliacea compounds S-benzyl-l-cysteine sulfoxide and S-2-hydroxyethyl-l-cysteine sulfoxide. The alliinase reacts with these substrates to produce S-benzyl phenylmethanethiosulfinate and S-(2-hydroxyethyl) 2-hydroxyethanethiosulfinate, respectively.
Neutrophil granulocytes uniquely express, among human blood cells, high levels of Methionine-sulfoxide-reductase enzymes.
Achilli, Cesare; Ciana, Annarita; Rossi, Antonio; Balduini, Cesare; Minetti, Giampaolo
L-Methionine (Met), in its free form or when inserted in proteins, is sensitive to oxidation of its thioether group by reactive oxygen species from exogenous or endogenous sources. Two stable diastereomers of Met sulfoxide [Met-(O)] may be formed [Met-S-(O) and Met-R-(O)], but these can be reduced by two classes of Methionine-sulfoxide-reductase (Msr) enzymes: MsrA, which reduces the S, and MsrB, which reduces the R sulfoxide. In this study, we have examined the levels of expression of Msr in human blood cells by enzymatic activity assay, Western blotting, and RT-PCR of purified populations of polymorphonuclear neutrophils and eosinophils, mononuclear cells, platelets, and erythrocytes. Our data indicate that of the blood cells analyzed, neutrophils expressed the highest activity, which was mainly of MsrB type. During degranulation of activated neutrophils, Msr activity was not released but remained confined within the cell, indicating a non-granular localization. Immunoprecipitation and RT-PCR studies indicated the almost complete lack of mitochondrial forms of Msrs in granulocytes. It is thus likely that Msrs are important as antioxidant/repair systems for neutrophils, cells with enormous capacity for the generation of reactive oxidants and hence, susceptible to oxidative damage.
Electrochemical degradation of dimethyl phthalate ester on a DSA® electrode
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Souza, Fernanda L.; Aquino, Jose M.; Miwa, Douglas W.; Motheo, Artur J. [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Instituto de Quimica; Rodrigo, Manuel A., E-mail: firstname.lastname@example.com [Department of Chemical Engineering, Faculty of Chemical Sciences and Technologies, Universidad de Castilla - La Mancha, Ciudad Real (Spain)
The electrochemical degradation of dimethyl phthalate (DMP) using a one-compartment filter press flow cell and a commercial dimensionally stable anode (DSA®) is presented. The best electrolysis conditions were determined by the analysis of the influence of the nature and concentration of the support electrolyte, pH, current density and temperature. The abatement of DMP concentration and total organic carbon (TOC) removal were superior in the presence of NaCl, as well as the apparent first order kinetic constants. Using constant ionic strength at 0.15 mol dm{sup -3} by adding Na{sub 2}SO{sub 4}, DMP concentration decreases faster at relative low NaCl concentrations while the TOC removal after 1 h of electrolysis increases with NaCl concentration. The DMP removal was very similar for all the current densities investigated at acidic solutions. When electric energy saving is considered, since the electrochemical system was under mass transport conditions, the best operational option is to use low current density values. (author)
Biodegradation of Dimethyl Phthalate by Freshwater Unicellular Cyanobacteria.
Zhang, Xiaohui; Liu, Lincong; Zhang, Siping; Pan, Yan; Li, Jing; Pan, Hongwei; Xu, Shiguo; Luo, Feng
The biodegradation characteristics of dimethyl phthalate (DMP) by three freshwater unicellular organisms were investigated in this study. The findings revealed that all the organisms were capable of metabolizing DMP; among them, Cyanothece sp. PCC7822 achieved the highest degradation efficiency. Lower concentration of DMP supported the growth of the Cyanobacteria; however, with the increase of DMP concentration growth of Cyanobacteria was inhibited remarkably. Phthalic acid (PA) was detected to be an intermediate degradation product of DMP and accumulated in the culture solution. The optimal initial pH value for the degradation was detected to be 9.0, which mitigated the decrease of pH resulting from the production of PA. The optimum temperature for DMP degradation of the three species of organisms is 30°C. After 72 hours' incubation, no more than 11.8% of the residual of DMP aggregated in Cyanobacteria cells while majority of DMP remained in the medium. Moreover, esterase was induced by DMP and the activity kept increasing during the degradation process. This suggested that esterase could assist in the degradation of DMP.
Heat capacities and asymmetric criticality of the (liquid + liquid) coexistence curves for {dimethyl carbonate + n-undecane, or n-tridecane}
International Nuclear Information System (INIS)
Chen, Zhiyun; Shi, Aiqin; Liu, Shixia; Yin, Tianxiang; Shen, Weiguo
Highlights: • Coexistence curves of dimethyl carbonate + n-undecane (or + n-tridecane) were measured. • Isobaric heat capacity per unit volume of critical binary solutions dimethyl carbonate + n-undecane (or + n-tridecane) were determined. • The critical exponent β are consistent with the 3D-Ising value. • The asymmetry of the coexistence curves were discussed by the complete scaling theory. - Abstract: The (liquid + liquid) coexistences and the critical behavior of isobaric heat capacity per unit volume for critical binary solutions {dimethyl carbonate + n-undecane, or n-tridecane} have been studied. The critical exponents β and α were deduced and found to be consistent with the 3D-Ising values. The critical amplitudes were determined and used to test the asymmetric criticality of coexistence curves. It was found that the heat capacity does play an important role in describing the asymmetric criticality of the coexistence curves
Hyperspectral Analysis for Standoff Detection of Dimethyl ...
Journal Article Detecting organophosphates in indoor settings requires more efficient and faster methods of surveying large surface areas than conventional approaches, which sample small surface areas followed by extraction and analysis. This study examined a standoff detection technique utilizing hyperspectral imaging for analysis of building materials in near-real time. In this proof-of-concept study, dimethyl methylphosphonate (DMMP) was applied to stainless steel and laminate coupons and spectra were collected during active illumination. Absorbance bands at approximately 1275 cm-1 and 1050 cm-1 were associated with phosphorus-oxygen double bond (P=O) and phosphorus-oxygen-carbon (P-O-C) bond stretches of DMMP, respectively. The magnitude of these bands increased linearly (r2 = 0.93) with DMMP across the full absorbance spectrum, between ν1 = 877 cm-1 to ν2 = 1262 cm-1. Comparisons between bare and contaminated surfaces on stainless steel using the spectral contrast angle technique indicated that the bare samples showed no sign of contamination, with large uniformly distributed contrast angles of 45˚-55˚, while the contaminated samples had smaller spectral contact angles of 40° in the uncontaminated region. The laminate contaminated region exhibited contact angles of detect DMMP on building materials, with detection levels similar to c
Extraction of U(VI) with N,N'-dimethyl-N,N'-dioctylsuccinylamide in toluene
International Nuclear Information System (INIS)
Cui Yu; Shandong University, Jinan; Sun Guoxin; Zhang Zhenwei; Hu Yufen; Sun Sixiu
The extraction of uranyl nitrate by the novel extractant N,N'-dimethyl-N,N'-dioctylsuccinylamide (DMDOSA) from aqueous nitric/nitrate solutions was investigated. The effects of concentration of HNO 3 and DMDOSA on the U(VI) extraction distribution was studied. The extraction mechanism was established and the stoichiometry of the main extracted species was confirmed to be UO 2 (NO 3 ) 2 x 2DMDOSA. The value of ΔH of the extraction is -23.9±1.7 kJ x mol -1 . A IR spectral study of the U(VI) extracted species was also made. (author)
Diclofenac topical solution compared with oral diclofenac: a pooled safety analysis
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Roth SH
Full Text Available Sanford H Roth1, Philip Fuller21Arizona Research and Education, Arthritis Laboratory, Arizona State University, Phoenix, AZ, USA; 2Medical Affairs, Covidien, Hazelwood, MO, USABackground: Topical nonsteroidal anti-inflammatory drug (NSAID formulations, which produce less systemic exposure compared with oral formulations, are an option for the management of osteoarthritis (OA. However, the overall safety and efficacy of these agents compared with oral or systemic therapy remains controversial.Methods: Two 12-week, double-blind, double-dummy, randomized, controlled, multicenter studies compared the safety and efficacy profiles of diclofenac topical solution (TDiclo with oral diclofenac (ODiclo. Each study independently showed that TDiclo had similar efficacy to ODiclo. To compare the safety profiles of TDiclo and ODiclo, a pooled safety analysis was performed for 927 total patients who had radiologically confirmed symptomatic OA of the knee. This pooled analysis included patients treated with TDiclo, containing 45.5% dimethyl sulfoxide (DMSO, and those treated with ODiclo. Safety assessments included monitoring of adverse events (AEs, recording of vital signs, dermatologic evaluation of the study knee, and clinical laboratory evaluation.Results: AEs occurred in 312 (67.1% patients using TDiclo versus 298 (64.5% of those taking ODiclo. The most common AE with TDiclo was dry skin at the application site (24.1% vs 1.9% with ODiclo; P < 0.0001. Fewer gastrointestinal (25.4% vs 39.0%; P < 0.0001 and cardiovascular (1.5% vs 3.5%; P = 0.055 AEs occurred with TDiclo compared with ODiclo. ODiclo was associated with significantly greater increases in liver enzymes and creatinine, and greater decreases in creatinine clearance and hemoglobin (P < 0.001 for all.Conclusions: These findings suggest that TDiclo represents a useful alternative to oral NSAID therapy in the management of OA, with a more favorable safety profile.Keywords: diclofenac, gastropathy
Sulfoxide stimulation of chondrogenesis in limb mesenchyme is accompanied by an increase in type II collagen enhancer activity
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Horton, W.E. Jr.; Higginbotham, J.D. (National Institute on Aging, Baltimore, MD (USA))
We have utilized a modification of the limb bud mesenchyme micromass culture system to screen compounds that might stimulate chondrogenesis. Two compounds in the sulfoxide family (methylphenylsulfoxide and p-chlorophenyl methyl sulfoxide) were stimulatory at 10(-2) M and 10(-3) M, respectively; whereas other sulfoxides and organic solvents were not active at these concentrations. In addition, specific growth factors (basic FGF, IGF-I, IGF-II) were not chondroinductive at concentrations that are active in other cell systems. Both sulfoxide compounds stimulated cartilage nodule formation, ({sup 35}S)sulfate incorporation, and activity of the regulatory sequences of the collagen II gene. In contrast, transforming growth factor beta-1 (10 ng/ml) stimulated sulfate incorporation but produced only a diffuse deposition of cartilage matrix and reduced the ability of the cells to utilize the regulatory sequences of the collagen II gene. The sulfoxides appear to promote the differentiation of limb bud cells to chondrocytes and thus exhibit chondroinductive activity.
Sulfoxide stimulation of chondrogenesis in limb mesenchyme is accompanied by an increase in type II collagen enhancer activity
International Nuclear Information System (INIS)
Horton, W.E. Jr.; Higginbotham, J.D.
We have utilized a modification of the limb bud mesenchyme micromass culture system to screen compounds that might stimulate chondrogenesis. Two compounds in the sulfoxide family (methylphenylsulfoxide and p-chlorophenyl methyl sulfoxide) were stimulatory at 10(-2) M and 10(-3) M, respectively; whereas other sulfoxides and organic solvents were not active at these concentrations. In addition, specific growth factors (basic FGF, IGF-I, IGF-II) were not chondroinductive at concentrations that are active in other cell systems. Both sulfoxide compounds stimulated cartilage nodule formation, [ 35 S]sulfate incorporation, and activity of the regulatory sequences of the collagen II gene. In contrast, transforming growth factor beta-1 (10 ng/ml) stimulated sulfate incorporation but produced only a diffuse deposition of cartilage matrix and reduced the ability of the cells to utilize the regulatory sequences of the collagen II gene. The sulfoxides appear to promote the differentiation of limb bud cells to chondrocytes and thus exhibit chondroinductive activity
Effects of vehicle microdialysis solutions on cutaneous vascular responses to local heating.
Smith, Caroline J; Craighead, Daniel H; Alexander, Lacy M
Microdialysis is a minimally invasive technique often paired with laser Doppler flowmetry to examine cutaneous microvascular function, yet presents with several challenges, including incompatibility with perfusion of highly lipophilic compounds. The present study addresses this methodological concern, with an emphasis on the independent effects of commonly used vehicle dialysis solutions to improve solubility of pharmacological agents with otherwise low aqueous solubility. Four microdialysis fibers were placed in the ventral forearm of eight subjects (4 men, 4 women; 25 ± 1 yr) with sites randomized to serve as 1) control (lactated Ringer's), 2) Sodium carbonate-bicarbonate buffer administered at physiological pH [SCB-HCl; pH 7.4, achieved via addition of hydrochloric acid (HCl)], 3) 0.02% ethanol, and 4) 2% dimethyl sulfoxide (DMSO). After baseline (34°C), vehicle solutions were administered throughout a standardized local heating protocol to 42°C. Laser Doppler flowmetry provided an index of blood flow. Cutaneous vascular conductance was calculated and normalized to maximum (%CVC max , sodium nitroprusside and 43°C local heat). The SCB-HCl solution increased baseline %CVC max (control: 9.7 ± 0.8; SCB-HCl: 21.5 ± 3.5%CVC max ; P = 0.03), but no effects were observed during heating or maximal vasodilation. There were no differences with perfusion of ethanol or DMSO at any stage of the protocol ( P > 0.05). These data demonstrate the potential confounding effects of some vehicle dialysis solutions on cutaneous vascular function. Notably, this study provides evidence that 2% DMSO and 0.02% ethanol are acceptable vehicles with no confounding local vascular effects to a standardized local heating protocol at the concentrations presented. NEW & NOTEWORTHY This study examined the independent effects of common vehicle solutions on cutaneous vascular responses. A basic buffer (SCB-HCl) caused baseline vasodilation; 2% DMSO and 0.02% ethanol had no effects
Radiolabelling and evaluation of a novel sulfoxide as a PET imaging agent for tumor hypoxia
International Nuclear Information System (INIS)
Laurens, Evelyn; Yeoh, Shinn Dee; Rigopoulos, Angela; Cao, Diana; Cartwright, Glenn A.; O'Keefe, Graeme J.; Tochon-Danguy, Henri J.; White, Jonathan M.; Scott, Andrew M.; Ackermann, Uwe
[ 18 F]FMISO is the most widely validated PET radiotracer for imaging hypoxic tissue. However, as a result of the pharmacokinetics of [ 18 F]FMISO a 2 h wait between tracer administration and patient scanning is required for optimal image acquisition. In order to develop hypoxia imaging agents with faster kinetics, we have synthesised and evaluated several F-18 labelled anilino sulfoxides. In this manuscript we report on the synthesis, in vitro and in vivo evaluation of a novel fluoroethyltriazolyl propargyl anilino sulfoxide. The radiolabelling of the novel tracer was achieved via 2-[ 18 F]fluoroethyl azide click chemistry. Radiochemical yields were 23 ± 4% based on 2-[ 18 F]fluoroethyl azide and 7 ± 2% based on K[ 18 F]F. The radiotracer did not undergo metabolism or defluorination in an in vitro assay using S9 liver fractions. Imaging studies using SK-RC-52 tumors in BALB/c nude mice have indicated that the tracer may have a higher pO 2 threshold than [ 18 F]FMISO for uptake in hypoxic tumors. Although clearance from muscle was faster than [ 18 F]FMISO, uptake in hypoxic tumors was slower. The average tumor to muscle ratio at 2 h post injection in large, hypoxic tumors with a volume greater than 686 mm 3 was 1.7, which was similar to the observed ratio of 1.75 for [ 18 F]FMISO. Although the new tracer showed improved pharmacokinetics when compared with the previously synthesised sulfoxides, further modifications to the chemical structure need to be made in order to offer significant in vivo imaging advantages over [ 18 F]FMISO
Theoretical methodology for prediction of tropospheric oxidation of dimethyl phosphonate and dimethyl methylphosphonate.
Cory, Marshall G; Taylor, DeCarlos E; Bunte, Steven W; Runge, Keith; Vasey, Joseph L; Burns, Douglas S
Rate constants for the reactions of OH radicals with dimethyl phosphonate [DMHP, (CH(3)O)(2)P(O)H] and dimethyl methylphosphonate [DMMP, (CH(3)O)(2)P(O)CH(3)] have been calculated by ab initio structural methods and semiclassical dynamics modeling and compared with experimental measurements over the temperature range 250-350 K. The structure and energetics of reactants and transition structures are determined for all hydrogen atom abstraction pathways that initiate the atmospheric oxidation mechanism. Structures are obtained at the CCSD/6-31++G** level of chemical theory, and the height of the activation barrier is determined by a variant of the G2MP2 method. A Transfer Hamiltonian is used to compute the minimum energy path in the neighborhood of the transition state (TS). This calculation provides information about the curvature of the potential energy surface in the neighborhood of the TS, as well as the internal forces that are needed by the semiclassical flux-flux autocorrelation function (SCFFAF) dynamics model used to compute the temperature-dependent reaction rate constants for the various possible abstraction pathways. The computed temperature-dependent rate curves frequently lie within the experimental error bars.
Synthesis and Nrf2 Activating Ability of Thiourea and Vinyl Sulfoxide Derivatives
Energy Technology Data Exchange (ETDEWEB)
Shim, Young Sun; Hwang, Hyun Sook; Nam, Ghilsoo; Choi, Kyung Il [Korea Institute of Science and Technology, Seoul (Korea, Republic of)
Thiourea and vinyl sulfoxide derivatives were designed based on the structures of sulforaphene and gallic acid, prepared and tested for HO-1 inducing activity as a measure of Nrf2 activation, and inhibitory effect on NO production as a measure of anti-inflammatory activity. Both series of compounds showed moderate activity on HO-1 induction, and no inhibitory effect on NO production. Interestingly the thiourea compound 6d showed better HO-1 induction (71% SFN) than the corresponding isothiocyanate compound 6a (55% SFN). Overall, it seemed that more efficient electrophile is needed to get more effective Nrf2 activator.
The role of molecular conformation and polarizable embedding for one- and two-photon absorption of disperse orange 3 in solution.
Silva, Daniel L; Murugan, N Arul; Kongsted, Jacob; Rinkevicius, Zilvinas; Canuto, Sylvio; Ågren, Hans
Solvent effects on the one- and two-photon absorption (1PA and 2PA) of disperse orange 3 (DO3) in dimethyl sulfoxide (DMSO) are studied using a discrete polarizable embedding (PE) response theory. The scheme comprises a quantum region containing the chromophore and an atomically granulated classical region for the solvent accounting for full interactions within and between the two regions. Either classical molecular dynamics (MD) or hybrid Car-Parrinello (CP) quantum/classical (QM/MM) molecular dynamics simulations are employed to describe the solvation of DO3 in DMSO, allowing for an analysis of the effect of the intermolecular short-range repulsion, long-range attraction, and electrostatic interactions on the conformational changes of the chromophore and also the effect of the solute-solvent polarization. PE linear response calculations are performed to verify the character, solvatochromic shift, and overlap of the two lowest energy transitions responsible for the linear absorption spectrum of DO3 in DMSO in the visible spectral region. Results of the PE linear and quadratic response calculations, performed using uncorrelated solute-solvent configurations sampled from either the classical or hybrid CP QM/MM MD simulations, are used to estimate the width of the line shape function of the two electronic lowest energy excited states, which allow a prediction of the 2PA cross-sections without the use of empirical parameters. Appropriate exchange-correlation functionals have been employed in order to describe the charge-transfer process following the electronic transitions of the chromophore in solution.
Dynamic kinetic resolution of allylic sulfoxides by Rh-catalyzed hydrogenation: a combined theoretical and experimental mechanistic study.
Dornan, Peter K; Kou, Kevin G M; Houk, K N; Dong, Vy M
A dynamic kinetic resolution (DKR) of allylic sulfoxides has been demonstrated by combining the Mislow [2,3]-sigmatropic rearrangement with catalytic asymmetric hydrogenation. The efficiency of our DKR was optimized by using low pressures of hydrogen gas to decrease the rate of hydrogenation relative to the rate of sigmatropic rearrangement. Kinetic studies reveal that the rhodium complex acts as a dual-role catalyst and accelerates the substrate racemization while catalyzing olefin hydrogenation. Scrambling experiments and theoretical modeling support a novel mode of sulfoxide racemization which occurs via a rhodium π-allyl intermediate in polar solvents. In nonpolar solvents, however, the substrate racemization is primarily uncatalyzed. Computational studies suggest that the sulfoxide binds to rhodium via O-coordination throughout the catalytic cycle for hydrogenation.
Asymmetric Dimethyl Arginine in Hypothyroid Patients
International Nuclear Information System (INIS)
Abdel-Messeih, P.L.
Thyroid diseases may lead to endothelial dysfunction, however, the mechanism underlying the endothelial dysfunction in thyroid disease is still not clear. Asymmetric dimethyl arginine (ADMA), a novel inhibitor of endothelial nitric oxide synthetase (eNOS), was reported to inhibit nitric oxide (NO) synthesis from L-arginine. The present study was carried out to investigate ADMA levels together with effects of dislipidemia in sub-clinical and overt hypothyroid females. There were significant increase in the levels of total cholesterol, low density lipoprotein-cholesterol (LDL-c), high density lipoprotein-cholesterol (HDL-c), thyroid stimulating hormone (TSH) and ADMA in hypothyroid females as compared to controls while the levels of NO and free T 4 were significantly decreased than controls. Sub-clinical hypothyroid females had significant high TSH, LDL-c and non-significantly high ADMA levels and total cholesterol as compared to controls while they had significant decrease in NO, HDL-c and non-significant decrease in free T 4 as compared to controls. There were significant negative correlations between NO and both ADMA (r 2 = 0.84) and free T 4 (r 2 = 0.95) in overt hypothyroid group while significant positive correlation (r 2 = 0.85) was detected between TSH and HDL-c in the same group. These results are highly suggestive that the decrease of nitric oxide secondary to accumulation of ADMA represent an important pathogenic factor together with dyslipidemia in endothelial dysfunction and increased cardiovascular risk especially in hypothyroid females
Lanthanide extraction with 2,5-dimethyl-2-hydroxyhexanoic acid
International Nuclear Information System (INIS)
Miller, J.H.
This research is concerned with the solvent extraction into chloroform of the lanthanides, using 2,5-dimethyl-2-hydroxyhexanoic acid (DMHHA). This acid is the first α-hydroxy aliphatic acid to be studied as an extracting agent for the lanthanides. The chloroform-water DMHHA partition constant was determined to be 1.0 (at 0.1 M ionic strength and 25 0 C). The acid dimerizes in chloroform with a constant of 56. The light lanthanides can be extracted into chloroform by forming complexes with the DMHHA anions. The extracted metal species is highly aggregated. This extraction has a solubility limit which increases with the addition of unionized acid. The resultant extract is also highly aggregated. At unionized acid-to-metal ratios greater than one, extractions first occur followed by the slow precipitation of the lanthanide. At the tracer level, neodymium is extracted primarily as NdA 3 (HA) 5 and (NdA 3 ) 2 (HA)/sub q/. Very small amounts of (NdA 3 ) 2 and other metal aggregates are also present. The heavy lanthanides do not extract from solutions of DMHHA and its potassium salt, but form aqueous emulsions and precipitates. In the presence of the organic soluble tetrabutylammonium ion the heavy lanthanides can be extracted, presumably as ion pairs. The stability constants of the light lanthanides and DMHHA were determined. The separation factors obtained from DMHHA extractions of the light lanthanides were also investigated and found to be comparable to those obtained employing normal aliphatic carboxylic acid
Palladium-Catalyzed Enantioselective C-H Olefination of Diaryl Sulfoxides through Parallel Kinetic Resolution and Desymmetrization.
Zhu, Yu-Chao; Li, Yan; Zhang, Bo-Chao; Zhang, Feng-Xu; Yang, Yi-Nuo; Wang, Xi-Sheng
The first example of Pd II -catalyzed enantioselective C-H olefination with non-chiral or racemic sulfoxides as directing groups was developed. A variety of chiral diaryl sulfoxides were synthesized with high enantioselectivity (up to 99 %) through both desymmetrization and parallel kinetic resolution (PKR). This is the first report of Pd II -catalyzed enantioselective C(sp 2 )-H functionalization through PKR, and it represents a novel strategy to construct sulfur chiral centers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Evidence for participation of the methionine sulfoxide reductase repair system in plant seed longevity.
Châtelain, Emilie; Satour, Pascale; Laugier, Edith; Ly Vu, Benoit; Payet, Nicole; Rey, Pascal; Montrichard, Françoise
Seeds are in a natural oxidative context leading to protein oxidation. Although inevitable for proper progression from maturation to germination, protein oxidation at high levels is detrimental and associated with seed aging. Oxidation of methionine to methionine sulfoxide is a common form of damage observed during aging in all organisms. This damage is reversible through the action of methionine sulfoxide reductases (MSRs), which play key roles in lifespan control in yeast and animal cells. To investigate the relationship between MSR capacity and longevity in plant seeds, we first used two Medicago truncatula genotypes with contrasting seed quality. After characterizing the MSR family in this species, we analyzed gene expression and enzymatic activity in immature and mature seeds exhibiting distinct quality levels. We found a very strong correlation between the initial MSR capacities in different lots of mature seeds of the two genotypes and the time to a drop in viability to 50% after controlled deterioration. We then analyzed seed longevity in Arabidopsis thaliana lines, in which MSR gene expression has been genetically altered, and observed a positive correlation between MSR capacity and longevity in these seeds as well. Based on our data, we propose that the MSR repair system plays a decisive role in the establishment and preservation of longevity in plant seeds.
Novel electrochemical route to cleaner fuel dimethyl ether.
Cassone, Giuseppe; Pietrucci, Fabio; Saija, Franz; Guyot, François; Sponer, Jiri; Sponer, Judit E; Saitta, A Marco
Methanol, the simplest alcohol, and dimethyl ether, the simplest ether, are central compounds in the search for alternative "green" combustion fuels. In fact, they are generally considered as the cornerstones of the envisaged "Methanol Economy" scenario, as they are able to efficiently produce energy in an environmentally friendly manner. However, despite a massive amount of research in this field, the synthesis of dimethyl ether from liquid methanol has never so far been reported. Here we present a computational study, based on ab initio Molecular Dynamics, which suggests a novel synthesis route to methanol dehydration - leading thus to the dimethyl ether synthesis - through the application of strong electric fields. Besides proving the impressive catalytic effects afforded by the field, our calculations indicate that the obtained dimethyl ether is stable and that it can be progressively accumulated thanks to the peculiar chemical pathways characterising the methanol reaction network under electric field. These results suggest that the experimental synthesis of dimethyl ether from liquid methanol could be achieved, possibly in the proximity of field emitter tips.
CCDC 1036601: Experimental Crystal Structure Determination : bis(dimethyl sulfoxide)-(1,3,6,8,11,13,16,18-octaazapentacyclo[184.108.40.206,6.18,11.113,16]tetracosa-4,9,14,19-tetraene-21,22,23,24-tetraylidene)-iron bis(hexafluorophosphate) dimethyl sulfoxide solvate
Anneser, Markus R.
An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
CCDC 974613: Experimental Crystal Structure Determination : catena-[bis(mu-5,5',5''-(1,3,4,6,7,9,9b-heptaazaphenalene-2,5,8-triyltriimino)triisophthalato)-tris(dimethyl sulfoxide)-triaqua-hexa-copper dimethyl sulfoxide solvate hydrate
Luebke, Ryan
An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Syntheses of Labeled Dimethyl Phthalate-D6
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XU Zhong-jie;LU Wei-jing;SUN Wen;JIANG Zhe;LI Bing-yao;PAN Jie
Full Text Available The synthesis of labeled standard dimethyl phthalate-D6,with CD3OD and benzene anhydride as raw materials by an efficient and no-dilution of isotopic enrichment method was presented, under the catalysis of condensing agent to generate dimethyl phthalate-D6。The yield of dimethyl phthalate-D6 was 88.0% based on CD3OD consumed.The product was confirmed by NMR and MS to be target compound.Its chemical purity was 99.0% and isotopic enrichment was 99.1 atom % D.The result showed that It could be used as internal standard in the field of food safety testing.
Vitrification of pronuclear-stage mouse embryos on solid surface (SSV) versus in cryotube: comparison of the effect of equilibration time and different sugars in the vitrification solution.
Bagis, H; Sagirkaya, H; Mercan, H Odaman; Dinnyès, A
The cryopreservation of pronuclear-stage embryos has particular importance in transgenic technology and human assisted reproductive technology (ART). The objective of this study was to improve the efficiency of cryopreservation of pronuclear-stage mouse embryos. Two vitrification methods (solid surface vitrification (SSV) vs. vitrification in cryotube) have been compared with special emphasis on the effect of the exposure of the embryos to the solutions for various times and the sugar content (trehalose, sucrose, or raffinose) of the vitrification solutions. Pronuclear-stage embryos were either exposed to 1 M dimethyl sulfoxide (DMSO) + 1 M propylene-glycol (PG) solution for 2, 5, 10, or 15 min or not exposed to this "equilibration" solution. The vitrification solutions consisted of 2.75 M DMSO and 2.75 M PG in M2 medium supplemented with 1 M trehalose (DPT), 1 M sucrose (DPS), or 1 M raffinose (DPR). In the cryotube method, groups of 15-25 embryos were transferred into a 1.8 ml cryotube containing 30 microl of DPT, DPS, or DPR. After 30 sec, the cryotubes were directly plunged into liquid nitrogen (LN(2)) and stored for 1 day to 1 month. Vitrified samples were warmed by immersing the cryotubes in a 40 degrees C water bath and then immediately diluted with 300 microl of 0.3 M trehalose, sucrose, or raffinose in M2. In the SSV method, after equilibration 15-20 embryos were exposed to DPT, DPS, or DPR solutions for around 20 sec before being dropped in 2-microl drops onto a pre-cooled (-150 to -180 degrees C) metal surface. Vitrified droplets were stored in cryovials in LN(2). Warming was performed by transferring the vitrified droplets into 0.3 M solutions of trehalose, sucrose, or raffinose at 37 degrees C, respectively. Results showed that both SSV and cryotube vitrification methods can result in high rates of in vitro blastocyst development (up to 58.3 and 68.5% with DPR, respectively), not statistically different from that of the controls (58.3 and 64.4%). Even
Study of the solution thermal conductivity effect on nonlinear refraction of colloidal gold nanoparticles
Sarkhosh, L.; Mansour, N.
In nanoparticle colloidal systems, the thermal nonlinearity is affected by the thermal parameters of the surrounding solution. Having a low temperature gradient rate solution may be a key factor in producing high thermal nonlinear properties in colloids. In this manuscript, the effect of the thermal conductivity of the surrounding liquid environment on the thermal nonlinear refraction of gold nanoparticles (AuNPs) synthesized by laser ablation of a gold target in different solutions is investigated. Gold nanoparticles colloids have been fabricated by the nanosecond pulsed laser ablation of a pure gold plate in different liquid environments with a thermal conductivity range of 0.14-0.60 W mK-1 including cyclohexanone, castor oil, dimethyl sulfoxide, ethylene glycol, glycerin and water. The AuNPs colloids exhibit a UV-Vis absorption spectrum with a surface plasmon absorption peak at about 540 ± 20 nm. The thermal nonlinear optical responses of the gold colloids are measured using the Z-scan technique under low power CW laser irradiation at 532 nm near the surface plasmon peak of the nanoparticles. Our results show that the nonlinear refractive index of the nanoparticle colloids is considerably affected by the thermal conductivity of liquid medium. The largest nonlinear refractive index of -3.1 × 10-7 cm2 W-1 is obtained for AuNP in cyclohexanone with the lowest thermal conductivity of 0.14 W mK-1 whereas the lowest one of -0.1 × 10-7 cm2 W-1 is obtained for AuNP in water with the highest thermal conductivity of 0.60 W mK-1. This study shows that the nonlinear refractive index value of colloids can be controlled by the thermal conductivity of the used liquid's environment. This allows us to design low threshold optical limiters by choosing a solution with low thermal conductivity for colloidal nanoparticles.
Methionine sulfoxides on prion protein Helix-3 switch on the alpha-fold destabilization required for conversion.
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Giorgio Colombo
Full Text Available BACKGROUND: The conversion of the cellular prion protein (PrP(C into the infectious form (PrP(Sc is the key event in prion induced neurodegenerations. This process is believed to involve a multi-step conformational transition from an alpha-helical (PrP(C form to a beta-sheet-rich (PrP(Sc state. In addition to the conformational difference, PrP(Sc exhibits as covalent signature the sulfoxidation of M213. To investigate whether such modification may play a role in the misfolding process we have studied the impact of methionine oxidation on the dynamics and energetics of the HuPrP(125-229 alpha-fold. METHODOLOGY/PRINCIPAL FINDINGS: Using molecular dynamics simulation, essential dynamics, correlated motions and signal propagation analysis, we have found that substitution of the sulfur atom of M213 by a sulfoxide group impacts on the stability of the native state increasing the flexibility of regions preceding the site of the modification and perturbing the network of stabilizing interactions. Together, these changes favor the population of alternative states which maybe essential in the productive pathway of the pathogenic conversion. These changes are also observed when the sulfoxidation is placed at M206 and at both, M206 and M213. CONCLUSIONS/SIGNIFICANCE: Our results suggest that the sulfoxidation of Helix-3 methionines might be the switch for triggering the initial alpha-fold destabilization required for the productive pathogenic conversion.
Cryopreservation of zebrafish (Danio rerio) primordial germ cells by vitrification of yolk-intact and yolk-depleted embryos using various cryoprotectant solutions.
