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"The single most important synthetic application of alkyl hydroperoxides is without doubt the metal-catalysed epoxidation of alkenes." In the Halcon process tert-butyl hydroperoxide (TBHP) is employed for the production of propylene oxide.
Of specialized interest, chiral epoxides are prepared using hydroperoxides as reagents in the Sharpless epoxidation. | 0 | Organic Chemistry |
Biocorrosion, biofouling and corrosion caused by living organisms are now known to have an electrochemistry foundation. Other marine creatures such as mussels, worms and even sponges have been known to degrade engineering materials. | 8 | Metallurgy |
The mechanism of the Hofmeister series is not entirely clear, but does not seem to result from changes in general water structure, instead more specific interactions between ions and proteins and ions and the water molecules directly contacting the proteins may be more important. Simulation studies have shown that the variation in solvation energy between the ions and the surrounding water molecules underlies the mechanism of the Hofmeister series. A quantum chemical investigation suggests an electrostatic origin to the Hofmeister series. This work provides site-centred radial charge densities of the ions' interacting atoms (to approximate the electrostatic potential energy of interaction), and these appear to quantitatively correlate with many reported Hofmeister series for electrolyte properties, reaction rates and macromolecular stability (such as polymer solubility, and virus and enzyme activities).
Early members of the series increase solvent surface tension and decrease the solubility of nonpolar molecules ("salting out"); in effect, they strengthen the hydrophobic interaction. By contrast, later salts in the series increase the solubility of nonpolar molecules ("salting in") and decrease the order in water; in effect, they weaken the hydrophobic effect.
The "salting out" effect is commonly exploited in protein purification through the use of ammonium sulfate precipitation. However, these salts also interact directly with proteins (which are charged and have strong dipole moments) and may even bind specifically (e.g., phosphate and sulfate binding to ribonuclease A).
Ions that have a strong "salting in" effect such as I and SCN are strong denaturants, because they salt in the peptide group, and thus interact much more strongly with the unfolded form of a protein than with its native form. Consequently, they shift the chemical equilibrium of the unfolding reaction towards unfolded protein. | 7 | Physical Chemistry |
Klaus Schmiegel was born in Chemnitz, Germany on June 28, 1939. After he immigrated to the United States in 1951, Schmiegel received a B.S. in chemistry from the University of Michigan, an A.M. in organic chemistry from Dartmouth College, and a Ph.D. in organic chemistry from Stanford University. His strong educational background secured him a prestigious position as a senior organic chemist at Eli Lilly, a prominent pharmaceutical company. | 0 | Organic Chemistry |
The steam engine was applied to power blast air, overcoming a shortage of water power in areas where coal and iron ore were located. This was first done at Coalbrookdale where a steam engine replaced a horse-powered pump in 1742. Such engines were used to pump water to a reservoir above the furnace. The first engines used to blow cylinders directly was supplied by Boulton and Watt to John Wilkinson's New Willey Furnace. This powered a cast iron blowing cylinder, which had been invented by his father Isaac Wilkinson. He patented such cylinders in 1736, to replace the leather bellows, which wore out quickly. Isaac was granted a second patent, also for blowing cylinders, in 1757. The steam engine and cast iron blowing cylinder led to a large increase in British iron production in the late 18th century. | 8 | Metallurgy |
Acetone, butanol, and ethanol are the most common products of solventogenesis. Some species such as Clostridium beijerinckii, Clostridium puniceum and Clostridium roseum are able to further reduce acetone to isopropanol. Several species are able to produce additional solvents under various culture conditions. For example, glycerol fermentation results in the production of 1,3-propanediol in several species. Acetoin is produced by several species and is further reduced to 2,3-butanediol by Clostridium beijerinckii. | 1 | Biochemistry |
D-glyceraldehyde 3-phosphate is formed from the following three compounds in reversible reactions:
*Fructose-1,6-bisphosphate (F1,6BP), catalyzed by aldolase.
The numbering of the carbon atoms indicates the fate of the carbons according to their position in fructose 6-phosphate.
*Dihydroxyacetone phosphate (DHAP), catalyzed by triose phosphate isomerase.
*1,3-bisphosphoglycerate (1,3BPG), catalyzed by glyceraldehyde 3-phosphate dehydrogenase. | 5 | Photochemistry |
Aged reagent can be destroyed with dilute acid to prevent the formation of the highly explosive silver nitride. | 3 | Analytical Chemistry |
The nitronium ion, , is a cation. It is an onium ion because its nitrogen atom has +1 charge, similar to ammonium ion . It is created by the removal of an electron from the paramagnetic nitrogen dioxide molecule , or the protonation of nitric acid (with removal of ).
It is stable enough to exist in normal conditions, but it is generally reactive and used extensively as an electrophile in the nitration of other substances. The ion is generated in situ for this purpose by mixing concentrated sulfuric acid and concentrated nitric acid according to the equilibrium: | 0 | Organic Chemistry |
By sperm washing, the risk that a chronic disease in the individual providing the sperm would infect the birthing parent or offspring can be brought to negligible levels.
If the sperm donor has hepatitis B, The Practice Committee of the American Society for Reproductive Medicine advises that sperm washing is not necessary in IVF to prevent transmission, unless the birthing partner has not been effectively vaccinated. In birthing people with hepatitis B, the risk of vertical transmission during IVF is no different from the risk in spontaneous conception. However, there is not enough evidence to say that ICSI procedures are safe in birthing people with hepatitis B in regard to vertical transmission to the offspring.
Regarding potential spread of HIV/AIDS, Japan's government prohibited the use of IVF procedures in which both partners are infected with HIV. Despite the fact that the ethics committees previously allowed the Ogikubo, Tokyo Hospital, located in Tokyo, to use IVF for couples with HIV, the Ministry of Health, Labour and Welfare of Japan decided to block the practice. Hideji Hanabusa, the vice president of the Ogikubo Hospital, states that together with his colleagues, he managed to develop a method through which scientists are able to remove HIV from sperm.
In the United States, people seeking to be an embryo recipient undergo infectious disease screening required by the Food and Drug Administration (FDA), and reproductive tests to determine the best placement location and cycle timing before the actual embryo transfer occurs. The amount of screening the embryo has already undergone is largely dependent on the genetic parents' own IVF clinic and process. The embryo recipient may elect to have their own embryologist conduct further testing. | 1 | Biochemistry |
Aquatic biomonitoring is the science of inferring the ecological condition of rivers, lakes, streams, and wetlands by examining the organisms (fish, invertebrates, insects, plants, and algae) that live there. While aquatic biomonitoring is the most common form of biomonitoring, any ecosystem can be studied in this manner. | 2 | Environmental Chemistry |
In November 2004 Rochdale councillor Tom Stott, a former employee at Turners, warned that any development of the site could be an environmental disaster, and that there could be so much asbestos waste in the ground that serious disturbance could lead to "Rochdales Chernobyl." He also expressed concern that the developers would be allowed by the council to carry out their own contamination survey to determine whether the site was fit for development, which was confirmed by the council: "Any developers would have to provide a full environmental assessment of the site as part of their planning application. The council wouldnt be doing any surveys of its own because it doesnt have the expertise or the resources to do this." | 2 | Environmental Chemistry |
DESI mass spectrometry is an ambient ionization technique developed by Professor Zoltan Takáts, et al., in Professor Graham Cooks' group from Purdue University. It combines the ESI and desorption ionization techniques, by directing an electrically charged mist to the sample surface that is a few millimeters away. The technique has been successfully applied to lipidomics as imaging tool to map the lipid distributions within tissue specimens. One of the advantages of DESI MS is that no matrix is required for tissue preparation, allowing multiple consecutive measurements on the same tissue specimen. DESI MS can also be used for imaging of lipids from tissue sections. | 1 | Biochemistry |
MMS methylates DNA predominantly on N7-deoxyguanosine and N3-deoxyadenosine, and to a much lesser extent also methylates at other oxygen and nitrogen atoms in DNA bases, and also methylates one of the non-carbon bound oxygen atoms of the phosphodiester linkage. Originally, this action was believed to directly cause double-stranded DNA breaks, because homologous recombination-deficient cells are particularly vulnerable to the effects of MMS. However, it is now believed that MMS stalls replication forks, and cells that are homologous recombination-deficient have difficulty repairing the damaged replication forks. | 0 | Organic Chemistry |
First, ion-specific microelectrodes can be used to measure the internal free ion concentration of cells and organelles. The major advantages are that readings can be made from cells over relatively long periods of time, and that unlike dyes very little extra ion buffering capacity is added to the cells.
Second, the technique of two-electrode voltage-clamp allows the direct measurement of the ion flux across the membrane of a cell. The membrane is held at an electric potential and the responding current is measured. All ions passing across the membrane contribute to the measured current.
Third, the technique of patch-clamp uses isolated sections of natural or artificial membrane in much the same manner as voltage-clamp but without the secondary effects of a cellular system. Under ideal conditions the conductance of individual channels can be quantified. This methodology gives the most direct measurement of the action of ion channels. | 1 | Biochemistry |
There are two principal signal transduction pathways involving the G protein-linked receptors: the cAMP signal pathway and the phosphatidylinositol signal pathway. | 1 | Biochemistry |
A sand rammer is a piece of equipment used in foundry sand testing to make test specimen of molding sand by compacting bulk material by free fixed height drop of fixed weight for 3 times. It is also used to determine compactibility of sands by using special specimen tubes and a linear scale. | 8 | Metallurgy |
Devapamil in rats can be used to decrease glutathione levels and increase oxidation of lipids, which makes it effective in preclusion of ulcers caused by stress. The medical characteristics of this drug, and other phenylalkylamines, depends greatly on the state of the calcium channels being targeted which results in a greater affinity and drug efficiency. | 1 | Biochemistry |
Volatility itself has no defined numerical value, but it is often described using vapor pressures or boiling points (for liquids). High vapor pressures indicate a high volatility, while high boiling points indicate low volatility. Vapor pressures and boiling points are often presented in tables and charts that can be used to compare chemicals of interest. Volatility data is typically found through experimentation over a range of temperatures and pressures. | 7 | Physical Chemistry |
The reaction mechanism for the industrial Wacker process (olefin oxidation via palladium(II) chloride) has received significant attention for several decades. Aspects of the mechanism are still debated. A modern formulation is described below:
The initial stoichiometric reaction was first reported by Phillips. The net reaction can also be described as follows:
:[PdCl] + CH + HO → CHCHO + Pd + 2 HCl + 2 Cl
This conversion is followed by reactions that regenerate the Pd(II) catalyst:
: Pd + 2 CuCl + 2 Cl → [PdCl] + 2 CuCl
: 2 CuCl + O + 2 HCl → 2 CuCl + HO
Only the alkene and oxygen are consumed. Without copper(II) chloride as an oxidizing agent, Pd(0) metal (resulting from beta-hydride elimination of Pd(II) in the final step) would precipitate, stopping the reaction after one cycle. This stoichiometric reaction was discovered in 1894. Air, pure oxygen, or a number of other reagents can then oxidise the resultant CuCl-chloride mixture back to CuCl, allowing the cycle to continue. | 0 | Organic Chemistry |
Due to its low thermal conductivity, a layer of concrete is frequently used for fireproofing of steel structures. However, concrete itself may be damaged by fire, with one notable example being the 1996 Channel Tunnel fire where fire damage extended along several hundred meters of the tunnel's length. For this reason, common fire testing standards, such as ASTM E119, do not permit fire testing of cementitious products unless the relative humidity inside the cementitious product is at or below 75%. Otherwise, concrete can be subject to significant spalling.
Up to about 300 °C, the concrete undergoes normal thermal expansion. Above that temperature, shrinkage occurs due to water loss; however, the aggregate continues expanding, which causes internal stresses. Up to about 500 °C, the major structural changes are carbonatation and coarsening of pores. At 573 °C, quartz undergoes rapid expansion due to phase transition, and at 900 °C calcite starts shrinking due to decomposition. At 450-550 °C the cement hydrate decomposes, yielding calcium oxide. Calcium carbonate decomposes at about 600 °C. Rehydration of the calcium oxide on cooling of the structure causes expansion, which can cause damage to material which withstood fire without falling apart. Concrete in buildings that experienced a fire and were left standing for several years shows extensive degree of carbonatation from carbon dioxide which is reabsorbed.
Concrete exposed to up to 100 °C is normally considered as healthy. The parts of a concrete structure that is exposed to temperatures above approximately 300 °C (dependent of water/cement ratio) will most likely get a pink color. Over approximately 600 °C the concrete will turn light grey, and over approximately 1000 °C it turns yellow-brown.
One rule of thumb is to consider all pink colored concrete as damaged that should be removed.
Fire will expose the concrete to gases and liquids that can be harmful to the concrete, among other salts and acids that occur when gases produced by a fire come into contact with water.
If concrete is exposed to very high temperatures very rapidly, explosive spalling of the concrete can result. In a very hot, very quick fire the water inside the concrete will boil before it evaporates. The steam inside the concrete exerts expansive pressure and can initiate and forcibly expel a spall. | 8 | Metallurgy |
PGLYRPs are conserved from insects to mammals. Mammals produce four secreted soluble peptidoglycan recognition proteins (PGLYRP-1, PGLYRP-2, PGLYRP-3 and PGLYRP-4) that recognize muramyl pentapeptide or tetrapeptide. They can also bind to LPS and other molecules by using binding sites outside of the peptidoglycan-binding groove. After recognition of peptidoglycan, PGLYRPs activate polyphenol oxidase (PPO) molecules, Toll, or immune deficiency (IMD) signalling pathways. That leads to production of antimicrobial peptides (AMPs).
Each of the mammalian PGLYRPs display unique tissue expression patterns. PGLYRP-1 is mainly expressed in the granules of neutrophils and eosinophils. PGLYRP-3 and 4 are expressed by several tissues such as skin, sweat glands, eyes or the intestinal tract. PGLYRP-1, 3 and 4 form disulphide-linked homodimers and heterodimers essential for their bactericidal activity. Their binding to bacterial cell wall peptidoglycans can induce bacterial cell death by interaction with various bacterial transcriptional regulatory proteins. PGLYRPs are likely to assist in bacterial killing by cooperating with other PRRs to enhance recognition of bacteria by phagocytes.
PGLYRP-2 is primarily expressed by the liver and secreted into the circulation. Also, its expression can be induced in skin keratinocytes, oral and intestinal epithelial cells. In contrast with the other PGLYRPs, PGLYRP-2 has no direct bactericidal activity. It possesses peptidoglycan amidase activity, it hydrolyses the lactyl-amide bond between the MurNAc and the first amino acid of the stem peptide of peptidoglycan. It is proposed, that the function of PGLYRP-2 is to prevent over-activation of the immune system and inflammation-induced tissue damage in response to NOD2 ligands (see below), as these muropeptides can no longer be recognized by NOD2 upon separation of the peptide component from MurNAc. Growing evidence suggests that peptidoglycan recognition protein family members play a dominant role in the tolerance of intestinal epithelial cells toward the commensal microbiota. It has been demonstrated that expression of PGLYRP-2 and 4 can influence the composition of the intestinal microbiota.
Recently, it has been discovered, that PGLYRPs (and also NOD-like receptors and peptidoglycan transporters) are highly expressed in the developing mouse brain. PGLYRP-2 and is highly expressed in neurons of several brain regions including the prefrontal cortex, hippocampus, and cerebellum, thus indicating potential direct effects of peptidoglycan on neurons. PGLYRP-2 is highly expressed also in the cerebral cortex of young children, but not in most adult cortical tissues. PGLYRP-1 is also expressed in the brain and continues to be expressed into adulthood. | 1 | Biochemistry |
A foundational discourse on the field of chemometrics by Kowalski, "Chemometrics: Views and Propositions," was published in 1975. In it he defines chemometrics as "any and all methods that can be used to extract useful chemical information from raw data." Kowalski takes up the question of what constitutes "new and viable research" in the field and goes on to explain how his training as an analytical chemist and experience with pattern recognition as a tool for chemical analysis has influenced his opinion about this. The included letter to a "prospective chemometrician," signed by Kowalski and Svante Wold, asserts "chemometrics should not involve theoretical calculations, but should deal primarily with the extraction of useful chemical information from measured data." The letter announces that an informal "Chemometrics Society" was begun on June 10, 1974, describes the purposes of the society and invites the interested researcher to join. Kowalskis research group was given as the Laboratory for Chemometrics, Department of Chemistry, University of Washington, and Wolds research group was given as Research Group for Chemometrics, Institute of Chemistry, Umea University, Sweden. This society, formed from Kowalksis and Wolds two research groups, eventually became the International Chemometrics Society.
Wold had coined the term "chemometrics" for a grant application in 1971. He and Kowalski first met in 1973 at a symposium in Tucson, Arizona, and after discussion, Kowalski agreed to use the term to describe his own research as well. Wold says Kowalski became "both a strong proponent and spokesman for this new field." | 3 | Analytical Chemistry |
The Campo de Cartagena has valuable remains of its ancient past. In the city of Cartagena can be seen numerous monuments, museums and archaeological remains.
An attempt was made during the First Spanish Republic, on July 12 of 1873 to establish a canton in the Cartagena area. The insurgency took the name Cantonal Revolution and in the following days it spread through many other regions. Following the revolt the city of Cartagena endured for several months the attack of the troops sent by Nicolás Salmerón to restore order. | 2 | Environmental Chemistry |
Oxacillin, through its β-lactam ring, covalently binds to penicillin-binding proteins, which are enzymes involved in the synthesis of the bacterial cell wall. This binding interaction interferes with the transpeptidation reaction and inhibits the synthesis of peptidoglycan, a prominent component of the cell wall. By decreasing the integrity of the bacterial cell wall, it is thought that oxacillin and other penicillins kill actively growing bacteria through cell autolysis. | 4 | Stereochemistry |
Roughly 5 grams of iron are present in the human body and is the most abundant trace metal. It is absorbed in the intestine as heme or non-heme iron depending on the food source. Heme iron is derived from the digestion of hemoproteins in meat. Non-heme iron is mainly derived from plants and exist as iron(II) or iron(III) ions.