Higaki, Shogo; Kawakami, Yutaka; Eto, Yoshiki; Yamaha, Etsuro; Nagano, Masashi; Katagiri, Seiji; Takada, Tatsuyuki; Takahashi, Yoshiyuki
The aim of this study was to examine the effects of partial removal of yolk and cryoprotectant mixtures on the viability of cryopreserved primordial germ cells (PGCs) and elucidated the differentiation ability of cryopreserved PGCs in zebrafish. First, dechorionated yolk-intact and yolk-depleted (partially yolk removed) embryos, PGCs of which were labeled with green fluorescence protein (GFP), were vitrified after serial exposures to pretreatment solution (PS) and vitrification solution (VS) that contained ethylene glycol (EG), dimethyl sulfoxide (Me 2 SO) or propylene glycol at 3 and 5 M, respectively. Although partial removal of yolk improved the viability of cryopreserved PGCs, numbers of PGCs with pseudopodial movement were limited (0 to 2.6 cells/embryo). Next, yolk-depleted embryos were cryopreserved using mixtures of two types of cryoprotectants. The maximum survival rate of PGCs (81%; 9.6 cells/embryo) was obtained from the yolk-depleted embryos vitrified using PS containing 2 M EG + 1 M Me 2 SO and VS containing 3 M EG + 2 M Me 2 SO and 56% (5.3 cells/embryo) of PGCs showed pseudopodial movement. Finally, PGCs recovered from yolk-depleted embryos (wild-type) that were vitrified under the optimum condition were transplanted individually into 236 sterilized recipient blastulae (recessive light-colored). Seven recipients matured and generated progeny with characteristics inherited from the PGC donor. In conclusion, the authors confirmed the beneficial effects of partial removal of yolk on the viability of cryopreserved PGCs and that the viability of the PGCs was improved by using PS and VS that contained two types of cryoprotectants, especially PS containing 2 M EG + 1 M Me 2 SO and VS containing 3 M EG + 2 M Me 2 SO, and that recovered PGCs retained ability to differentiate into functional gametes. Copyright © 2013. Published by Elsevier Inc.
⁹⁹mTc pyrene derivative complex causes double-strand breaks in dsDNA mainly through cluster-mediated indirect effect in aqueous solution.
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Wei-Ju Chung
Full Text Available Radiation therapy for cancer patients works by ionizing damage to nuclear DNA, primarily by creating double-strand breaks (DSB. A major shortcoming of traditional radiation therapy is the set of side effect associated with its long-range interaction with nearby tissues. Low-energy Auger electrons have the advantage of an extremely short effective range, minimizing damage to healthy tissue. Consequently, the isotope ⁹⁹mTc, an Auger electron source, is currently being studied for its beneficial potential in cancer treatment. We examined the dose effect of a pyrene derivative ⁹⁹mTc complex on plasmid DNA by using gel electrophoresis in both aqueous and methanol solutions. In aqueous solutions, the average yield per decay for double-strand breaks is 0.011±0.005 at low dose range, decreasing to 0.0005±0.0003 in the presence of 1 M dimethyl sulfoxide (DMSO. The apparent yield per decay for single-strand breaks (SSB is 0.04±0.02, decreasing to approximately a fifth with 1 M DMSO. In methanol, the average yield per decay of DSB is 0.54±0.06 and drops to undetectable levels in 2 M DMSO. The SSB yield per decay is 7.2±0.2, changing to 0.4±0.2 in the presence of 2 M DMSO. The 95% decrease in the yield of DSB in DMSO indicates that the main mechanism for DSB formation is through indirect effect, possibly by cooperative binding or clustering of intercalators. In the presence of non-radioactive ligands at a near saturation concentration, where radioactive Tc compounds do not form large clusters, the yield of SSB stays the same while the yield of DSB decreases to the value in DMSO. DSBs generated by ⁹⁹mTc conjugated to intercalators are primarily caused by indirect effects through clustering.
Dynamic viscosities of the ternary liquid mixtures (dimethyl carbonate + methanol + ethanol) and (dimethyl carbonate + methanol + hexane) at several temperatures
Energy Technology Data Exchange (ETDEWEB)
Rodriguez, A. [Chemical Engineering Department, Vigo University, 36310 Vigo (Spain); Pereiro, A.B. [Chemical Engineering Department, Vigo University, 36310 Vigo (Spain); Canosa, J. [Chemical Engineering Department, Vigo University, 36310 Vigo (Spain); Tojo, J. [Chemical Engineering Department, Vigo University, 36310 Vigo (Spain)]. E-mail: firstname.lastname@example.com
Densities, {rho} speeds of sound, u and dynamic viscosities, {eta} of the ternary mixtures {l_brace}dimethyl carbonate (DMC) + methanol + ethanol{r_brace} and (dimethyl carbonate + methanol + hexane) were gathered at T = (293.15, 298.15, 308.15, and 313.15) K. From experimental data viscosity deviations, {delta}{eta} of the ternary mixtures were evaluated. These results have been correlated using the Cibulka equation. The fitting parameters and the standard deviations of the ternary viscosity deviations are given. UNIFAC-VISCO group contribution method was used to predict the dynamic viscosities of the ternary mixtures at several temperatures.
Methionine sulfoxide reductase A protects neuronal cells against brief hypoxia/reoxygenation
Yermolaieva, Olena; Xu, Rong; Schinstock, Carrie; Brot, Nathan; Weissbach, Herbert; Heinemann, Stefan H.; Hoshi, Toshinori
Hypoxia/reoxygenation induces cellular injury by promoting oxidative stress. Reversible oxidation of methionine in proteins involving the enzyme peptide methionine sulfoxide reductase type A (MSRA) is postulated to serve a general antioxidant role. Therefore, we examined whether overexpression of MSRA protected cells from hypoxia/reoxygenation injury. Brief hypoxia increased the intracellular reactive oxygen species (ROS) level in PC12 cells and promoted apoptotic cell death. Adenovirus-mediated overexpression of MSRA significantly diminished the hypoxia-induced increase in ROS and facilitated cell survival. Measurements of the membrane potentials of intact mitochondria in PC12 cells and of isolated rat liver mitochondria showed that hypoxia induced depolarization of the mitochondrial membrane. The results demonstrate that MSRA plays a protective role against hypoxia/reoxygenation-induced cell injury and suggest the therapeutic potential of MSRA in ischemic heart and brain disease.
Solubility of sulfoxide complexes of uranyl chlorides and uranyl nitrates in hydrocarbons
International Nuclear Information System (INIS)
Murinov, Yu.I.; Kurochkin, A.V.; Nikitin, Yu.E.
Solubility of uranylnitrate and uranylchloride complexes with sulfoxides of different structure in hydrocarbons of different types at 15 deg C has been studied. Solubility of the complexes with DHSO in hydrocarbons in the temperature range 0-20 deg C is determined. Thermodynamic functions of the complexes dissolution are calculated. It is shown that solubility of uranyl salt complexes depends considerably on the structure of ligand hydrocarbon radicals, and especially on the number of ''available'' methylene groups and varies from 5x10 -7 to 0.5 mol parts. A connection between the number of available methylene groups of ligands in the complexes with solubility spread of the complex in the given set of organic solvents is detected. Analysis of the thermodynamics of the complexes dissolution has shown that entropy constituent makes the determining contribution to the interaction. Complex-hydrocarbon interactions are accompanied by a strong braking of both rotational and translational movements of hydrocarbon melecules
On the Additions of Lithium Methyl p-Tolyl Sulfoxide to N-(PMPArylaldimines
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Matteo Zanda
Full Text Available The results presented in this paper confirm that the stereochemical outcome of the reversible additions of lithium (R-methyl p-tolyl sulfoxide to N-arylidene-p-anisidines (NPMP imines depends on: (a the reaction conditions used and (b the electronic properties of the arylidene moiety on the starting imine. In particular, we show that under kinetic control (-70 °C the additions involving electron-rich N-arylidene groups occur with very high stereocontrol in favor of the (2S,RS-diastereomers, whereas an electron-deficient group favors the opposite stereochemical outcome. Based on the observations above, a mechanistic hypothesis is proposed.
21 CFR 172.824 - Sodium mono- and dimethyl naphthalene sulfonates.
... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium mono- and dimethyl naphthalene sulfonates... FOOD FOR HUMAN CONSUMPTION Multipurpose Additives § 172.824 Sodium mono- and dimethyl naphthalene sulfonates. The food additive sodium mono- and dimethyl naphthalene sulfonates may be safely used in...
Dimethyl ether in diesel engines - progress and perspectives
DEFF Research Database (Denmark)
Sorenson, Spencer C
A review of recent developments related to the use of dimethyl ether (DME) in engines is presented Research work discussed is in the areas of engine performance and emissions, fuel injection systems, spray and ignition delay, and detailed chemical kinetic modeling. DME's properties and safety...
Binary mixtures of carbon dioxide and dimethyl ether as alternative ...
African Journals Online (AJOL)
Vapor-liquid equilibrium (VLE) data were predicted for the binary mixture of carbon dioxide (CO2) and dimethyl ether (DME) at ten temperatures ranging from 273.15 to 386.56 K and pressure upto 7.9 MPa to observe this mixture's potential of COP enhancement and capacity modulation as a working fluid in a refrigeration ...
Kinetics and mechanism of oxidation of dimethyl sulphoxide by ...
Indian Academy of Sciences (India)
evaluated in the temperature range 308–323 K. Activation parameters have also been determined while the orders in [DMSO] are unity and zero. The reaction product has been identified as dimethyl sulphone (DMSO2). Keywords. Oxidation of DMSO; sodium bromate–sodium bisulphite reagent. 1. Introduction. Kinetic ...
Coordination chemistry of highly hemilabile bidentate sulfoxide N-heterocyclic carbenes with palladium(II).
Yu, Kuo-Hsuan; Wang, Chia-Ching; Chang, I-Hsin; Liu, Yi-Hung; Wang, Yu; Elsevier, Cornelis J; Liu, Shiuh-Tzung; Chen, Jwu-Ting
Imidazolium salts, [RS(O)-CH2 (C3 H3 N2 )Mes]Cl (R=Me (L1a), Ph (L1b)); Mes=mesityl), make convenient carbene precursors. Palladation of L1a affords the monodentate dinuclear complex, [(PdCl2 {MeS(O)CH2 (C3 H2 N2 )Mes})2 ] (2a), which is converted into trans-[PdCl2 (NHC)2] (trans-4a; N-heterocyclic carbene) with two rotamers in anti and syn configurations. Complex trans-4a can isomerize into cis-4a(anti) at reflux in acetonitrile. Abstraction of chlorides from 4a or 4b leads to the formation of a new dication: trans-[Pd{RS(O)CH2(C3H2N2)Mes}2](PF6)2 (R=Me (5a), Ph (5b)). The X-ray structure of 5a provides evidence that the two bidentate SO-NHC ligands at palladium(II) are in square-planar geometry. Two sulfoxides are sulfur- and oxygen-bound, and constitute five- and six-membered chelate rings with the metal center, respectively. In acetonitrile, complexes 5a or 5b spontaneously transform into cis-[Pd(NHC)2(NCMe)2](PF6)2. Similar studies of thioether-NHCs have also been examined for comparison. The results indicate that sulfoxides are more labile than thioethers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Synthesis and structure of Bis(3,3-dimethyl-3,4-dihydroisoquinolyl-1) ketoxime
International Nuclear Information System (INIS)
Sokol, V.I.; Davydov, V.V.; Shklyaev, Yu.V.; Kartashova, I.V.; Sergienko, V.S.; Zaitsev, B.E.
The reaction of bis(3,3-dimethyl-3,4-dihydroisoquinolyl-1)methane with NaNO 2 resulted in the formation of bis(3,3-dimethyl-3,4-dihydroisoquinolyl-1) ketoxime (I). The crystal and molecular structure of I was determined (x-ray structure analysis, Enraf-Nonius CAD-4, MoK α -radiation, graphite monochromator, θ/2θ scan, 2θ max =58 deg. , 4800 unique reflections; a=10.327(4), b=9.070(5), and c=21.62(1) A; β=94.02(3) deg.; V=2020(1) A 3 ; Z=4; and sp. gr. Pn). In the crystal, I exists in the oxime tautomeric form. Two symmetry-independent molecules are bound into a dimer through the intermolecular N=OH···N cycl 3 hydrogen bond. Both molecules are nonplanar; the dihedral angles between the mean planes of their 3,4-dihydroisoquinoline moieties are 72 deg. and 74 deg. According to IR and electron absorption spectra, the tautomeric form of compound I is also retained in solutions, and the π-conjugation between the 3,4-dihydroisoquinoline fragments of I is actually absent
Bandgap tunable Csx(CH3NH3)1-xPbI3perovskite nanowires by aqueous solution synthesis for optoelectronic devices.
Dong, Dongdong; Deng, Hui; Hu, Chao; Song, Huaibing; Qiao, Keke; Yang, Xiaokun; Zhang, Jian; Cai, Fensha; Tang, Jiang; Song, Haisheng
To date, all the lead halide based full-inorganic or organic-inorganic hybrid perovskites have been synthesized from organic solvent, such as N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO), by a solution method. Herein, water has been utilized as a 'green' solvent to develop an efficient synthetic route to grow various kinds of lead halide perovskite nanowires (NWs). By controlling the proportion of the hybrid cations, Cs x (CH 3 NH 3 ) 1-x PbI 3 perovskite NWs were successfully synthesized. Every Cs x (CH 3 NH 3 ) 1-x PbI 3 perovskite NW demonstrated single crystal characteristics with uniform stoichiometric element distribution. Because of the controllable cation composition, the NW bandgaps could be finely tuned from 1.5 to 1.7 eV. Transient photoluminescence spectra showed superior NW quality when compared with those of the conventional DMF-based NWs. Based on the abovementioned high quality single Cs 0.5 (CH 3 NH 3 ) 0.5 PbI 3 perovskite NW, a reliable single-NW photodetector was fabricated to investigate the optoelectronic application. It demonstrated a responsivity of 23 A/W, exceeding most of the reported values in the perovskite nanowire photoconductive detectors, and the shot-noise normalized detectivity was 2.5 × 10 11 Jones comparable to the parameters of the commercial silicon-based nanowires. The green and robust synthesis method, finely tunable NW bandgaps, and superior optoelectronic properties are expected to open a new door for the development of perovskite optoelectronic devices.
Methylation of Eugenol Using Dimethyl Carbonate and Bentonite as Catalyst
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Dina Asnawati
Full Text Available Eugenol is a compound with a variety of reactive functional groups such as allyl, hydroxy and methoxy. The presence of the functional groups brings eugenol possible to undertake the transformation into various derivative compounds with diverse activities. One of the simple and possible transformations is methylation or alkylation. Commonly, methyl halides and dimethyl sulphate are used as methylation agent. However, those kinds of methylation agents are toxic and carcinogenic. In this research dimethyl carbonate, an alternative methylation agent is used, because of its low toxicity, green, and economic. The synthesis has been carried out by using a catalyst. Bentonite was activated by heating to a temperature using 300 °C. Methylation was shown by the formation of a light yellow liquid (25.71% yield. The structures of products were characterized by GC-MS and obtained a compound, namely bis eugenol (4-allyl-2-methoxyphenoxy methane (2.37% yield.
Diastereoselective Addition of α-Metalated Sulfoxides to Imines Revisited: Mechanism, Computational Studies, and the Effect of External Chiral Ligands
DEFF Research Database (Denmark)
Pedersen, Brian; Rein, Tobias; Søtofte, Inger
Some new results on asymmetric synthesis via the addition of a-metalated methyl tolyl sulfoxides to imines are presented. Good diastereoselectivity (up to > 98% d.e. for product 3g) can be obtained under conditions of kinetic control (short reaction time, low temperature). The transition state (a......) to (> 99 : 1) by use of a readily available C2-symmetric bis(sulfonamide) ligand....
Mixed-component sulfone-sulfoxide tagged zinc IRMOFs:In situ ligand oxidation, carbon dioxide, and water sorption studies
Bryant, Macguire R; Burrows, Andrew D; Kepert, Cameron J; Southon, Peter D; Qazvini, Omid T; Telfer, Shane G; Richardson, Christopher
Reported here are the syntheses and adsorption properties of a series of single- and mixed-component zinc IRMOFs derived from controlled ratios of sulfide and sulfone functionalized linear biphenyldicarboxylate (bpdc) ligands. During MOF synthesis the sulfide moieties undergo in situ oxidation, giving rise to sulfoxide functionalized ligands, which are incorporated to give mixed-component sulfoxide–sulfone functionalized MOFs. The single- and mixed-component systems all share the IRMOF-9 stru...
Detonation characteristics of dimethyl ether and ethanol-air mixtures
Diakow, P.; Cross, M.; Ciccarelli, G.
The detonation cell structure in dimethyl ether vapor and ethanol vapor-air mixtures was measured at atmospheric pressure and initial temperatures in the range of 293-373 K. Tests were carried out in a 6.2-m-long, 10-cm inner diameter tube. For more reactive mixtures, a series of orifice plates were used to promote deflagration-to-detonation transition in the first half of the tube. For less reactive mixtures prompt detonation initiation was achieved with an acetylene-oxygen driver. The soot foil technique was used to capture the detonation cell structure. The measured cell size was compared to the calculated one-dimensional detonation reaction zone length. For fuel-rich dimethyl ether mixtures the calculated reaction zone is highlighted by a temperature gradient profile with two maxima, i.e., double heat release. The detonation cell structure was interpreted as having two characteristic sizes over the full range of mixture compositions. For mixtures at the detonation propagation limits the large cellular structure approached a single-head spin, and the smaller cells approached the size of the tube diameter. There is little evidence to support the idea that the two cell sizes observed on the foils are related to the double heat release predicted for the rich mixtures. There was very little influence of initial temperature on the cell size over the temperature range investigated. A double heat release zone was not predicted for ethanol-air detonations. The detonation cell size for stoichiometric ethanol-air was found to be similar to the size of the small cells for dimethyl ether. The measured cell size for ethanol-air did not vary much with composition in the range of 30-40 mm. For mixtures near stoichiometric it was difficult to discern multiple cell sizes. However, near the detonation limits there was strong evidence of a larger cell structure similar to that observed in dimethyl ether air mixtures.
Regioselective synthesis of chiral dimethyl-bis(ethylenedithiotetrathiafulvalene sulfones
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Flavia Pop
Full Text Available Enantiopure (R,R and (S,S-dimethyl-bis(ethylenedithiotetrathiafulvalene monosulfones have been synthesized by the aerial oxidation of the chiral dithiolates generated from the propionitrile-protected precursors. Both enantiomers crystallize in the orthorhombic chiral space group P212121. They show a boat-type conformation of the TTF moiety, a rather rigid dithiin sulfone ring and the methyl groups in a bisequatorial conformation. Cyclic voltammetry measurements indicate fully reversible oxidation in radical cation and dication species.
Studies of a Novel Cysteine Sulfoxide Lyase from Petiveria alliacea: The First Heteromeric Alliinase1[W][OA
Musah, Rabi A.; He, Quan; Kubec, Roman; Jadhav, Abhijit
A novel alliinase (EC 18.104.22.168) was detected and purified from the roots of the Amazonian medicinal plant Petiveria alliacea. The isolated enzyme is a heteropentameric glycoprotein composed of two α-subunits (68.1 kD each), one β-subunit (56.0 kD), one γ-subunit (24.8 kD), and one δ-subunit (13.9 kD). The two α-subunits are connected by a disulfide bridge, and both α- and β-subunits are glycosylated. The enzyme has an isoelectric point of 4.78 and pH and temperature optima of 8.0 and approximately 52°C, respectively. Its activation energy with its natural substrate S-benzyl-l-cysteine sulfoxide is 64.6 kJ mol−1. Kinetic studies showed that both Km and Vmax vary as a function of substrate structure, with the most preferred substrates being the naturally occurring P. alliacea compounds S-benzyl-l-cysteine sulfoxide and S-2-hydroxyethyl-l-cysteine sulfoxide. The alliinase reacts with these substrates to produce S-benzyl phenylmethanethiosulfinate and S-(2-hydroxyethyl) 2-hydroxyethanethiosulfinate, respectively. PMID:19789290
Fragrance material review on 2,2-dimethyl-3-phenylpropanol.
Scognamiglio, J; Jones, L; Letizia, C S; Api, A M
A toxicologic and dermatologic review of 2,2-dimethyl-3-phenylpropanol when used as a fragrance ingredient is presented. 2,2-Dimethyl-3-phenylpropanol is a member of the fragrance structural group Aryl Alkyl Alcohols and is a primary alcohol. The AAAs are a structurally diverse class of fragrance ingredients that includes primary, secondary, and tertiary alkyl alcohols covalently bonded to an aryl (Ar) group, which may be either a substituted or unsubstituted benzene ring. The common structural element for the AAA fragrance ingredients is an alcohol group -C-(R1)(R2)OH and generically the AAA fragrances can be represented as an Ar-C-(R1)(R2)OH or Ar-Alkyl-C-(R1)(R2)OH group. This review contains a detailed summary of all available toxicology and dermatology papers that are related to this individual fragrance ingredient and is not intended as a stand-alone document. Available data for 2,2-dimethyl-3-phenylpropanol were evaluated then summarized and includes physical properties, acute toxicity, skin irritation, mucous membrane (eye) irritation, skin sensitization, phototoxicity, and photoallergy data. A safety assessment of the entire Aryl Alkyl Alcohols will be published simultaneously with this document; please refer to Belsito et al. (2012) for an overall assessment of the safe use of this material and all Aryl Alkyl Alcohols in fragrances. Copyright © 2011 Elsevier Ltd. All rights reserved.
Dimethyl 1,4-Dihydro-2,6-dimethyl-1-(4-methylphenyl-4-(4-methoxylphenylpyridine-3,5-dicarboxylate
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Qingjian Liu
Full Text Available Dimethyl 1,4-dihydro-2,6-dimethyl-1-(4-methylphenyl-4-(4-methoxylphenyl–pyridine-3,5-dicarboxylate has been synthesized via Hantzsch condensation reaction of p-methoxybenzaldehyde, methyl acetoacetate and p-toluidine promoted by microwave irradiation (MWI in the presence of iodine under solvent-free conditions.
Extraction of Dy(III and Sm(III with N,N-dimethyl-N,N-dioctylsuccinamide
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Full Text Available This work was focused on the applicability of a new diamide N,N-dimethyl- N,N-dioctylsuccinamide (DMDOSA employing cyclohexane as the diluent to extract Dy(III and Sm(III from nitric acid solutions. The extraction from HNO3 was investigated by distributionmeasurements. The stoichiometry of the predominant adducts of DMDOSA with HNO3 is 1:1 (HNO3 .DMDOSA under the studied conditions. The effect of the concentrations of nitric acid, lithium nitrate and extractant on the distribution ratio was investigated. An IR spectral study was also made of the extracted species.
Nine supramolecular assemblies from 5,7-dimethyl-1,8-naphthyridine-2-amine and carboxylic acids by strong classical H-bonds and other noncovalent associations
Ding, Aihua; Jin, Shouwen; Jin, Shide; Guo, Ming; Liu, Hui; Guo, Jianzhong; Wang, Daqi
This article demonstrates 5,7-dimethyl-1,8-naphthyridine-2-amine based organic salt formation in nine crystalline solids 1-9, in which the carboxylates have been integrated. Addition of equivalents of the COOH to the solution of 5,7-dimethyl-1,8-naphthyridine-2-amine generates the singly protonated cationic species which direct the carboxylates. The nine compounds crystallize as their organic salts with the COOH proton transferred to the aromatic N of the 5,7-dimethyl-1,8-naphthyridine-2-amine. All salts have been characterized by IR, mp, EA and XRD technique. The major driving force in 1-9 is the classical H-bonds from 5,7-dimethyl-1,8-naphthyridine-2-amine and the acids, here the Nsbnd H⋯O H-bonds were found in all salts. Other extensive non-covalent interactions also exhibit great functions in space association of the molecular counterparts in relevant crystals. Except 4, all salts had the CHsbnd O, or CH3sbnd O interactions or both. Except 9, the common R22 (8) graph set has been observed in all salts due to the H-bonds and the non-covalent associations. For the synergistic interactions of the classical H-bonds and the various non-covalent associations, the salts displayed 1D-3D structures.
Supramolecular salts of 5,7-dimethyl-1,8-naphthyridine-2-amine and acids through classical H-Bonds and other intermolecular interactions
Dong, Lingfeng; Jin, Shouwen; Jin, Shide; Gao, Xingjun; Xie, Xinxin; Lin, Zhihao; Wang, Yining; Xu, Weiqiang; Wang, Daqi
This article demonstrates 5,7-dimethyl-1,8-naphthyridine-2-amine based organic salts formation of crystalline solids 1-9, in which the acidic units have been integrated via a variety of non-covalent bonds. Addition of equivalents of the acidic units to the solution of 5,7-dimethyl-1,8-naphthyridine-2-amine generates the single protonated species which direct the anions. The nine compounds crystallize as their salts with the acidic H transferred to the aromatic N of the 5,7-dimethyl-1,8-naphthyridine-2-amine. In 2, 3, 4, and 7 the methyl substituted N-rings were protonated, while others were protonated at the NH2 substituted N-ring. All salts have been characterized via IR, mp, EA and XRD technique. The major driving force for the salt formation is attributed to the classical H-bonds from 5,7-dimethyl-1,8-naphthyridine-2-amine and the acids. Other extensive intermolecular interactions also play great functions in space association of the molecular assemblies in the relevant crystals. The common R22(8) graph set has been observed in all salts due to the H-bonds and other intermolecular interactions, except 2, 4, and 6. For the synergistic interactions of the various non-covalent bonds, all salts displayed 3D structures.
Alkanediyl-α, ω-bis (dimethyl cetylammonium bromide gemini surfactants as novel corrosion inhibitors for mild steel in formic acid
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Mohammad Mobin
Full Text Available Gemini surfactants, butanediyl 1,4-bis(dimethyl cetylammonium bromide, pentanediyl 1,5 - bis (dimethyl cetylammonium bromide and hexanediyl 1,6 - bis (dimethyl cetylammonium bromide from Alkanediyl-α, ω-bis (dimethyl cetylammonium bromide series were synthesized in laboratory and were characterized by using Nuclear Magnetic Resonance (NMR spectroscopy. The surfactants were tested as corrosion inhibitors for mild steel in 20% formic acid. The influence of surfactants on mild steel corrosion inhibition was investigated by measuring the corrosion rate of mild steel in their absence and presence by weight loss measurements, solvent analysis of iron ions into the test solution and potentiodynamic polarization measurements. The surface morphology of the corroded steel samples in presence and absence of surfactants was evaluated by using Scanning Electron Microscopy (SEM. The synthesized gemini surfactants performed as excellent corrosion inhibitor, the inhibition efficiency (IE being in the range of 76.66-97.41%. The IE of surfactants is slightly affected by the spacer length. The IE increased with increase in surfactant concentration and temperature. The adsorption of gemini surfactants on the steel surface was found to obey Langmuir adsorption isotherm. The results of the potentiodynamic polarization studies are consistent with the results of weight loss studies.
Pressure and temperature dependence of excess enthalpies of methanol + tetraethylene glycol dimethyl ether and methanol + polyethylene glycol dimethyl ether 250
Energy Technology Data Exchange (ETDEWEB)
Lopez, E.R.; Coxam, J.Y.; Fernandez, J.; Grolier, J.P.E.
The excess molar enthalpies at 323.15 K, 373.15 K, and 423.15 K, at 8 MPa, are reported for the binary mixtures methanol + tetraethylene glycol dimethyl ether (TEGDME) and methanol + poly(ethylene glycol) dimethyl ether 250 (PEGDME 250). Excess molar enthalpies were determined with a Setaram C-80 calorimeter equipped with a flow mixing cell. For both systems, the excess enthalpies are positive over the whole composition range, increasing with temperature. The H{sup E}(x) curves are slightly asymmetrical, and their maxima are skewed toward the methanol-rich region. The excess enthalpies slightly change with the pressure, the sign of this change being composition-dependent. In the case of mixtures with TEGDME, the experimental H{sup E} values have been compared with those predicted with the Gmehling et al. version of UNIFAC (Dortmund) and the Nitta-Chao and DISQUAC group contribution models.
Solvent extraction of plutonium(IV) into dodecane by bis(2-ethylhexyl)sulfoxide from mixed aqueous-organic solutions
International Nuclear Information System (INIS)
Shukla, J.P.; Kedari, C.S.
The extraction of Pu(IV) from nitric acid media by BESO/dodecane in the presence of several polar water-miscible organic solvents and possible synergistic effects have been investigated. Methanol, ethanol, n-propanol, dioxane, acetone and acetonitrile were used as the organic component of the mixed (polar) phase; the maximum enhancement was obtained with acetonitrile. Possible reasons for such behaviour are briefly discussed. (orig.)
Solvent extraction of plutonium(IV) into dodecane by bis(2-ethylhexyl)sulfoxide from mixed aqueous-organic solutions
Energy Technology Data Exchange (ETDEWEB)
Shukla, J.P.; Kedari, C.S. (Bhabha Atomic Research Centre, Bombay (India). Radiochemistry Div.)
The extraction of Pu(IV) from nitric acid media by BESO/dodecane in the presence of several polar water-miscible organic solvents and possible synergistic effects have been investigated. Methanol, ethanol, n-propanol, dioxane, acetone and acetonitrile were used as the organic component of the mixed (polar) phase; the maximum enhancement was obtained with acetonitrile. Possible reasons for such behaviour are briefly discussed. (orig.).
(Liquid + liquid) equilibria of (water + ethanol + dimethyl glutarate) at several temperatures[(Liquid+liquid) equilibria; Ethanol; Dimethyl glutarate; UNIFAC method
Energy Technology Data Exchange (ETDEWEB)
Ince, Erol. E-mail: firstname.lastname@example.com; Kirbaslar, S. Ismail. E-mail: email@example.com
(Liquid + liquid) equilibrium (LLE) data of (water + ethanol + dimethyl glutarate) have been determined experimentally at T=(298.15,308.15 and 318.15) K. The reliability of the experimental tie-line data was ascertained by using the Othmer and Tobias correlation. The LLE data of the ternary mixture were predicted by UNIFAC method. Distribution coefficients and separation factors were evaluated for the immiscibility region.
Enantioresolution and stereochemical characterization of two chiral sulfoxides endowed with COX-2 inhibitory activity.
Sardella, Roccaldo; Ianni, Federica; Di Michele, Alessandro; Di Capua, Angela; Carotti, Andrea; Anzini, Maurizio; Natalini, Benedetto
The capacity of nonsteroidal antiinflammatory drugs (NSAIDs) to prevent prostanoids biosynthesis through the inhibition of COX-2 enzyme is related to their structural backbone, based on the fusion of a cis-stilbene unit with a variety of heterocyclic and carbocyclic rings. By this route, a series of new selective COX-2 inhibitors was developed, by maintaining the 4-methylsulfone or 4-methylsulfonamide substituent on the phenyl moiety, essential for their activity. In this frame, two novel propyl sulfoxide derivatives were synthesized, which proved selective and sufficiently potent COX-2 inhibition activity when tested as racemates. In the present study, the use of a cellulose tris(3,5-dichlorophenylcarbamate)-based chiral stationary phase, in a polar-organic mode of elution, enabled the successful enantioseparation of the investigated compounds. The developed chromatography method reveals a useful tool of monitoring in view of a proper forthcoming enantioselective synthetic protocol. Moreover, the optimized chromatographic conditions allowed the isolation of appropriate amounts of single enantiomers for the electronic circular dichroism studies that, coupled with in silico simulations, allowed assessing the absolute configuration of each species. © 2017 Wiley Periodicals, Inc.
Peptide methionine sulfoxide reductase A (MsrA): direct electrochemical oxidation on carbon electrodes.
Enache, T A; Oliveira-Brett, A M
The direct electrochemical behaviour of peptide methionine sulfoxide reductase A (MsrA) adsorbed on glassy carbon and boron doped diamond electrodes surface, was studied over a wide pH range by cyclic and differential pulse voltammetry. MsrA oxidation mechanism occurs in three consecutive, pH dependent steps, corresponding to the oxidation of tyrosine, tryptophan and histidine amino acid residues. At the glassy carbon electrode, the first step corresponds to the oxidation of tyrosine and tryptophan residues and occurs for the same potential. The advantage of boron doped diamond electrode was to enable the separation of tyrosine and tryptophan oxidation peaks. On the second step occurs the histidine oxidation, and on the third, at higher potentials, the second tryptophan oxidation. MsrA adsorbs on the hydrophobic carbon electrode surface preferentially through the three hydrophobic domains, C1, C2 and C3, which contain the tyrosine, tryptophan and histidine residues, and tryptophan exists only in these regions, and undergo electrochemical oxidation. Copyright © 2012 Elsevier B.V. All rights reserved.
Preparation and characterization of organotin-oxomolybdate coordination polymers and their use in sulfoxidation catalysis.
Abrantes, Marta; Valente, Anabela A; Pillinger, Martyn; Gonçalves, Isabel S; Rocha, João; Romão, Carlos C
The organotin-oxomolybdates [(R(3)Sn)(2)MoO(4)].n H(2)O (R=methyl, n-butyl, cyclohexyl, phenyl, benzyl) have been prepared and tested as catalysts for the oxidation of benzothiophene with aqueous hydrogen peroxide, at 35 degrees C and atmospheric pressure. In all cases, the 1,1-dioxide was the only observed product. The kinetic profiles depend on the nature of the tin-bound R group and also on the addition of a co-solvent. For the tribenzyltin derivative, the apparent activation energies for sulfoxidation as a function of the co-solvent are in the order 1,2-dichloroethane (5 kcal mol(-1))ethanolpolymers also have different structures, as evidenced by Xray powder diffraction. Mo K-edge and Sn K-edge EXAFS spectroscopy confirmed that the structures arise from the self-assembly of tetrahedral [MoO(4)](2-) subunits and [R(3)Sn](+) spacers. The Mo...Sn separation in the trimethyltin derivative is a uniform 3.84 A. By contrast, the EXAFS results revealed the coexistence of short (3.67-3.79 A) and long (3.93-4.07 A) Mo.Sn separations in the other coordination polymers. The catalyst precursors were also characterized in the solid state by thermogravimetric analysis, FTIR, and Raman spectroscopy, and MAS NMR ((13)C, (119)Sn) spectroscopy.