Iron is essential for more than 500 hemeproteins, the likes of which include hemoglobin and myoglobin, and account for 80% of iron usage. The other 20% is present in ferritin, hemosiderin, iron-sulfur (Fe/S) proteins, such as ferrochelatase, and more. | 9 | Geochemistry |
While in photosynthesis each chloroplast is capable of completing light reactions and dark reactions, chloroplasts differentiate in two populations, contained in the mesophyll and bundle sheath cells. The division of the photosynthetic work between two types of chloroplasts results inevitably in a prolific exchange of intermediates between them. The fluxes are large and can be up to ten times the rate of gross assimilation. The type of metabolite exchanged and the overall rate will depend on the subtype. To reduce product inhibition of photosynthetic enzymes (for instance PECP) concentration gradients need to be as low as possible. This requires increasing the conductance of metabolites between mesophyll and bundle sheath, but this would also increase the retro-diffusion of out of the bundle sheath, resulting in an inherent and inevitable trade off in the optimisation of the concentrating mechanism. | 5 | Photochemistry |
The parabolic model for heat conduction discussed above shows that the Fourier equation (and the more general Fick's law of diffusion) is incompatible with the theory of relativity for at least one reason: it admits infinite speed of propagation of the continuum field (in this case: heat, or temperature gradients). To overcome this contradiction, workers such as Carlo Cattaneo, Vernotte, Chester, and others proposed that Fourier equation should be upgraded from the parabolic to a hyperbolic form, where the n, the temperature field is governed by:
In this equation, C is called the speed of second sound (that is related to excitations and quasiparticles, like phonons). The equation is known as the "hyperbolic heat conduction" (HHC) equation. Mathematically, the above equation is called "telegraph equation", as it is formally equivalent to the telegrapher's equations, which can be derived from Maxwell’s equations of electrodynamics.
For the HHC equation to remain compatible with the first law of thermodynamics, it is necessary to modify the definition of heat flux vector, q, to
where is a relaxation time, such that This equation for the heat flux is often referred to as "Maxwell-Cattaneo equation". The most important implication of the hyperbolic equation is that by switching from a parabolic (dissipative) to a hyperbolic (includes a conservative term) partial differential equation, there is the possibility of phenomena such as thermal resonance and thermal shock waves. | 7 | Physical Chemistry |
A versatile dialkylborane is 9-BBN. Also called "banana borane", it exists as a dimer. It can be distilled without decomposition at 195 °C (12mm Hg). Reactions with 9-BBN typically occur at 60–80 °C, with most alkenes reacting within one hour. Tetrasubstituted alkenes add 9-BBN at elevated temperature. Hydroboration of alkenes with 9-BBN proceeds with excellent regioselectivity. It is more sensitive to steric differences than SiaBH, perhaps because of it rigid C backbone. 9-BBN is more reactive towards alkenes than alkynes. | 0 | Organic Chemistry |
DNA synthesis begins at specific sites called origins of replication. These are regions of the genome where the DNA replication machinery is assembled and the DNA is unwound to begin DNA synthesis. In most cases, replication proceeds in both directions from the replication origin.
The main features of replication origins are sequences where specific initiation proteins are bound. A typical replication origin covers about 100-200 base pairs of DNA. Prokaryotes have one origin of replication per chromosome or plasmid but there are usually multiple origins in eukaryotic chromosomes. The human genome contains about 100,000 origins of replication representing about 0.3% of the genome. | 1 | Biochemistry |
In the late 1970s and early 1980s Franklin A. Davis synthesized the first N-sulfonyloxaziridines, which act exclusively as oxygen transfer reagents, and are the most predominantly used class of oxaziridines today. While originally synthesized with mCPBA and the phase transfer catalyst benzyltrimethylammonium chloride, an improved synthesis using oxone as the oxidant is now most prevalent.
Many N-sulfonyloxaziridines are used today, each with slightly different properties and reactivity. These reagents are summarized in the table below. | 0 | Organic Chemistry |
Esters react with nucleophiles at the carbonyl carbon. The carbonyl is weakly electrophilic but is attacked by strong nucleophiles (amines, alkoxides, hydride sources, organolithium compounds, etc.). The C–H bonds adjacent to the carbonyl are weakly acidic but undergo deprotonation with strong bases. This process is the one that usually initiates condensation reactions. The carbonyl oxygen in esters is weakly basic, less so than the carbonyl oxygen in amides due to resonance donation of an electron pair from nitrogen in amides, but forms adducts. | 0 | Organic Chemistry |
"Sequencing by synthesis" involves taking a single strand of the DNA to be sequenced and then synthesizing its complementary strand enzymatically. The pyrosequencing method is based on detecting the activity of DNA polymerase (a DNA synthesizing enzyme) with another chemoluminescent enzyme. Essentially, the method allows sequencing a single strand of DNA by synthesizing the complementary strand along it, one base pair at a time, and detecting which base was actually added at each step. The template DNA is immobile, and solutions of A, C, G, and T nucleotides are sequentially added and removed from the reaction. Light is produced only when the nucleotide solution complements the first unpaired base of the template. The sequence of solutions which produce chemiluminescent signals allows the determination of the sequence of the template.
For the solution-based version of pyrosequencing, the single-strand DNA (ssDNA) template is hybridized to a sequencing primer and incubated with the enzymes DNA polymerase, ATP sulfurylase, luciferase and apyrase, and with the substrates adenosine 5´ phosphosulfate (APS) and luciferin.
# The addition of one of the four deoxynucleotide triphosphates (dNTPs) (dATPαS, which is not a substrate for a luciferase, is added instead of dATP to avoid noise) initiates the second step. DNA polymerase incorporates the correct, complementary dNTPs onto the template. This incorporation releases pyrophosphate (PPi).
# ATP sulfurylase converts PPi to ATP in the presence of adenosine 5´ phosphosulfate. This ATP acts as a substrate for the luciferase-mediated conversion of luciferin to oxyluciferin that generates visible light in amounts that are proportional to the amount. The light produced in the luciferase-catalyzed reaction is detected by a camera and analyzed in a program.
# Unincorporated nucleotides and ATP are degraded by the apyrase, and the reaction can restart with another nucleotide.
The process can be represented by the following equations:
* PPi + APS → ATP + Sulfate (catalyzed by ATP-sulfurylase);
* ATP + luciferin + O2 → AMP + PPi + oxyluciferin + + hv (catalyzed by luciferase);
where:
* PPi is pyrophosphate
* APS is adenosine 5-phosphosulfate;
* ATP is adenosine triphosphate;
* O2 is oxygen molecule;
* AMP is adenosine monophosphate;
* is carbon dioxide;
* hv is light. | 1 | Biochemistry |
The structure of triethyloxonium tetrafluoroborate has not been characterized by X-ray crystallography, but the structure of triethyloxonium hexafluorophosphate has been examined. The measurements confirm that the cation is pyramidal with C-O-C angles in the range 109.4°–115.5°. The average C–O distance is 1.49 Å. | 0 | Organic Chemistry |
The benzene ligand in (η-CH)Cr(CO)Mi is prone to deprotonation. For example, Organolithium compounds form adducts featuring cyclohexadienyl ligands. Subsequent oxidation of the complex results in the release of a substituted benzene. Oxidation of the chromium atom by I and other iodine reagents has been shown to promote exchange of arene ligands, but the intermediate chromium iodide species has not been characterized.
(η-CH)Cr(CO) complexes exhibit "cine" and "tele" nucleophilic aromatic addition. Processes of this type involve reaction of (η-CH)Cr(CO) with an alkyl lithium reagent. Subsequent treatment with an acid results in the addition of a nucleophile to the benzene ring at a site ortho ("cine"), meta or para ("tele") to the ipso carbon (see Arene substitution patterns).
Reflecting its increased acidity, the benzene ligand can be lithiated with n-butyllithium. The resulting organolithium compound serves as a nucleophile in various reactions, for example, with trimethylsilyl chloride:
(η-CH)Cr(CO) is a useful catalyst for the hydrogenation of 1,3-dienes. The product alkene results from 1,4-addition of hydrogen. The complex does not hydrogenate isolated double bonds.
A variety of arenes ligands have been installed aside from benzene. Weakly coordinating ligands may be employed to improve ligand exchange and thus the turnover rates for (η-CH)M(CO) complexes.(η-CH)M(CO) complexes have been incorporated into high surface area porous materials.
(η-CH)M(CO) complexes serve as models for the interaction of metal carbonyls with graphene and carbon nanotubes. The presence of M(CO) on extended π-network materials has been shown to improve electrical conductivity across the material. | 0 | Organic Chemistry |
One of the key factors associated with the toxicity of CYN is its stability. Although the toxin has been found to degrade rapidly in an algal extract when exposed to sunlight, it is resistant to degradation by changes in pH and temperature, and shows no degradation in either the pure solid form or in pure water. As a result, in turbid and unmoving water the toxin can persist for long periods, and although boiling water will kill the cyanobacteria, it may not remove the toxin. | 0 | Organic Chemistry |
The Association organizes a series of biennial International Applied Geochemistry Symposia (titled the International Geochemical Exploration Symposium until 2005), held recently in Oviedo, Spain, and Perth, Australia. | 9 | Geochemistry |
The vast majority of plants are C3, meaning they photorespire when necessary.Certain species of plants or algae have mechanisms to lower uptake of molecular oxygen by RuBisCO. These are commonly referred to as Carbon Concentrating Mechanisms (CCMs), as they increase the concentration of so that RuBisCO is less likely to produce glycolate through reaction with . | 5 | Photochemistry |
The use of natural bitumen for waterproofing, and as an adhesive dates at least to the fifth millennium BC, with a crop storage basket discovered in Mehrgarh, of the Indus Valley civilization, lined with it. By the 3rd millennium BC refined rock asphalt was in use in the region, and was used to waterproof the Great Bath in Mohenjo-daro.
In the ancient Near East, the Sumerians used natural bitumen deposits for mortar between bricks and stones, to cement parts of carvings, such as eyes, into place, for ship caulking, and for waterproofing. The Greek historian Herodotus said hot bitumen was used as mortar in the walls of Babylon.