Regulation of Expression of Oxacillin-Inducible Methionine Sulfoxide Reductases in Staphylococcus aureus
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Kyle R. Baum
Full Text Available Cell wall-active antibiotics cause induction of a locus that leads to elevated synthesis of two methionine sulfoxide reductases (MsrA1 and MsrB in Staphylococcus aureus. To understand the regulation of this locus, reporter strains were constructed by integrating a DNA fragment consisting of the msrA1/msrB promoter in front of a promoterless lacZ gene in the chromosome of wild-type and MsrA1-, MsrB-, MsrA1/MsrB-, and SigB-deficient methicillin-sensitive S. aureus strain SH1000 and methicillin-resistant S. aureus strain COL. These reporter strains were cultured in TSB and the cellular levels of β-galactosidase activity in these cultures were assayed during different growth phases. β-galactosidase activity assays demonstrated that the lack of MsrA1, MsrB, and SigB upregulated the msrA1/msrB promoter in S. aureus strain SH1000. In S. aureus strain COL, the highest level of β-galactosidase activity was observed under the conditions when both MsrA1 and MsrB proteins were absent. The data suggest that the msrA1/msrB locus, in part, is negatively regulated by MsrA1, MsrB, and SigB in S. aureus.
On synergistic effects in uranyl sulfate extraction by mixtures of organophosphoric acids with oil sulfoxides
International Nuclear Information System (INIS)
Torgov, V.G.; Us, T.V.
Extraction properties of mixtures of organophosphoric acids (HX) of different compositions (di-2-ethylhexyldithiophosphoric (D2EHDTPA), di-2-ethylhexylphosphoric (D2EHPA), amyl-2-ethylhexylphosphonic (A2EHPA) and diheptylphosphinic (DHPA)) with oil sulfoxides (B) with respect to uranyl sulfate in an iodide range of its concentrations were compared. The presence of cation-exchange (at low HX saturations) and noncation-exchange (after HX saturations) synergistic effects was established. Their nature is the same one and is related with urabium atom acceptor ability in acid and neutral uranyl salts to add B and UO 2 SO 4 xB respectively. HX are arranged in the following series with respect to synergistic effect: D2EHDTPA > D2EHPA > A2EHPA > DHPA. The series is opposite to the stability series of intracomplexes (IC) of HX with uranyl. A quantitative description of the process of UO 2 SO 4 xB addition to IC was given and corresponding extraction constants were determined
Preparation, characterization and thermal behaviour study of 4-dimethyl amino benzal pyruvate of lanthanides (III) and yttrium (III) in solid state
International Nuclear Information System (INIS)
Miyano, M.H.
Solid state compounds involving Ln and DMBP, where Ln trivalent lanthanides (except promethium) and yttrium; DMBP 4-dimethyl amino benzylidene pyruvate, were prepared by addition of ligand to the corresponding metal ions chlorides, both in aqueous solution. The precipitates were washed with distilled water and dried at 40 0 C in a forced circulation oven. Complexometry with EDTA, thermogravimetry (TG), differential thermal analysis (DTA), infra-red absorption and X-ray diffraction have been used in the study of these compounds. (author)
77 FR 50613 - Didecyl Dimethyl Ammonium Carbonate and Didecyl Dimethyl Ammonium Bicarbonate; Exemption From the...
... public facility) and that the residual solution remaining on the surface or pesticide migration fraction... to Address Environmental Justice in Minority Populations and Low-Income Populations (59 FR 7629... States or tribal governments, on the relationship between the national government and the States or...
Performance of long straw tubes using dimethyl ether
International Nuclear Information System (INIS)
Benussi, L.; Bertani, M.; Bianco, S.; Fabbri, F.L.; Gianotti, P.; Giardoni, M.; Guaraldo, C.; Lanaro, A.; Lucherini, V.; Mecozzi, A.; Passamonti, L.; Russo, V.; Sarwar, S.
A cylindrical tracking detector with an inner radius of one meter employing straw tubes is being envisaged for the FINUDA experiment aimed at hyper-nuclear physics at DAΦNE, the Frascati φ-factory. A prototype using several 10 mm and 20 mm diameter, two meter long aluminized mylar straws has been assembled and tested with a one GeV/c pion beam. While operating with dimethyl ether, gas gain, space resolution, and device systematics have been studied. A simple method of correction for systematics due to straw eccentricity has been developed and, once applied, a space resolution better than 40 μm can be reached. (orig.)
Dimethyl ether production from methanol and/or syngas
Dagle, Robert A; Wang, Yong; Baker, Eddie G; Hu, Jianli
Disclosed are methods for producing dimethyl ether (DME) from methanol and for producing DME directly from syngas, such as syngas from biomass. Also disclosed are apparatus for DME production. The disclosed processes generally function at higher temperatures with lower contact times and at lower pressures than conventional processes so as to produce higher DME yields than do conventional processes. Certain embodiments of the processes are carried out in reactors providing greater surface to volume ratios than the presently used DME reactors. Certain embodiments of the processes are carried out in systems comprising multiple microchannel reactors.
Direct dimethyl ether high temperature polymer electrolyte membrane fuel cells
DEFF Research Database (Denmark)
Vassiliev, Anton; Jensen, Jens Oluf; Li, Qingfeng
A high temperature polybenzimidazole (PBI) polymer fuel cell was fed with dimethyl ether (DME) and water vapour mixture on the anode at ambient pressure with air as oxidant. A peak power density of 79 mW/cm2 was achieved at 200°C. A conventional polymer based direct DME fuel cell is liquid fed...... and suffers from low DME solubility in water. When the DME - water mixture is fed as vapour miscibility is no longer a problem. The increased temperature is more beneficial for the kinetics of the direct oxidation of DME than of methanol. The Open Circuit Voltage (OCV) with DME operation was 50 to 100 m...
Dimethyl(4-methylphenylammonium naphthalene-1,5-disulfonate dihydrate
Directory of Open Access Journals (Sweden)
Bin Wei
Full Text Available The asymmetric unit of the organic–inorganic hybrid salt, 2C9H14N+·C10H6O6S22−·2H2O, consists of one dimethyl(4-methylphenylammonium cation, one half of a naphthalene-1,5-disulfonate anion lying on a crystallographic centre of inversion, and one water molecule. In the crystal, O—H...O(S and N—H...OH2 hydrogen bonds link the cations and anions forming ring motifs.
Directory of Open Access Journals (Sweden)
Salman A. Khan
Full Text Available The title compound, (2E-3-(3,5-dimethyl-1-phenyl-1H-pyrazol-4-yl-1-(2,5-dimethyl-3-thienylprop-2-en-1-one (3 was synthesized in high yield by aldol condensation of 3-acetyl-2,5-dimethylthiophene and 3,5-dimethyl-1-phenylpyrazole-4-carboxaldehyde in ethanolic NaOH at room temperature. Its structure was fully characterized by elemental analysis, IR, 1H NMR, 13C NMR and EI-MS spectral analysis.
Methionine sulfoxides on PrPSc: a prion-specific covalent signature.
Canello, Tamar; Engelstein, Roni; Moshel, Ofra; Xanthopoulos, Konstantinos; Juanes, María E; Langeveld, Jan; Sklaviadis, Theodoros; Gasset, Maria; Gabizon, Ruth
Prion diseases are fatal neurodegenerative disorders believed to be transmitted by PrP (Sc), an aberrant form of the membrane protein PrP (C). In the absence of an established form-specific covalent difference, the infectious properties of PrP (Sc) were uniquely ascribed to the self-perpetuation properties of its aberrant fold. Previous sequencing of the PrP chain isolated from PrP(27-30) showed the oxidation of some methionine residues; however, at that time, these findings were ascribed to experimental limitations. Using the unique recognition properties of alphaPrP mAb IPC2, protein chemistry, and state of the art mass spectrometry, we now show that while a large fraction of the methionine residues in brain PrP (Sc) are present as methionine sulfoxides this modification could not be found on brain PrP (C) as well as on its recombinant models. In particular, the pattern of oxidation of M213 with respect to the glycosylation at N181 of PrP (Sc) differs both within and between species, adding another diversity factor to the structure of PrP (Sc) molecules. Our results pave the way for the production of prion-specific reagents in the form of antibodies against oxidized PrP chains which can serve in the development of both diagnostic and therapeutic strategies. In addition, we hypothesize that the accumulation of PrP (Sc) and thereafter the pathogenesis of prion disease may result from the poor degradation of oxidized aberrantly folded PrP.
Cytotoxicity of selected medicinal plants used in Mt. Frere District ...
African Journals Online (AJOL)
Stock solutions were prepared at 40 mg/ml Dimethyl sulfoxide (DMSO) and test solutions were transferred into vials and 10 brine shrimps introduced in each. The number of dead shrimps was counted to ascertain toxicity. Ten A. salina nauplii (larva) were transferred into each sample vial and filtered brine solution was ...
Synergistic roles of Helicobacter pylori methionine sulfoxide reductase and GroEL in repairing oxidant-damaged catalase.
Mahawar, Manish; Tran, ViLinh; Sharp, Joshua S; Maier, Robert J
Hypochlorous acid (HOCl) produced via the enzyme myeloperoxidase is a major antibacterial oxidant produced by neutrophils, and Met residues are considered primary amino acid targets of HOCl damage via conversion to Met sulfoxide. Met sulfoxide can be repaired back to Met by methionine sulfoxide reductase (Msr). Catalase is an important antioxidant enzyme; we show it constitutes 4-5% of the total Helicobacter pylori protein levels. msr and katA strains were about 14- and 4-fold, respectively, more susceptible than the parent to killing by the neutrophil cell line HL-60 cells. Catalase activity of an msr strain was much more reduced by HOCl exposure than for the parental strain. Treatment of pure catalase with HOCl caused oxidation of specific MS-identified Met residues, as well as structural changes and activity loss depending on the oxidant dose. Treatment of catalase with HOCl at a level to limit structural perturbation (at a catalase/HOCl molar ratio of 1:60) resulted in oxidation of six identified Met residues. Msr repaired these residues in an in vitro reconstituted system, but no enzyme activity could be recovered. However, addition of GroEL to the Msr repair mixture significantly enhanced catalase activity recovery. Neutrophils produce large amounts of HOCl at inflammation sites, and bacterial catalase may be a prime target of the host inflammatory response; at high concentrations of HOCl (1:100), we observed loss of catalase secondary structure, oligomerization, and carbonylation. The same HOCl-sensitive Met residue oxidation targets in catalase were detected using chloramine-T as a milder oxidant.
Synergistic Roles of Helicobacter pylori Methionine Sulfoxide Reductase and GroEL in Repairing Oxidant-damaged Catalase*
Mahawar, Manish; Tran, ViLinh; Sharp, Joshua S.; Maier, Robert J.
Hypochlorous acid (HOCl) produced via the enzyme myeloperoxidase is a major antibacterial oxidant produced by neutrophils, and Met residues are considered primary amino acid targets of HOCl damage via conversion to Met sulfoxide. Met sulfoxide can be repaired back to Met by methionine sulfoxide reductase (Msr). Catalase is an important antioxidant enzyme; we show it constitutes 4–5% of the total Helicobacter pylori protein levels. msr and katA strains were about 14- and 4-fold, respectively, more susceptible than the parent to killing by the neutrophil cell line HL-60 cells. Catalase activity of an msr strain was much more reduced by HOCl exposure than for the parental strain. Treatment of pure catalase with HOCl caused oxidation of specific MS-identified Met residues, as well as structural changes and activity loss depending on the oxidant dose. Treatment of catalase with HOCl at a level to limit structural perturbation (at a catalase/HOCl molar ratio of 1:60) resulted in oxidation of six identified Met residues. Msr repaired these residues in an in vitro reconstituted system, but no enzyme activity could be recovered. However, addition of GroEL to the Msr repair mixture significantly enhanced catalase activity recovery. Neutrophils produce large amounts of HOCl at inflammation sites, and bacterial catalase may be a prime target of the host inflammatory response; at high concentrations of HOCl (1:100), we observed loss of catalase secondary structure, oligomerization, and carbonylation. The same HOCl-sensitive Met residue oxidation targets in catalase were detected using chloramine-T as a milder oxidant. PMID:21460217
Metal-free catalytic oxidation of sulfides to sulfoxides with ammonium nitrate, ammonium hydrogen sulfate and ammonium bromide as catalyst
Ghorbani-Choghamarani, Arash; Zolfigol, Mohammad Ali; Ayazi-Nasrabadi, Roia
A general and metal-free catalytic oxidation of aliphatic and aromatic sulfides to their corresponding sulfoxides via combination of ammonium nitrate (NH4NO3), supported ammonium hydrogen sulfate on silica gel (NH4HSO4-SiO2) and a catalytic amount of ammonium bromide (NH4Br) in the presence of wet SiO2 (50%, w/w) has been investigated. The reactions were carried out heterogeneously and selectively in short reaction times in CH2Cl2 at room temperature. This protocol is mild and efficient compa...
Phenyl-N,N-dibutylcarbamoylmethyl sulfoxide as a new bifunctional extractant for extraction of uranium(VI) in toluene
International Nuclear Information System (INIS)
Han Jing-Tian; Sun Guo-Xin; Shao Hua; Bao Bo-Rong; Chen Shu-Feng
A new bifunctional extractant named phenyl-N,N-dibutylcarbamoylmethyl sulfoxide (PCMSO) is synthesized and characterized in order to investigate its selectivity and capability in the extraction from acidic nitrate media in nuclear reprocessing. The extraction of uranium(VI) with PCMSO in toluene has been studied at various concentrations of nitric acid, extractant and salting-out agent (LiNO 3 ). The mechanism of extraction is discussed in the light of the results obtained. The extracted species has also been investigated using FT-IR spectrometry. The related thermodynamic functions were calculated. The IR spectral study was also made of the extracted species. (author)
Enantioselective syntheses of sulfoxides in octahedral ruthenium(II) complexes via a chiral-at-metal strategy.
Li, Zheng-Zheng; Wen, A-Hao; Yao, Su-Yang; Ye, Bao-Hui
The preparation of chiral 2-(alkylsulfinyl)phenol compounds by enantioselective coordination-oxidation of the thioether ruthenium complexes with a chiral-at-metal strategy has been developed. The enantiomerically pure sulfoxide complexes Δ-[Ru(bpy)2{(R)-LO-R}](PF6) (bpy is 2,2'-bipyridine, HLO-R is 2-(alkylsulfinyl)phenol, R = Me (Δ-1a), Et (Δ-2a), iPr (Δ-3a), Bn (Δ-4a), and Nap (Δ-5a)) and Λ-[Ru(bpy)2{(S)-LO-R}](PF6) (R = Me (Λ-1a), Et (Λ-2a), iPr (Λ-3a), Bn (Λ-4a), and Nap (Λ-5a)) have been synthesized by the reaction of Δ-[Ru(bpy)2(py)2](2+) or Λ-[Ru(bpy)2(py)2](2+) with the prochiral thioether ligands 2-(alkylthio)phenol (HL-R), followed by enantioselective oxidation with m-CPBA as oxidant. The X-ray crystallography was used to verify the stereochemistry of ruthenium complexes and sulfur atoms. The configurations of the ruthenium complexes are stable during the coordination and oxidation reactions. Moreover, the chiral sulfoxide ligands are enantioselectively generated by controlling of the configuration of ruthenium centers in the course of oxidation reaction. That is, the Λ configuration at the ruthenium center generates the S sulfoxide ligand; on the contrary, the Δ configuration of the ruthenium complex originates the R sulfoxide ligand. Acidolysis of Λ-[Ru(bpy)2{(R)-LO-R}](PF6) and Δ-[Ru(bpy)2{(S)-LO-R}](PF6) complexes in the presence of TFA-MeCN afforded the chiral ligands (R)-HLO-R and (S)-HLO-R in 96-99% ee values, respectively. Importantly, the chiral ruthenium complexes can be recycled as Δ/Λ-[Ru(bpy)2(MeCN)2](PF6)2 and reused in a next reaction cycle with complete retention of the configurations at ruthenium centers.
Entropy Generation Minimization in Dimethyl Ether Synthesis: A Case Study
Kingston, Diego; Razzitte, Adrián César
Entropy generation minimization is a method that helps improve the efficiency of real processes and devices. In this article, we study the entropy production (due to chemical reactions, heat exchange and friction) in a conventional reactor that synthesizes dimethyl ether and minimize it by modifying different operating variables of the reactor, such as composition, temperature and pressure, while aiming at a fixed production of dimethyl ether. Our results indicate that it is possible to reduce the entropy production rate by nearly 70 % and that, by changing only the inlet composition, it is possible to cut it by nearly 40 %, though this comes at the expense of greater dissipation due to heat transfer. We also study the alternative of coupling the reactor with another, where dehydrogenation of methylcyclohexane takes place. In that case, entropy generation can be reduced by 54 %, when pressure, temperature and inlet molar flows are varied. These examples show that entropy generation analysis can be a valuable tool in engineering design and applications aiming at process intensification and efficient operation of plant equipment.
Metabolism of the fungicide Denmert (S-n-butyl S'-p-tert-butyl-benzyl N-3-pyridyldithiocarbonimidate, S-1358) and Denmert sulfoxides in liver enzyme systems
International Nuclear Information System (INIS)
Ohkawa, Hideo; Okihara, Yukiko; Miyamoto, Junshi
On incubation with rat liver microsomes plus MADPH, Denmert (S-n-butyl S'-p-tert-butylbenzyl N-3-pyridyldithiocarbonimidate) underwent at least two different types of oxidation; hydroxylation and sulfoxidation. Hydroxylation of Denmert at the tert-butyl group was one of the major metabolic attacks in mammalian metabolism. Sulfoxidation of Denmert gave two isomers of Denmert sulfoxides which were intermediates in the metabolism and readily transformed into 2-(3'-pyridylimino)-4-carboxylthiazolidine (HM) in the presence of L-cysteine without enzymatic mediation. This type of conjugation with cysteine appears to be a new class of metabolic reactions in mammals. Denmert S-oxide showed increased fungicidal activity when assayed in liquid cultures, but not on plant leaves. (auth.)
Efficient and Simple Synthesis of 6-Aryl-1,4-dimethyl-9H-carbazoles
Directory of Open Access Journals (Sweden)
Sylvain Rault
Full Text Available A synthetic method for the preparation of 6-aryl-1,4-dimethyl-9H-carbazoles involving a palladium catalyzed coupling reaction of 1,4-dimethyl-9H-carbazole-6-boronic acids and (heteroaryl halides is described.
Direct dimethyl ether fueling of a high temperature polymer fuel cell
DEFF Research Database (Denmark)
Jensen, Jens Oluf; Vassiliev, Anton; Olsen, M.I.
Direct dimethyl ether (DME) fuel cells suffer from poor DME–water miscibility and so far peak powers of only 20–40 mW cm−2 have been reported. Based on available literature on solubility of dimethyl ether (DME) in water at ambient pressure it was estimated that the maximum concentration of DME at...
Hydrogen-deuterium (h-d) exchange reaction of warfarin in D(2)O solution.
Tode, Chisato; Takeuchi, Atsuko; Iwakawa, Seigo; Tatsumi, Akitoshi; Sugiura, Makiko
To prove the presence of a hydrogen-deuterium (H-D) exchange reaction, (1)H- and (13)C-NMR spectra of warfarin were measured in solvents containing D(2)O and H(2)O. In D(2)O or D(2)O/dimethyl sulfoxide (DMSO)-d(6) solvent, signal pattern changes were observed on H12 and H11 as well as 14 methyl protons over time while no changes were observed on H(2)O or H(2)O/DMSO-d(6) solvent. The observed changes in the solvents containing D(2)O were concluded to be caused by the H-D exchange reaction on H12, the process of CH(2)-->CHD-->CD(2). MS spectroscopy also confirmed these H-D exchanges. The kinetics of this reaction were analyzed as the successive reaction, and the mechanism was also proposed.
Thermodynamics of Hydrogen Production from Dimethyl Ether Steam Reforming and Hydrolysis
Energy Technology Data Exchange (ETDEWEB)
T.A. Semelsberger
The thermodynamic analyses of producing a hydrogen-rich fuel-cell feed from the process of dimethyl ether (DME) steam reforming were investigated as a function of steam-to-carbon ratio (0-4), temperature (100 C-600 C), pressure (1-5 atm), and product species: acetylene, ethanol, methanol, ethylene, methyl-ethyl ether, formaldehyde, formic acid, acetone, n-propanol, ethane and isopropyl alcohol. Results of the thermodynamic processing of dimethyl ether with steam indicate the complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide for temperatures greater than 200 C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure (P = 1 atm). Increasing the operating pressure was observed to shift the equilibrium toward the reactants; increasing the pressure from 1 atm to 5 atm decreased the conversion of dimethyl ether from 99.5% to 76.2%. The order of thermodynamically stable products in decreasing mole fraction was methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol--formaldehyde, formic acid, and acetylene were not observed. The optimal processing conditions for dimethyl ether steam reforming occurred at a steam-to-carbon ratio of 1.5, a pressure of 1 atm, and a temperature of 200 C. Modeling the thermodynamics of dimethyl ether hydrolysis (with methanol as the only product considered), the equilibrium conversion of dimethyl ether is limited. The equilibrium conversion was observed to increase with temperature and steam-to-carbon ratio, resulting in a maximum dimethyl ether conversion of approximately 68% at a steam-to-carbon ratio of 4.5 and a processing temperature of 600 C. Thermodynamically, dimethyl ether processed with steam can produce hydrogen-rich fuel-cell feeds--with hydrogen concentrations exceeding 70%. This substantiates dimethyl ether as a viable source of hydrogen for PEM fuel cells.
Membrane separation of ionic liquid solutions
Campos, Daniel; Feiring, Andrew Edward; Majumdar, Sudipto; Nemser, Stuart
A membrane separation process using a highly fluorinated polymer membrane that selectively permeates water of an aqueous ionic liquid solution to provide dry ionic liquid. Preferably the polymer is a polymer that includes polymerized perfluoro-2,2-dimethyl-1,3-dioxole (PDD). The process is also capable of removing small molecular compounds such as organic solvents that can be present in the solution. This membrane separation process is suitable for drying the aqueous ionic liquid byproduct from precipitating solutions of biomass dissolved in ionic liquid, and is thus instrumental to providing usable lignocellulosic products for energy consumption and other industrial uses in an environmentally benign manner.
Establishment of Dimethyl Labeling-based Quantitative Acetylproteomics in Arabidopsis.
Liu, Shichang; Yu, Fengchao; Yang, Zhu; Wang, Tingliang; Xiong, Hairong; Chang, Caren; Yu, Weichuan; Li, Ning
Protein acetylation, one of many types of post-translational modifications (PTMs), is involved in a variety of biological and cellular processes. In the present study, we applied both C sCl d ensity g radient (CDG) centrifugation-based protein fractionation and a dimethyl-labeling-based 4C quantitative PTM proteomics workflow in the study of dynamic acetylproteomic changes in Arabidopsis. This workflow integrates the dimethyl c hemical labeling with c hromatography-based acetylpeptide separation and enrichment followed by mass spectrometry (MS) analysis, the extracted ion chromatogram (XIC) quantitation-based c omputational analysis of mass spectrometry data to measure dynamic changes of acetylpeptide level using an in-house software program, named S table isotope-based Qua ntitation- D imethyl labeling (SQUA-D), and finally the c onfirmation of ethylene hormone-regulated acetylation using immunoblot analysis. Eventually, using this proteomic approach, 7456 unambiguous acetylation sites were found from 2638 different acetylproteins, and 5250 acetylation sites, including 5233 sites on lysine side chain and 17 sites on protein N termini, were identified repetitively. Out of these repetitively discovered acetylation sites, 4228 sites on lysine side chain ( i.e. 80.5%) are novel. These acetylproteins are exemplified by the histone superfamily, ribosomal and heat shock proteins, and proteins related to stress/stimulus responses and energy metabolism. The novel acetylproteins enriched by the CDG centrifugation fractionation contain many cellular trafficking proteins, membrane-bound receptors, and receptor-like kinases, which are mostly involved in brassinosteroid, light, gravity, and development signaling. In addition, we identified 12 highly conserved acetylation site motifs within histones, P-glycoproteins, actin depolymerizing factors, ATPases, transcription factors, and receptor-like kinases. Using SQUA-D software, we have quantified 33 ethylene hormone-enhanced and
Detection of oxidized methionine in selected proteins, cellular extracts, and blood serums by novel anti-methionine sulfoxide antibodies
Oien, Derek B.; Canello, Tamar; Gabizon, Ruth; Gasset, Maria; Lundquist, Brandi L.; Burns, Jeff M; Moskovitz, Jackob
Methionine sulfoxide (MetO) is a common posttranslational modification to proteins occurring in vivo. These modifications are prevalent when reactive oxygen species levels are increased. To enable the detection of MetO in pure and extracted proteins from various sources, we have developed novel antibodies that can recognize MetO-proteins. These antibodies are polyclonal antibodies raised against an oxidized methionine-rich zein protein (MetO-DZS18) that are shown to recognize methionine oxidation in pure proteins and mouse and yeast extracts. Furthermore, mouse serum albumin and immunoglobulin (IgG) were shown to accumulate MetO as function of age especially in serums of methionine sulfoxide reductase A knockout mice. Interestingly, high levels of methionine-oxidized IgG in serums of subjects diagnosed with Alzheimer's disease were detected by western blot analysis using these antibodies. It is suggested that anti-MetO-DZS18 antibodies can be applied in the identification of proteins that undergo methionine oxidation under oxidative stress, aging, or disease state conditions. PMID:19388147
Senile hair graying: H2O2-mediated oxidative stress affects human hair color by blunting methionine sulfoxide repair.
Wood, J M; Decker, H; Hartmann, H; Chavan, B; Rokos, H; Spencer, J D; Hasse, S; Thornton, M J; Shalbaf, M; Paus, R; Schallreuter, K U
Senile graying of human hair has been the subject of intense research since ancient times. Reactive oxygen species have been implicated in hair follicle melanocyte apoptosis and DNA damage. Here we show for the first time by FT-Raman spectroscopy in vivo that human gray/white scalp hair shafts accumulate hydrogen peroxide (H(2)O(2)) in millimolar concentrations. Moreover, we demonstrate almost absent catalase and methionine sulfoxide reductase A and B protein expression via immunofluorescence and Western blot in association with a functional loss of methionine sulfoxide (Met-S=O) repair in the entire gray hair follicle. Accordingly, Met-S=O formation of Met residues, including Met 374 in the active site of tyrosinase, the key enzyme in melanogenesis, limits enzyme functionality, as evidenced by FT-Raman spectroscopy, computer simulation, and enzyme kinetics, which leads to gradual loss of hair color. Notably, under in vitro conditions, Met oxidation can be prevented by L-methionine. In summary, our data feed the long-voiced, but insufficiently proven, concept of H(2)O(2)-induced oxidative damage in the entire human hair follicle, inclusive of the hair shaft, as a key element in senile hair graying, which does not exclusively affect follicle melanocytes. This new insight could open new strategies for intervention and reversal of the hair graying process.
40 CFR 721.10056 - Benzenemethanaminium, N-(3-aminopropyl)-N,N-dimethyl-, N-soya acyl derivs., chlorides.
...)-N,N-dimethyl-, N-soya acyl derivs., chlorides. 721.10056 Section 721.10056 Protection of Environment...-aminopropyl)-N,N-dimethyl-, N-soya acyl derivs., chlorides. (a) Chemical substance and significant new uses...-dimethyl-, N-soya acyl derivs., chlorides (PMN P-03-47; CAS No. 90194-13-1) is subject to reporting under...
40 CFR 721.1225 - Benzene, 1,2-dimethyl-, poly-propene derivatives, sulfonated, po-tas-sium salts.
... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Benzene, 1,2-dimethyl-, poly-propene... Significant New Uses for Specific Chemical Substances § 721.1225 Benzene, 1,2-dimethyl-, poly-propene... reporting. (1) The chemical substance identified as benzene, 1,2-dimethyl-, polypropene derivatives...
Study of an efficient conversion of 1,3-dimethyl-5-(Arylazo)-6-Amino-Uracils to 1,3-dimethyl-8-(Aryl)-Azapurin-2,6-Diones
Debnath, Diptanu; Purkayastha, Atanu; Kirillov, Alexander; Ganguly, Rakesh; Misra, Tarun Kumar
6-Aminouracils have extensively been used as precursors for synthesizing numerous uracil derivatives of biological and pharmaceutical significance. This study describes an application of 1,3-dimethyl-5-(arylazo)-6-aminouracils (Uazo: Uazo1-Uazo4, precursors) for an efficient synthesis of a series of 8-substituted-azapurins (AP), namely 1,3-dimethyl-8-(aryl)-azapurin-2,6-diones (aryl = p-HC6H4 (AP1), -MeC6H4 (AP2), sbnd ClC6H4 (AP3), and sbnd SO2NH2C6H4 (AP4)) following an oxidation method in the presence of copper (II) nitrate and in alkaline medium. The obtained compounds were isolated in good yields as crystalline air-stable products and have been fully characterized in the solution by UV-vis and NMR spectroscopy, as well as in the solid state by FT-IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction (for AP2 and AP4). UV-vis study evidences that the conversion of the 6-aminouracil precursors occurs via an intermediate, Cu(II)-complex and a plausible mechanism for the formation of AP1-AP4 has been proposed. Unlike AP2 the crystal structure of AP4 reveals the formation of interdigitated 1D H-bonded chains that has been topologically classified within the 2C1 type. The 1H NMR spectra of the products have proton signals that completely devoid of hydrazone (sbnd NHsbnd) and imine (=NH) signals of their parent Uazo derivatives, thus confirming their full conversion and a stability of the AP1-AP4 in solution. The excitation and emission spectra of AP1-AP4 were also recorded in solution, revealing electronic transitions between similar vibrational energy levels of S0 (singlet ground state) and S1 (singlet first excited state).
Synthesis of dimethyl carbonate in supercritical carbon dioxide
Directory of Open Access Journals (Sweden)
D. Ballivet-Tkatchenko
Full Text Available The reactivity of carbon dioxide with methanol to form dimethyl carbonate was studied in the presence of the n-butylmethoxytin compounds n-Bu3SnOCH3, n-Bu2Sn(OCH32 , and [n-Bu2(CH3OSn]2 O. The reaction occurred under solventless conditions at 423 K and was produced by an increase in CO2 pressure. This beneficial effect is primarily attributed to phase behavior. The mass transfer under liquid-vapor biphasic conditions was not limiting when the system reached the supercritical state for a CO2 pressure higher than 16 MPa. Under these conditions, CO2 acted as a reactant and a solvent.
Crystal structure of dichloridobis(dimethyl N-cyanodithioiminocarbonatecobalt(II
Directory of Open Access Journals (Sweden)
Mouhamadou Birame Diop
Full Text Available The structure of the mononuclear title complex, [{(H3CS2C=NC[triple-bond] N}2CoCl2], consists of a CoII atom coordinated in a distorted tetrahedral manner by two Cl− ligands and the terminal N atoms of two dimethyl N-cyanodithioiminocarbonate ligands. The two organic ligands are almost coplanar, with a dihedral angle of 5.99 (6° between their least-squares planes. The crystal packing features pairs of inversion-related complexes that are held together through C—H...Cl and C—H...S interactions and π–π stacking [centroid-to-centroid distance = 3.515 (su? Å]. Additional C—H...Cl and C—H...S interactions, as well as Cl...S contacts < 3.6 Å, consolidate the crystal packing.
Changes in Dimethyl Sulfide Oceanic Distribution due to Climate Change
Energy Technology Data Exchange (ETDEWEB)
Cameron-Smith, P; Elliott, S; Maltrud, M; Erickson, D; Wingenter, O
Dimethyl sulfide (DMS) is one of the major precursors for aerosols and cloud condensation nuclei in the marine boundary layer over much of the remote ocean. Here they report on coupled climate simulations with a state-of-the-art global ocean biogeochemical model for DMS distribution and fluxes using present-day and future atmospheric CO{sub 2} concentrations. They find changes in zonal averaged DMS flux to the atmosphere of over 150% in the Southern Ocean. This is due to concurrent sea ice changes and ocean ecosystem composition shifts caused by changes in temperature, mixing, nutrient, and light regimes. The largest changes occur in a region already sensitive to climate change, so any resultant local CLAW/Gaia feedback of DMS on clouds, and thus radiative forcing, will be particularly important. A comparison of these results to prior studies shows that increasing model complexity is associted with reduced DMS emissions at the equator and increased emissions at high latitudes.
Application of Dimethyl Ether in Compression Ignition Engines
DEFF Research Database (Denmark)
Hansen, Kim Rene
. The elastomer seals that provided the sealing instead of the metal-to-metal contact could do that because of the low injection pressure. The engine developed in this way was based on a 50cc Peugeot two-stroke engine. The fuel injector used was a Bosch HDEV originally developed for direct injection of gasoline......This study has its roots in two separate events at the Department of Mechanical Engineering at DTU. In 1995 the first attempt to operate a diesel engine on dimethyl ether (DME) was successfully concluded. In 2004 the department decided to compete in the vehicle fuel efficiency competition Shell Eco......-Marathon. The diesel engine test results from 1995 showed that DME is a superb diesel fuel. DME is easy to ignite by compression ignition and it has a molecular structure that results in near-zero emission of particulates when burned. These are features of a fuel that are highly desirable in a diesel engine...
Mutant form C115H of Clostridium sporogenes methionine γ-lyase efficiently cleaves S-Alk(en)yl-l-cysteine sulfoxides to antibacterial thiosulfinates.