The long Euphrates Tunnel beneath the river Euphrates at Babylon in the time of Queen Semiramis () was reportedly constructed of burnt bricks covered with bitumen as a waterproofing agent.
Bitumen was used by ancient Egyptians to embalm mummies. The Persian word for asphalt is moom, which is related to the English word mummy. The Egyptians primary source of bitumen was the Dead Sea, which the Romans knew as Palus Asphaltites' (Asphalt Lake).
In approximately 40 AD, Dioscorides described the Dead Sea material as Judaicum bitumen, and noted other places in the region where it could be found. The Sidon bitumen is thought to refer to material found at Hasbeya in Lebanon. Pliny also refers to bitumen being found in Epirus. Bitumen was a valuable strategic resource. It was the object of the first known battle for a hydrocarbon deposit – between the Seleucids and the Nabateans in 312 BC.
In the ancient Far East, natural bitumen was slowly boiled to get rid of the higher fractions, leaving a thermoplastic material of higher molecular weight that, when layered on objects, became hard upon cooling. This was used to cover objects that needed waterproofing, such as scabbards and other items. Statuettes of household deities were also cast with this type of material in Japan, and probably also in China.
In North America, archaeological recovery has indicated that bitumen was sometimes used to adhere stone projectile points to wooden shafts. In Canada, aboriginal people used bitumen seeping out of the banks of the Athabasca and other rivers to waterproof birch bark canoes, and also heated it in smudge pots to ward off mosquitoes in the summer. Bitumen was also used to waterproof plank canoes used by indigenous peoples in pre-colonial southern California. | 7 | Physical Chemistry |
Leprecan is a protein associated with osteogenesis imperfecta type VIII.
Leprecan is part of a superfamily of 2OG-Fe(II) dioxygenase, along with DNA repair protein AlkB, and disease resistant EGL-9. The enzyme was found to be a type of hydroxylases used in the substrate formation of protein glycosylation. | 1 | Biochemistry |
Carbon is capable of forming a vast number of compounds, more than any other element, with almost ten million compounds described to date, and yet that is but a fraction of the number of compounds that are theoretically possible under standard conditions. The enormous diversity of carbon compounds, known as organic compounds, has led to a distinction between them and the inorganic compounds that do not contain carbon. The branch of chemistry that studies organic compounds is known as organic chemistry.
Carbon is the 15th most abundant element in the Earths crust, and the fourth most abundant element in the universe by mass, after hydrogen, helium, and oxygen. Carbons widespread abundance, its ability to form stable bonds with numerous other elements, and its unusual ability to form polymers at the temperatures commonly encountered on Earth enables it to serve as a common element of all known living organisms. In a 2018 study, carbon was found to compose approximately 550 billion tons of all life on Earth. It is the second most abundant element in the human body by mass (about 18.5%) after oxygen.
The most important characteristics of carbon as a basis for the chemistry of cellular life are that each carbon atom is capable of forming up to four valence bonds with other atoms simultaneously, and that the energy required to make or break a bond with a carbon atom is at an appropriate level for building large and complex molecules which may be both stable and reactive. Carbon atoms bond readily to other carbon atoms; this allows the building of arbitrarily long macromolecules and polymers in a process known as catenation. "What we normally think of as life is based on chains of carbon atoms, with a few other atoms, such as nitrogen or phosphorus", per Stephen Hawking in a 2008 lecture, "carbon [...] has the richest chemistry."
Norman Horowitz was the head of the Jet Propulsion Laboratory's bioscience section for the first U.S. mission, Viking Lander of 1976, to successfully land an unmanned probe on the surface of Mars. He considered that the great versatility of the carbon atom makes it the element most likely to provide solutions, even exotic solutions, to the problems of survival on other planets. However, the results of this mission indicated that Mars was presently extremely hostile to carbon-based life. He also considered that, in general, there was only a remote possibility that non-carbon life forms would be able to evolve with genetic information systems capable of self-replication and adaptation. | 1 | Biochemistry |
The FluoroSpot assay is very similar to the ELISpot assay. The main difference is that the FluoroSpot assay is able to analyze the presence of multiple analytes on one plate of wells, whereas the ELISpot assay can only analyze one analyte at a time. The FluoroSpot assay accomplishes this by using fluorescence rather than an enzymatic reaction for detection. The steps for a FluoroSpot assay are also similar, with a few differences.
# Antibody Coating: Similar to the ELISpot, cytokine-specific monoclonal capture antibodies are added to a plate with wells. For both assays, the plates are ethanol-treated to avoid contamination and skewed data collection. For the FluoroSpot assay, a mixture of different types of capture antibodies are attached to the wells in order to detect multiple types of analytes. In order to get optimal results with the ELISpot and the FluoroSpot assay, proper plate coating techniques should be followed. The plates should be treated with ethanol, washed, and then coated with antibodies. Ethanol treatment methods also vary depending on the type of plates that are used. For MSIP and IPFL plates, you should add 15 micro liters of 35% ethanol to all of the wells. Allow the ethanol to sit in the wells for one minute, and then pour it out. For MAIPSWU plates, you should instead add 50 micro liters of 70% ethanol to all of the wells. Allow the ethanol to sit in the wells for two minutes, and then pour it out. After you have treated the wells with ethanol, you need to wash all of the wells with 200 micro liters of sterile water. This washing process should be repeated for a total of 5 times. Once the wells have been treated with ethanol and washed, the cytokine-specific monoclonal capture antibodies can be added to each well.
# Cell Incubation: Cell are added to the wells and are incubated in the presence or absence of stimuli that affect protein secretion.
# Cytokine Capture: Proteins/analytes that are secreted by the incubated cells will bind to the capture antibodies attached to the wells during the first step.
# Detection Antibodies: Similar to the ELISpot, once the wells are rinsed to get rid of the cells and other substances that we are not interested in identifying or measuring, a biotinylated detection antibody is added (this is specific for one type of analyte that you wish to quantify) and then tag-labeled detection antibodies are added for the second and third types of analytes being studied.
# Fluorophore-labeled Conjugates: Instead of adding a streptavidin-enzyme conjugate, the detection of multiple analytes is amplified in the FluoroSpot with the use of fluorophore-labeled anti-tag antibody and streptavidin-fluorophore conjugate. A fluorescence enhancer solution is also added during this step in order to enhance the signals later used when analyzing the fluorescence colors in the wells. This fluorescence is what makes it possible for the FluoroSpot to analyze and compare multiple analytes, unlike the ELISpot.
# Analysis: Since the FluoroSpot relies on the use of fluorescence and not an enzymatic reaction, there is no need for a step that adds a substrate to react with enzymes (as needed for the ELISpot). The last step for the FluoroSpot assay is to analyze the fluorophores under an automated fluorescence reader that has separate filters for the different fluorophores being analyzed. These filters should be selected for the specific wavelengths of the fluorophores if you want accurate measurements.
Since the FluoroSpot assay identifies and quantifies the presence of multiple analytes, it is possible that the absorption of one analyte can affect the secretion of another analyte; this is called capture effects. The effect an analyte has on another analyte could be positive or negative (the production of the second analyte can either increase or decrease). To counteract capture effects, it is possible to use co-stimulation in order to bypass the decreased production of an analyte. This is when a second antibody that stimulates the production of the same analyte is added to the wells. | 1 | Biochemistry |
Structural genomics takes advantage of completed genome sequences in several ways in order to determine protein structures. The gene sequence of the target protein can also be compared to a known sequence and structural information can then be inferred from the known protein's structure. Structural genomics can be used to predict novel protein folds based on other structural data. Structural genomics can also take modeling-based approach that relies on homology between the unknown protein and a solved protein structure. | 1 | Biochemistry |
From 2000 to 2010, the U.S. Army Research Laboratory (ARL) researched potential extensions to LIBS technology, which focused on hazardous material detection. Applications investigated at ARL included the standoff detection of explosive residues and other hazardous materials, plastic landmine discrimination, and material characterization of various metal alloys and polymers. Results presented by ARL suggest that LIBS may be able to discriminate between energetic and non-energetic materials. | 7 | Physical Chemistry |
After the initial carousel stripping machine development and the later development of the linear stripping machine, Falconbridge personnel developed the Kidd Process High Capacity Linear Machine (“HCLM”). This machine included a loading and unloading system that was based on robotics.
The new design improved, among other things, the discharge area of the stripper. This had been a problem area for the carousel stripping machines, in which copper released from the cathode plate fell into an envelope and was then transferred to a material handling device. Copper that misbehaved and failed to transfer often required manual intervention. The new robot discharge system eliminated the free falling of the copper and physically transferred the released copper to the discharge location. | 8 | Metallurgy |
Hyperspectral imaging is most often applied to either solid or gel samples, and has applications in chemistry, biology, medicine, pharmacy (see also for example: food science, biotechnology, agriculture and industry. NIR, IR and Raman chemical imaging is also referred to as hyperspectral, spectroscopic, spectral or multispectral imaging (also see microspectroscopy). However, other ultra-sensitive and selective imaging techniques are also in use that involve either UV-visible or fluorescence microspectroscopy. Many imaging techniques can be used to analyze samples of all sizes, from the single molecule to the cellular level in biology and medicine, and to images of planetary systems in astronomy, but different instrumentation is employed for making observations on such widely different systems.