Kulikova, Vitalia V; Anufrieva, Natalya V; Revtovich, Svetlana V; Chernov, Alexander S; Telegin, Georgii B; Morozova, Elena A; Demidkina, Tatyana V
Pyridoxal 5'-phosphate-dependent methionine γ-lyase (MGL) catalyzes the β-elimination reaction of S-alk(en)yl-l-cysteine sulfoxides to thiosulfinates, which possess antimicrobial activity. Partial inactivation of the enzyme in the course of the reaction occurs due to oxidation of active site cysteine 115 conserved in bacterial MGLs. In this work, the C115H mutant form of Clostridium sporogenes MGL was prepared and the steady-state kinetic parameters of the enzyme were determined. The substitution results in an increase in the catalytic efficiency of the mutant form towards S-substituted l-cysteine sulfoxides compared to the wild type enzyme. We used a sulfoxide/enzyme system to generate antibacterial activity in situ. Two-component systems composed of the mutant enzyme and three S-substituted l-cysteine sulfoxides were demonstrated to be effective against Gram-positive and Gram-negative bacteria and three clinical isolates from mice. © 2016 IUBMB Life, 68(10):830-835, 2016. © 2016 International Union of Biochemistry and Molecular Biology.
Observed and calculated 1H and 13C chemical shifts induced by the in situ oxidation of model sulfides to sulfoxides and sulfones
Czech Academy of Sciences Publication Activity Database
Dračínský, Martin; Pohl, Radek; Slavětínská, Lenka; Buděšínský, Miloš
Roč. 48, č. 9 (2010), s. 718-726 ISSN 0749-1581 R&D Projects: GA ČR GA203/09/1919 Institutional research plan: CEZ:AV0Z40550506 Keywords : NMR * DFT calculations * sulfoxides * 1H * 13C Subject RIV: CC - Organic Chemistry Impact factor: 1.247, year: 2010
Innovative Catalyst Development for Synthesis of Dimethyl Ether (DME): A Renewable Diesel Substitute
Taveras, Elizabeth
As a way to manage increasing levels of atmospheric carbon dioxide, advanced research has focused on efficient and sustainable biofuel production from catalytic carbon dioxide conversion. Furthermore, atmospheric levels of methane remain the second largest greenhouse gas emitted globally. Methane can be used as a feedstock to produce dimethyl ether (DME), a clean fuel that is a substitute for fossil diesel. Production of DME as an alternative diesel fuel is a two-step process: methanol synthesis followed by methanol dehydration. Research has shown that supported Cu-ZnO with gamma alumina is a promising catalyst for DME production. The focus of this research is catalytic dehydration of methanol over catalysts based on nano-sized Ni, Co and Cu. The catalysts were prepared by depositing nano-sized metal particles onto a mesoporous alumina support using sonolysis in a hexadecane solvent. The catalysts were separated from solution by centrifuge, dried and then evaluated for methanol dehydration reaction in a 300-mL Parr batch reactor. Initial reaction conditions were 260 ?C and 150 psig under nitrogen. The data demonstrated that Cu achieved the highest methanol conversion for DME production. DME was identified using FT-IR.
Research on the degradation mechanism of dimethyl phthalate in drinking water by strong ionization discharge
Hong, ZHAO; Chengwu, YI; Rongjie, YI; Huijuan, WANG; Lanlan, YIN; I, N. MUHAMMAD; Zhongfei, MA
The degradation mechanism of dimethyl phthalate (DMP) in the drinking water was investigated using strong ionization discharge technology in this study. Under the optimized condition, the degradation efficiency of DMP in drinking water was up to 93% in 60 min. A series of analytical techniques including high-performance liquid chromatography, liquid chromatography mass spectrometry, total organic carbon analyzer and ultraviolet-visible spectroscopy were used in the study. It was found that a high concentration of ozone (O3) produced by dielectric barrier discharge reactor was up to 74.4 mg l-1 within 60 min. Tert-butanol, isopropyl alcohol, carbonate ions ({{{{CO}}}3}2-) and bicarbonate ions ({{{{HCO}}}3}-) was added to the sample solution to indirectly prove the presence and effect of hydroxyl radicals (·OH). These analytical findings indicate that mono-methyl phthalate, phthalic acid (PA) and methyl ester PA were detected as the major intermediates in the process of DMP degradation. Finally, DMP and all products were mineralized into carbon dioxide (CO2) and water (H2O) ultimately. Based on these analysis results, the degradation pathway of DMP by strong ionization discharge technology were proposed.
Model films of cellulose. I. Method development and initial results
Gunnars, S.; Wågberg, L.; Cohen Stuart, M.A.
This report presents a new method for the preparation of thin cellulose films. NMMO (N- methylmorpholine- N-oxide) was used to dissolve cellulose and addition of DMSO (dimethyl sulfoxide) was used to control viscosity of the cellulose solution. A thin layer of the cellulose solution is spin- coated
Natural 4-Hydroxy-2,5-dimethyl-3(2H)-furanone (Furaneol®)
Wilfried Schwab
4-Hydroxy-2,5-dimethyl-3(2H)-furanone (HDMF, furaneol®) and its methyl ether 2,5-dimethyl-4-methoxy-3(2H)-furanone (DMMF) are import aroma chemicals and are considered key flavor compounds in many fruit. Due to their attractive sensory properties they are highly appreciated by the food industry. In fruits 2,5-dimethyl-3(2H)-furanones are synthesized by a series of enzymatic steps whereas HDMF is also a product of the Maillard reaction. Numerous methods for the synthetic preparation of these c...
Adsorption kinetics of diblock copolymers from a micellar solution on silica and titania.
Bijsterbosch, H.D.; Cohen Stuart, M.A.; Fleer, G.J.
The solution and adsorption behavior of a series of diblock copolymers of hydrophobic poly(dimethyl siloxane) and hydrophilic poly(2-ethyl-2-oxazoline) was studied. These block copolymers formed large polydisperse micelles in an aqueous solution. The critical micelle concentration was lower than 2
CCDC 894987: Experimental Crystal Structure Determination : (2-(1,3-bis(2,6-Di-isopropylphenyl)-1,3,2-diazaphospholidin-2-yl)benzenesulfonato)-(dimethyl sulfoxide-O)-methyl-palladium(ii)
Wucher, Philipp
An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Hydration of Sulpho and Methyl Groups in Dimethyl Sulfoxide is Accompanied by Formation of Red-Shifted Hydrogen Bonds and Improper Blue-Shifted Hydrogen Bonds: An ab initio Quantum Chemical Study
Czech Academy of Sciences Publication Activity Database
Mrázková, Eva; Hobza, Pavel
Roč. 107, č. 7 (2003), s. 1032-1039 ISSN 1089-5639 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : DONOR * fluorobenzene * spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.792, year: 2003
Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions.
Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G
We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the "D" stands for "density" to denote that the full solute electron density is used without defining partial atomic charges. "Continuum" denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where "universal" denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which a few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous
Microwave-Assisted Synthesis of Nanoporous Aluminum-Based Coordination Polymers as Catalysts for Selective Sulfoxidation Reaction
Directory of Open Access Journals (Sweden)
Madhan Vinu
Full Text Available A series of aluminum-based coordination polymers or metal–organic frameworks (Al–MOFs, i.e., DUT-4, DUT-5, MIL-53, NH2-MIL-53, and MIL-100, have been facile prepared by microwave (MW-assisted reactions and used as catalysts for selective sulfoxidation reactions. The MW-assisted synthesis drastically reduced the reaction time from few days to hours. The prepared MOFs have smaller and uniform particle sizes and better yield compared to conventional hydrothermal method. Furthermore, the Al–MOFs have been successfully demonstrated as catalysts in oxidation reaction of methyl phenyl sulfide with H2O2 as oxidant, even under mild conditions, with more than 95% conversion.
Functional Null Mutations of MSRB3 Encoding Methionine Sulfoxide Reductase Are Associated with Human Deafness DFNB74
Ahmed, Zubair M.; Yousaf, Rizwan; Lee, Byung Cheon; Khan, Shaheen N.; Lee, Sue; Lee, Kwanghyuk; Husnain, Tayyab; Rehman, Atteeq Ur; Bonneux, Sarah; Ansar, Muhammad; Ahmad, Wasim; Leal, Suzanne M.; Gladyshev, Vadim N.; Belyantseva, Inna A.; Van Camp, Guy; Riazuddin, Sheikh; Friedman, Thomas B.; Riazuddin, Saima
The DFNB74 locus for autosomal-recessive, nonsyndromic deafness segregating in three families was previously mapped to a 5.36 Mb interval on chromosome 12q14.2-q15. Subsequently, we ascertained five additional consanguineous families in which deafness segregated with markers at this locus and refined the critical interval to 2.31 Mb. We then sequenced the protein-coding exons of 18 genes in this interval. The affected individuals of six apparently unrelated families were homozygous for the same transversion (c.265T>G) in MSRB3, which encodes a zinc-containing methionine sulfoxide reductase B3. c.265T>G results in a substitution of glycine for cysteine (p.Cys89Gly), and this substitution cosegregates with deafness in the six DFNB74 families. This cysteine residue of MSRB3 is conserved in orthologs from yeast to humans and is involved in binding structural zinc. In vitro, p.Cys89Gly abolished zinc binding and MSRB3 enzymatic activity, indicating that p.Cys89Gly is a loss-of-function allele. The affected individuals in two other families were homozygous for a transition mutation (c.55T>C), which results in a nonsense mutation (p.Arg19X) in alternatively spliced exon 3, encoding a mitochondrial localization signal. This finding suggests that DFNB74 deafness is due to a mitochondrial dysfunction. In a cohort of 1,040 individuals (aged 53–67 years) of European ancestry, we found no association between 17 tagSNPs for MSRB3 and age-related hearing loss. Mouse Msrb3 is expressed widely. In the inner ear, it is found in the sensory epithelium of the organ of Corti and vestibular end organs as well as in cells of the spiral ganglion. Taken together, MSRB3-catalyzed reduction of methionine sulfoxides to methionine is essential for hearing. PMID:21185009
Methionine sulfoxide reductase B3 deficiency stimulates heme oxygenase-1 expression via ROS-dependent and Nrf2 activation pathways
Energy Technology Data Exchange (ETDEWEB)
Kwak, Geun-Hee; Kim, Ki Young; Kim, Hwa-Young, E-mail: firstname.lastname@example.com
Methionine sulfoxide reductase B3 (MsrB3), which is primarily found in the endoplasmic reticulum (ER), is an important protein repair enzyme that stereospecifically reduces methionine-R-sulfoxide residues. We previously found that MsrB3 deficiency arrests the cell cycle at the G{sub 1}/S stage through up-regulation of p21 and p27. In this study, we report a critical role of MsrB3 in gene expression of heme oxygenase-1 (HO-1), which has an anti-proliferative effect associated with p21 up-regulation. Depletion of MsrB3 elevated HO-1 expression in mammalian cells, whereas MsrB3 overexpression had no effect. MsrB3 deficiency increased cellular reactive oxygen species (ROS), particularly in the mitochondria. ER stress, which is associated with up-regulation of HO-1, was also induced by depletion of MsrB3. Treatment with N-acetylcysteine as an ROS scavenger reduced augmented HO-1 levels in MsrB3-depleted cells. MsrB3 deficiency activated Nrf2 transcription factor by enhancing its expression and nuclear import. The activation of Nrf2 induced by MsrB3 depletion was confirmed by increased expression levels of its other target genes, such as γ-glutamylcysteine ligase. Taken together, these data suggest that MsrB3 attenuates HO-1 induction by inhibiting ROS production, ER stress, and Nrf2 activation. -- Highlights: •MsrB3 depletion induces HO-1 expression. •MsrB3 deficiency increases cellular ROS and ER stress. •MsrB3 deficiency activates Nrf2 by increasing its expression and nuclear import. •MsrB3 attenuates HO-1 induction by inhibiting ROS production and Nrf2 activation.
Methionine Sulfoxide Reductase A Deficiency Exacerbates Cisplatin-Induced Nephrotoxicity via Increased Mitochondrial Damage and Renal Cell Death.
Noh, Mi Ra; Kim, Ki Young; Han, Sang Jun; Kim, Jee In; Kim, Hwa-Young; Park, Kwon Moo
Methionine sulfoxide reductase A (MsrA), which is abundantly localized in the mitochondria, reduces methionine-S-sulfoxide, scavenging reactive oxygen species (ROS). Cisplatin, an anticancer drug, accumulates at high levels in the mitochondria of renal cells, causing mitochondrial impairment that ultimately leads to nephrotoxicity. Here, we investigated the role of MsrA in cisplatin-induced mitochondrial damage and kidney cell death using MsrA gene-deleted (MsrA -/- ) mice. Cisplatin injection resulted in increases of ROS production, methionine oxidation, and oxidative damage in the kidneys. This oxidative stress was greater in MsrA -/- mouse kidneys than in wild-type (MsrA +/+ ) mouse kidneys. MsrA gene deletion exacerbated cisplatin-induced reductions in the expression and activity of MsrA and MsrBs, and the expression of thioredoxin 1, glutathione peroxidase 1 and 4, mitochondrial superoxide dismutase, cystathionine-β-synthase, and cystathionine-γ-lyase. Cisplatin induced swelling, cristae loss, and fragmentation of mitochondria with increased lipid peroxidation, more so in MsrA -/- than in MsrA +/+ kidneys. The ratio of mitochondrial fission regulator (Fis1) to fusion regulator (Opa1) was higher in MsrA -/- than MsrA +/+ mice. MsrA deletion exacerbated cisplatin-induced increases in Bax to Bcl-2 ratio, cleaved caspase-3 level, and apoptosis, whereas MsrA overexpression attenuated cisplatin-induced oxidative stress and apoptosis. MsrA gene deletion in mice exacerbates cisplatin-induced renal injury through increases of mitochondrial susceptibility, whereas MsrA overexpression protects cells against cisplatin. This study demonstrates that MsrA protects kidney cells against cisplatin-induced methionine oxidation, oxidative stress, mitochondrial damage, and apoptosis, suggesting that MsrA could be a useful target protein for the treatment of cisplatin-induced nephrotoxicity. Antioxid. Redox Signal. 27, 727-741.
Kinetics of periodate oxidation of tris -(4,4'-dimethyl-2,2'-bipyridine ...
African Journals Online (AJOL)
dimethyl-2,2'-bipyridine) iron(II) in acid medium was investigated. The complex undergoes extensive protonation in acid medium. Both protonated and the unprotonated species undergo electron transfer reaction with the active periodate species ...
Biosynthesis of glycerol carbonate from glycerol by lipase in dimethyl carbonate as the solvent.
Lee, Kyung Hwa; Park, Chang-Ho; Lee, Eun Yeol
Glycerol carbonate was synthesized from renewable glycerol and dimethyl carbonate using lipase in solvent-free reaction system in which excess dimethyl carbonate played as the reaction medium. A variety of lipases have been tested for their abilities to catalyze transesterification reaction, and Candida antartica lipase B and Novozyme 435 exhibited higher catalytic activities. The silica-coated glycerol with a 1:1 ratio was supplied to prevent two-phase formation between hydrophobic dimethyl carbonate and hydrophilic glycerol. Glycerol carbonate was successfully synthesized with more than 90% conversion from dimethyl carbonate and glycerol with a molar ratio of 10 using Novozyme 435-catalyzed transesterification at 70 °C. The Novozyme 435 [5% (w/w) and 20% (w/w)] and silica gel were more than four times recycled with good stability in a repeated batch operation for the solvent-free synthesis of glycerol carbonate.
Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether
DeMore, W.; Bayes, K.
Relative rate experiements were used to measure rate constants and temperature denpendencies of the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, and dimethyl ether.
Oxovanadium and oxouranium complexes of 3-7 dimethyl 7-hydroxy octane-1-al
International Nuclear Information System (INIS)
Nagar, Meena; Baslas, R.K.
The present communication deals with the preparation and characterisation of metal complexes of vanadyl and uranyl ions with 3-7 dimethyl 7-hydroxy octane 1-al and their stabilities were calculated by Job's and Bjerrum methods. (author)
Fixation of carbon dioxide into dimethyl carbonate over titanium-based zeolitic thiophene-benzimidazolate framework
U.S. Environmental Protection Agency — A titanium-based zeolitic thiophene-benzimidazolate framework has been designed for the direct synthesis of dimethyl carbonate (DMC) from methanol and carbon...
Modeling of a Reaction-Distillation-Recycle System to Produce Dimethyl Ether through Methanol Dehydration
Muharam, Y.; Zulkarnain, L. M.; Wirya, A. S.
The increase in the dimethyl ether yield through methanol dehydration due to a recycle integration to a reaction-distillation system was studied in this research. A one-dimensional phenomenological model of a methanol dehydration reactor and a shortcut model of distillation columns were used to achieve the aim. Simulation results show that 10.7 moles/s of dimethyl ether is produced in a reaction-distillation system with the reactor length being 4 m, the reactor inlet pressure being 18 atm, the reactor inlet temperature being 533 K, the reactor inlet velocity being 0.408 m/s, and the distillation pressure being 8 atm. The methanol conversion is 90% and the dimethyl ether yield is 48%. The integration of the recycle stream to the system increases the dimethyl ether yield by 8%.
The stability study of myristyl dimethyl amine oxide as an amphoteric ...
African Journals Online (AJOL)
The stability study of myristyl dimethyl amine oxide as an amphoteric surfactant in strong oxidant media containing 5 % m/m sodium hypochlorite through measurement of decomposing rate using high performance liquid chromatography and two phase titration.
Alkaline hydrolysis of dimethyl terephthalate in the presence of [LiAl2(OH)6]Cl.2H2O
International Nuclear Information System (INIS)
Lei Lixu; Zhang Weifeng; Hu Meng; Zheng Hegen
The alkaline hydrolysis of dimethyl terephthalate (DMT) in the presence of [LiAl 2 (OH) 6 ]Cl has been investigated to demonstrate a possible application of anion exchange facility of layered double hydroxides (LDHs) to control chemical reactions. The results show that (i) in the alkaline hydrolysis of DMT in the presence of [LiAl 2 (OH) 6 ]Cl, most of the interlayer Cl - of [LiAl 2 (OH) 6 ]Cl is quickly replaced by OH - in the alkaline solution because the LDH host favors OH - more; (ii) the alkaline hydrolysis of DMT in the presence of [LiAl 2 (OH) 6 ]Cl is faster than the reaction of DMT and [LiAl 2 (OH) 6 ]OH; (iii) The hydrolysis of DMT in a buffer solution of pH∼8 takes longer time to reach equilibrium than the alkaline hydrolysis of DMT in the presence of [LiAl 2 (OH) 6 ]Cl. It is believed that the selective anion exchange chemistry of the LDH plays a key role in storage and controlled release of active reactant, that is, OH - , thus make the hydrolysis proceeds in a controlled way. - Graphical abstract: XRD patterns of the solid products of the alkaline hydrolysis of dimethyl terephthalate (DMT) in the presence of [LiAl 2 (OH) 6 ]Cl at 70 deg. C halted at different time, which shows that [LiAl 2 (OH) 6 ]Cl turns out to be [LiAl 2 (OH) 6 ]OH, and [LiAl 2 (OH) 6 ] 2 TP forms gradually. In this reaction, the alkaline hydrolysis of DMT is controlled by replacement of Cl - in [LiAl 2 (OH) 6 ]Cl by OH - , and subsequent replacement of OH - in [LiAl 2 (OH) 6 ]OH by terephthalate anion
Synthesis of Dimethyl Aryl Acylsulfonium Bromides from Aryl Methyl Ketones in a DMSO-HBr System
Directory of Open Access Journals (Sweden)
Zhiling Cao
Full Text Available A new, simplified method for the synthesis of dimethyl aryl acylsulfonium salts has been developed. A series of dimethyl aryl acylsulfonium bromides were prepared by the reaction of aryl methyl ketones with hydrobromic acid and dimethylsulfoxide (DMSO. This sulfonium salt confirms that bromine production and the bromination reaction take place in the DMSO-HBr oxidation system. What's more, it is also a key intermediate for the synthesis of arylglyoxals.
Synthesis of dimethyl aryl acylsulfonium bromides from aryl methyl ketones in a DMSO-HBr system.
Cao, Zhiling; Shi, Dahua; Qu, Yingying; Tao, Chuanzhou; Liu, Weiwei; Yao, Guowei
A new, simplified method for the synthesis of dimethyl aryl acylsulfonium salts has been developed. A series of dimethyl aryl acylsulfonium bromides were prepared by the reaction of aryl methyl ketones with hydrobromic acid and dimethylsulfoxide (DMSO). This sulfonium salt confirms that bromine production and the bromination reaction take place in the DMSO-HBr oxidation system. What's more, it is also a key intermediate for the synthesis of arylglyoxals.
A novel preparation of methyl-β-cyclodextrin from dimethyl carbonate and β-cyclodextrin
DEFF Research Database (Denmark)
Gan, Yongjiang; Zhang, Yimin; Xiao, Chuanhao
A novel green synthesis process about methyl-β-cyclodextrin has been investigated through the reaction between β-cyclodextrin and dimethyl carbonate by anhydrous potassium carbonate as catalyst in DMF. The influence of experimental factors including the molar ratio of dimethyl carbonate to β-cycl...... of methyl-β-cyclodextrin were characterized by TLC, IR, MS, 1H NMR, and 13C NMR....
Dimethyl ether. A fuel for the 21st century
Energy Technology Data Exchange (ETDEWEB)
Fleisch, T.H.; Basu, A.; Gradassi, M.J.; Masin, J.G. [Gas Transportation and Upgrading Division, Amoco, Exploration and Production Technology Group, Naperville, IL (United States)
For several years Amoco has been involved in research and development work on the synthesis of liquid fuels from natural gas. In a recent collaborative work with Haldor Topsoe S/A, AVL LIST GmbH and Navistar, Amoco has identified Dimethyl Ether (DME) as a new, ultraclean alternative fuel for diesel engines. DME can be handled like LPG, an important alternative transportation fuel. Preliminary engine test data for DME, showing emission levels better than the California 1998 ULEV standards, were recently reported at the 1995 SAE conference in Detroit, Michigan. DME is today manufactured from methanol and is primarily used as an aerosol propellant due to its environmentally benign characteristics. Haldor Topsoe has developed a process for direct production of DME from natural gas, coal or biomass. The process can be used for large scale (about 40.000 BSD diesel equivalent) manufacture of DME from natural gas using predominantly single-train process units. In this paper, we will provide an overview of the attractiveness of DME as an environmentally and customer-friendly diesel fuel option. 14 refs.
Removal of dimethyl phthalate from water by ozone microbubbles.
Jabesa, Abdisa; Ghosh, Pallab
This work investigates the removal of dimethyl phthalate (DMP) from water using ozone microbubbles in a pilot plant of 20 dm 3 capacity. Experiments were performed under various reaction conditions to examine the effects of the initial concentration of DMP, pH of the medium, ozone generation rate, and the role of H 2 O 2 on the removal of DMP. The DMP present in water was effectively removed by the ozone microbubbles. The removal was effective in neutral and alkaline media. Increase in the initial concentration of the target pollutant negatively affected its removal efficiency. The removal efficiency dramatically increased from 1% to 99% when the ozone generation rate was increased from 0.28 to 1.94 mg s -1 at pH 7. The total organic carbon measurements revealed that a complete mineralization of DMP was achieved within 1.8 ks at the high ozone feed rate. The use of t-butyl alcohol as the hydroxyl radical scavenger confirmed that the reaction between the target organic compound and ·OH radical dominated over its direct reaction with ozone. The reaction between DMP and ozone followed an overall second-order kinetics. The volumetric mass transfer coefficient of ozone in the reacting system and the enhancement factor increased with increasing initial concentration of DMP. Very low values of Hatta number were obtained at all initial concentrations of DMP and pH, which show that the mass transfer resistance was small.
Photoluminescence of 1,3-dimethyl pyrazoloquinoline derivatives
International Nuclear Information System (INIS)
Koscien, E.; Gondek, E.; Pokladko, M.; Jarosz, B.; Vlokh, R.O.; Kityk, A.V.
This paper presents absorption and photoluminescence of 6-F, 6-Br, 6-Cl, 7-TFM and 6-COOEt derivatives of 1,3-dimethyl-1H-Pyrazolo[3,4-b]quinoline (DMPQ). The measured absorption and emission spectra are compared with the quantum chemical calculations performed by means of the semi-empirical methods (AM1 or PM3) that are applied either to the equilibrium conformations in vacuo (T = 0 K) or combined with the molecular dynamics simulations (T = 300 K). The spectra calculated by the AM1 method appear to be for all dyes in practically excellent agreement with the measured ones. In particular, the position of the first absorption band is obtained with the accuracy up to a few nanometers, whereas the calculated photoluminescence spectra predict the positions of the emission maxima for a gas phase with the accuracy up to 10-18 nm. The photoemission spectra of DMPQ dyes are considerably less solvatochromic comparing to phenyl-containing pyrazoloquinoline derivatives. According to the quantum chemical analysis the reason for such behaviour lies in a local character of the electronic transitions of DMPQ dyes which are characterized by a relatively small difference between the excited state and ground state dipole moments. Importantly that the rotational dynamics of both methyl subunits does not change this situation
Aeration tank odour by dimethyl sulphoxide (DMSO) waste in sewage.
Glindemann, D; Novak, J T; Witherspoon, J
Sewage plants can experience dimethyl sulphide (DMS) odour problems by at least one mg/L dimethylsulphoxide (DMSO) waste residue in plant influent, through a DMSO/DMS reduction mechanism. This bench-scale batch study simulates in bottles the role of poor aeration in wastewater treatment on the DMSO/DMS and sulphate/H2S reduction. The study compares headspace concentrations of sulphide odorants developed by activated sludge (closed bottles, half full) after six hours under anoxic versus anaerobic conditions, with 0 versus 2 mg/L DMSO addition. Anoxic sludge (0.1 - 2 mg/L dissolved oxygen, DO) with DMSO resulted in about 50 ppmv DMS and no other sulphide, while DMSO-free sludge was free of detectable sulphides. Anaerobic sludge (no measurable DO to the point of sulphate reduction) with DMSO resulted in 22/4/37 ppmv of H2S/methanethiol (MT)/DMS, while DMSO-free sludge resulted in 44/8/2 ppmv of H2S/MT/DMS. It is concluded that common "anoxic" aeration tank zones with measurable DO in bulk water but immeasurable DO inside sludge flocs (nitrate reducing) experience DMSO reduction to DMS that is oxidation resistant and becomes the most important odorant. Under anaerobic conditions, H2S from sulphate reduction becomes an additional important odorant. A strategy is developed that allows operators to determine from the quantity of different sulphides whether the DMSO/DMS mechanism is important at their wastewater plant.
Examining Dimethyl Sulfide Emissions in California's San Joaquin Valley
Huber, D.; Hughes, S.; Blake, D. R.
Dimethyl Sulfide (DMS) is a sulfur-containing compound that leads to the formation of aerosols which can lead to the formation of haze and fog. Whole air samples were collected on board the NASA C-23 Sherpa aircraft during the 2017 Student Airborne Research Program (SARP) over dairies and agricultural fields in the San Joaquin Valley. Analysis of the samples indicate average DMS concentrations of 23 ± 9 pptv, with a maximum concentration of 49 pptv. When compared with DMS concentrations from previous SARP missions (2009-2016), 2017 by far had the highest frequency of elevated DMS in this region. For this study, agricultural productivity of this region was analyzed to determine whether land use could be contributing to the elevated DMS. Top down and bottom up analysis of agriculture and dairies were used to determine emission rates of DMS in the San Joaquin Valley. Correlations to methane and ethanol were used to determine that DMS emissions were strongly linked to dairies, and resulted in R2 values of 0.61 and 0.43, respectively. These values indicate a strong correlation between dairies and DMS emissions. Combined with NOAA HySPLIT back trajectory data and analysis of ground air samples, results suggest that the contribution of dairies to annual DMS emissions in the San Joaquin Valley exceeds those from corn and alfalfa production.
Dimethyl Sulfide is a Chemical Attractant for Reef Fish Larvae.
Foretich, Matthew A; Paris, Claire B; Grosell, Martin; Stieglitz, John D; Benetti, Daniel D
Transport of coral reef fish larvae is driven by advection in ocean currents and larval swimming. However, for swimming to be advantageous, larvae must use external stimuli as guides. One potential stimulus is "odor" emanating from settlement sites (e.g., coral reefs), signaling the upstream location of desirable settlement habitat. However, specific chemicals used by fish larvae have not been identified. Dimethyl sulfide (DMS) is produced in large quantities at coral reefs and may be important in larval orientation. In this study, a choice-chamber (shuttle box) was used to assess preference of 28 pre-settlement stage larvae from reef fish species for seawater with DMS. Swimming behavior was examined by video-tracking of larval swimming patterns in control and DMS seawater. We found common responses to DMS across reef fish taxa - a preference for water with DMS and change in swimming behavior - reflecting a switch to "exploratory behavior". An open water species displayed no response to DMS. Affinity for and swimming response to DMS would allow a fish larva to locate its source and enhance its ability to find settlement habitat. Moreover, it may help them locate prey accumulating in fronts, eddies, and thin layers, where DMS is also produced.
Synthesis of dimethyl carbonate from urea and methanol
Energy Technology Data Exchange (ETDEWEB)
Polyakov, M.; Kalevaru, V.N.; Martin, A. [Rostock Univ. (Germany). Leibniz Institute for Catalysis; Mueller, K.; Arlt, W. [Erlangen-Nuernberg Univ. (Germany); Strautmann, J.; Kruse, D. [Evonik Industries AG, Marl (Germany). Creavis Technologies and Innovation
Alcoholation of urea with methanol to produce dimethyl carbonate (DMC) is an interesting approach from both the ecological and economical points of view because the urea synthesis usually occurs by the direct use of carbon dioxide. Literature survey reveals that metal oxide catalysts for instance MgO, ZnO, etc. or polyphosphoric acids are mostly used as catalysts for this reaction. In this contribution, we describe the application of ZnO, MgO, CaO, TiO{sub 2}, ZrO{sub 2} or Al{sub 2}O{sub 3} catalysts for the above mentioned reaction. The catalytic activity of different metal oxides towards DMC synthesis was checked and additionally a comparison of achieved conversions with that of predictions made by thermodynamic calculations was also carried out. The achieved conversions are in good agreement with those of calculated ones. The test results reveal that the reaction pressure and temperature have a strong influence on the formation of DMC. Higher reaction pressure improved the yield of DMC. Among different catalysts investigated, ZnO displayed the best performance. The conversion of urea in most cases is close to 100 % and methyl carbamate MC is the major product of the reaction. A part of MC is subsequently converted to DMC, which however depends upon the reaction conditions applied and nature of catalyst used. From the best case, a DMC yield of ca. 8 % could be successfully achieved over ZnO catalyst. (orig.)
Penguins are attracted to dimethyl sulphide at sea.
Wright, Kyran L B; Pichegru, Lorien; Ryan, Peter G
Breeding Spheniscus penguins are central place foragers that feed primarily on schooling pelagic fish. They are visual hunters, but it is unclear how they locate prey patches on a coarse scale. Many petrels and storm petrels (Procellariiformes), the penguins' closest relatives, use olfactory cues to locate prey concentrations at sea, but this has not been demonstrated for penguins. Procellariiforms are attracted to a variety of olfactory cues, including dimethyl sulphide (DMS), an organosulphur compound released when phytoplankton is grazed, as well as fish odorants such as cod liver oil. A recent study found that African penguins Spheniscus demersus react to DMS on land. We confirm this result and show that African penguins are also attracted by DMS at sea. DMS-scented oil slicks attracted 2-3 times more penguins than control slicks, whereas penguins showed no response to slicks containing cod liver oil. The number of penguins attracted to DMS increased for at least 30 min, suggesting penguins could travel up to 2 km to reach scent cues. Repeats of land-based trials confirmed previous results showing DMS sensitivity of penguins on land. Our results also support the hypothesis that African penguins use DMS as an olfactory cue to locate prey patches at sea from a distance, which is particularly important given their slow commuting speed relative to that of flying seabirds.
Metformin (dimethyl-biguanide induced DNA damage in mammalian cells
Directory of Open Access Journals (Sweden)
Rubem R. Amador
Full Text Available Metformin (dimethyl-biguanide is an insulin-sensitizing agent that lowers fasting plasma-insulin concentration, wherefore it's wide use for patients with a variety of insulin-resistant and prediabetic states, including impaired glucose tolerance. During pregnancy it is a further resource for reducing first-trimester pregnancy loss in women with the polycystic ovary syndrome. We tested metformin genotoxicity in cells of Chinese hamster ovary, CHO-K1 (chromosome aberrations; comet assays and in mice (micronucleus assays. Concentrations of 114.4 µg/mL and 572 µg/mL were used in in vitro tests, and 95.4 mg/kg, 190.8 mg/kg and 333.9 mg/kg in assaying. Although the in vitro tests revealed no chromosome aberrations in metaphase cells, DNA damage was detected by comet assaying after 24 h of incubation at both concentrations. The frequency of DNA damage was higher at concentrations of 114.4 µg/mL. Furthermore, although mortality was not observed in in vitro tests, the highest dose of metformin suppressed bone marrow cells. However, no statistically significant differences were noted in micronuclei frequencies between treatments. In vitro results indicate that chronic metformin exposure may be potentially genotoxic. Thus, pregnant woman undergoing treatment with metformin should be properly evaluated beforehand, as regards vulnerability to DNA damage.
Bio-Based Production of Dimethyl Itaconate From Rice Wine Waste-Derived Itaconic Acid.
Joo, Young-Chul; You, Seung Kyou; Shin, Sang Kyu; Ko, Young Jin; Jung, Ki Ho; Sim, Sang A; Han, Sung Ok
Dimethyl itaconate is an important raw material for copolymerization, but it is not synthesized from itaconic acid by organisms. Moreover, Corynebacterium glutamicum is used as an important industrial host for the production of organic acids, but it does not metabolize itaconic acid. Therefore, the biosynthetic route toward dimethyl itaconate from itaconic acid is highly needed. In this study, a biological procedure for dimethyl itaconate production is developed from rice wine waste-derived itaconic acid using the engineered C. glutamicum strain. The first step is to investigate the effect of the co-overexpression of the codon-optimized cis-aconitic acid decarboxylase (CadA*) and a transcriptional regulator of genes involved in acetic acid metabolism (RamA) on itaconic acid production. The second step is to convert itaconic acid into dimethyl itaconate by lipase-catalyzed esterification. The CadA* and RamA-overexpressing CG4 strain increases the itaconic acid concentration under N-starvation with glucose and acetic acid compared with the concentration produced in the base mCGXII medium with glucose. Furthermore, the rice wine waste-derived itaconic acid is successfully converted into dimethyl itaconate using lipase from Rhizomucor miehei and a methanol substrate. This study is the first trial for bio-based production of dimethyl itaconate from rice wine waste-derived itaconic acid. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Energy Technology Data Exchange (ETDEWEB)
Elana M. Chapman; Shirish Bhide; Jennifer Stefanik; Howard Glunt; Andre L. Boehman; Allen Homan; David Klinikowski
The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethyl ether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. Their strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. The bulk of the efforts over the past year were focused on the conversion of the campus shuttle bus. This process, started in August 2001, took until April 2002 to complete. The process culminated in an event to celebrate the launching of the shuttle bus on DME-diesel operation on April 19, 2002. The design of the system on the shuttle bus was patterned after the system developed in the engine laboratory, but also was subjected to a rigorous failure modes effects analysis (FMEA, referred to by Air Products as a ''HAZOP'' analysis) with help from Dr. James Hansel of Air Products. The result of this FMEA was the addition of layers of redundancy and over-pressure protection to the system on the shuttle bus. The system became operational in February 2002. Preliminary emissions tests and basic operation of the shuttle bus took place at the Pennsylvania Transportation Institute's test track facility near the University Park airport. After modification and optimization of the system on
Evaluation of the dimethyl sulphide distribution in the ECHAM model
Energy Technology Data Exchange (ETDEWEB)
Glantz, P.; Kjellstroem, E. [Stockholm Univ. (Sweden). Dept. of Meteorology, Arrhenius Lab.; Feichter, J. [Max-Planck-Institut fuer Meteorologie, Hamburg (Germany)
The three-dimensional model ECHAM has been used to simulate dimethyl sulphide (DMS) concentrations in the global troposphere. Emission of DMS from natural sources and a simple scheme for the oxidation of DMS have been introduced in the ECHAM sulphur model developed at the Max-Planck-Institute for meteorology in Hamburg. In this study we focus on the contribution to the atmospheric sulphur burden of DMS emissions from the oceans. Calculation with the ECHAM model, based on prescribed ocean water concentrations, gives a global annual oceanic emission of 13 Tg DMS-S. This figure has been adjusted to 16 Tg in order to bring it in better agreement with other estimates. The calculated turn-over time for DMS is 2.2 days globally, which is in the range of previous estimates. For DMS in the atmospheric surface layer, the agreement between simulated and observed concentrations is within a factor of {+-} 2 at low latitudes. However, in the southern hemisphere a significant overestimate of the simulated DMS occurs at high latitudes in summer and at mid and high latitudes in winter. Comparing with long-term measurements at Cape Grim and Amsterdam Island in the Southern Ocean during winter gives a difference of one order of magnitude and a factor of 3, respectively. At Drake Passage in the Antarctic Ocean during November the model predicts a factor of 5 higher concentrations than measurements performed over this area. The limited number of observations of DMS concentrations in sea-water indicates that the concentrations prescribed in the model might be nearly a factor of 2 too high in the southern hemisphere during fall, winter and spring. The results indicate the need for future model refinements with respect both to the biogenic emission and possibly also oxidants. 48 refs, 6 figs, 3 tabs
Design, synthesis and biological evaluation of (E)-3,4-dihydroxystyryl 4-acylaminophenethyl sulfone, sulfoxide derivatives as dual inhibitors of HIV-1 CCR5 and integrase.
Sun, Yixing; Xu, Weisi; Fan, Ningning; Sun, Xuefeng; Ning, Xianling; Ma, Liying; Liu, Junyi; Wang, Xiaowei
Aiming at the limited effectiveness of current clinical therapeutic effect of AIDS, novel series of compounds bearing (E)-3,4-dihydroxystyryl sulfone (or sulfoxide) and anilide fragments were designed and synthesized as dual inhibitors of HIV-1 CCR5/IN. The biological results indicated that several target compounds showed inhibitory activity against HIV-1 Bal (R5) infection in TZM-bl cells. Besides targeting the chemokine receptor on the host cell surface, they also displayed binding affinities with HIV-1 integrase using the surface plasmon resonance (SPR) binding assays. Molecular docking studies have inferred the possible binding mode of target compounds against integrase. These data demonstrate that the structure of (E)-3,4-dihydroxystyryl sulfone and sulfoxide derivatives have the potential to derive potent dual inhibitors of HIV-1 Integrase and CCR5. Copyright © 2017 Elsevier Ltd. All rights reserved.
Tocolytic action and underlying mechanism of galetin 3,6-dimethyl ether on rat uterus.
Carreiro, Juliana da Nóbrega; Souza, Iara Leão Luna de; Pereira, Joedna Cavalcante; Vasconcelos, Luiz Henrique César; Travassos, Rafael de Almeida; Santos, Barbara Viviana de Oliveira; Silva, Bagnólia Araújo da
Galetin 3,6-dimethyl ether (FGAL) is a flavonoid isolated from aerial parts of Piptadenia stipulacea. Previously, FGAL was shown to inhibit both carbachol- and oxytocin-induced phasic contractions in the rat uterus, which was more potent with oxytocin. Thus, in this study, we aimed to investigate the tocolytic action mechanism of FGAL on the rat uterus. Segments of rat uterus ileum were suspended in organ bath containing modified Locke-Ringer solution at 32 °C, bubbled with carbogen mixture under a resting tension of 1 g. Isotonic contractions were registered using kymographs and isometric contractions using force transducer. FGAL was more potent in relaxing uterus pre-contracted with oxytocin than with KCl. Additionally, FGAL shifted oxytocin-induced cumulative contractions curves to the right in a non-parallel manner, with E max reduction, indicating a pseudo-irreversible noncompetitive antagonism of oxytocin receptors (OTR) or a downstream pathway target. Moreover, FGAL shifted CaCl 2 -induced cumulative contraction curves to the right in a non-parallel manner in depolarizing medium, nominally without Ca 2+ , with E max reduction, suggesting the inhibition of Ca 2+ influx through Ca V . The relaxant potency of FGAL was reduced by CsCl, a non-selective K + channel blocker, suggesting positive modulation of these channels. Furthermore, in presence of apamin, 4-aminopyridine, glibenclamide or 1 mM TEA + , the relaxant potency of FGAL was attenuated, indicating the participation of SK Ca , K V , K ATP and highlighting BK Ca . Aminophylline, a non-selective phosphodiesterase (PDE) blocker, did not affect the FGAL relaxant potency, excluding the modulation of cyclic nucleotide PDEs pathway by FGAL. Tocolytic effect of FGAL on rat uterus occurs by pseudo-irreversible noncompetitive antagonism of OTR and activation of K + channels, primarily BK Ca , leading to calcium influx reduction through Ca V .
Hydroxymethylnitrofurazone:dimethyl-beta-cyclodextrin inclusion complex: a physical-chemistry characterization.
Grillo, Renato; Melo, Nathalie Ferreira Silva; Moraes, Carolina Morales; Rosa, André Henrique; Roveda, José Arnaldo Frutuoso; Menezes, Carla M S; Ferreira, Elizabeth Igne; Fraceto, Leonardo Fernandes
Hydroxymethylnitrofurazone (NFOH) is active against Trypanosoma cruzi; however, its low solubility and high toxicity precludes its current use in treatment of parasitosis. Cyclodextrin can be used as a drug carrier system, as it is able to form inclusion (host-guest) complexes with a wide variety of organic (guest) molecules. Several reports have shown the interesting use of modified beta-cyclodextrins in pharmaceutical formulation, to improve the bioavailability of drugs and to decrease their toxicity. The aim of this work was to characterize inclusion complexes formed between NFOH and dimethyl-beta-cyclodextrin (DM-beta-CD) by complexation/release kinetics and solubility isotherm experiments using ultraviolet (UV)-visible spectrophotometry and by the measurement of the dynamics information obtained from T(1) relaxation times and diffusion (DOSY) experiments using nuclear magnetic resonance (NMR) spectroscopy. The complex was prepared at different NFOH and DM-beta-CD molar ratios. The UV-visible measurements were recorded in a spectrophotometer, and NMR experiments were recorded at 20 degrees C on a NMR spectrometer (Varian Inova) operating at 500 MHz. Longitudinal relaxation times were obtained by the conventional inversion-recovery method and the DOSY experiments were carried out using the BPPSTE sequence. The kinetics of complexation revealed that 30 h is enough for stabilization of the NFOH absorbance in presence of cyclodextrin. Solubility isotherm studies show a favorable complexation and increase in solubility when NFOH interacts with cyclodextrin. The analysis of the NMR-derived diffusion coefficients and T(1) relaxation times shows that in the presence of DM-beta-CD, NFOH decreases its mobility in solution, indicating that this antichagasic compound interacts with the cyclodextrin cavity. The release kinetics assays showed that NFOH changes its release profile when in the presence of cyclodextrin due to complexation. This study was focused on the
Liquid-liquid extraction of americium(III) by bis (2-ethylhexyl) sulfoxide from aqueous nitrate media (Preprint no. SSC-16)
International Nuclear Information System (INIS)
Shukla, J.P.; Kedari, C.S.
Extraction of Am(III) was studied from acidic nitrate media into n-dodecane by bis (2-ethylhexyl) sulfoxide (BESO). Ca(NO 3 ) 2 was used as the salting-out agent. Effect of several water-miscible polar organic solvents was examined for their possible synergistic effects on its extraction. Slope analysis revealed a predominant formation of the trisolvated organic phase complex, Am(NO 3 ) 3 .3BESO. (author). 2 refs., 1 tab
Reaction parameters for the synthesis of N,N-dimethyl fatty hydrazides from oil.
Ahmad, Norashikin; Azizul Hasan, Zafarizal Aldrin; Hassan, Hazimah Abu; Ahmad, Mansor; Zin Wan Yunus, Wan Md
Hydrazide derivatives have been synthesized from methyl esters, hydrazones and vegetable oils. They are important due to their diverse applications in pharmaceutical products, detergents as well as in oil and gas industries. The chemical synthesis of fatty hydrazides is well-established; however, only a few publications described the synthesis of fatty hydrazide derivatives, particularly, when produced from refined, bleached and deodorized palm olein. Here, the synthesis and characterization of N,N-dimethyl fatty hydrazides are reported. The N,N-dimethyl fatty hydrazides was successfully synthesized from fatty hydrazides and dimethyl sulfate in the presence of potassium hydroxide with the molar ratio of 1:1:1, 6 hours reaction time and 80℃ reaction temperature in ethanol. The product yield and purity were 22% and 89%, respectively. The fatty hydrazides used were synthesized from refined, bleached and deodorized palm olein with hydrazine monohydrate at pH 12 by enzymatic route. Fourier transform infrared, gas chromatography and nuclear magnetic resonance (NMR) spectroscopy techniques were used to determine the chemical composition of N,N-dimethyl fatty hydrazides. Proton NMR confirmed the product obtained were N,N-dimethyl fatty hydrazides.
Characterization of N,N-dimethyl amino acids by electrospray ionization-tandem mass spectrometry.
Naresh Chary, V; Sudarshana Reddy, B; Kumar, Ch Dinesh; Srinivas, R; Prabhakar, S
Methylation is an essential metabolic process for a number of critical reactions in the body. Methyl groups are involved in the healthy function of the body life processes, by conducting methylation process involving specific enzymes. In these processes, various amino acids are methylated, and the occurrence of methylated amino acids in nature is diverse. Nowadays, mass-spectrometric-based identification of small molecules as biomarkers for diseases is a growing research. Although all dimethyl amino acids are metabolically important molecules, mass spectral data are available only for a few of them in the literature. In this study, we report synthesis and characterization of all dimethyl amino acids, by electrospray ionization-tandem mass spectrometry (MS/MS) experiments on protonated molecules. The MS/MS spectra of all the studied dimethyl amino acids showed preliminary loss of H2O + CO to form corresponding immonium ions. The other product ions in the spectra are highly characteristic of the methyl groups on the nitrogen and side chain of the amino acids. The amino acids, which are isomeric and isobaric with the studied dimethyl amino acids, gave distinctive MS/MS spectra. The study also included MS/MS analysis of immonium ions of dimethyl amino acids that provide information on side chain structure, and it is further tested to determine the N-terminal amino acid of the peptides. Copyright © 2015 John Wiley & Sons, Ltd.
Cryopreservation of yamú (Brycon amazonicus) sperm for large scale fertilization
DEFF Research Database (Denmark)
Velasco-Santamaría, Yohana M.; Medina-Robles, Mauricio; Cruz-Casallas, Pablo E.
. Sperm was diluted (1:4) in a solution of glucose, egg yolk and dimethyl sulfoxide (DMSO). Sperm concentration was determined using a Neubauer chamber, and motility evaluated after activation with 1% NaHCO3. In the laboratory, four sizes of straw (0.5, 1.8, 2.5 and 4.0 mL) and two thawing temperatures...
Journal of Chemical Sciences | Indian Academy of Sciences
Indian Academy of Sciences (India)
A theoretical study of solvent effects on the characteristics of the intramolecular hydrogen bond in Droxidopa ... with different polarities and different types of interactions with solute molecules: water, ethanol, carbon tetrachloride, dimethyl sulfoxide, and tetrahydrofuran, utilizing the polarizable continuum model (PCM) model.
Azis et al., Afr J Tradit Complement Altern Med. (2015) 12(2):126 ...
African Journals Online (AJOL)
-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl-tetrazoliumbromide. (MTT) solution was added to each well, then further incubated for another 4 h at 37ºC (Steenkamp et al., 2004). Finally, 100 μL of dimethyl sulfoxide (DMSO) was added to each well ...
Cynodon dactylon (L) Pers (Poaceae) root extract induces apoptotic ...
African Journals Online (AJOL)
treated with different concentrations of plant extract. Dilutions of stock solutions were adjusted to a final concentration of 0.1 % in the culture medium with dimethyl sulfoxide (DMSO); this concentration of DMSO did not affect cell viability. Control cells were incubated in culture medium only. The experiment was conducted in.
Confined crystallization of organic materials in nanopipettes : tracking the early stages of crystal growth and making seeds for unusual polymorphs
Maddar, Faduma; Perry, David; Unwin, Patrick R.
Nanopipettes are used as nanoreactors to study the crystallization of bicalutamide, in a nanoscale antisolvent configuration. Potential controlled ion migration is used to mix an aqueous solution and a dimethyl sulfoxide phase containing bicalutamide, inducing crystallization at the nanopore interface, and generating current blockades due to the nucleation and growth of crystal seeds.
Study on effect of 1,3-dimethyl urea doping on optical properties of L-arginine phosphate monohydrate (LAP) single crystal
Wankhade, Pratik M.; Muley, Gajanan G.
Pure and 1,3-dimethyl urea doped L-arginine phosphate monohydrate (LAP) crystals were grown by a solution growth technique from aqueous solution at a constant temperature. The effect of dopant on the optical properties, crystal structure and second harmonic generation (SHG) efficiency was studied. Dopant modifies the SHG efficiency of the LAP crystal at a greater extent. The SHG efficiency of 0.01 mol% 1,3-dimethyl urea doped LAP crystal corresponds to 1.37 times more as compared to the pure LAP. Absorption and transmission were measured in the spectral range 190-1083 nm. The increase in the optical transparency of the doped crystal is reported. The band gap of the grown crystals has been determined. The presence of the dopant in the doped crystals was confirmed qualitatively by the FT-IR spectroscopy. A slight variation in unit cell parameters has been reported. Thermal and dielectric study of the doped crystal has also been presented.
A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state.
Krakowiak, Joanna; Lundberg, Daniel; Persson, Ingmar
The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen-donor solvents water, dimethyl sulfoxide (DMSO), and N,N'-dimethylpropyleneurea (DMPU) has been studied in solution by extended X-ray absorption fine structure (EXAFS) and large-angle X-ray scattering (LAXS) and in the solid state by single-crystal X-ray diffraction and EXAFS. The hydrated vanadium(III) ion has a regular octahedral configuration with a mean V-O bond distance of 1.99 Å. In the hydrated and DMSO-solvated oxovanadium(IV) ions, vanadium binds strongly to an oxo group at ca. 1.6 Å. The solvent molecule trans to the oxo group is very weakly bound, at ca. 2.2 Å, while the remaining four solvent molecules, with a mean V-O bond distance of 2.0 Å, form a plane slightly below the vanadium atom; the mean O═V-O(perp) bond angle is ca. 98°. In the DMPU-solvated oxovanadium(IV) ion, the space-demanding properties of the DMPU molecule leave no solvent molecule in the trans position to the oxo group, which reduces the coordination number to 5. The O═V-O bond angle is consequently much larger, 107°, and the mean V═O and V-O bond distances decrease to 1.58 and 1.97 Å, respectively. The hydrated and DMSO-solvated dioxovanadium(V) ions display a very distorted octahedral configuration with the oxo groups in the cis position with a mean V═O bond distance of 1.6 Å and a O═V═O bond angle of ca. 105°. The solvent molecules trans to the oxo groups are weakly bound, at ca. 2.2 Å, while the remaining two have bond distances of 2.02 Å. The experimental studies of the coordination chemistry of hydrated and solvated vanadium(III,IV,V) ions are complemented by summarizing previously reported crystal structures to yield a comprehensive description of the coordination chemistry of vanadium with oxygen-donor ligands.
Energy Technology Data Exchange (ETDEWEB)
Elana M. Chapman; Shirish Bhide; Jennifer Stefanik; Howard Glunt; Andre L. Boehman; Allen Homan; David Klinikowski
The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethylether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. The strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. The bulk of the efforts over the past year were focused on the conversion of the campus shuttle bus. This process, started in August 2001, took until April 2002 to complete. The process culminated in an event to celebrate the launching of the shuttle bus on DME-diesel operation on April 19, 2002. The design of the system on the shuttle bus was patterned after the system developed in the engine laboratory, but also was subjected to a rigorous failure modes effects analysis with help from Dr. James Hansel of Air Products. The result of this FMEA was the addition of layers of redundancy and over-pressure protection to the system on the shuttle bus. The system became operation in February 2002. Preliminary emissions tests and basic operation of the shuttle bus took place at the Pennsylvania Transportation institute's test track facility near the University Park airport. After modification and optimization of the system on the bus, operation on the campus shuttle route began in early June 2002. However, the
A self-healing poly(dimethyl siloxane) elastomer
Keller, Michael Wade
In this work, self-healing functionality is imparted to a poly(dimethyl siloxane) (PDMS) elastomer with low modulus and high strain-to-failure behavior. This material utilizes a two-microcapsule system to provide a mechanism for autonomic repair of damage. One microcapsule type contains a functionalized high-molecular-weight resin and organometallic catalyst compounds. The second microcapsule type contains a functional copolymer (initiator) that facilitates the crosslinking of the resin via the action of the catalyst. The healing response is triggered when damage, in the form of a tear, puncture, or crack, propagates through the material and ruptures a resin and initiator capsule. Ruptured capsules release their contents onto the crack plane, initiating polymerization. The polymerized material bonds the two crack faces together regaining much of the original strength, of the matrix material. The mechanical behavior of the microcapsules is studied using a combination of individual microcapsule compression tests and in-situ microscopic analysis. Single-capsule compression tests are performed to extract the modulus of the capsule shell wall and to investigate the behavior of microcapsules under large deformations. The capsules are shown to survive matrix deformation in excess of 45%. Although the microcapsules are robust and endure large matrix deformations, an approaching tear does successfully rupture the capsules. A tear test protocol is adopted to assess the healing efficiency of this new material. Self-healing PDMS specimens with 5 wt% initiator and 5 wt% resin microcapsules recover 97% of the original tear strength. Complete recovery of tear strength is possible under certain conditions. Addition of microcapsules to the PDMS matrix increases the tear strength of the material by 25%. Embedded microcapsules also increase the elastic stiffness by as much as 57%. The self-healing performance of the elastomer is also investigated under torsional fatigue loading. The
Treatment with dimethyl fumarate ameliorates liver ischemia/reperfusion injury.
Takasu, Chie; Vaziri, Nosratola D; Li, Shiri; Robles, Lourdes; Vo, Kelly; Takasu, Mizuki; Pham, Christine; Farzaneh, Seyed H; Shimada, Mitsuo; Stamos, Michael J; Ichii, Hirohito
To investigate the hypothesis that treatment with dimethyl fumarate (DMF) may ameliorate liver ischemia/reperfusion injury (I/RI). Rats were divided into 3 groups: sham, control (CTL), and DMF. DMF (25 mg/kg, twice/d) was orally administered for 2 d before the procedure. The CTL and DMF rats were subjected to ischemia for 1 h and reperfusion for 2 h. The serum alanine aminotransferase (ALT) and malondialdehyde (MDA) levels, adenosine triphosphate (ATP), NO × metabolites, anti-oxidant enzyme expression level, anti-inflammatory effect, and anti-apoptotic effect were determined. Histological tissue damage was significantly reduced in the DMF group (Suzuki scores: sham: 0 ± 0; CTL: 9.3 ± 0.5; DMF: 2.5 ± 1.2; sham vs CTL, P < 0.0001; CTL vs DMF, P < 0.0001). This effect was associated with significantly lower serum ALT (DMF 5026 ± 2305 U/L vs CTL 10592 ± 1152 U/L, P = 0.04) and MDA (DMF 18.2 ± 1.4 μmol/L vs CTL 26.0 ± 1.0 μmol/L, P = 0.0009). DMF effectively improved the ATP content (DMF 20.3 ± 0.4 nmol/mg vs CTL 18.3 ± 0.6 nmol/mg, P = 0.02), myeloperoxidase activity (DMF 7.8 ± 0.4 mU/mL vs CTL 6.0 ± 0.5 mU/mL, P = 0.01) and level of endothelial nitric oxide synthase expression (DMF 0.38 ± 0.05-fold vs 0.17 ± 0.06-fold, P = 0.02). The higher expression levels of anti-oxidant enzymes (catalase and glutamate-cysteine ligase modifier subunit and lower levels of key inflammatory mediators (nuclear factor-kappa B and cyclooxygenase-2 were confirmed in the DMF group. DMF improved the liver function and the anti-oxidant and inflammation status following I/RI. Treatment with DMF could be a promising strategy in patients with liver I/RI.
Methionine sulfoxide reductase A (MsrA) associated with bipolar I disorder and executive functions in A Han Chinese population.
Ni, Peiyan; Ma, Xiaohong; Lin, Yin; Lao, Guohui; Hao, Xiaoyu; Guan, Lijie; Li, Xuan; Jiang, Zeyu; Liu, Yuping; Ye, Biyu; Liu, Xiang; Wang, Yingcheng; Zhao, Liansheng; Cao, Liping; Li, Tao
The oxidative stress hypothesis proposed to explain bipolar I disorder (BD I) pathogenesis has gained growing attention based on its association with cognitive impairment. The aim of the present study was to explore the association of the methionine sulfoxide reductase A (MsrA) gene with BD I as well as executive functions of BD I patients. A total of 44 tagging single-nucleotide polymorphisms within the MsrA gene were selected to analyze gene association with BD I in 375 BD I patients and 475 controls in a Han Chinese population. The association of MsrA haplotypes with executive functions was analyzed in 157 clinically stable BD I patients and 210 controls. Allele frequencies of the rs4840463 polymorphism were significantly different between BD I patients and controls, and between patients with psychotic symptoms and controls. BD I patients performed more poorly in 11 of the 13 neurocognitive measurements compared with controls. Three MsrA haplotypes showed significant associations with different executive functions. The limited sample size requires a cautious conclusion, and further comprehensive approaches are needed to explore the mechanism of MsrA's effect on BD I. The rs4840463 polymorphism in the MsrA gene may be associated with the increased risk of BD I in a Chinese population. The association of MsrA haplotypes with executive functions indicated that MsrA is associated with executive function defects in BD I patients. Copyright © 2015 Elsevier B.V. All rights reserved.
Deficiency of methionine sulfoxide reductase A causes cellular dysfunction and mitochondrial damage in cardiac myocytes under physical and oxidative stresses
International Nuclear Information System (INIS)
Nan, Changlong; Li, Yuejin; Jean-Charles, Pierre-Yves; Chen, Guozhen; Kreymerman, Alexander; Prentice, Howard; Weissbach, Herbert; Huang, Xupei
Research highlights: → Deficiency of MsrA in the heart renders myocardial cells more sensitive to oxidative stress. → Mitochondrial damage happens in the heart lacking MsrA. → More protein oxidation in myocardial cells lacking MsrA. → MsrA protects the heart against oxidative stress. -- Abstract: Methionine sulfoxide reductase A (MsrA) is an enzyme that reverses oxidation of methionine in proteins. Using a MsrA gene knockout (MsrA -/- ) mouse model, we have investigated the role of MsrA in the heart. Our data indicate that cellular contractility and cardiac function are not significantly changed in MsrA -/- mice if the hearts are not stressed. However, the cellular contractility, when stressed using a higher stimulation frequency (2 Hz), is significantly reduced in MsrA -/- cardiac myocytes. MsrA -/- cardiac myocytes also show a significant decrease in contractility after oxidative stress using H 2 O 2 . Corresponding changes in Ca 2+ transients are observed in MsrA -/- cardiomyocytes treated with 2 Hz stimulation or with H 2 O 2 . Electron microscope analyses reveal a dramatic morphological change of mitochondria in MsrA -/- mouse hearts. Further biochemical measurements indicate that protein oxidation levels in MsrA -/- mouse hearts are significantly higher than those in wild type controls. Our study demonstrates that the lack of MsrA in cardiac myocytes reduces myocardial cell's capability against stress stimulations resulting in a cellular dysfunction in the heart.
Pharmacokinetics of toltrazuril and its metabolites, toltrazuril sulfoxide and toltrazuril sulfone, after a single oral administration to pigs.
Lim, Jong-Hwan; Kim, Myoung-Seok; Hwang, Youn-Hwan; Song, In-Bae; Park, Byung-Kwon; Yun, Hyo-In
Toltrazuril (TZR) is a triazine-based antiprotozoal agent. Following a single oral administration of TZR at 10 and 20 mg/kg to male pigs, the mean TZR concentration in plasma peaked at 4.24 and 8.18 microg/ml at 15.0 and 12.0 hr post-dose, respectively. TZR absorbed was rapidly converted to the short-lived intermediary metabolite toltrazuril sulfoxide (TZR-SO), and then metabolized to the reactive toltrazuril sulfone (TZR-SO2). TZR-SO2 was actually more slowly eliminated, with average half-lives of 231 and 245 hr, compared with TZR (48.7 and 68.9 hr) or TZR-SO (51.9 and 53.2 hr) in the 10 and 20 mg/kg groups, respectively. This study demonstrates that TZR metabolizes to TZR-SO2 having a long-terminal half-life, enabling the persistent clinical efficacy in the treatment of I. suis infection. In contrast, special consideration should be given to the residual of TZR-SO2.
Identification of oxygenated ions in premixed flames of dimethyl ether and oxygen
DEFF Research Database (Denmark)
Frøsig Østergaard, L.; Egsgaard, H.; Hammerum, S.
dimethyl ether, (CH3)(2)OH+. The flame-ion m/z 61 is a mixture of the trimethyloxonium ion, (CH3)(3)O+ and lesser amounts of protonated methyl formate and/or protonated ethyl methyl ether. The viability of an ionic mechanism to soot formation for dimethyl ether-oxygen flames is discussed on the background......The structure of characteristic flame-ions in premixed flames of dimethyl ether and oxygen was studied by ion-molecule reactions with ammonia and collision activation with argon. The results obtained show that the flame-ions m/z 45 and m/z 47 are the methoxymethyl cation, CH3OCH2+, and protonated...
Gas chromatographic--mass spectrometric quantitation of 16, 16-dimethyl-trans-delta 2-PGE1
Energy Technology Data Exchange (ETDEWEB)
Dimov, V.; Green, K.; Bygdeman, M.; Konishi, Y.; Imaki, K.; Hayashi, M.
Di-deuterated and di-tritiated 16,16-dimethyl-trans-delta 2-PGE1 has been synthesized and used for development of a GC-MS method for quantitation of corresponding unlabelled drug in patient plasma. Although these carrier/internal standard molecules only contain 2 deuterium atoms the lower limit of detection at each injection is as low as about 40 pg. The maximum plasma levels of this drug following administration of vaginal suppositories used in clinical studies (1 mg 16,16-dimethyl-trans-delta 2-PGE1 methyl ester in 0.8 g Witepsol S-52) were 100-350 pg/ml i.e. in the same order of magnitude as earlier seen for 16,16-dimethyl-PGE2.
Gas chromatographic--mass spectrometric quantitation of 16, 16-dimethyl-trans-delta 2-PGE1
International Nuclear Information System (INIS)
Dimov, V.; Green, K.; Bygdeman, M.; Konishi, Y.; Imaki, K.; Hayashi, M.
Di-deuterated and di-tritiated 16,16-dimethyl-trans-delta 2-PGE1 has been synthesized and used for development of a GC-MS method for quantitation of corresponding unlabelled drug in patient plasma. Although these carrier/internal standard molecules only contain 2 deuterium atoms the lower limit of detection at each injection is as low as about 40 pg. The maximum plasma levels of this drug following administration of vaginal suppositories used in clinical studies (1 mg 16,16-dimethyl-trans-delta 2-PGE1 methyl ester in 0.8 g Witepsol S-52) were 100-350 pg/ml i.e. in the same order of magnitude as earlier seen for 16,16-dimethyl-PGE2
Electrochemical activation of carbon dioxide for synthesis of dimethyl carbonate in an ionic liquid
International Nuclear Information System (INIS)
Yuan Dandan; Yan Cuihong; Lu Bin; Wang Hongxia; Zhong Chongmin; Cai Qinghai
The direct synthesis of dimethyl carbonate from methanol and carbon dioxide is challenging due to the thermodynamic stability and kinetic inertness of CO 2 . Electrochemical technique can overcome this challenge by providing a method for preliminary activation of CO 2 . Electrocatalytic activation and conversion of carbon dioxide to dimethyl carbonate with platinum electrodes in a dialkylimidazolium ionic liquids-basic compounds-methanol system was conducted under ambient conditions. Among the basic compounds and ionic liquids, CH 3 OK acts as a co-catalyst and 1-butyl-3-methylimidazolium bromide (bmimBr) acts as an electrolyte. In the bmimBr-CH 3 OK-methanol system, the absence of CH 3 I and/or any other organic additives allows dimethyl carbonate to be effectively synthesized. The reaction mechanism proposed here is different from those previously reported
Reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite
DEFF Research Database (Denmark)
Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, B.
concentrations in CO between 0.2 and 2.0%, and at a temperature of 438 K. The theoretical study showed that the reaction of CO with surface methyl groups, the rate-limiting step, is faster in the eight-membered side pockets than in the twelve-membered main channel of the zeolite; the subsequent reaction......The reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite was studied theoretically with periodic density functional theory calculations including dispersion forces and experimentally in a fixed bed flow reactor at pressures between 10 and 100 bar, dimethyl ether...... of dimethyl ether with surface acetyl to form methyl acetate was demonstrated to occur with low energy barriers in both the side pockets and in the main channel. The present analysis has thus identified a path, where the entire reaction occurs favourably on a single site within the side pocket, in good...
Natural 4-hydroxy-2,5-dimethyl-3(2H)-furanone (Furaneol®).
Schwab, Wilfried
4-Hydroxy-2,5-dimethyl-3(2H)-furanone (HDMF, furaneol®) and its methyl ether 2,5-dimethyl-4-methoxy-3(2H)-furanone (DMMF) are import aroma chemicals and are considered key flavor compounds in many fruit. Due to their attractive sensory properties they are highly appreciated by the food industry. In fruits 2,5-dimethyl-3(2H)-furanones are synthesized by a series of enzymatic steps whereas HDMF is also a product of the Maillard reaction. Numerous methods for the synthetic preparation of these compounds have been published and are applied by industry, but for the development of a biotechnological process the knowledge and availability of biosynthetic enzymes are required. During the last years substantial progress has been made in the elucidation of the biological pathway leading to HDMF and DMMF. This review summarizes the latest advances in this field.
Natural 4-Hydroxy-2,5-dimethyl-3(2H-furanone (Furaneol®
Directory of Open Access Journals (Sweden)
Wilfried Schwab
Full Text Available 4-Hydroxy-2,5-dimethyl-3(2H-furanone (HDMF, furaneol® and its methyl ether 2,5-dimethyl-4-methoxy-3(2H-furanone (DMMF are import aroma chemicals and are considered key flavor compounds in many fruit. Due to their attractive sensory properties they are highly appreciated by the food industry. In fruits 2,5-dimethyl-3(2H-furanones are synthesized by a series of enzymatic steps whereas HDMF is also a product of the Maillard reaction. Numerous methods for the synthetic preparation of these compounds have been published and are applied by industry, but for the development of a biotechnological process the knowledge and availability of biosynthetic enzymes are required. During the last years substantial progress has been made in the elucidation of the biological pathway leading to HDMF and DMMF. This review summarizes the latest advances in this field.
Photodegradation of dimethyl sulfide (DMS) in natural waters: laboratory assessment of the nitrate-photolysis-induced DMS oxidation.