Any material that depends on chemical gradients for functionality may be amenable to study by an analytical technique that couples spatial and chemical characterization. To efficiently and effectively design and manufacture such materials, the ‘what’ and the ‘where’ must both be measured. The demand for this type of analysis is increasing as manufactured materials become more complex. Chemical imaging techniques are critical to understanding modern manufactured products and in some cases is a non-destructive technique so that samples are preserved for further testing.
Many materials, both manufactured and naturally occurring, derive their functionality from the spatial distribution of sample components. For example, extended release pharmaceutical formulations can be achieved by using a coating that acts as a barrier layer. The release of active ingredient is controlled by the presence of this barrier, and imperfections in the coating, such as discontinuities, may result in altered performance. In the semi-conductor industry, irregularities or contaminants in silicon wafers or printed micro-circuits can lead to failure of these components. The functionality of biological systems is also dependent upon chemical gradients – a single cell, tissue, and even whole organs function because of the very specific arrangement of components. It has been shown that even small changes in chemical composition and distribution may be an early indicator of disease. | 7 | Physical Chemistry |
Sulfonate esters are often leaving groups in nucleophilic substitution reactions. See the articles on sulfonyl and sulfonate groups for further information.
*Bs for the brosyl (p-bromobenzenesulfonyl) group; OBs is the brosylate group
*Ms for the mesyl (methanesulfonyl) group; OMs is the mesylate group
*Ns for the nosyl (p-nitrobenzenesulfonyl) group (Ns was the chemical symbol for nielsbohrium, but that was renamed bohrium, Bh); ONs is the nosylate group
*Tf for the triflyl (trifluoromethanesulfonyl) group; OTf is the triflate group
*Nf for the nonaflyl (nonafluorobutanesulfonyl) group, ; ONf is the nonaflate group
*Ts for tosyl (p-toluenesulfonyl) group (Ts is also the symbol for the element tennessine. However, tennessine is too unstable to ever be encountered in organic chemistry, so the use of Ts to represent tosyl never causes confusion); OTs is the tosylate group | 0 | Organic Chemistry |
The earliest application of photoredox catalysis to Reductive dehalogenation were limited by narrow substrate scope or competing reductive coupling.
Unactivated carbon-iodine bonds can be reduced using the strongly reducing photocatalyst tris-(2,2’-phenylpyridine)iridium (Ir(ppy)). The increased reduction potential of Ir(ppy) compared to [Ru(bipy)] allows direct reduction of the carbon-iodine bond without interacting with a stoichiometric reductant. Thus, the iridium complex transfers an electron to the substrate, causing fragmentation of the substrate and oxidizing the catalyst to the Ir(IV) oxidation state. The oxidized photocatalyst is returned to its original oxidation state by oxidising a reaction additives.
Like tin-mediated radical dehalogenation reactions, photocatalytic reductive dehalogenation can be used to initiate cascade cyclizations | 5 | Photochemistry |
Most carbon incorporated in organic and inorganic biological matter is formed at the sea surface where it can then start sinking to the ocean floor. The deep ocean gets most of its nutrients from the higher water column when they sink down in the form of marine snow. This is made up of dead or dying animals and microbes, fecal matter, sand and other inorganic material. A single phytoplankton cell has a sinking rate around one metre per day. Given that the average depth of the ocean is about four kilometres, it can take over ten years for these cells to reach the ocean floor. However, through processes such as coagulation and expulsion in predator fecal pellets, these cells form aggregates. These aggregates, known as marine snow, have sinking rates orders of magnitude greater than individual cells and complete their journey to the deep in a matter of days.
In the diagram on the right, phytoplankton fix CO in the euphotic zone using solar energy and produce particulate organic carbon (POC). POC formed in the euphotic zone is processed by microbes, zooplankton and their consumers into organic aggregates (marine snow), which is thereafter exported to the mesopelagic (200–1000 m depth) and bathypelagic zones by sinking and vertical migration by zooplankton and fish. Export flux is defined as the sedimentation out of the surface layer (at approximately 100 m depth) and sequestration flux is the sedimentation out of the mesopelagic zone (at approximately 1000 m depth). A portion of the POC is respired back to CO in the oceanic water column at depth, mostly by heterotrophic microbes and zooplankton, thus maintaining a vertical gradient in concentration of dissolved inorganic carbon (DIC). This deep-ocean DIC returns to the atmosphere on millennial timescales through thermohaline circulation. Between 1% and 40% of the primary production is exported out of the euphotic zone, which attenuates exponentially towards the base of the mesopelagic zone and only about 1% of the surface production reaches the sea floor.
Of the 50–60 Pg of carbon fixed annually, roughly 10% leaves the surface mixed layer of the oceans, while less than 0.5% of eventually reaches the sea floor. Most is retained in regenerated production in the euphotic zone and a significant portion is remineralized in midwater processes during particle sinking. The portion of carbon that leaves the surface mixed layer of the ocean is sometimes considered "sequestered", and essentially removed from contact with the atmosphere for many centuries. However, work also finds that, in regions such as the Southern Ocean, much of this carbon can quickly (within decades) come back into contact with the atmosphere.
Budget calculations of the biological carbon pump are based on the ratio between sedimentation (carbon export) and remineralization (release to the atmosphere). It has been estimated that sinking particles export up to 25% of the carbon captured by phytoplankton in the surface ocean to deeper water layers. About 20% of this export (5% of surface values) is buried in the ocean sediments mainly due to their mineral ballast. During the sinking process, these organic particles are hotspots of microbial activity and represent important loci for organic matter mineralization and nutrient redistribution in the water column. | 9 | Geochemistry |
Aciculitin A-C exhibits cytotoxicity against human colon tumor cell line HCT-116 with IC value of 0.5 μg/mL.
Aciculitin D exhibits cytotoxicity against human colon tumor cell line HCT-116 with IC value of 0.51 μM. Aciculitin D also exhibits cytotoxicity against HeLa, human cervical cells with IC value of 0.57 μM. | 1 | Biochemistry |
There are currently several labeling methods for tracking biomolecules. Some of the methods include the following. | 1 | Biochemistry |
In March researchers reported that three of five adult subjects who had acute lymphocytic leukemia (ALL) had been in remission for five months to two years after being treated with genetically modified T cells which attacked cells with CD19 genes on their surface, i.e. all B cells, cancerous or not. The researchers believed that the patients' immune systems would make normal T cells and B cells after a couple of months. They were also given bone marrow. One patient relapsed and died and one died of a blood clot unrelated to the disease.
Following encouraging Phase I trials, in April, researchers announced they were starting Phase II clinical trials (called CUPID2 and SERCA-LVAD) on 250 patients at several hospitals to combat heart disease. The therapy was designed to increase the levels of SERCA2, a protein in heart muscles, improving muscle function. The U.S. Food and Drug Administration (FDA) granted this a breakthrough therapy designation to accelerate the trial and approval process. In 2016, it was reported that no improvement was found from the CUPID 2 trial.
In July researchers reported promising results for six children with two severe hereditary diseases had been treated with a partially deactivated lentivirus to replace a faulty gene and after 7–32 months. Three of the children had metachromatic leukodystrophy, which causes children to lose cognitive and motor skills. The other children had Wiskott–Aldrich syndrome, which leaves them to open to infection, autoimmune diseases, and cancer. Follow up trials with gene therapy on another six children with Wiskott–Aldrich syndrome were also reported as promising.
In October researchers reported that two children born with adenosine deaminase severe combined immunodeficiency disease (ADA-SCID) had been treated with genetically engineered stem cells 18 months previously and that their immune systems were showing signs of full recovery. Another three children were making progress. In 2014, a further 18 children with ADA-SCID were cured by gene therapy. ADA-SCID children have no functioning immune system and are sometimes known as "bubble children".
Also in October researchers reported that they had treated six people with haemophilia in early 2011 using an adeno-associated virus. Over two years later all six were producing clotting factor. | 1 | Biochemistry |
Fahy is the world's foremost expert in organ cryopreservation by vitrification. Fahy introduced the modern successful approach to vitrification for cryopreservation in cryobiology and he is widely credited, along with William F. Rall, for introducing vitrification into the field of reproductive biology.
In 2005, where he was a keynote speaker at the annual Society for Cryobiology meeting, Fahy announced that Twenty-First Century Medicine had successfully cryopreserved a rabbit kidney at −130 °C by vitrification and transplanted it into a rabbit after rewarming, with subsequent long-term life support by the vitrified-rewarmed kidney as the sole kidney. This research breakthrough was later published in the peer-reviewed journal Organogenesis.
Fahy is also a biogerontologist and is the originator and Editor-in-Chief of The Future of Aging: Pathways to Human Life Extension, a multi-authored book on the future of biogerontology. He currently serves on the editorial boards of Rejuvenation Research and the Open Geriatric Medicine Journal and served for 16 years as a Director of the American Aging Association and for 6 years as the editor of AGE News, the organization's newsletter. | 1 | Biochemistry |
Researchers in biochemistry use specific techniques native to biochemistry, but increasingly combine these with techniques and ideas developed in the fields of genetics, molecular biology, and biophysics. There is not a defined line between these disciplines. Biochemistry studies the chemistry required for biological activity of molecules, molecular biology studies their biological activity, genetics studies their heredity, which happens to be carried by their genome. This is shown in the following schematic that depicts one possible view of the relationships between the fields:
* Biochemistry is the study of the chemical substances and vital processes occurring in live organisms. Biochemists focus heavily on the role, function, and structure of biomolecules. The study of the chemistry behind biological processes and the synthesis of biologically active molecules are applications of biochemistry. Biochemistry studies life at the atomic and molecular level.