Bouillon, René-Christian; Miller, William L
The interaction of sunlight and dissolved chromophoric matter produces reactive chemical species that are significant in the removal of dimethyl sulfide (DMS) in the surface ocean. Using artificial solar radiation, we examined the role of several inorganic components of seawater on the kinetics of NO3- -photolysis-induced DMS removal in aqueous solution. This study strongly suggests that NO3- photolysis products react significantly with DMS in aqueous solution possibly via an electrophilic attack on the electron-rich sulfur atom. This supports previous field observations that indicate that NO3- photolysis has a substantial control on DMS photochemistry in nutrient-rich waters. A key finding of this research is that the oxidation rate of DMS induced by NO3- photolysis is dramatically enhanced in the presence of bromide ion. Moreover, our results suggest that bicarbonate/carbonate ions are involved in free radical production/scavenging processes important for DMS photochemistry. These reactions are pH dependent. We propose that DMS removal by some selective free radicals derived from bromide and bicarbonate/carbonate ion oxidation is a potentially important and previously unrecognized pathway for DMS photodegradation in marine waters.
Absolute rate parameters for the reaction of ground state atomic oxygen with dimethyl sulfide and episulfide
Lee, J. H.; Timmons, R. B.; Stief, L. J.
It is pointed out that the investigated reaction of oxygen with dimethyl sulfide may play an important role in photochemical smog formation and in the chemical evolution of dense interstellar clouds. Kinetic data were obtained with the aid of the flash photolysis-resonance fluorescence method. The photodecomposition of molecular oxygen provided the oxygen atoms for the experiments. The decay of atomic oxygen was studied on the basis of resonance fluorescence observations. Both reactions investigated were found to be fast processes. A negative temperature dependence of the rate constants for reactions with dimethyl sulfide was observed.
Data on hepatobiliary examination by sup(99m)Tc dimethyl IDA
International Nuclear Information System (INIS)
Herry, J.Y.; Messner, M.; Le Jeune, J.J.; Moisan, A.
Hepatobiliary elimination of sup(99m)Tc dimethyl IDA was studied by scintiphotographic detection in 16 normal subjects. Normal criterion were established. Scintiphotographic modifications due to the principal hepatobiliary disease were described. Abnormal scintiphotographic sequences can be described in terms of accumulative figures in the biliary tract, of deficit of hepatocytary collecting, of figures of hepatocytary retention of deficit of local fixation, of absence of gallbladder illumination. Examination by sup(99m)Tc dimethyl IDA is a precious help for diagnosis of icterus, of disease of the gallbladder. An interesting indication is control of biliarydigestive anastomosis [fr
Chernyshev, Alexander N.; Bokach, Nadezhda A.; Izotova, Youlia A.; Haukka, Matti
In the title compound, trans-[PtCl2(C7H9N)2], the PtII atom is located on an inversion center and is coordinated by two 3,4-dimethylpyridine ligands and two chloride ligands, resulting in a typical slightly distorted square-planar geometry. The crystallographic inversion centre forces the value of the C—N—N—C torsion angle to be linear and the 3,4-dimethyl-pyridine ligands to be coplanar. PMID:21581530
21 CFR 878.4015 - Wound dressing with poly (diallyl dimethyl ammonium chloride) (pDADMAC) additive.
... of a primary dressing, and as a wound packing. (b) Classification. Class II (special controls). The... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Wound dressing with poly (diallyl dimethyl... DEVICES Surgical Devices § 878.4015 Wound dressing with poly (diallyl dimethyl ammonium chloride) (pDADMAC...
Measurement of (vapor + liquid) equilibrium for the systems {methanol + dimethyl carbonate} and {methanol + dimethyl carbonate + tetramethylammonium bicarbonate} at p = (34.43, 67.74) kPa
International Nuclear Information System (INIS)
Yang Changsheng; Zeng Hao; Yin Xia; Ma Shengyong; Sun Feizhong; Li Yafei; Li Jiao
Highlights: ► VLE data for the binary system and the ternary system were measured. ► Methanol, dimethyl carbonate, and tetramethylammonium bicarbonate were studied. ► Isobaric experimental data were measured at p = (34.43, 67.74) kPa. ► VLE data of binary system were correlated with the Wilson, NRTL, and UNIQUAC models. ► The salt effect of TMAB on the VLE of {methanol + DMC} system was investigated. - Abstract: Isobaric (vapor + liquid) equilibrium (VLE) data for the binary system (methanol + dimethyl carbonate) and the ternary system (methanol + dimethyl carbonate + tetramethylammonium bicarbonate) have been measured at p = (34.43, 67.74) kPa using a modified Rose–Williams still. The experimental data for the binary system were well correlated by Wilson, NRTL, and UNIQUAC activity-coefficient models at the two reduced pressures. All the experimental results of the binary system passed the thermodynamic consistency test by the area test of Redlich–Kister and the point test of Van Ness et al. The experimental results of ternary system show that the salt tetramethylammonium bicarbonate has a salting-in effect on methanol. And this effect enhances when the salt concentration increases.
Electrochemical Performance of Low-Carbon Steel in Alkaline Model Solutions Containing Hybrid Aggregates
Koleva, D.A.; Hu, J.; De Wit, J.H.W.; Boshkov, N.; Radeva, T.; Milkova, V.; Van Breugel, K.
This work reports on the electrochemical performance of low-carbon steel electrodes in model alkaline solutions in the presence of 4.9.10-4 g/l hybrid aggregates i.e. cement extract, containing PDADMAC (poly (diallyl, dimethyl ammonium chloride) / PAA (Poly (acrylic acid)/ PDADMAC over a CaO core.
Carbohydrate modified polysiloxanes, 3 - Solution properties of carbohydrate-polysiloxane conjugates in toluene
Loos, Katja; Jonas, Gerd; Stadler, Reimund
High molecular weight poly(hydromethyl-co-dimethyl) siloxanes containing 0.6 and 3 mol-% of Si-H units are polar functionalized by the addition of various mono-, di- and oligosaccharides. Due to the hydrogen bond interaction between the carbohydrate moieties, the solution properties are strongly
Electrochemical stability and transformations of fluorinated poly(2,6-dimethyl-1,4-phenylene oxide)
Pud, A.A.; Rogalsky, S.P.; Ghapoval, G.S.; Kharitonov, A.P.; Kemperman, Antonius J.B.
Fluorination of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) leads to narrowing of its window of electrochemical stability in a cathodic range of potentials. It is found this is connected with appearance of both perfluorinated and incompletely fluorinated units in the polymer. The former units are
Structural and spectroscopic studies of 2,9-dimethyl-1,10 ...
African Journals Online (AJOL)
The crystal structures of the pronated ligand, 2,9-dimethyl-1,10-phenanthrolinium (DPH) cation with selected counter anions (chloride (1), triflate (2), and gold dicyanide (3)) are reported. The role of a hydrogen bond interaction in influencing the solid state p-p stacking found in all three compounds has been investigated.
The putative oncogene GASC1 demethylates tri- and dimethylated lysine 9 on histone H3
DEFF Research Database (Denmark)
Cloos, Paul A C; Christensen, Jesper; Agger, Karl
Methylation of lysine and arginine residues on histone tails affects chromatin structure and gene transcription. Tri- and dimethylation of lysine 9 on histone H3 (H3K9me3/me2) is required for the binding of the repressive protein HP1 and is associated with heterochromatin formation...
Direct synthesis of dimethyl carbonate from CO 2 and methanol over ...
Indian Academy of Sciences (India)
The direct synthesis of dimethyl carbonate (DMC) from carbon dioxide CO2 and methanol is an attractive approach towards conversion of the greenhouse gas - CO2 into value-added chemicals and fuels.Ceria CeO2 catalyzes this reaction. But the conversion efficiency of CeO2 is enhanced when the byproductwater in the ...
The process of dimethyl carbonate to diphenyl carbonate: Thermodynamics, reaction kinetics and conceptional process design
Haubrock, J.
Diphenyl carbonate (DPC) is a precursor in the production of Polycarbonate (PC), a widely employed engineering plastic. To overcome the drawbacks of the traditional PC process - e.g. phosgene as a reactant and methylene chloride as solvent- a new process route starting from Dimethyl carbonate (DMC)
Investigation of Dimethyl Ether Solubility in Liquid Hexadecane by UNIFAC Method
F. Raouf; M. Taghizadeh
It is shown that a modified UNIFAC model can be applied to predict solubility of hydrocarbon gases and vapors in hydrocarbon solvents. Very good agreement with experimental data has been achieved. In this work we try to find best way for predicting dimethyl ether solubility in liquid paraffin by using group contribution theory.
The industrial production of dimethyl carbonate from methanol and carbon dioxide
De Groot, Frank F T; Lammerink, Roy R G J; Heidemann, Casper; Van Der Werff, Michiel P M; Garcia, Taiga Cafiero; Van Der Ham, Louis A G J; Van Den Berg, Henk
This work discusses the design of a dimethyl carbonate (DMC) production plant based on methanol and CO2 as feed materials, which are a cheap and environment-friendly feedstock. DMC is a good alternative for methyl-tert-butyl ether (MTBE) as a fuel oxygenating agent, due to its low toxicity and fast
Thermodynamicy of Catalytic Formation of Dimethyl Ether from Methanol in Acidic Zeolites
Czech Academy of Sciences Publication Activity Database
Hyťha, Marek; Štich, I.; Gale, J. D.; Terakura, K.; Payne, M.
Roč. 7, č. 12 (2001), s. 2521-2527 ISSN 0947-6539 Institutional research plan: CEZ:AV0Z1010914 Keywords : dimethyl ether * formation * theoretical study Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.614, year: 2001
Fixation of carbon dioxide into dimethyl carbonate over titanium-based zeolitic thiophene-benzimidazolate framework
A titanium-based zeolitic thiophene-benzimidazolate framework has been designed for the direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide. The developed catalyst activates carbon dioxide and delivers over 16% yield of DMC without the use of any dehydra...
On-board conversion of methanol to dimethyl ether as an alternative diesel fuel
Energy Technology Data Exchange (ETDEWEB)
Armbruster, H.; Heinzelmann, G.; Struis, R.; Stucki, S. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)
The catalytic dehydration of methanol to dimethyl ether was investigated for application on-board a methanol fuelled vehicle. Several catalysts have been tested in a fixed bed reactor. Our approach is to develop a small and efficient reactor converting liquid MeOH under pressure and at low reaction temperatures. (author) 2 figs., 5 refs.
Controls of dimethyl sulphide in the Bay of Bengal during BOBMEX ...
Indian Academy of Sciences (India)
The air-sea exchange is one of the main mechanisms maintaining the abundances of trace gases in the atmosphere. Some of these, such as carbon dioxide and dimethyl sulphide (DMS), will have a bearing on the atmospheric heat budget. While the former facilitates the trapping of radiation (greenhouse effect) the latter ...
Remarkable enhancement of Cu catalyst activity in hydrogenation of dimethyl oxalate to ethylene glycol using gold
Wang, Ya-nan; Duan, Xinping; Zheng, Jianwei; Lin, Haiqiang; Yuan, Youzhu; Ariga, Hiroko; Takakusagi, Satoru; Asakura, Kiyotaka
The performance of an SBA-15 supported Cu catalyst for hydrogenation of dimethyl oxalate to ethylene glycol is markedly promoted with Au. A key genesis of the high activity of the catalyst is ascribed to the formation of Cu-Au alloy nanoparticles which stabilize the active species and retard their agglomeration during the hydrogenation process.
Kinetic studies on substitution of cis-diaqua-chloro-tris-(dimethyl ...
Indian Academy of Sciences (India)
4, July 2012, pp. 801–807. c Indian Academy of Sciences. Kinetic studies on substitution of cis-diaqua-chloro-tris-(dimethyl sulphoxide)-ruthenium(II) complex with some dipeptides in aqueous medium. ARUP MANDAL, PARNAJYOTI KARMAKAR, SUBHASIS MALLICK, BIPLAB K BERA,. SUBALA MONDAL, SUMON RAY ...
Directory of Open Access Journals (Sweden)
Grzegorz Cholewinski
Full Text Available The title compound, C6H13O3PSe, was obtained in the reaction of 5,5-dimethyl-2-oxo-2-seleno-1,3,2-dioxaphosphorinane potassium salt with methyl iodide. The selenomethyl group is in the axial position in relation to the six-membered dioxaphosphorinane ring.
Direct synthesis of dimethyl carbonate from CO2 and methanol over ...
Indian Academy of Sciences (India)
Catalytic activity correlates with the concentration of acid and base sites of medium strength as well as defect sites. Ce - S has an optimum number of these active sites and thereby shows superior catalytic performance. Keywords. CO2 utilization; dimethyl carbonate; ceria; acid-base catalysis; influence of morphology. 1.
Synthesis, structure characterization and biological studies on a new aromatic hydrazone, 5-(2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)hydrazono)-2,2-dimethyl-1,3-dioxane-4,6-dione, and its transition metal complexes
Kumar, Shubha S.; Biju, S.; Sadasivan, V.
A new aromatic hydrazone 5-(2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)hydrazono)-2,2-dimethyl-1,3-dioxane-4,6-dione has been synthesized by Japp-Klingemann reaction from diazotized 4-aminoantipyrine and Meldrum's acid. A few 3d-metal ion complexes of this hydrazone were synthesized. The compound and its complexes were characterized by UV-Visible, 1H NMR, ESR, Mass spectral, molar conductance and magnetic susceptibility measurements. The compound was found to exist in hydrazone form in solid state and solution from SXRD and 1H NMR study. The influence of pH on the molecule was studied and found that it shows azo/enol-hydrazone tautomerism in solution. This molecule act as a univalent tridentate ligand and the complexes were assigned to have a 1:2 stoichiometry (M:L). The antioxidant properties of the compounds were explored by DPPH assay and found that the ligand possesses better free radical scavenging effect than the complexes. Antimicrobial activities of these compounds were investigated and were found to be active.
Formation of a third phase in the extraction of uranium(VI) and plutonium(IV) nitrates into various diluents by bis(2-ethylhexyl)sulfoxide
International Nuclear Information System (INIS)
Shukla, J.P.; Kedari, C.S.
The formation of a third phase in the extraction of large amounts of uranium(VI) and plutonium(IV) by bis(2-ethylhexyl)sulfoxide (BESO) into various hydrocarbon diluents was investigated over a wide range of experimental conditions. Solubility of both the extracted solvates UO 2 (NO 3 ) 2 .2BESO and Pu(NO 3 ) 4 .2BESO was maximum in polarizable benzene and the tendency to form third phase increased in the order: benzene < n-hexane < SST < dodecane. Usefulness of some commonly employed polar modifiers like tributylphosphate (TBP), 2-ethylhexanol and isodecanol on improving the metal solvate solubility was also assessed. (orig.)
Oxidative degradation of dimethyl phthalate (DMP) by UV/H{sub 2}O{sub 2} process
Energy Technology Data Exchange (ETDEWEB)
Xu Bin [Key Laboratory of Yangtze Aquatic Environment, Ministry of Education, State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China)], E-mail: email@example.com; Gao Naiyun [Key Laboratory of Yangtze Aquatic Environment, Ministry of Education, State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China)], E-mail: email@example.com; Cheng Hefa [Department of Civil and Environmental Engineering, Stanford University, Stanford, CA 94305 (United States); Xia Shengji; Rui Min; Zhao Dandan [Key Laboratory of Yangtze Aquatic Environment, Ministry of Education, State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China)
The photochemical degradation of dimethyl phthalate (DMP) in UV/H{sub 2}O{sub 2} advanced oxidation process was studied and a kinetic model based on the elementary reactions involved was developed in this paper. Relatively slow DMP degradation was observed during UV radiation, while DMP was not oxidized by H{sub 2}O{sub 2} alone. In contrast, the combined UV/H{sub 2}O{sub 2} process could effectively degraded DMP, which is attributed to the strong oxidation strength of hydroxyl radical produced. Results show that DMP degradation rate was affected by H{sub 2}O{sub 2} concentration, intensity of UV radiation, initial DMP concentration, and solution pH. A kinetic model without the pseudo-steady state assumption was established according to the generally accepted elementary reactions in UV/H{sub 2}O{sub 2} advanced oxidation process. The rate constant for the reaction between DMP and hydroxyl radical was found to be 4.0 x 10{sup 9} M{sup -1} s{sup -1} through fitting the experimental data to this model. The kinetic model could adequately describe the influence of key factors on DMP degradation rate in UV/H{sub 2}O{sub 2} advanced oxidation process, and could serve as a guide in designing treatment systems for DMP removal.
Detection of a nerve agent simulant using single-walled carbon nanotube networks: dimethyl-methyl-phosphonate
International Nuclear Information System (INIS)
Kim, Yeonju; Lee, Seunghyun; Choi, Hyang Hee; Noh, Jin-Seo; Lee, Wooyoung
Single-walled carbon nanotube (SWNT) networks were used to detect hazardous dimethyl-methyl-phosphonate (DMMP) gas in real time, employing two different metals as electrodes. Random networks of SWNTs were simply obtained by drop-casting a SWNT-containing solution onto a surface-oxidized Si substrate. Although the electrical responses to DMMP at room temperature were reversible for both metals, the Pd-contacting SWNT network sensors exhibited a higher response and a shorter response time than those of the Au-contacting SWNT network sensors at the same DMMP concentration, due to the stronger interactions between the SWNTs and Pd surface atoms. In Pd-contacting SWNT network sensors, the response increased linearly with increasing DMMP concentration and reproducible response curves were obtained for DMMP levels as low as 1 ppm. These results indicate that SWNT networks in contact with Pd electrodes can function as good DMMP sensors at room temperature with scalable and fast response and excellent recovery.
Structural studies of lanthanide nitrate-N,N'-dimethyl-N,N'-diphenylpyridine-2,6-dicarboxyamide complexes
International Nuclear Information System (INIS)
Fujiwara, Asako; Nakano, Yoshiharu; Yaita, Tsuyoshi; Okuno, Kenji
The tridentate ligand N,N'-dimethyl-N,N'-diphenylpyridine-2,6-dicarboxyamide (DMDPhPDA) and the corresponding lanthanum complex [La(NO 3 ) 3 (DMDPhPDA) 2 ] have been prepared and structurally characterised. The crystal structure of DMDPhPDA shows syn-anti conformation. In the lanthanum complex, two DMDPhPDA molecules coordinated to La(III) in a tridentate fashion and to three nitrate ions in a bidentate fashion make the lanthanum atom 12-coordinate. The crystal structure of [La(NO 3 ) 3 (DMDPhPDA) 2 ] has a C 2 symmetry. The stability constants determined by spectrophotometric titration suggest that [Ln(DMDPhPDA) 2 ] 3+ is the primary product in CH 3 CN solution and [Ln(DMDPhPDA) 3 ] 3+ is difficult to form. However, [Ln(DMDPhPDA) 2 ] 3+ could not be distinguished in 1 H NMR spectra. The 1 H NMR titration results imply that a fast ligand exchange process takes place
Detection of a nerve agent simulant using single-walled carbon nanotube networks: dimethyl-methyl-phosphonate
Kim, Yeonju; Lee, Seunghyun; Choi, Hyang Hee; Noh, Jin-Seo; Lee, Wooyoung
Single-walled carbon nanotube (SWNT) networks were used to detect hazardous dimethyl-methyl-phosphonate (DMMP) gas in real time, employing two different metals as electrodes. Random networks of SWNTs were simply obtained by drop-casting a SWNT-containing solution onto a surface-oxidized Si substrate. Although the electrical responses to DMMP at room temperature were reversible for both metals, the Pd-contacting SWNT network sensors exhibited a higher response and a shorter response time than those of the Au-contacting SWNT network sensors at the same DMMP concentration, due to the stronger interactions between the SWNTs and Pd surface atoms. In Pd-contacting SWNT network sensors, the response increased linearly with increasing DMMP concentration and reproducible response curves were obtained for DMMP levels as low as 1 ppm. These results indicate that SWNT networks in contact with Pd electrodes can function as good DMMP sensors at room temperature with scalable and fast response and excellent recovery.
Plasma disposition of toltrazuril and its metabolites, toltrazuril sulfoxide and toltrazuril sulfone, in rabbits after oral administration.
Kim, Myoung-Seok; Lim, Jong-Hwan; Hwang, Youn-Hwan; Park, Byung-Kwon; Song, In-Bae; Yun, Hyo-In
The objective of this study was to evaluate the pharmacokinetic profiles of toltrazuril (TZR), and its major metabolites toltrazuril sulfoxide (TZR x SO) and toltrazuril sulfone (TZR x SO(2)) in rabbits after oral administrations. Rabbits were dosed once with 10 and 20mg/kg TZR via stomach tube with manual restraint. The plasma concentrations of TZR, TZR x SO and TZR x SO(2) were determined by liquid chromatography/mass spectrometry. Plasma concentration-time data after single oral administration were analyzed by a non-compartmental analysis. Plasma peak concentrations of TZR, TZR x SO and TZR x SO(2) were 30.2+/-1.5microg/mL at 20.0+/-6.9h, 8.9+/-1.3microg/mL at 20.0+/-6.9h and 14.7+/-3.9microg/mL at 96.0+/-0.0h after oral administration of TZR with 10mg/kg bw, respectively. The terminal elimination half-lives for TZR, TZR x SO and TZR x SO(2) after oral dose of 10mg/kg were 52.7+/-3.6, 56.1+/-10.7 and 76.7+/-7.5h, respectively. Plasma peak concentrations of TZR, TZR x SO and TZR x SO(2) were 39.4+/-1.2microg/mL at 28.0+/-6.9h, 12.5+/-3.9microg/mL at 20.0+/-6.9h and 24.9+/-8.74microg/mL at 112.0+/-6.9h after oral administration of TZR with 20mg/kg bw, respectively. The terminal elimination half-lives for TZR, TZR x SO and TZR x SO(2) after oral dose of 20mg/kg were 56.7+/-1.9, 68.8+/-12.5 and 82.3+/-12.6h, respectively. In conclusion, TZR was very well-absorbed through the gastrointestinal tract and rapidly metabolized to TZR x SO and TZR x SO(2) in rabbits after oral administration. TZR x SO(2) was actually more slowly eliminated than TZR and TZR x SO.
Camilli, Fabio; Prados, Emmanuel
International audience; Viscosity solution is a notion of weak solution for a class of partial differential equations of Hamilton-Jacobi type. The range of applications of the notions of viscosity solution and Hamilton-Jacobi equations is enormous, including common class of partial differential equations such as evolutive problems and problems with boundary conditions, equations arising in optimal control theory, differential games, second-order equations arising in stochastic optimal control...
Assessment of anticancer effect of chlorin e6 dimethyl ether for photodynamic therapy
Directory of Open Access Journals (Sweden)
M. A. Kaplan
Full Text Available Results of the study for anticancer efficacy of photodynamic therapy with chlorin e6 dimethyl ether for treatment of outbread rats with sarcoma M-1 are represented. The drug was given intravenously or intraperitonealy at a dose of 1.25 mg/kg body weight (light dose – 300 J/cm2 or 2,5 mg/kg body weight (light dose – 150 J/cm2. The spectrometry showed that maximal drug accumulation in tumor was in 2 h after intravenous injection or 3 h after intraperitoneal injection of photosensitizer, thus, sensitized tumors were irradiated according to these time intervals. Intraperitoneal injection of chlorin е6 dimethyl ether at a dose of 1.25 mg/kg body weight with treatment session in 3 h and light dose of 300 J/cm2 was the most effective (the complete response in animals – 86%.
Tabular silver halide crystals prepared by controlled Ostwald growth in the presence of dimethyl sulphoxide
Energy Technology Data Exchange (ETDEWEB)
Dyonizy, A.; Nowak, P.; Mora, C.; Krol-Gracz, A.; Michalak, E. [Institute of Physical and Theoretical Chemistry, Wroclaw University of Technology, Wybrzeze St. Wyspianskiego 27, 50-370 Wroclaw (Poland)
The results of research in the size and shape of silver bromide crystals precipitated by the Ostwald controlled growth method at the presence of dimethyl sulphoxide were presented in the paper. The silver bromide crystals were produced in the form of microcrystal suspension stabilised by gelatine. In the course of the synthesis of crystals, the constant concentration of dimethyl sulphoxide, concentration of excessive bromide ions and the constant ionic strength were achieved. The tabular crystals of silver bromide with their average size of 50 {mu}m and their aspect ratio equal to 100 were obtained by means of this method. The suspensions of flat silver bromide crystals produced in this manner can be used in the production of high-sensitivity materials. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)
O-methylation of natural phenolic compounds based on green chemistry using dimethyl carbonate
Prakoso, N. I.; Pangestu, P. H.; Wahyuningsih, T. D.
The alkyl aryl ether compounds, of which methyl eugenol and veratraldehyde are the simplest intermediates can be synthesized by reacting eugenol and vanillin with the green reagent dimethyl carbonate (DMC). The reaction was carried out under mild of temperature and pressure. Excellent yields and selective products were obtained (95-96%) after a few hours. In the end of the reaction, the catalysts (base and Phase Transfer Catalyst) can be recovered and regenerated.
Dimethyl Ether as an Ignition Improver for Hydrous Methanol Fuelled Homogeneous Charge Compression Ignition (HCCI) Engine
M. Venkatesan; N. Shenbaga Vinayaga Moorthi; R. Karthikeyan; A. Manivannan
Homogeneous Charge Compression (HCCI) Ignition technology has been around for a long time, but has recently received renewed attention and enthusiasm. This paper deals with experimental investigations of HCCI engine using hydrous methanol as a primary fuel and Dimethyl Ether (DME) as an ignition improver. A regular diesel engine has been modified to work as HCCI engine for this investigation. The hydrous methanol is inducted and DME is injected into a single cylinder engine. Hence, hydrous me...
(Liquid + liquid) equilibria of (water + propionic acid + dimethyl phthalate) at several temperatures
Energy Technology Data Exchange (ETDEWEB)
Oezmen, Dilek [Engineering Faculty, Department of Chemical Engineering, Istanbul University, 34320 Istanbul (Turkey); Cehreli, Sueheyla [Engineering Faculty, Department of Chemical Engineering, Istanbul University, 34320 Istanbul (Turkey)]. E-mail: email@example.com; Dramur, Umur [Engineering Faculty, Department of Chemical Engineering, Istanbul University, 34320 Istanbul (Turkey)
(Liquid + liquid) equilibrium (LLE) data for (water + propionic acid + dimethyl phthalate) were measured under atmospheric pressure and at T (298.2, 303.2, 308.2 and 313.2) K. Phase diagrams were obtained by determining solubility and tie-line data. The LLE data of the ternary systems were predicted by UNIFAC method. Distribution coefficients and separation factors were evaluated over the immiscibility regions.
Synthesis of dimethyl carbonate from methyl carbamate and methanol over lanthanum compounds
Energy Technology Data Exchange (ETDEWEB)
Wang, Dengfeng; Zhang, Xuelan; Gao, Yangyan [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001 (China); Graduate university of Chinese, Academy of Sciences, Beijing, 100049 (China); Xiao, Fukui; Wei, Wei; Sun, Yuhan [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001 (China)
Various lanthanum compounds were used as the catalyst for the synthesis of dimethyl carbonate (DMC) from methyl carbamate and methanol. Among them, La(NO{sub 3}){sub 3} presented the best catalytic performance with the DMC yield of 53.7% under suitable reaction conditions. Based on the results of X-ray diffraction, Fourier transform infrared spectroscopy and element analysis, a possible reaction mechanism over lanthanum nitrate was proposed for this reaction. (author)
Direct dimethyl ether synthesis from synthesis gas: The influence of methanol dehydration on methanol synthesis reaction
Dadgar, Farbod; Myrstad, Rune; Pfeifer, Peter; Holmen, Anders; Venvik, Hilde Johnsen
Direct dimethyl ether (DME) synthesis from synthesis gas is studied with regard to potential effects of methanol dehydration on methanol formation and copper-based catalyst performance. For this, the influence of the operating conditions (space velocity, temperature, pressure, time-on-stream and syngas composition) on activity, selectivity and stability of the catalyst was studied and compared for methanol synthesis and direct DME synthesis. The advantage of the direct over the two-step DME s...
Nano-Structured Crystalline Te Films by Laser Gas-Phase Pyrolysis of Dimethyl Tellurium
Czech Academy of Sciences Publication Activity Database
Pola, Josef; Pokorná, Veronika; Boháček, Jaroslav; Bastl, Zdeněk; Ouchi, A.
Roč. 71, č. 2 (2004), s. 739-746 ISSN 0165-2370 R&D Projects: GA AV ČR IAA4072107; GA MŠk OC 523.60 Institutional research plan: CEZ:AV0Z4072921; CEZ:AV0Z4032918; CEZ:AV0Z4040901 Keywords : dimethyl tellurium * tellurium films * laser Subject RIV: CA - Inorganic Chemistry Impact factor: 1.352, year: 2004
21 CFR 177.2460 - Poly(2,6-dimethyl-1,4-phenylene) oxide resins.
... for Use Only as Components of Articles Intended for Repeated Use § 177.2460 Poly(2,6-dimethyl-1,4... this section may be used as an article or as a component of an article intended for use in contact with... will pass through a U.S. Standard Sieve No. 6 and 100 percent of the pellets will be held on a U.S...
Accurate spectroscopic characterization of ethyl mercaptan and dimethyl sulfide isotopologues: a route toward their astrophysical detection
Energy Technology Data Exchange (ETDEWEB)
Puzzarini, C. [Dipartimento di Chimica, " Giacomo Ciamician," Università diBologna, Via F. Selmi 2, I-40126 Bologna (Italy); Senent, M. L. [Departamento de Química y Física Teóricas, Institsuto de Estructura de la Materia, IEM-C.S.I.C., Serrano 121, Madrid E-28006 (Spain); Domínguez-Gómez, R. [Doctora Vinculada IEM-CSIC, Departamento de Ingeniería Civil, Cátedra de Química, E.U.I.T. Obras Públicas, Universidad Politécnica de Madrid (Spain); Carvajal, M. [Departamento de Física Aplicada, Facultad de Ciencias Experimentales, Unidad Asociada IEM-CSIC-U.Huelva, Universidad de Huelva, E-21071 Huelva (Spain); Hochlaf, M. [Université Paris-Est, Laboratoire de Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 boulevard Descartes, F-77454 Marne-la-Vallée (France); Al-Mogren, M. Mogren, E-mail: email@example.com, E-mail: email@example.com, E-mail: firstname.lastname@example.com, E-mail: email@example.com, E-mail: email@example.com, E-mail: email@example.com [Chemistry Department, Faculty of Science, King Saud University, PO Box 2455, Riyadh 11451 (Saudi Arabia)
Using state-of-the-art computational methodologies, we predict a set of reliable rotational and torsional parameters for ethyl mercaptan and dimethyl sulfide monosubstituted isotopologues. This includes rotational, quartic, and sextic centrifugal-distortion constants, torsional levels, and torsional splittings. The accuracy of the present data was assessed from a comparison to the available experimental data. Generally, our computed parameters should help in the characterization and the identification of these organo-sulfur molecules in laboratory settings and in the interstellar medium.
Effect of thermodynamic history on secondary relaxation in glassy phenolphthalein-dimethyl-ether
Prevosto, D.; Capaccioli, S.; Lucchesi, M.; Rolla, P. A.; Paluch, M.; Pawlus, S.
We present a study of the intermediate secondary relaxation process of phenolphthalein-dimethyl-ether. Though this process is intramolecular in nature, it reveals pronounced pressure dependence. Moreover, its relaxation frequency and intensity exhibit pronounced dependence on the thermal history followed during vitrification. These results suggest that the nonequilibrium nature of the glassy state influences this secondary relaxation principally through the dependence on the specific volume.
Optimal conditions in direct dimethyl ether synthesis from syngas utilizing a dual-type fluidized bed reactor
International Nuclear Information System (INIS)
Yousefi, Ahmad; Eslamloueyan, Reza; Kazerooni, Nooshin Moradi
Concerns over environmental pollution and ever-increasing energy demand have urged the global community to tap clean-burning fuels among which dimethyl ether is a promising candidate for contribution in the transportation sector. Direct dimethyl ether synthesis from syngas, in which methanol production and dehydration take place simultaneously, is arguably the preferred route for large scale production. In this study, direct dimethyl ether synthesis is proposed in an industrial dual-type fluidized bed reactor. This configuration involves two fluidized bed reactors operating in different conditions. In the first catalytic reactor (water-cooled reactor), the synthesis gas is partly converted to methanol after being preheated by the reaction heat in the second reactor (gas-cooled reactor). A two-phase generalized comprehensive reactor model, comprised of the flow in three different regimes is applied and a smooth transition between flow regimes is provided based on the probabilistic averaging approach. The optimal operating conditions are sought by employing differential evolution algorithm as a robust optimization strategy. The dimethyl ether mole fraction is considered as the objective function during the optimization. The results show considerable dimethyl ether enhancement by 16% and 14% compared to the conventional direct dimethyl ether synthesis reactor and dual-type fixed bed dimethyl ether reactor arrangements, respectively. - Highlights: • Dual-type catalytic fluidized bed reactors for dimethyl ether synthesis is studied. • A two-phase comprehensive model comprised of flow in three regimes is used. • Probabilistic averaging approach is applied for smooth transitions between regimes. • Differential evolution method is employed to determine optimal operating conditions. • Production capacity is remarkably enhanced compared to conventional reactor.
[Determination of dimethyl fumarate in bakery food by d-SPE-HPLC-PDA].
Yang, Jie; Luo, Mengtian; Feng, Di; Miao, Hong; Song, Shufeng; Zhao, Yunfeng
To establish a simple and rapid pretreatment method with dispersive solid phase extraction ( d-SPE) by HPLC for determination of dimethyl fumarate in bakery foods. Dimethyl fumarate in samples was ultrasonically extracted by methanol, and cleaned up with d-SPE. Then, it was separated on C18 chromatographic column (4.6 mm x 25 mm, 5 μm) with a mixture of methanol--0.03 mol/L sodium acetate and 0.008 mol/L tetrabutyl ammonium bromide (40: 60, V/V) as mobile phase. The photodiode array detector was used in the determination under λ = 220 nm. In the linear range of 0.1 -25 μg/ml, the correlation coefficients was r > 0.999, and the average recoveries of the spiked samples were in the range of 82.8% - 107.5% with relative standard deviations (RSD) in the range of 3.30% - 7.30% (n = 6). The limit of detection ( LOD) was 0.4 mg/kg, and the limit of quantification was 1.0 mg/kg. The method is simple, rapid, sensitive and accurate, and suitable for determine dimethyl fumarate in bakery foods.
Volumetric Properties of the Mixture Hexane C6H14 + C6H14S2 2,5-Dimethyl-3,4-dithiahexane (VMSD1212, LB3240_V)
Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.
This document is part of Subvolume B 'Binary Liquid Systems of Nonelectrolytes II' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Hexane C6H14 + C6H14S2 2,5-Dimethyl-3,4-dithiahexane (VMSD1212, LB3240_V)' providing data by calculation of molar excess volume from low-pressure density measurements at variable mole fraction and constant temperature.
Volumetric Properties of the Mixture Hexane C6H14 + C6H14S2 2,5-Dimethyl-3,4-dithiahexane (VMSD1111, LB3245_V)
Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.
This document is part of Subvolume B 'Binary Liquid Systems of Nonelectrolytes II' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Volumetric Properties of the Mixture Hexane C6H14 + C6H14S2 2,5-Dimethyl-3,4-dithiahexane (VMSD1111, LB3245_V)' providing data from direct low-pressure measurement of mass density at variable mole fraction and constant temperature, in the single-phase region(s).
The synergistic effects of 2,4-D dimethyl amine and propanil herbicides on weed population in rice agroecosystem
International Nuclear Information System (INIS)
Nashriyah Mat; Ramli Ishak; Sabri Junoh; Ismail Sahid
Four treatments with the herbicides 2,4-D dimethyl amine and propanil were carried out in two consecutive rice planting seasons, to study the synergistic effect of 2,4-D dimethyl amine and propanil on rice weed populations at Pasir Panjang, the Northwest Selangor Project (PBLS), Projek Barat Laut Selangor) rice granary area. The treatments were control, 1x recommended rate (single dose), 2x recommended rate (double dose) of 2,4-D dimethyl amine and farmer practice. In all plots, propanil herbicide was applied at similar rate. Among the ecological indices measured were Simpson Index of diversity and importance (I.V.). A total number of 19 weed species was identified and the most common important weed was Najas graminae Del. The second most commonly found important weed was Scirpus lateriflorus Gmel. Other important weeds frequently found were Echinochloa crus-galli (L.) Beauv. and Fimbristylis miliacea (L.) Vahl. In the rice agroecosystem, species diversity of weeds was affected but total weed biomass was not affected synergistically by the mixture of 2,4-D dimethyl amine and propanil. The negative synergistic effect of 2,4-D dimethyl amine and propanil was to increase the total biomass of Scirpus lateriflorus, at 2x recommended dose rate of 2,4-D dimethyl amine. (Author)
Hydrogen/deuterium substitution methods: understanding water structure in solution
International Nuclear Information System (INIS)
Soper, A.K.
The hydrogen/deuterium substitution method has been used for different applications, such as the short range order between water molecules in a number of different environments (aqueous solutions of organic molecules), or to study the partial structure factors of water at high pressure and temperature. The absolute accuracy that can be obtained remains uncertain, but important qualitative information can be obtained on the local organization of water in aqueous solution. Some recent results with pure water, methanol and dimethyl sulphoxide (DMSO) solutions are presented. It is shown that the short range water structure is not greatly affected by most solutes except at high concentrations and when the solute species has its own distinctive interaction with water (such as a dissolved small ion). 3 figs., 14 refs
International Nuclear Information System (INIS)
Seitz, M.G.
Reviewed in this statement are methods of preparing solutions to be used in laboratory experiments to examine technical issues related to the safe disposal of nuclear waste from power generation. Each approach currently used to prepare solutions has advantages and any one approach may be preferred over the others in particular situations, depending upon the goals of the experimental program. These advantages are highlighted herein for three approaches to solution preparation that are currently used most in studies of nuclear waste disposal. Discussion of the disadvantages of each approach is presented to help a user select a preparation method for his particular studies. Also presented in this statement are general observations regarding solution preparation. These observations are used as examples of the types of concerns that need to be addressed regarding solution preparation. As shown by these examples, prior to experimentation or chemical analyses, laboratory techniques based on scientific knowledge of solutions can be applied to solutions, often resulting in great improvement in the usefulness of results
Characterization of the chemical reactivity and nephrotoxicity of N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide, a potential reactive metabolite of trichloroethylene
Energy Technology Data Exchange (ETDEWEB)
Irving, Roy M. [Molecular and Environmental Toxicology Center, University of Wisconsin-Madison, Madison, WI 53706 (United States); Pinkerton, Marie E. [Department of Pathobiological Sciences, University of Wisconsin-Madison, Madison, WI 53706 (United States); Elfarra, Adnan A., E-mail: firstname.lastname@example.com [Molecular and Environmental Toxicology Center, University of Wisconsin-Madison, Madison, WI 53706 (United States); Department of Comparative Biosciences, University of Wisconsin-Madison, Madison, WI 53706 (United States)
N-Acetyl-S-(1,2-dichlorovinyl)-L-cysteine (NA-DCVC) has been detected in the urine of humans exposed to trichloroethylene and its related sulfoxide, N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (NA-DCVCS), has been detected as hemoglobin adducts in blood of rats dosed with S-(1,2-dichlorovinyl)-L-cysteine (DCVC) or S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS). Because the in vivo nephrotoxicity of NA-DCVCS was unknown, in this study, male Sprague–Dawley rats were dosed (i.p.) with 230 μmol/kg b.w. NA-DCVCS or its potential precursors, DCVCS or NA-DCVC. At 24 h post treatment, rats given NA-DCVC or NA-DCVCS exhibited kidney lesions and effects on renal function distinct from those caused by DCVCS. NA-DCVC and NA-DCVCS primarily affected the cortico-medullary proximal tubules (S{sub 2}–S{sub 3} segments) while DCVCS primarily affected the outer cortical proximal tubules (S{sub 1}–S{sub 2} segments). When NA-DCVCS or DCVCS was incubated with GSH in phosphate buffer pH 7.4 at 37 °C, the corresponding glutathione conjugates were detected, but NA-DCVC was not reactive with GSH. Because NA-DCVCS exhibited a longer half-life than DCVCS and addition of rat liver cytosol enhanced GSH conjugate formation, catalysis of GSH conjugate formation by the liver could explain the lower toxicity of NA-DCVCS in comparison with DCVCS. Collectively, these results provide clear evidence that NA-DCVCS formation could play a significant role in DCVC, NA-DCVC, and trichloroethylene nephrotoxicity. They also suggest a role for hepatic metabolism in the mechanism of NA-DCVC nephrotoxicity. - Highlights: ► NA-DCVCS and NA-DCVC toxicity are distinct from DCVCS toxicity. ► NA-DCVCS readily reacts with GSH to form mono- and di-GSH conjugates. ► Liver glutathione S-transferases enhance NA-DCVCS GSH conjugate formation. ► Renal localization of lesions suggests a role for NA-DCVCS in TCE nephrotoxicity.
Quevedo, Hernando
A class of exact solutions of the Einstein-Maxwell equations is presented which contains infinite sets of gravitoelectric, gravitomagnetic and electromagnetic multipole moments. The multipolar structure of the solutions indicates that they can be used to describe the exterior gravitational field of an arbitrarily rotating mass distribution endowed with an electromagnetic field. The presence of gravitational multipoles completely changes the structure of the spacetime because of the appearance...
Dimethyl Sulfide-Dimethyl Ether and Ethylene Oxide-Ethylene Sulfide Complexes Investigated by Fourier Transform Microwave Spectroscopy and AB Initio Calculation
Kawashima, Yoshiyuki; Tatamitani, Yoshio; Mase, Takayuki; Hirota, Eizi
The ground-state rotational spectra of the dimethyl sulfide-dimethyl ether (DMS-DME) and the ethylene oxide and ethylene sulfide (EO-ES) complexes were observed by Fourier transform microwave spectroscopy, and a-type and c-type transitions were assigned for the normal, 34S, and three 13C species of the DMS-DME and a-type and b-type rotational transitions for the normal, 34S, and two 13C species of the EO-ES. The observed transitions were analyzed by using an S-reduced asymmetric-top rotational Hamiltonian. The rotational parameters thus derived for the DMS-DME were found consistent with a structure of Cs symmetry with the DMS bound to the DME by two C-H(DMS)---O and one S---H-C(DME) hydrogen bonds. The barrier height V3 to internal rotation of the "free" methyl group in the DME was determined to be 915.4 (23) wn, which is smaller than that of the DME monomer, 951.72 (70) wn, and larger than that of the DME dimer, 785.4 (52) wn. For the EO-ES complex the observed data were interpreted in the terms of an antiparallel Cs geometry with the EO bound to the ES by two C-H(ES)---O and two S---H-C(EO) hydrogen bonds. We have applied a natural bond orbital (NBO) analysis to the DMS-DME and EO-ES to calculate the stabilization energy CT (= ΔEσσ*), which were closely correlated with the binding energy EB, as found for other related complexes. Y. Niide and M. Hayashi, J. Mol. Spectrosc. 220, 65-79 (2003). Y. Tatamitani, B. Liu, J. Shimada, T. Ogata, P. Ottaviani, A. Maris, W. Caminati, and J. L. Alonso, J. Am. Chem. Soc. 124, 2739-2743 (2002).
On-line mixing and emission characteristics of diesel engine with dimethyl ether injected into fuel pipeline
Directory of Open Access Journals (Sweden)
Li Xiaolu
Full Text Available This article presents a new on-line dimethyl ether/diesel mixing method, researches its blend characteristics, and also validates combustion and emission effects on a light-duty direct injection engine. This new blend concept is that dimethyl ether is injected into the fuel pipeline to mix with local diesel as the injector stops injection, and this mixing method has some advantages, such as utilization of the original fuel system to mix dimethyl ether with diesel intensively, flexibility on adjustable mixing ratio varying with the engine operating condition, and so on. A device was designed to separate dimethyl ether from the blends, and its mixing ratios and injection quantity per cycle were also measured on a fuel pump bench. The results show that compared with the injected diesel, the percentages of dimethyl ether injected into fuel pipeline are 13.04, 9.74, 8.55, and 7.82% by mass as the fuel pump speeds increase, while dimethyl ether injected into fuel pipeline are 45.46, 35.53, 31.45, and 28.29% of wasting dimethyl ether. The power outputs of engine fueled with the blends are slight higher than those of neat diesel at low speeds, while at high speeds, its power outputs are a little lower. Smoke emissions of the blends are lower about 30% than that of neat diesel fuel at medium and high loads with hardly any penalty on smoke and NOx emissions at light loads. The NOx and HC emissions of the blends are slight lower than that of neat diesel fuel at all loads.
40 CFR 721.10055 - 1-Propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts.
...-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts. 721.10055 Section 721.10055 Protection of...-amino-N-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts. (a) Chemical substance and...-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts (PMN P-03-46; CAS No. 136504-87-5) is subject to...
Formation of a third phase in the extraction of uranium(VI) and plutonium(IV) nitrates into various diluents by bis(2-ethylhexyl)sulfoxide
Energy Technology Data Exchange (ETDEWEB)
Shukla, J.P. (Radiochemistry Div., Bhabha Atomic Research Centre, Bombay (India)); Kedari, C.S. (Radiochemistry Div., Bhabha Atomic Research Centre, Bombay (India))
The formation of a third phase in the extraction of large amounts of uranium(VI) and plutonium(IV) by bis(2-ethylhexyl)sulfoxide (BESO) into various hydrocarbon diluents was investigated over a wide range of experimental conditions. Solubility of both the extracted solvates UO[sub 2](NO[sub 3])[sub 2].2BESO and Pu(NO[sub 3])[sub 4].2BESO was maximum in polarizable benzene and the tendency to form third phase increased in the order: benzene < n-hexane < SST < dodecane. Usefulness of some commonly employed polar modifiers like tributylphosphate (TBP), 2-ethylhexanol and isodecanol on improving the metal solvate solubility was also assessed. (orig.)
Synthesis and Luminescence Properties of the Binary/Ternary Complex of Samarium Ion with Phenacylmethyl P-Tolyl Sulfoxide and Benzoic Acid
Directory of Open Access Journals (Sweden)
Yang Kui-Suo
Full Text Available A new ligand phenacylmethyl p-tolyl sulfoxide (denoted as L1 has been synthesized by an asymmetric synthesis method. Its novel binary complex Sm(L17·(ClO43·6H2O, and ternary complex Sm(L16·(L2·(ClO42·6H2O (benzoic acid denoted as L2 have been synthesized. The structure and composition of the samarium complexes characterized by elemental analysis, molar conductivity, IR, UV, and 1HNMR. Additionally, fluorescence spectra measurements shows that the complexes display stronger fluorescence intensity in solid state, indicating the ligands could efficiently transfer the energy to Sm3+ ions in the complexes. The ternary complex has stronger fluorescence intensity than the binary complex.
Heat capacities of thiane sulfones and thiane sulfoxide Refining of C{sub p} group values for organosulfur compounds and their oxides
Energy Technology Data Exchange (ETDEWEB)
Victoria Roux, Maria; Temprado, Manuel; Jimenez, Pilar; Guzman-Mejia, Ramon; Juaristi, Eusebio; Chickos, James S
A thermophysical study of thiane sulfone, 1; 1,3-dithiane sulfone, 2; and 1,3-dithiane sulfoxide, 3 in the temperature intervals between T=268 K and their respective melting temperatures has been carried out. The experimental values for the mole fraction, temperature, enthalpy and entropy of fusion and the associated standard deviation as determined by differential scanning calorimetry (DSC) are x = (0.9996{+-}0.0001), T{sub fus}=(370.8{+-}0.1) K, {delta}{sub fus}H{sub m}=(18.4{+-}0.2) kJ mol{sup -1}, {delta}{sub fus}S{sub m}=(49.6{+-}0.5) J mol{sup -1} K{sup -1} for thiane sulfone, 1; x = (0.9994{+-}0.0001), T{sub fus}=(414.0{+-}0.2) K, {delta}{sub fus}H{sub m}=(22.0{+-}0.2) kJ mol{sup -1}, {delta}{sub fus}S{sub m}=(53.1{+-}0.4) J mol{sup -1} K{sup -1} for 1,3-dithiane sulfone, 2; and x = (0.9977{+-}0.0001), T{sub fus}=(361.9{+-}0.1) K, {delta}{sub fus}H{sub m}=(22.6{+-}0.2) kJ mol{sup -1}, {delta}{sub fus}S{sub m}=(62.4{+-}0.5) J mol{sup -1} K{sup -1} for 1,3-dithiane sulfoxide, 3. Heat capacities in those temperature intervals and in condensed state were measured and no additional solid-solid phase transitions were observed. The heat capacities at T=298.15 K were used to refine group values for organosulfur compounds and their oxides.
Calcium-activated potassium channels in insect pacemaker neurons as unexpected target site for the novel fumigant dimethyl disulfide.
Gautier, Hélène; Auger, Jacques; Legros, Christian; Lapied, Bruno
Dimethyl disulfide (DMDS), a plant-derived insecticide, is a promising fumigant as a substitute for methyl bromide. To further understand the mode of action of DMDS, we examined its effect on cockroach octopaminergic neurosecretory cells, called dorsal unpaired median (DUM) neurons, using whole-cell patch-clamp technique, calcium imaging and antisense oligonucleotide strategy. At low concentration (1 microM), DMDS modified spontaneous regular spike discharge into clear bursting activity associated with a decrease of the amplitude of the afterhyperpolarization. This effect led us to suspect alterations of calcium-activated potassium currents (IKCa) and [Ca(2+)](i) changes. We showed that DMDS reduced amplitudes of both peak transient and sustained components of the total potassium current. IKCa was confirmed as a target of DMDS by using iberiotoxin, cadmium chloride, and pSlo antisense oligonucleotide. In addition, we showed that DMDS induced [Ca(2+)](i) rise in Fura-2-loaded DUM neurons. Using calcium-free solution, and (R,S)-(3,4-dihydro-6,7-dimethoxy-isoquinoline-1-yl)-2-phenyl-N,N-di-[2-(2,3,4-trimethoxy-phenyl)ethyl]-acetamide (LOE 908) [an inhibitor of transient receptor potential (TRP)gamma], we demonstrated that TRPgamma initiated calcium influx. By contrast, omega-conotoxin GVIA (an inhibitor of N-type high-voltage-activated calcium channels), did not affect the DMDS-induced [Ca(2+)](i) rise. Finally, the participation of the calcium-induced calcium release mechanism was investigated using thapsigargin, caffeine, and ryanodine. Our study revealed that DMDS-induced elevation in [Ca(2+)](i) modulated IKCa in an unexpected bell-shaped manner via intracellular calcium. In conclusion, DMDS affects multiple targets, which could be an effective way to improve pest control efficacy of fumigation.
Effect of Organic Solvent on the Enzyme Bleaching Agent System
コマツ, エミコ; モリタ, ミユキ; Emiko, KOMATSU; Miyuki, MORITA
The Orange n decoloration reaction in the presence of various organic solvents with the HRP-H_2O_2 system was examined. In 5% organic solvent mixing aqueous solutions, the decoloration rates of Orange n were about 0.9-0.5 times of those in the aqueous solutions. Decoloration rate of Orange II decreased, as the concentration of organic solvent increases. The reaction of Orange n decoloration stopped at the 60% dimethyl sulfoxide concentration.
Preparation, Characterization and Permeation Behavior of Poly(methyl acrylate-Poly(dimethyl siloxane-Poly(methyl acrylate Block Copolymer/Poly(vinyl acetate Blend Membranes
Directory of Open Access Journals (Sweden)
Mohammad Ali Semsarzadeh
Full Text Available Structure of polymeric materials is of the most important factors in determination of the characteristics and properties of the membranes. Various research and developments on polymeric membranes confirm the direct correlation between structure-properties of polymeric membranes. In this research, the structural outcome of poly(methyl acrylate-poly(dimethyl siloxane-poly(methyl acrylate/poly(vinyl acetate blend membranes and its relationship with gas permeation behavior of the blends were investigated. The flexible block copolymer of poly(methyl acrylate-poly(dimethyl siloxane-poly(methyl acrylate (PMA-PDMS-PMA was synthesized via atom transfer radical polymerization. Morphology and chemical structure of the synthesized block copolymer was investigated by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, gel permeation chromatography, X-ray diffraction analysis, differential scanning calorimetry and scanning electron microscopy. Blend membranes of PMA-PDMS-PMA and poly(vinyl acetate (PVAc were prepared by solution casting method in different compositions. By adding poly(vinyl acetate to PMA-PDMS-PMA block copolymer, the selectivity of the membranes for carbon dioxide/methane pair gases were increased by 55%. Fractional free volume (an indication of chain packing efficiency in blend membranes and dielectric constant (an indication of the molar volume and molar polarization of the blend membranes were obtained as the factors reflected the microstructural effect of PMA-PDMS-PMA and PVAc blend membranes. The efforts were directed toward expressing more precise structure-properties relationship of PMA-PDMS-PMA/PVAc blend membranes. The experimental permeability values of the blend membranes reported in this research were compared with the modified logarithmic model. The modified logarithmic model was evaluated for other blend membranes.
Luminescent lanthanide coordination polymers synthesized via in-situ hydrolysis of dimethyl-3,4-furandicarboxylate
Energy Technology Data Exchange (ETDEWEB)
Greig, Natalie E.; Einkauf, Jeffrey D.; Clark, Jessica M.; Corcoran, Eric J.; Karram, Joseph P.; Kent, Charles A.; Eugene, Vadine E. [Department of Chemistry & Biochemistry, Florida Atlantic University, 777 Glades Road, Boca Raton, FL 33431 (United States); Chan, Benny C. [Department of Chemistry, The College of New Jersey, 2000 Pennington Road, Ewing, NJ 08628 (United States); Lill, Daniel T. de, E-mail: firstname.lastname@example.com [Department of Chemistry & Biochemistry, Florida Atlantic University, 777 Glades Road, Boca Raton, FL 33431 (United States)
Dimethyl-3,4-furandicarboxylate undergoes hydrolysis under hydrothermal conditions with lanthanide (Ln) ions to form two-dimensional coordination polymers, [Ln(C{sub 6}H{sub 2}O{sub 5})(C{sub 6}H{sub 3}O{sub 5})(H{sub 2}O)]{sub n} (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The resulting materials exhibit luminescent properties with quantum yields and lifetimes for the Eu(III) and Tb(III) compounds of 1.1±0.3% and 0.387±0.0001 ms, and 3.3±0.8% and 0.769±0.006 ms, respectively. Energy values for the singlet and triplet states were determined for dimethyl-3,4-furandicarboxylate and 3,4-furandicarboxylic acid. Excited state dynamics and structural features are examined to explicate the reported quantum yields. A series of other FDC structures is briefly presented. - Graphical abstract: A new two-dimensional coordination polymer derived from the in-situ hydrolysis of a furan dimethyl ester with lanthanide(III) ions was obtained in order to study its photophysical behavior when constructed from trivalent Eu and Tb. Quantum yields, lifetime measurements, and singlet/triplet state energies values were obtained. The nature of the material's excited state dynamics is examined and correlated to its structure in order to explain the overall luminescent efficiency of the system. - Highlights: • A new lanthanide–furandicarboxylate coordination polymer is presented. • Eu and Tb compounds display luminescent properties, albeit with low quantum yields. • Photophysical behavior explained through the compound's triplet state and structure. • Nonradiative deactivation of luminescence through high-energy oscillators was noted. • Molecular modeling of the organic moiety was conducted.
DFT investigations for the reaction mechanism of dimethyl carbonate synthesis on Pd(II)/β zeolites.
Shen, Yongli; Meng, Qingsen; Huang, Shouying; Gong, Jinlong; Ma, Xinbin
Density functional theory (DFT) calculations have been used to investigate the oxidative carbonylation of methanol on Pd(II)/β zeolite. Activation energies for all the elementary steps involved in the commonly accepted mechanism, including the formation of dimethyl carbonate, methyl formate and dimethoxymethane, are presented. Upon conducting the calculations, we identify that the Pd(2+) cation bonded with four O atoms of the zeolite framework acts as the active site of the catalyst. Molecularly adsorbed methanol starts to react with oxygen molecules to produce a methanediol intermediate (CH2(OH)2) and O atom. Then, another methanol can react with the O atom to produce the (CH3O)(OH)-Pd(II)/β zeolite species. (CH3O)(OH)-Pd(II)/β zeolite can further react with carbon monoxide or methanol to give monomethyl carbonate or di-methoxide species ((CH3O)2-Pd(II)/β zeolite). Dimethyl carbonate can form via two distinct reaction pathways: (I) methanol reacts with monomethyl carbonate or (II) carbon monoxide inserts into di-methoxide. Our calculation results show the activation energy of reaction (I) is too high to be achieved. The methanediol intermediate is unstable and can decompose to formaldehyde and H2O immediately. Formaldehyde can either react with an O atom or methanol to form formic acid or a CH3OCH2OH intermediate. Both of them can react with methanol to form the secondary products (methyl formate or dimethoxymethane). Upon conducting calculations, we confirmed that the activation energies for the formation of methyl formate and dimethoxymethane are higher than that of dimethyl carbonate. All these conformations were characterized at the same calculation level.
Divergent mechanistic routes for the formation of gem-dimethyl groups in the biosynthesis of complex polyketides.
Poust, Sean; Phelan, Ryan M; Deng, Kai; Katz, Leonard; Petzold, Christopher J; Keasling, Jay D
The gem-dimethyl groups in polyketide-derived natural products add steric bulk and, accordingly, lend increased stability to medicinal compounds, however, our ability to rationally incorporate this functional group in modified natural products is limited. In order to characterize the mechanism of gem-dimethyl group formation, with a goal toward engineering of novel compounds containing this moiety, the gem-dimethyl group producing polyketide synthase (PKS) modules of yersiniabactin and epothilone were characterized using mass spectrometry. The work demonstrated, contrary to the canonical understanding of reaction order in PKSs, that methylation can precede condensation in gem-dimethyl group producing PKS modules. Experiments showed that both PKSs are able to use dimethylmalonyl acyl carrier protein (ACP) as an extender unit. Interestingly, for epothilone module 8, use of dimethylmalonyl-ACP appeared to be the sole route to form a gem-dimethylated product, while the yersiniabactin PKS could methylate before or after ketosynthase condensation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Effects of methyl prednisolone, dimethyl sulphoxide and naloxone in experimental spinal cord injuries in rats.
Zileli, M; Ovül, I; Dalbasti, T
The effects of methyl prednisolone (MPD), dimethyl sulphoxide (DMSO), and naloxone were examined in 38 albino rats after making an impact spinal cord injury on the midthoracic segments with a modified Allen's weight dropping trauma method. Somatosensorial evoked potentials (SEPs) were recorded before and 12 h and 14 d after the injury from epidurally inserted electrodes on the parietal cortex with sciatic nerve stimulations. Lower extremity motor functions of the animals were also examined. It may be concluded that in this study model, DMSO has a moderate effect which can be demonstrated clinically and through SEPs. Naloxone has no effect on the clinical outcome but causes reasonable improvement electrophysiologically.
Selective and efficient synthesis of ethanol from dimethyl ether and syngas
DEFF Research Database (Denmark)
Rasmussen, Dominik Bjørn
an important role as a gasoline additive or substitute and a catalytic process has been demonstrated, in which dimethyl ether (DME) produced from synthesis gas is converted to methyl acetate (MA), which is subsequently converted to EtOH and methanol (MeOH). MeOH can afterwards be easily converted to DME, using...... well-established processes. Syngas can be produced from biomass, making the entire process sustainable and environmentally friendly. The main benefit of this method is its unprecedented selectivity towards EtOH, while MeOH, the primary by-product, and the unreacted syngas are easily recycled...
Dimethyl ether reviewed: New results on using this gas in a high-precision drift chamber
International Nuclear Information System (INIS)
Basile, M.; Bonvicini, G.; Cara Romeo, G.; Cifarelli, L.; Contin, A.; D'Ali, G.; Del Papa, C.; Maccarrone, G.; Massam, T.; Motta, F.; Nania, R.; Palmonari, F.; Rinaldi, G.; Sartorelli, G.; Spinetti, M.; Susinno, G.; Villa, F.; Voltano, L.; Zichichi, A.
Two years ago, dimethyl ether (DME) was presented, for the first time, as a suitable gas for high-precision drift chambers. In fact our tests show that resolutions can be obtained which are better by at least a factor of 2 compared to what one can get with conventional gases. Moreover, DME is very well quenched. The feared formation of whiskers on the wires has not occurred, at least after months of use with a 10 μCi 106 Ru source. (orig.)
Control and interannual variability of dimethyl sulfide in the Indian Ocean
Digital Repository Service at National Institute of Oceanography (India)
Shenoy, D.M.; Joseph, S.; DileepKumar, M.; George, M.D.
sweater, Nature, 345, 702–705, 1990. Malin, G., Sulfur, climate and microbial maze, Nature, 387, 857–859, 1997. Niki, T., M. Kunugi, and A. Otsuki, DMSP-lyase activity in five marine phytoplankton species: Its potential importance in DMS production, Mar... radiation budget, because these gases absorb energy in the thermal infrared. Sulfur gases such as dimethyl sulfide (DMS) have an indirect effect on climate through forming sulfate-based aerosols [Andreae, 1990], which have poten- tial to change Earth's...
Krawczyk, Gerhard Erich [Bremen, DE; Miller, Kevin Michael [West Dundee, IL
There is provided a method of making a polymer solution comprising polymerizing one or more monomer in a solvent, wherein said monomer comprises one or more ethylenically unsaturated monomer that is a multi-functional Michael donor, and wherein said solvent comprises 40% or more by weight, based on the weight of said solvent, one or more multi-functional Michael donor.
DEFF Research Database (Denmark)
Efeoglu, Arkin; Møller, Charles; Serie, Michel
environment. The solution prototype that is composed from blending product and service prototype has particular impacts on the dualism of DSR's "Build" and "Evaluate". Since the mix between product and service prototyping can be varied, there is a demand for a more agile and iterative framework. Van de Ven...
Geoghegan, Michael W
Podcasting is the art of recording radio show style audio tracks, then distributing them to listeners on the Web via podcasting software such as iPodder. From downloading podcasts to producing a track for fun or profit, ""Podcast Solutions"" covers the entire world of podcasting with insight, humor, and the unmatched wisdom of experience.
Qualitative and quantitative analysis of light hydrocarbons produced by radiation degradation of N, N-dimethyl hydroxylamine
International Nuclear Information System (INIS)
Wang Jinhua; Bao Borong; Wu Minghong; Sun Xilian; Zhang Xianye; Hu Jingxin; Ye Guoan
This paper reports the qualitative and quantitative analysis of light hydrocarbons produced by radiation degradation of N, N-dimethyl hydroxylamine. These analyses were performed on the gas chromatograph, in which porous layer open tubular column coated with aluminum oxide and flame-ionization detector are used. For the doses between 10 and 1000 kGy, the light hydrocarbons produced by radiation degradation of N,N-dimethyl hydroxylamine are methane, ethane, ethene, propane, propene and n-butane. When the concentration of N,N-dimethyl hydroxylamine is 0.2 mol/L, the volume fraction of methane is (9.996-247.5) x 10 -6 , the volume fraction of ethane, propane and n-butane is lower and that of ethene and propene is much lower. With the increase of dose the volume fraction of methane is increased but the volume fraction of ethane, ethene, propane, propene and n-butane is not obviously changed. (authors)
Catalyst activity maintenance study for the liquid phase dimethyl ether process
Energy Technology Data Exchange (ETDEWEB)
Peng, X.D.; Toseland, B.A.; Underwood, R.P. [Air Products and Chemicals, Inc., Allentown, PA (United States)
The co-production of dimethyl ether (DME) and methanol from syngas is a process of considerable commercial attractiveness. DME coproduction can double the productivity of a LPMEOH process when using coal-derived syngas. This in itself may offer chemical producers and power companies increased flexibility and more profitable operation. DME is also known as a clean burning liquid fuel; Amoco and Haldor-Topsoe have recently announced the use of DME as an alternative diesel fuel. Moreover, DME can be an interesting intermediate in the production of chemicals such as olefins and vinyl acetate. The current APCl liquid phase dimethyl ether (LPDME) process utilizes a physical mixture of a commercial methanol synthesis catalyst and a dehydration catalyst (e.g., {gamma}-alumina). While this arrangement provides a synergy that results in much higher syngas conversion per pass compared to the methanol-only process, the stability of the catalyst system suffers. The present project is aimed at reducing catalyst deactivation both by understanding the cause(s) of catalyst deactivation and by developing modified catalyst systems. This paper describes the current understanding of the deactivation mechanism.
Chloro-1,4-dimethyl-9H-carbazole Derivatives Displaying Anti-HIV Activity
Directory of Open Access Journals (Sweden)
Carmela Saturnino
Full Text Available Background: Despite the progress achieved by anti-retroviral drug research in the last decades, the discovery of novel compounds endowed with selective antiviral activity and reduced side effects is still a necessity. At present, the most urgent requirement includes the improvement of HIV (Human Immunodeficiency Virus prevention and sexual transmission and the development of new drugs to treat the chronic lifelong infection. Methods: Six chloro-1,4-dimethyl-9H-carbazoles (2a,b–4a,b have been prepared following opportunely modified known chemical procedures and tested in luciferase and Escherichia coli β-galactosidase expressing CD4+, CXCR4+, CCR5+ TZM-bl cells. Results and Conclusion: a preliminary biological investigation on the synthesized small series of chloro-1,4-dimethyl-9H-carbazoles has been carried out. Among all tested compounds, a nitro-derivative (3b showed the most interesting profile representing a suitable lead for the development of novel anti-HIV drugs.
Study of the role of microbes as source and sink of Dimethyl Sulphide in Dona Paula bay
Digital Repository Service at National Institute of Oceanography (India)
Kumar, S.S.
) The biological production of dimethyl sulfide in the ocean and its role in the global atmospheric sulfur budget. Ecological Bulletin 35:167 – 77 Andreae MO, Ferek RJ, Bermond F, Byrd KP, Engstrom RT, Hardin S, Houmere PD, LeMarec F, Raemdonk H, Chatfield RB... production in marine surface waters: evaluation and field results. Marine Biology 66: 109 - 120 Fuse H, Takimura O, Murakami K, Yamaoka Y, Omori T (2000) Utilization of dimethyl sulfide as a sulfur source with the aid of light by Marinobacterium sp strain...
Directory of Open Access Journals (Sweden)
Monika Dziełak
Full Text Available N-(4-Bromobenzyl-2-(5,6-dimethyl-1H-benzo[d]imidazol-2-ylbenzeneamine was obtained by condensation of N-(4-bromobenzyl-3,1-benzoxazine-2,4-dione (N-(4-bromobenzylisatoic anhydride with 4,5-dimethyl-1,2-phenylenediamine in refluxing acetic acid. This is a rare example of condensation of N-substituted 3,1-benzoxazine-2,4-dione with 1,2-phenylenediamine, which resulted in the formation of a benzimidazole derivative with a moderate yield. Crystallographic studies and initial biological screening were performed for the obtained product.