* Genetics is the study of the effect of genetic differences in organisms. This can often be inferred by the absence of a normal component (e.g. one gene). The study of "mutants" – organisms that lack one or more functional components with respect to the so-called "wild type" or normal phenotype. Genetic interactions (epistasis) can often confound simple interpretations of such "knockout" studies.
* Molecular biology is the study of molecular underpinnings of the biological phenomena, focusing on molecular synthesis, modification, mechanisms and interactions. The central dogma of molecular biology, where genetic material is transcribed into RNA and then translated into protein, despite being oversimplified, still provides a good starting point for understanding the field. This concept has been revised in light of emerging novel roles for RNA.
* Chemical biology seeks to develop new tools based on small molecules that allow minimal perturbation of biological systems while providing detailed information about their function. Further, chemical biology employs biological systems to create non-natural hybrids between biomolecules and synthetic devices (for example emptied viral capsids that can deliver gene therapy or drug molecules). | 1 | Biochemistry |
A silylium ion is a silicon cation with only three bonds and a positive charge. The abstraction of the silylium ion is seen from the ruthenium complex shown below.
In the first step of this mechanism one of the acetonitrile groups is replaced by a silicon molecule where the bond between the silicon and the hydrogen is coordinating to the ruthenium. In the second step a ketone is added for the nucleophilic abstraction of the silylium ion and the hydrogen is left on the metal. | 0 | Organic Chemistry |
One of the challenges of DNA computing is its speed. While DNA as a substrate is biologically compatible i.e. it can be used at places where silicon technology cannot, its computation speed is still very slow. For example, the square-root circuit used as a benchmark in field took over 100 hours to complete. While newer ways with external enzyme sources are reporting faster and more compact circuits, Chatterjee et al. demonstrated an interesting idea in the field to speed up computation through localized DNA circuits, a concept being further explored by other groups. This idea, while originally proposed in the field of computer architecture, has been adopted in this field as well. In computer architecture, it is very well-known that if the instructions are executed in sequence, having them loaded in the cache will inevitably lead to fast performance, also called the principle of localization. This is because with instructions in fast cache memory, there is no need swap them in and out of main memory, which can be slow. Similarly, in [https://www.nature.com/articles/nnano.2017.127 localized DNA computing], the DNA strands responsible for computation are fixed on a breadboard-like substrate ensuring physical proximity of the computing gates. Such localized DNA computing techniques have shown to potentially reduce the computation time by [https://www.nature.com/articles/nnano.2017.127 orders of magnitude]. | 1 | Biochemistry |
6-(Methylsulfinyl)hexyl isothiocyanate (6-MITC or 6-MSITC) is a compound within the isothiocyanate group of organosulfur compounds. 6-MITC is obtained from cruciferous vegetables, chiefly wasabi. Like other isothiocyanates, it is produced when the enzyme myrosinase transforms the associated glucosinolate into 6-MITC upon cell injury.
It is a trend in Japan to apply freshly grated wasabi stem to the hair because Kinin Corporation, the world's largest wasabi producer, claims that 6-MITC promotes hair regrowth.
In a 2023 study of healthy older adults aged 60 years and over, the group taking one tablet (0.8 mg of 6-MSITC) every day for 12 weeks showed a significant improvement in working and episodic memory performances. These results have been reported in the popular press, using the name "hexaraphane" for 6-MSITC. | 1 | Biochemistry |
Using tiled arrays, ChIP-on-chip allows for high resolution of genome-wide maps. These maps can determine the binding sites of many DNA-binding proteins like transcription factors and also chromatin modifications.
Although ChIP-on-chip can be a powerful technique in the area of genomics, it is very expensive. Most published studies using ChIP-on-chip repeat their experiments at least three times to ensure biologically meaningful maps. The cost of the DNA microarrays is often a limiting factor to whether a laboratory should proceed with a ChIP-on-chip experiment. Another limitation is the size of DNA fragments that can be achieved. Most ChIP-on-chip protocols utilize sonication as a method of breaking up DNA into small pieces. However, sonication is limited to a minimal fragment size of 200 bp. For higher resolution maps, this limitation should be overcome to achieve smaller fragments, preferably to single nucleosome resolution. As mentioned previously, the statistical analysis of the huge amount of data generated from arrays is a challenge and normalization procedures should aim to minimize artifacts and determine what is really biologically significant. So far, application to mammalian genomes has been a major limitation, for example, due to the significant percentage of the genome that is occupied by repeats. However, as ChIP-on-chip technology advances, high resolution whole mammalian genome maps should become achievable.
Antibodies used for ChIP-on-chip can be an important limiting factor. ChIP-on-chip requires highly specific antibodies that must recognize its epitope in free solution and also under fixed conditions. If it is demonstrated to successfully immunoprecipitate cross-linked chromatin, it is termed "ChIP-grade". Companies that provide ChIP-grade antibodies include Abcam, Cell Signaling Technology, Santa Cruz, and Upstate. To overcome the problem of specificity, the protein of interest can be fused to a tag like FLAG or HA that are recognized by antibodies. An alternative to ChIP-on-chip that does not require antibodies is DamID.
Also available are antibodies against a specific histone modification like H3 tri methyl K4. As mentioned before, the combination of these antibodies and ChIP-on-chip has become extremely powerful in determining whole genome analysis of histone modification patterns and will contribute tremendously to our understanding of the histone code and epigenetics.
A study demonstrating the non-specific nature of DNA binding proteins has been published in PLoS Biology. This indicates that alternate confirmation of functional relevancy is a necessary step in any ChIP-chip experiment. | 1 | Biochemistry |
Compounds possessing a methylene bridge located between two strong electron withdrawing groups (such as nitro, carbonyl or nitrile groups) are sometimes called active methylene compounds. Treatment of these with strong bases can form enolates or carbanions, which are often used in organic synthesis. Examples include the Knoevenagel condensation and the malonic ester synthesis. | 0 | Organic Chemistry |
Homocitric acid is an organic compound with the formula HOC(COH)(CHCOH)(CHCOH). This tricarboxylic acid occurs naturally as a component of the iron-molybdenum cofactor of certain nitrogenase proteins. Biochemists often refer to this cofactor as homocitrate, which is the conjugate bases that predominate in neutral aqueous solutions of this species.
The molecule is related to citric acid by the addition of one methylene unit, hence the prefix "homo." Unlike citric acid, homocitric acid is chiral. The acid exists in equilibrium with the lactone. | 1 | Biochemistry |
Levocetirizine, sold under the brand name Xyzal, among others, is a second-generation antihistamine used for the treatment of allergic rhinitis (hay fever) and long-term hives of unclear cause. It is less sedating than older antihistamines. It is taken by mouth.
Common side effects include sleepiness, dry mouth, cough, vomiting, and diarrhea. Use in pregnancy appears safe but has not been well studied and use when breastfeeding is of unclear safety. It is classified as a second-generation antihistamine and works by blocking histamine H-receptors.
Levocetirizine was approved for medical use in the United States in 2007. It is available as a generic medication. In 2021, it was the 190th most commonly prescribed medication in the United States, with more than 2million prescriptions. | 4 | Stereochemistry |
The following processes are often used to describe different stages of a thermodynamic cycle:
*Adiabatic : No energy transfer as heat (Q) during that part of the cycle (). Energy transfer is considered as work done by the system only.
*Isothermal : The process is at a constant temperature during that part of the cycle (T=constant, ). Energy transfer is considered as heat removed from or work done by the system.
*Isobaric : Pressure in that part of the cycle will remain constant. (P=constant, ). Energy transfer is considered as heat removed from or work done by the system.
*Isochoric : The process is constant volume (V=constant, ). Energy transfer is considered as heat removed from the system, as the work done by the system is zero.
*Isentropic : The process is one of constant entropy (S=constant, ). It is adiabatic (no heat nor mass exchange) and reversible.
*Isenthalpic : The process that proceeds without any change in enthalpy or specific enthalpy.
*Polytropic : The process that obeys the relation .
*Reversible : The process where the net entropy production is zero; . | 7 | Physical Chemistry |
In vertebrate biology, iodine's primary function is as a constituent of the thyroid hormones, thyroxine (T4) and triiodothyronine (T3). These molecules are made from addition-condensation products of the amino acid tyrosine, and are stored prior to release in an iodine-containing protein called thyroglobulin. T4 and T3 contain four and three atoms of iodine per molecule, respectively; iodine accounts for 65% of the molecular weight of T4 and 59% of T3. The thyroid gland actively absorbs iodine from the blood to produce and release these hormones into the blood, actions which are regulated by a second hormone, called thyroid-stimulating hormone (TSH), which is produced by the pituitary gland. Thyroid hormones are phylogenetically very old molecules which are synthesized by most multicellular organisms, and which even have some effect on unicellular organisms.
Thyroid hormones play a fundamental role in biology, acting upon gene transcription mechanisms to regulate the basal metabolic rate. T3 acts on small intestine cells and adipocytes to increase carbohydrate absorption and fatty acid release, respectively. A deficiency of thyroid hormones can reduce basal metabolic rate up to 50%, while an excessive production of thyroid hormones can increase the basal metabolic rate by 100%. T4 acts largely as a precursor to T3, which is (with minor exceptions) the biologically active hormone.