Enhanced catalytic performance of zeolite ZSM-5 for conversion of methanol to dimethyl ether by combining alkaline treatment and partial activation
Wei, Ying; de Jongh, Petra E.|info:eu-repo/dai/nl/186125372; Bonati, Matteo L. M.; Law, David J.; Sunley, Glenn J.; de Jong, Krijn P.|info:eu-repo/dai/nl/06885580X
Zeolite ZSM-5 (MFI) due to its excellent hydrothermal stability and high catalytic activity for methanol dehydration to dimethyl ether (MID) has been considered for use in combination with a methanol synthesis catalyst, such as Cu/ZnO/Al2O3, in the conversion of syngas to dimethyl ether. However,
Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane.
Itami, Kenichiro; Mitsudo, Koichi; Nishino, Akira; Yoshida, Jun-ichi
Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane is described. The hydrosilylation of alkenes using dimethyl(2-pyridyl)silane (2-PyMe(2)SiH) proceeded well in the presence of a catalytic amount of RhCl(PPh(3))(3) with virtually complete regioselectivity. By taking advantage of the phase tag property of the 2-PyMe(2)Si group, hydrosilylation products were isolated in greater than 95% purity by simple acid-base extraction. Strategic catalyst recovery was also demonstrated. The hydrosilylation of alkynes using 2-PyMe(2)SiH proceeded with a Pt(CH(2)=CHSiMe(2))(2)O/P(t-Bu)(3) catalyst to give alkenyldimethyl(2-pyridyl)silanes in good yield with high regioselectivity. A reactivity comparison of 2-PyMe(2)SiH with other related hydrosilanes (3-PyMe(2)SiH, 4-PyMe(2)SiH, and PhMe(2)SiH) was also performed. In the rhodium-catalyzed reaction, the reactivity order of hydrosilane was 2-PyMe(2)SiH > 3-PyMe(2)SiH, 4-PyMe(2)SiH, PhMe(2)SiH, indicating a huge rate acceleration with 2-PyMe(2)SiH. In the platinum-catalyzed reaction, the reactivity order of hydrosilane was PhMe(2)SiH, 3-PyMe(2)SiH > 4-PyMe(2)SiH > 2-PyMe(2)SiH, indicating a rate deceleration with 2-PyMe(2)SiH and 4-PyMe(2)SiH. It seems that these reactivity differences stem primarily from the governance of two different mechanisms (Chalk-Harrod and modified Chalk-Harrod mechanisms). From the observed reactivity order, coordination and electronic effects of dimethyl(pyridyl)silanes have been implicated.
PMP, a novel solute for liquid and plastic scintillation counting
International Nuclear Information System (INIS)
Gusten, Hans
The excellent fluorescence properties of PMP ( 11-phenyl-3-mesityl-2-pyrazoline) such as long wavelength emission of over 400 nm, and high fluorescence quantum yield with a short decay time together with a solubility of more than one Mol/L in toluene make this compound a promising solute for scintillation counting. The Stokes' shift of PMP of over 10,000 cm -1 is twice as large as that of the commonly used PPO. Due to this unusually large Stokes' shift PMP can be used as a primary solute without requiring a secondary solute as wavelength shifter. A comparison of the scintillation properties of PMP and PPO in toluene reveals that the counting efficiency for 14 C is better for PMP while the 3 H efficiency is equally good. Due to the large Stokes' shift, PMP is about 50 percent less sensitive to color quenching than PPO. Compared to the solute combinations PPO/secondary solutes, the scintillation counting efficiency of PMP for 14 C in toluene or xylene is the same, while the absolute 3 H efficiency of PPO/secondary solutes in cocktails with emulsifiers is about 10 percent higher. The PMP scintillation efficiency for 14 C as well as 3 H in chemical quenching by urine is more or less the same as for PPO/dimethyl-POPOP. PMP is more sensitive to quenching by halogenated solvents. In the dioxane-based scintillation, this sensitivity to chemical quenching by CHCl 3 vanishes and the counting efficiencies for 14 C and 3 H are as good as for PPO/dimethyl-POPOP or PPO/bis-MSB. Due to the large Stokes' shift, the self-absorption of the scintillation light by PMP is lower than in conventional scintillators. This offers good possibilities in very large-volume applications of liquid as well as plastic scintillators
Composition dependent multiple structural transformations of myoglobin in aqueous ethanol solution: A combined experimental and theoretical study
Energy Technology Data Exchange (ETDEWEB)
Ghosh, R.; Samajdar, R. N.; Bhattacharyya, Aninda Jiban; Bagchi, B., E-mail: firstname.lastname@example.com [Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012 (India)
Experimental studies (circular dichroism and ultra-violet (UV) absorption spectra) and large scale atomistic molecular dynamics simulations (accompanied by order parameter analyses) are combined to establish a number of remarkable (and unforeseen) structural transformations of protein myoglobin in aqueous ethanol mixture at various ethanol concentrations. The following results are particularly striking. (1) Two well-defined structural regimes, one at x{sub EtOH} ∼ 0.05 and the other at x{sub EtOH} ∼ 0.25, characterized by formation of distinct partially folded conformations and separated by a unique partially unfolded intermediate state at x{sub EtOH} ∼ 0.15, are identified. (2) Existence of non-monotonic composition dependence of (i) radius of gyration, (ii) long range contact order, (iii) residue specific solvent accessible surface area of tryptophan, and (iv) circular dichroism spectra and UV-absorption peaks are observed. Interestingly at x{sub EtOH} ∼ 0.15, time averaged value of the contact order parameter of the protein reaches a minimum, implying that this conformational state can be identified as a molten globule state. Multiple structural transformations well known in water-ethanol binary mixture appear to have considerably stronger effects on conformation and dynamics of the protein. We compare the present results with studies in water-dimethyl sulfoxide mixture where also distinct structural transformations are observed along with variation of co-solvent composition.
Synthesis and characterisation of telechelic poly(2,6-dimethyl-1,4-phenylene ether) for copolymerisation
Krijgsman, J.; Feijen, Jan; Gaymans, R.J.
Telechelic poly(2,6-dimethyl-1,4-phenylene ether) (PPE) segments are interesting starting materials, for example for copolymerisation. A good method to make partly bifunctional PPE-2OH is by redistribution or depolymerisation of high molecular weight commercial PPE with tetramethyl bisphenol A. The
Physicochemical and biological evaluation of poly(ethylene glycol) methacrylate grafted onto poly(dimethyl siloxane) surfaces for prosthetic devices
Goncalves, Sara; Leiros, Ana; Van Kooten, Theo; Dourado, Fernando; Rodrigues, Ligia R.
Poly(dimethyl siloxane) (PDMS) was surface-polymerized with poly(ethylene glycol)methacrylate (PEGMA) by surface-initiated atom transfer radical polymerization (SI-ATRP) in aqueous media at room temperature. Modification of the PDMS surface followed a three-step procedure: (i) PDMS surface
An exploration towards a more sustainable process for dimethyl naphthalene-2,6-dicarboxylate over acidic zeolites
Bouvier, C.P.
This thesis describes the challenge to apply a breakthrough in the synthesis of acidic zeolitic catalysts in the development of a sustainable process for dimethyl naphthalene-2,6-dicarboxylate. BiModal POrous Materials (BIPOMs) are zeolitic materials, which provide highway access to confined
Compound instability in dimethyl sulphoxide, case studies with 5-aminopyrimidines and the implications for compound storage and screening
Czech Academy of Sciences Publication Activity Database
Procházková, Eliška; Jansa, Petr; Březinová, Anna; Čechová, Lucie; Mertlíková-Kaiserová, Helena; Holý, Antonín; Dračínský, Martin
Roč. 22, č. 20 (2012), s. 6405-6409 ISSN 0960-894X Institutional support: RVO:61388963 Keywords : 5-aminopyrimidines * dimethyl sulphoxide * oxidation * self-condensation * pyrimidopteridines Subject RIV: CC - Organic Chemistry Impact factor: 2.338, year: 2012
Voltammetric Determination of N,N-Dimethyl-4-amine-carboxyazobenzene at a Silver Solid Amalgam Electrode
Czech Academy of Sciences Publication Activity Database
Barek, J.; Dodova, E.; Navrátil, Tomáš; Josypčuk, Bohdan; Novotný, Ladislav; Zima, J.
Roč. 15, č. 22 (2003), s. 1778-1781 ISSN 1040-0397 Grant - others:GIT(AR) 101/02/U111/CZ Institutional research plan: CEZ:AV0Z4040901 Keywords : N,N-dimethyl-4-amino-carboxyazobenzene * differential pulse voltammetry * silver solid amalgam electrode Subject RIV: CG - Electrochemistry Impact factor: 1.811, year: 2003
Perfluoroalkylation of Aryl-N,N-dimethyl Hydrazones Using Hypervalent Iodine(III) Reagents or Perfluoroalkyl Iodides.
Janhsen, Benjamin; Studer, Armido
Radical trifluoromethylation of aryl N,N-dimethyl hydrazones using TBAI as an initiator and Togni's reagent as a trifluoromethyl radical source is described. Cascades proceed via electron-catalysis; this approach is generally more applicable to hydrazone perfluoroalkylation using perfluoroalkyl iodides as the radical precursors in combination with a base under visible-light initiation.
Combination of accelerated solvent extraction and vortex-assisted liquid-liquid microextraction for the determination of dimethyl fumarate in textiles and leathers by gas chromatography-mass spectrometry.
Lu, Yang; Zhu, Yan
A simple and environmentally friendly sample preparation procedure coupled with gas chromatography-mass spectrometry was developed to assay dimethyl fumarate in textiles and leathers. The sample preparation procedure involved an accelerated solvent extraction (ASE) using water as the extract solvent, followed by the extraction and concentration of dimethyl fumarate from the aqueous solution using vortex-assisted liquid-liquid microextraction (VALLME). The parameters affecting the ASE and VALLME were optimized to achieve the maximum extraction efficiency, and the performance of the developed method was evaluated. Good linearity was observed over the range assayed (0.01-1mg/kg) with a regression coefficient of 0.998. The limit of detection and enrichment factor for the VALLME step were 0.001 mg/kg and 53, respectively. The intra- and inter-day precision were below 8.9%, and the recovery was approximately 84-103%. The as-developed method was successfully applied to textiles and leather samples. © 2013 Elsevier B.V. All rights reserved.
Spectral, thermal, structural and quantum chemical calculations of 3,5-dimethyl-1H-pyrazol-2-ium-3-hydroxy-2,4,6-trinitrophenolate - A new organic proton transfer crystal
Dhamodharan, P.; Sathya, K.; Dhandapani, M.
Single crystals of a new proton transfer optical material, 3,5-dimethyl-1H-pyrazol-2-ium-3-hydroxy-2,4,6-trinitrophenolate (DPHTP), were obtained using slow evaporation of methanolic solution containing 1:1 M quantities of 3,5 dimethyl-1H-pyrazole and 3-hydroxy 2,4,6-trinitro phenol (styphnic acid). Asymmetric unit of DPHTP contains a univalent 3,5- dimethylpyrazolium cation with a univalent 3-hydroxy-2,4,6-trinitrophenolate anion. The various types of carbon atoms and protons in the compound were established using 1H and 13C NMR spectral studies. Thermal stability and decomposition pattern of DPHTP were studied by TG/DTA. The optical nonlinearities of DPHTP have been investigated by Z-scan technique with He-Ne laser radiation of wavelength 632.8 nm. The equilibrium optimized geometry, the first order hyperpolarizability calculations, molecular electrostatic interactions, frontier molecular orbital analysis, Mulliken population analysis have been calculated by density functional theoretical (DFT) method with (B3LYP)/6-311++G(d,p) level of basis set. First order hyperpolarizability (β) of DPHTP is 22 times greater than that of urea.
Techno-economic evaluation of different CO2-based processes for dimethyl carbonate production
DEFF Research Database (Denmark)
Kongpanna, Pichayapan; Pavarajarn, Varong; Gani, Rafiqul
In this work, several chemical processes for production of dimethyl carbonate (DMC) based on CO2 utilization are evaluated. Four CO2-based processes for production of DMC are considered: (1) direct synthesis from CO2 and methanol; (2) synthesis from urea; (3) synthesis from propylene carbonate......; and (4) synthesis from ethylene carbonate. The processes avoid the use of toxic chemicals such as phosgene, CO and NO that are required in conventional DMC production processes. From preliminary thermodynamic analysis, the yields of DMC are found to have the following order (higher to lower): ethylene...... carbonate route > urea route > propylene carbonate route > direct synthesis from CO2. Therefore, only the urea and ethylene carbonate routes are further investigated by comparing their performances with the commercial BAYER process on the basis of kg of DMC produced at a specific purity. The ethylene...
Lubrication and wear in diesel engine injection equipment fuelled by dimethyl ether (DME)
DEFF Research Database (Denmark)
Sivebæk, Ion Marius
Dimethyl ether (DME) has been recognised as an excellent fuel for diesel engines for over one decade now. DME fueled engines emit virtually no particulate matter even at low NOx levels. DME has thereby the potential of reducing the diesel engine emissions without filters or other devices...... oil. Fueling diesel engines with DME presents two significant problems: The injection equipment can break down due to extensive wear and DME attacks nearly all known elastomers. The latter problem renders dynamic sealing diƣult whereas the first one involves the poor lubrication qualities of DME which...... that jeopardise the high efficiency of the engine and increase the manufacturing costs. DME has a low toxicity and can be made from anything containing carbon including biomass. If DME is produced from cheap natural gas from remote locations, the price of this new fuel could even become lower than that of diesel...
C-4 Gem-Dimethylated Oleanes of Gymnema sylvestre and Their Pharmacological Activities
Directory of Open Access Journals (Sweden)
Giovanni Di Fabio
Full Text Available Gymnema sylvestre R. Br., one of the most important medicinal plants of the Asclepiadaceae family, is a herb distributed throughout the World, predominantly in tropical countries. The plant, widely used for the treatment of diabetes and as a diuretic in Indian proprietary medicines, possesses beneficial digestive, anti-inflammatory, hypoglycemic and anti-helmentic effects. Furthermore, it is believed to be useful in the treatment of dyspepsia, constipation, jaundice, hemorrhoids, cardiopathy, asthma, bronchitis and leucoderma. A literature survey revealed that some other notable pharmacological activities of the plant such as anti-obesity, hypolipidemic, antimicrobial, free radical scavenging and anti-inflammatory properties have been proven too. This paper aims to summarize the chemical and pharmacological reports on a large group of C-4 gem-dimethylated pentacyclic triterpenoids from Gymnema sylvestre.
Methyl 2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl-4-nitrobenzoate
Directory of Open Access Journals (Sweden)
S. F. Jenkinson
Full Text Available The six-membered boronate ester ring of the title compound, C13H16BNO6, adopts an envelope conformation with the C atom bearing the dimethyl substituents at the flap. The O—B—C—C torsion angles between the boronate group and the benzene ring are 72.5 (2 and 81.0 (2°. The 4-nitrobenzoate unit adopts a slightly twisted conformation, with dihedral angles between the benzene ring and the nitrate and methyl ester groups of 17.5 (2 and 14.4 (3°, respectively. In the crystal, inversion-related pairs of molecules show weak π–π stacking interactions [centroid–centroid distance = 4.0585 (9 Å and interplanar spacing = 3.6254 (7 Å].
Establishing a green platform for biodiesel synthesis via strategic utilization of biochar and dimethyl carbonate.
Lee, Jechan; Jung, Jong-Min; Oh, Jeong-Ik; Sik Ok, Yong; Kwon, Eilhann E
To establish a green platform for biodiesel production, this study mainly investigates pseudo-catalytic (non-catalytic) transesterification of olive oil. To this end, biochar from agricultural waste (maize residue) and dimethyl carbonate (DMC) as an acyl acceptor were used for pseudo-catalytic transesterification reaction. Reaction parameters (temperature and molar ratio of DMC to olive oil) were also optimized. The biodiesel yield reached up to 95.4% under the optimal operational conditions (380°C and molar ratio of DMC to olive oil (36:1)). The new sustainable environmentally benign biodiesel production introduced in this study is greener and faster than conventional transesterification reactions. Copyright © 2017 Elsevier Ltd. All rights reserved.
XPS and NEXAFS analysis of dimethyl sulfide adsorbed on the Rh(PVP) nanoparticle surface
International Nuclear Information System (INIS)
Niwa, Hironori; Ogawa, Satoshi; Yagi, Shinya; Kutluk, Galif
We have studied the adsorption reaction of dimethyl sulfide (DMS: (CH 3 ) 2 S) on the surface of Rh(PVP) nanoparticles by using AFM, XPS and NEXAFS techniques. The AFM images show the degree of dispersion of the Rh(PVP) nanoparticles depends on the amount of them. The in-situ XPS results indicate that the dissociation reaction of DMS into atomic S does not depend upon the existence of the Rh(PVP) nanoparticles. The NEXAFS results show that there is a strong chemical bonding between Rh(PVP) nanoparticle and atomic S. The ex-situ XPS results show the atomic S adsorbed on the Rh(PVP) nanoparticles partially desorb by exposing to the air. (author)
Dimethyl Ether: New Advances in Wear Testing: Theoretical and Experimental Results
DEFF Research Database (Denmark)
Sivebæk, Ion Marius; Sorenson, Spencer C; Jakobsen, J.
) on the ball. Up to now, all analyses indicated that fuel viscosity influences the wear scar size and fuel performance in full-scale pumps. The wear scar size could then be a result of hydrodynamic lubrication (at least a significant part of it) and not of boundary lubrication as it was the original intention...... of the test. The appearance of an excellent volatile fuel for diesel engines, Dimethyl Ether (DME), has resulted in new wear tests such as the Medium Frequency Pressurised Reciprocating Rig (MFPRR), a pressurised version of the HFRR. DME has a about 25 times lower viscosity than diesel oil so the MFPRR...... viscosity sensibility issue is seriously aggravated for this fuel. Molecular dynamics calculations involving straight alkanes with lengths from 3 to 14 carbon atoms have been performed. The model is based on simple inter-atomic and surface interactions and it simulates an asperity contact between curved...
Assessment of Lubricity Properties of Dimethyl Ether Using the Medium Frequency Reciprocating Rig
DEFF Research Database (Denmark)
Sivebæk, Ion Marius; Sorenson, Spencer C
Adequate lubricity of a fuel is an important issue when the wear in diesel engine injection equipment is to be minimised. For conventional diesel oils, there exist methods capable of measuring the lubricity of the fuels. These methods cannot handle Dimethyl Ether (DME), as it has to be pressurised...... exceptionally low. By mixing the DME with very small quantities of additives the lubricity can be redressed. Only one additive was capable of giving DME a lubricity higher than the one of diesel oil. Even at such high lubricities it cannot be concluded that wear in the diesel injection pumps....... The calibration was achieved by using both the standard method for diesel oil and the MFPRR, to test three liquid fuels of varying lubricities. The result was that the MFPRR discriminated just as well between the fuel lubricities as did the standard method. The lubricity of DME was measured and was found...
Chun, Tiejun; Zhu, Deqing; Pan, Jian; He, Zhen
Recovery of alumina from magnetic separation tailings of red mud has been investigated by Na2CO3 solution leaching. X-ray diffraction (XRD) results show that most of the alumina is present as 12CaO·7Al2O3 and CaO·Al2O3 in the magnetic separation tailings. The shrinking core model was employed to describe the leaching kinetics. The results show that the calculated activation energy of 8.31 kJ/mol is characteristic for an internal diffusion-controlled process. The kinetic equation can be used to describe the leaching process. The effects of Na2CO3 concentration, liquid-to-solid ratio, and particle size on recovery of Al2O3 were examined.
The sensitivity of dimethyl sulfide production to simulated climate change in the Eastern Antarctic Southern Ocean
International Nuclear Information System (INIS)
Gabric, Albert J.; Cropp, Roger; Marchant, Harvey
Dimethyl sulfide (DMS) is a radiatively active trace gas produced by enzymatic cleavage of its precursor compound, dimethyl sulfoniopropionate (DMSP), which is released by marine phytoplankton in the upper ocean. Once ventilated to the atmosphere, DMS is oxidised to form non-sea-salt sulfate and methane sulfonate (MSA) aerosols, which are a major source of cloud condensation nuclei (CCN) in remote marine air and may thus play a role in climate regulation. Here we simulate the change in DMS flux in the Eastern Antarctic ocean from 1960-2086, corresponding to equivalent CO 2 tripling relative to pre-industrial levels. Calibration to contemporary climate conditions was carried out using a genetic algorithm to fit the model to surface chlorophyll from the 4-yr SeaWiFs satellite archive and surface DMS from an existing global database. Following the methodology used previously in the Subantarctic Southern Ocean, we then simulated DMS emissions under enhanced greenhouse conditions by forcing the DMS model with output from a coupled atmospheric-ocean general circulation model (GCM). The GCM was run in transient mode under the IPCC/IS92a radiative forcing scenario. By 2086, the change simulated in annual integrated DMS flux is around 20% in ice-free waters, with a greater increase of 45% in the seasonal ice zone (SIZ). Interestingly, the large increase in flux in the SIZ is not due to higher in situ production but mainly because of a loss of ice cover during summer-autumn and an increase in sea-to-air ventilation of DMS. These proportional changes in areal mean flux (25%) are much higher than previously estimated for the Subantarctic Southern Ocean (5%), and point to the possibility of a significant DMS-climate feedback at high Southern latitudes. Due to the nexus between ice cover and food-web structure, the potential for ecological community shifts under enhanced greenhouse conditions is high, and the implications for DMS production are discussed
Relative potency of albendazole and its sulfoxide metabolite in two in vitro tests for developmental toxicity: the rat whole embryo culture and the mouse embryonic stem cell test.
Eckardt, Kathrin; Kaltenhäuser, Johanna; Kilb, Caroline; Seiler, Andrea; Stahlmann, Ralf
The benzimidazole carbamate albendazole (ABZ), a potent anthelmintic, is a teratogenic compound in rats. At present it is unclear to which degree this effect is caused by the parent compound or its major metabolite, albendazole sulfoxide (ASO). Both substances were studied separately and in combinations to mimic incomplete bioactivation in two in vitro tests: mouse embryonic stem cell test (EST) and rat whole embryo culture (WEC). In both assays, ABZ and mixtures with ASO induced detrimental effects at lower concentrations compared to ASO alone. While ABZ caused half-maximal effects on cardiomyocyte differentiation at a mean concentration of 0.26 μM (EST) and dysmorphogenic development of rat embryos at 3.7 μM (WEC), effective concentrations of ASO were similar in both assays (10-13 μM). By using WEC and EST we demonstrate that ABZ exhibits stronger inherent embryotoxic potency although ASO might be the proximate teratogen in vivo because of higher plasma concentrations. Copyright © 2012 Elsevier Inc. All rights reserved.
Simultaneous quantification of methiocarb and its metabolites, methiocarb sulfoxide and methiocarb sulfone, in five food products of animal origin using tandem mass spectrometry.
Rahman, Md Musfiqur; Abd El-Aty, A M; Na, Tae-Woong; Park, Joon-Seong; Kabir, Md Humayun; Chung, Hyung Suk; Lee, Han Sol; Shin, Ho-Chul; Shim, Jae-Han
A simultaneous analytical method was developed for the determination of methiocarb and its metabolites, methiocarb sulfoxide and methiocarb sulfone, in five livestock products (chicken, pork, beef, table egg, and milk) using liquid chromatography-tandem mass spectrometry. Due to the rapid degradation of methiocarb and its metabolites, a quick sample preparation method was developed using acetonitrile and salts followed by purification via dispersive- solid phase extraction (d-SPE). Seven-point calibration curves were constructed separately in each matrix, and good linearity was observed in each matrix-matched calibration curve with a coefficient of determination (R 2 ) ≥ 0.991. The limits of detection and quantification were 0.0016 and 0.005mg/kg, respectively, for all tested analytes in various matrices. The method was validated in triplicate at three fortification levels (equivalent to 1, 2, and 10 times the limit of quantification) with a recovery rate ranging between 76.4-118.0% and a relative standard deviation≤10.0%. The developed method was successfully applied to market samples, and no residues of methiocarb and/or its metabolites were observed in the tested samples. In sum, this method can be applied for the routine analysis of methiocarb and its metabolites in foods of animal origins. Copyright © 2017 Elsevier B.V. All rights reserved.
Changes in trans-S-1-Propenyl-l-cysteine Sulfoxide and Related Sulfur-Containing Amino Acids during Onion Storage.
Kamata, Yasuhiro; Aoyagi, Morihiro; Sawada, Yuji; Nakabayashi, Ryo; Hirai, Masami Yokota; Saito, Kazuki; Imai, Shinsuke
trans-S-1-Propenyl-l-cysteine sulfoxide (PRENCSO) is the most abundant flavor precursor in onions. The changes in PRENCSO, its biosynthetic precursors, and cycloalliin contents in bulbs stored at 0 °C [i.e., recommended by the Food and Agriculture Organization of the United Nations (FAO)] are investigated. Ion-exchange high-performance liquid chromatography analysis revealed larger amounts of PRENCSO and cycloalliin, which were stoichiometrically balanced by the decrease in the combined amounts of the three biosynthetic precursors. The molar balance of the PRENCSO biosynthesis process during onion storage was explained well by the changes of these five compounds. High-throughput integrated liquid chromatography-tandem mass spectrometry analysis was employed to analyze multiple samples at 5 and 20 °C. The molar concentration data, converted using linear regression equations, showed a similar molar balance for the PRENCSO biosynthesis process comprising these five compounds during storage at all temperatures tested. Furthermore, the content of cycloalliin significantly increased at the expense of that of PRENCSO during storage at 20 °C.
H2O2/UV-C oxidation of potential endocrine disrupting compounds: a case study with dimethyl phthalate.
Olmez-Hanci, Tugba; Imren, Ceren; Arslan-Alaton, Idil; Kabdaşli, Işik; Tünay, Olcay
This paper discusses the feasibility of the ultraviolet radiation-hydrogen peroxide (H(2)O(2)/UV-C) process as an advanced oxidation process (AOP) in the treatment of endocrine disrupting compounds (EDC). Dimethyl phthalate (DMP) was chosen as the model compound owing to its classification as an EDC. Experiments have been conducted at various pH values (3.5, 6.0 and 9.0) and initial H(2)O(2) concentrations (0-60 mM) in a batch reactor equipped with a low-pressure mercury UV-C lamp in order to evaluate the optimal operation conditions of the H(2)O(2)/UV-C process. The most effective pH value for the degradation of DMP by H(2)O(2)/UV-C treatment was found as 6.0. DMP abatement increased with increasing H(2)O(2) concentrations from 5 to 30 mM. Further increase in initial H(2)O(2) concentration, however, reduced both the rate and extent of DMP removal as well as chemical oxygen demand (COD) and total organic carbon (TOC) removals. A simple kinetic model was proposed for DMP, COD and TOC abatements confirmed pseudo-first-order reaction. The electrical energy per order (EE/O) values for DMP oxidation and TOC mineralization were calculated as 3.3 and 19 kWh m(-3) order(-1) respectively for the optimum treatment conditions (H(2)O(2,o) = 30 mM, pH(o) = 6.0, DMP(o)= 100 mg L(-1)). Inhibition of oxygen uptake rate by activated sludge (ISO 8192) was evaluated as a tool for assessing the acute toxicity of untreated and H(2)O(2)/UV-C treated DMP. According to the results obtained in this work, the use of the H(2)O(2)/UV-C process is recommended to achieve a complete DMP oxidation and high mineralization degree of aqueous solution of DMP.
The preparation, characterization, and pharmacokinetic studies of chitosan nanoparticles loaded with paclitaxel/dimethyl-β-cyclodextrin inclusion complexes
Directory of Open Access Journals (Sweden)
Ye YJ
Full Text Available Ya-Jing Ye,1 Yun Wang,1 Kai-Yan Lou,1 Yan-Zuo Chen,1 Rongjun Chen,2 Feng Gao1,3,4 1Department of Pharmaceutics, School of Pharmacy, East China University of Science and Technology, Shanghai, People's Republic of China; 2Department of Chemical Engineering, Imperial College London, London, United Kingdom; 3Shanghai Key Laboratory of Functional Materials Chemistry, 4Shanghai Key Laboratory of New Drug Design, East China University of Science and Technology, Shanghai, People's Republic of China Abstract: A novel biocompatible and biodegradable drug-delivery nanoparticle (NP has been developed to minimize the severe side effects of the poorly water-soluble anticancer drug paclitaxel (PTX for clinical use. PTX was loaded into the hydrophobic cavity of a hydrophilic cyclodextrin derivative, heptakis (2,6-di-O-methyl-β-cyclodextrin (DM-β-CD, using an aqueous solution-stirring method followed by lyophilization. The resulting PTX/DM-β-CD inclusion complex dramatically enhanced the solubility of PTX in water and was directly incorporated into chitosan (CS to form NPs (with a size of 323.9–407.8 nm in diameter using an ionic gelation method. The formed NPs had a zeta potential of +15.9–23.3 mV and showed high colloidal stability. With the same weight ratio of PTX to CS of 0.7, the loading efficiency of the PTX/DM-β-CD inclusion complex-loaded CS NPs was 30.3-fold higher than that of the PTX-loaded CS NPs. Moreover, it is notable that PTX was released from the DM-β-CD/CS NPs in a sustained-release manner. The pharmacokinetic studies revealed that, compared with reference formulation (Taxol®, the PTX/DM-β-CD inclusion complex-loaded CS NPs exhibited a significant increase in AUC0→24h (the area under the plasma drug concentration–time curve over the period of 24 hours and mean residence time by 2.7-fold and 1.4-fold, respectively. Therefore, the novel drug/DM-β-CD inclusion complex-loaded CS NPs have promising applications for the
EPR-study of reversible oxygenation process of coordination compounds of cobalt(II) with S-substituted N1,N4-di(salicylidene)-isothiosemicarbazides
International Nuclear Information System (INIS)
Gerbeleu, N.V.; Revenko, M.D.; Rusu, V.G.; Shames, A.T.
The reaction between molecular oxygen and coordination compounds of cobalt(II) with S-substituted N 1 ,N 4 -di(salicylidene)isothiosemicarbazides in dimethyl sulfoxide solution was studied by the EPR method. It was found that paramagnetic monomeric adducts and diamagnetic μ-peroxo-dimers are formed. The spin-Hamiltonian parameters of the EPR spectra of the initial cobalt complexes, as well as of the paramagnetic adducts were determined. The nature of the Co-O 2 bond is discussed
CdS nanobubbles and Cd-DMS nanosheets: solvothermal synthesis and formation mechanism.
Feng, Miao; Zhan, Hongbing
CdS nanobubbles and Cd-DMS nanosheets have been prepared by a solvothermal method from a solution of Cd2+ in dimethyl sulfoxide in the absence of elemental S. A formation mechanism for the nanobubble morphology arising during the CdS nanocrystal growth has been proposed, based on the results of transmission electron microscopy and photoluminescence spectrophotometry. The correlation of the morphology with reaction time was also suggested, and may be applicable to the solvothermal synthesis of other nanomaterials.
Recommended methods for purification of solvents and tests for impurities
Coetzee, J F
Recommended Methods for Purification of Solvents and Tests for Impurities is a compilation of recommended procedures for purification of solvents and tests for solvent impurities. Ten solvents are covered: acetonitrile, sulfolane, propylene carbonate, dimethyl sulfoxide, dimethylformamide, hexamethylphosphoramide, pyridine, ethylenediamine, N-methylacetamide, and N-methylpropionamide. This book is comprised of 12 chapters and opens with an introduction to general aspects of impurity effects. The rationale for the selection of solvent is explained, and the relative reactivities of solutes in di
Targeting Cancer Protein Profiles with Split-Enzyme Reporter Fragments to Achieve Chemical Resolution for Molecular Imaging
SPIE BiOS: Biomedical Optics Symposium. • Optical imaging of targeted beta-galactosidase in brain tumors to detect EGFR levels. (2015) Nanotech ...the coordinated expression of cell surface receptors in glioblastomas. World Molecular Imaging Congress. Best Poster in Category. • Agnes, R.S...of stock Cy5.5- labeled peptide solutions in dimethyl sulfoxide (DMSO) was determined by UV-Vis spectrometry [Cy5.5 molar extinction coefficient is
Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) Process. Peroxide formation of dimethyl ether in methanol mixtures
Energy Technology Data Exchange (ETDEWEB)
Waller, F.J.
Organic peroxides could form when dimethyl ether in methanol is stored for three to six months at a time. The objective of this work was to determine the level of peroxide formation from dimethyl ether in reagent grade methanol and raw methanol at room temperature under 3 atmospheres (45 psig) of air. Raw methanol is methanol made from syngas by the LPMEOH Process without distillation. Aliphatic ethers tend to react slowly with oxygen from the air to form unstable peroxides. However, there are no reports on peroxide formation from dimethyl ether. After 172 days of testing, dimethyl ether in either reagent methanol or raw methanol at room temperature and under 60--70 psig pressure of air does not form detectable peroxides. Lack of detectable peroxides suggests that dimethyl ether or dimethyl ether and methanol may be stored at ambient conditions. Since the compositions of {approximately} 1.3 mol% or {approximately} 4.5 mol% dimethyl ether in methanol do not form peroxides, these compositions can be considered for diesel fuel or an atmospheric turbine fuel, respectively.
NMR Chemical Shift Ranges of Urine Metabolites in Various Organic Solvents
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Benjamin Görling
Full Text Available Signal stability is essential for reliable multivariate data analysis. Urine samples show strong variance in signal positions due to inter patient differences. Here we study the exchange of the solvent of a defined urine matrix and how it affects signal and integral stability of the urinary metabolites by NMR spectroscopy. The exchange solvents were methanol, acetonitrile, dimethyl sulfoxide, chloroform, acetone, dichloromethane, and dimethyl formamide. Some of these solvents showed promising results with a single batch of urine. To evaluate further differences between urine samples, various acid, base, and salt solutions were added in a defined way mimicking to some extent inter human differences. Corresponding chemical shift changes were monitored.