Via the thyroid hormones, iodine has a nutritional relationship with selenium. A family of selenium-dependent enzymes called deiodinases converts T4 to T3 (the active hormone) by removing an iodine atom from the outer tyrosine ring. These enzymes also convert T4 to reverse T3 (rT3) by removing an inner ring iodine atom, and also convert T3 to 3,3'-Diiodothyronine (T2) by removing an inner ring atom. Both of the latter products are inactivated hormones which have essentially no biological effects and are quickly prepared for disposal. A family of non-selenium-dependent enzymes then further deiodinates the products of these reactions.
The total amount of iodine in the human body is still controversial, and in 2001, M.T. Hays published in Thyroid that "it is surprising that the total iodine content of the human body remains uncertain after many years of interest in iodine metabolism. Only the iodine content of the thyroid gland has been measured accurately by fluorescent scanning, and it is now well estimate of 5–15 mg in the normal human thyroid. But similar methods are not available for other tissues and for the extrathyroidal organs. Many researchers reported different numbers of 10–50 mg of the total iodine content in human body".
Selenium also plays a very important role in the production of glutathione, the body's most powerful antioxidant. During the production of the thyroid hormones, hydrogen peroxide is produced in large quantities, and therefore high iodine in the absence of selenium can destroy the thyroid gland (often described as a sore throat feeling); the peroxides are neutralized through the production of glutathione from selenium. In turn, an excess of selenium increases demand for iodine, and deficiency will result when a diet is high in selenium and low in iodine. | 1 | Biochemistry |
The sugar-carbamino is formed through a C-glycosidic linkage with the amino acid side chain via various linkers. The synthesis involves introducing annulation to appropriate amino acid residues to rigidify glycopeptides, followed by Diels-Alder cycloadditions to fuse cyclic α- and β-amino acids to the sugar moiety. This also involves the preparation of fused bicyclic C-glycosyl α-amino acid 4, which is confirmed through 2D NMR experiments, particularly NOESY. The approach to conformationally constrained (annulated)-C-glycosyl α- and β-amino acids is based upon the Diels-Alder reaction of pyranose dienes with α- and β-nitro acrylic esters. | 0 | Organic Chemistry |
In general there are three major categories of pH meters. Benchtop pH meters are often used in laboratories and are used to measure samples which are brought to the pH meter for analysis. Portable, or field pH meters, are handheld pH meters that are used to take the pH of a sample in a field or production site. In-line or in situ pH meters, also called pH analyzers, are used to measure pH continuously in a process, and can stand-alone, or be connected to a higher level information system for process control.
pH meters range from simple and inexpensive pen-like devices to complex and expensive laboratory instruments with computer interfaces and several inputs for indicator and temperature measurements to be entered to adjust for the variation in pH caused by temperature. The output can be digital or analog, and the devices can be battery-powered or rely on line power. Some versions use telemetry to connect the electrodes to the voltmeter display device.
Specialty meters and probes are available for use in special applications, such as harsh environments and biological microenvironments. There are also holographic pH sensors, which allow pH measurement colorimetrically, making use of the variety of pH indicators that are available. Additionally, there are commercially available pH meters based on solid state electrodes, rather than conventional glass electrodes. | 7 | Physical Chemistry |
Carbohydrate Polymers is a peer-reviewed scientific journal that covers the entire scope of carbohydrate polymers and the research and exploitation of polysaccharides. The journal is published by Elsevier. | 0 | Organic Chemistry |
The term macromolecule (macro- + molecule) was coined by Nobel laureate Hermann Staudinger in the 1920s, although his first relevant publication on this field only mentions high molecular compounds (in excess of 1,000 atoms). At that time the term polymer, as introduced by Berzelius in 1832, had a different meaning from that of today: it simply was another form of isomerism for example with benzene and acetylene and had little to do with size.
Usage of the term to describe large molecules varies among the disciplines. For example, while biology refers to macromolecules as the four large molecules comprising living things, in chemistry, the term may refer to aggregates of two or more molecules held together by intermolecular forces rather than covalent bonds but which do not readily dissociate.
According to the standard IUPAC definition, the term macromolecule as used in polymer science refers only to a single molecule. For example, a single polymeric molecule is appropriately described as a "macromolecule" or "polymer molecule" rather than a "polymer," which suggests a substance composed of macromolecules.
Because of their size, macromolecules are not conveniently described in terms of stoichiometry alone. The structure of simple macromolecules, such as homopolymers, may be described in terms of the individual monomer subunit and total molecular mass. Complicated biomacromolecules, on the other hand, require multi-faceted structural description such as the hierarchy of structures used to describe proteins. In British English, the word "macromolecule" tends to be called "high polymer". | 7 | Physical Chemistry |
There are two fundamental classifications of cells: prokaryotic and eukaryotic. Prokaryotic cells are distinguished from eukaryotic cells by the absence of a cell nucleus or other membrane-bound organelle. Prokaryotic cells are much smaller than eukaryotic cells, making them the smallest form of life. Prokaryotic cells include Bacteria and Archaea, and lack an enclosed cell nucleus. Eukaryotic cells are found in plants, animals, fungi, and protists. They range from 10 to 100 μm in diameter, and their DNA is contained within a membrane-bound nucleus. Eukaryotes are organisms containing eukaryotic cells. The four eukaryotic kingdoms are Animalia, Plantae, Fungi, and Protista.
They both reproduce through binary fission. Bacteria, the most prominent type, have several different shapes, although most are spherical or rod-shaped. Bacteria can be classed as either gram-positive or gram-negative depending on the cell wall composition. Gram-positive bacteria have a thicker peptidoglycan layer than gram-negative bacteria. Bacterial structural features include a flagellum that helps the cell to move, ribosomes for the translation of RNA to protein, and a nucleoid that holds all the genetic material in a circular structure. There are many processes that occur in prokaryotic cells that allow them to survive. In prokaryotes, mRNA synthesis is initiated at a promoter sequence on the DNA template comprising two consensus sequences that recruit RNA polymerase. The prokaryotic polymerase consists of a core enzyme of four protein subunits and a σ protein that assists only with initiation. For instance, in a process termed conjugation, the fertility factor allows the bacteria to possess a pilus which allows it to transmit DNA to another bacteria which lacks the F factor, permitting the transmittance of resistance allowing it to survive in certain environments. | 1 | Biochemistry |
In 1957, Marks married sculptor and artist Averil Sherrard and had two children. Marks was known to have been an atheist and a humanist who was opposed to religion. Along with his wife, he campaigned for various causes including saving a park in Guildford, Surrey, where they lived, from developers. His brother John Marks was also a doctor, and the chair of the British Medical Association.
Marks died on 6 November 2023, at the age of 93. | 1 | Biochemistry |
Dr. Kenneth B. Storey is among the top 2% of highly cited scientists in the world.
*[https://pubmed.ncbi.nlm.nih.gov/?term=storey+kb&sort=date&size=100 PubMed]
* [https://scholar.google.com/citations?user=mzhKxEoAAAAJ&hl=en Google Scholar] | 1 | Biochemistry |
In the Late Bronze Age, Cyprus produced numerous bronze stands that depicted a man carrying an oxhide ingot. The stands were designed to hold vases, and they were cast through the lost-wax process. The ingots show the familiar shape of four protruding handles, and the men carry them over their shoulders. These Cypriot stands were exported to Crete and Sardinia, and both islands created similar stands in local bronze workshops. | 8 | Metallurgy |
A hydrogen on the α position of a carbonyl compound is weakly acidic and can be removed by a strong base to yield an enolate ion. In comparing acetone (pK= 19.3) with ethane (pK= 60), for instance, the presence of a neighboring carbonyl group increases the acidity of the ketone over the alkane by a factor of 10.
Abstraction of a proton from a carbonyl compound occurs when the a C-H bond is oriented roughly parallel to the p orbitals of the carbonyl group. The α carbon atom of the enolate ion is sp-hybridized and has a p orbital that overlaps the neighboring carbonyl p orbitals. Thus, the negative charge is shared by the electronegative oxygen atom, and the enolate ion is stabilized by resonance.
Carbonyl compounds are more acidic than alkanes for the same reason that carboxylic acids are more acidic than alcohols. In both cases, the anions are stabilized by resonance. Enolate ions differ from carboxylate ions, however, in that their two resonance forms are not equivalent- the form with the negative charge on oxygen is lower in energy than the form with the charge on carbon. Nevertheless, the principle behind resonance stabilization is the same in both cases.
Because carbonyl compounds are only weakly acidic, a strong base is needed for enolate ion formation . If an alkoxide such as sodium ethoxide is used as base, deprotonation takes place only to the extent of about 0.1% because acetone is a weaker acid than ethanol (pK= 16). If, however, a more powerful base such as sodium hydride (NaH) or lithium diisopropylamide (LDA) is used, a carbonyl compound can be completely converted into its enolate ion. Lithium diisopropylamide (LDA), which is easily prepared by reaction of the strong base butyllithium with diisopropylamine, is widely used in the laboratory as a base for preparing enolate ions from carbonyl compounds.
Many types of carbonyl compounds, including aldehydes, ketones, esters, thioesters, acids, and amides, can be converted into enolate ions by reaction with LDA. Note that nitriles, too, are acidic and can be converted into enolate-like anions (referred to as nitrile anions).
When a hydrogen atom is flanked by two carbonyl groups, its acidity is enhanced even more. This enhanced acidity of β-dicarbonyl compounds is due to the stabilization of the resultant enolate ions by delocalization of the negative charge over both carbonyl groups. | 0 | Organic Chemistry |
Bi-metallic coins are coins consisting of two (bi-) metals or alloys, generally arranged with an outer ring around a contrasting center. Common circulating examples include the €1, €2, United Kingdom £1 and £2, Canadian $2, South Africa R5, Turkish 1 lira and 50 kurus, Indian ₹10 and ₹20, Indonesian Rp1,000, Polish 2 and 5 zł, Czech 50 Kč, Hungarian 100 and 200 Ft, Bulgarian 1 and 2 lv., Hong Kong $10, Argentine $1 and $2, Brazilian R$1, Chilean $100 and $500, Colombian $500 and $1000, Peruvian S/2 and S/5, Albanian 100 Lekë, and all Mexican coins of $1 or higher denomination. | 8 | Metallurgy |
In the kinetic theory of gases, the pressure is assumed to be equal to the force (per unit area) exerted by the individual gas atoms or molecules hitting and rebounding from the gas container's surface.
Consider a gas particle traveling at velocity, , along the -direction in an enclosed volume with characteristic length, , cross-sectional area, , and volume, . The gas particle encounters a boundary after characteristic time
The momentum of the gas particle can then be described as
We combine the above with Newton's second law, which states that the force experienced by a particle is related to the time rate of change of its momentum, such that
Now consider a large number, N, of gas particles with random orientation in a three-dimensional volume. Because the orientation is random, the average particle speed, , in every direction is identical
Further, assume that the volume is symmetrical about its three dimensions, , such that
The total surface area on which the gas particles act is therefore
The pressure exerted by the collisions of the N gas particles with the surface can then be found by adding the force contribution of every particle and dividing by the interior surface area of the volume,
The total translational kinetic energy of the gas is defined as
providing the result
This is an important, non-trivial result of the kinetic theory because it relates pressure, a macroscopic property, to the translational kinetic energy of the molecules, which is a microscopic property. | 7 | Physical Chemistry |
TFIIIB remains bound to DNA following the initiation of transcription by Pol III, unlike bacterial σ factors and most of the basal transcription factors for Pol II transcription. This leads to a high rate of transcriptional reinitiation of Pol III-transcribed genes. One study conducted on Saccharomyces cerevisiae found the average rate of chain elongation was 21 to 22 nucleotides per second, with the fastest being 29 nucleotides per second. These rates were comparable to elongation rates of RNA polymerase II found by an in vivo study conducted on Drosophila. The analysis of the individual steps of RNA chain elongation depicted that adding U and A to U-terminated RNA chains was slow. | 1 | Biochemistry |
The pressure–volume conjugate pair is concerned with the transfer of mechanical energy as the result of work.
* An isobaric process occurs at constant pressure. An example would be to have a movable piston in a cylinder, so that the pressure inside the cylinder is always at atmospheric pressure, although it is separated from the atmosphere. In other words, the system is dynamically connected, by a movable boundary, to a constant-pressure reservoir.
* An isochoric process is one in which the volume is held constant, with the result that the mechanical PV work done by the system will be zero. On the other hand, work can be done isochorically on the system, for example by a shaft that drives a rotary paddle located inside the system. It follows that, for the simple system of one deformation variable, any heat energy transferred to the system externally will be absorbed as internal energy. An isochoric process is also known as an isometric process or an isovolumetric process. An example would be to place a closed tin can of material into a fire. To a first approximation, the can will not expand, and the only change will be that the contents gain internal energy, evidenced by increase in temperature and pressure. Mathematically, . The system is dynamically insulated, by a rigid boundary, from the environment. | 7 | Physical Chemistry |
Metabolic regulation achieves a balance between the rate of input of a substrate and the rate that it is degraded or converted, and thus maintains steady state. The rate of metabolic flow, or flux, is variable and subject to metabolic demands. However, in a metabolic pathway, steady state is maintained by balancing the rate of substrate provided by a previous step and the rate that the substrate is converted into product, keeping substrate concentration relatively constant.
Thermodynamically speaking, living organisms are open systems, meaning that they constantly exchange matter and energy with their surroundings. A constant supply of energy is required for maintaining steady state, as maintaining a constant concentration of a molecule preserves internal order and thus is entropically unfavorable. When a cell dies and no longer utilizes energy, its internal composition will proceed toward equilibrium with its surroundings.
In some occurrences, it is necessary for cells to adjust their internal composition in order to reach a new steady state. Cell differentiation, for example, requires specific protein regulation that allows the differentiating cell to meet new metabolic requirements. | 7 | Physical Chemistry |
Gasulla, Casano and Guéra, concluded that the longer the lichen are subjected to darkness, the quicker the chlororespiratory pathways can begin. This is due to the fast depletion of PTOX molecules which reduce the PQ pool. These events then stimulate chlororespiratory ETCs into an ongoing loop until the lichen are placed in a luminous environment.
They also derived LHC to be another indicator for chlororespiration. When LHC concentrations inside the chloroplast increased, PS II activity decreased due to loss in ETC activity. This reduction then stimulated chlororespiratory activity to compensate for chemical energy synthesis.<br /> | 1 | Biochemistry |
REMS technology performance has been evaluated through multicentre clinical studies. The work of Di Paola et al. has investigated precision and diagnostic accuracy of REMS in comparison with DXA on a sample of 2000 patients. A very high correlation has been observed between the T-Score values obtained by both technologies (Pearson correlation coefficient > 0.93; Cohen’s Kappa equals to 0.82 for lumbar spine and 0.79 for femoral neck) as well as a very low average BMD difference between the two techniques (mean ± 2 standard deviations): −0.004±0.088 g/cm for lumbar spine and −0.006±0.076 g/cm for femoral neck. Furthermore, specificity and sensitivity of REMS in the discrimination between osteoporotic and non-osteoporotic patients has been evaluated: sensitivity and specificity exceed 91% for both skeletal sites. Additional outcomes of this study are the values of precision and repeatability of REMS estimates, assessed using the Root Mean Square Coefficient of Variation (CV-RMS): precision has been evaluated as being 0.38% for lumbar spine and 0.32% for femoral neck, whereas the Least Significant Change (LSC) resulted in 1.05% and 0.88%, respectively. Finally, inter-operator repeatability has been calculated, which has resulted in 0.54% for lumbar spine and 0.48% for femoral neck. These values are significantly lower than those reported about DXA in the scientific literature and offer concrete advantages from the point of view of short-term follow-up of patients undergoing therapeutic treatments. | 7 | Physical Chemistry |
Smear layer refers to a layer of debris on the inorganic surface of substrate which comprises residual inorganic and organic components. This layer is produced whenever the tooth structure undergoes a preparation with a bur.
Smear layer will fill the orifices of the dentinal tubules, hence forming smear plugs. These smear plugs decrease dentin permeability by 90% and the smear plug alone can prevent adhesive resin penetration into dentinal tubules. The thickness of smear layer can range from 0.5-2 µmeter and for the smear plug, 1 to 10 µmeter.
Smear layer poses some threat for optimal bonding to occur. That is why it needs to be removed. For example, smear layer needs to be removed prior to bonding by etch-and-rinse (total etch) adhesives. This will lead to thicker hybrid layer and long, denser resin tags which results in better bond strength. | 7 | Physical Chemistry |
*NDUFA2NM_002488
*NDUFA3 NM_004542
*NDUFA4 NM_002489
*NDUFA5 NM_005000
*NDUFA6 NM_002490
*NDUFA7 NM_005001 Homo sapiens NADH dehydrogenase (ubiquinone) 1 alpha subcomplex, 7, 14.5kDa
*NDUFA8 NM_014222
*NDUFA9 NM_005002
*NDUFA10 NM_004544
*NDUFA11 NM_175614
*NDUFA12 NM_018838
*NDUFA13 NM_015965
*NDUFAF2 NM_174889
*NDUFAF3 NM_199069
*NDUFAF4 NM_014165
*NDUFB2 NM_004546
*NDUFB3 NM_002491
*NDUFB4 NM_004547
*NDUFB5 NM_002492
*NDUFB6 NM_002493
*NDUFB7 NM_004146 Homo sapiens NADH dehydrogenase (ubiquinone) 1 beta subcomplex, 7, 18kDa
*NDUFB10 NM_004548
*NDUFB11 NM_019056
*NDUFB8 NM_005004
*NDUFB9 NM_005005
*NDUFC1 NM_002494Homo sapiens NADH dehydrogenase (ubiquinone) 1, subcomplex unknown, 1, 6kDa
*NDUFC2 NM_004549
*NDUFC2-KCTD14 NM_001203260
*NDUFS5
*NDUFV2
*NDUFS2 NM_004550
*NDUFS3 NM_004551
*NDUFS4 NM_002495
*NDUFS5 NM_004552 Homo sapiens NADH dehydrogenase (ubiquinone) Fe-S protein 5, 15kDa
*NDUFS6 NM_004553
*NDUFS7 NM_024407
*NDUFS8 NM_002496
*NDUFV1 NM_007103 Homo sapiens NADH dehydrogenase (ubiquinone) flavoprotein 1, 51kDa (NDUFV1),
*NDUFV2 NM_021074 Homo sapiens NADH dehydrogenase (ubiquinone) flavoprotein 2, 24kDa (NDUFV2), | 1 | Biochemistry |
Its water-solubility, together with its status as the only known photoactive protein containing a carotenoid, makes the OCP a valuable model for studying solution-state energetic and photophysical properties of carotenoids, which are a diverse class of molecules found across all domains of life. Moreover, carotenoids are widely investigated for their properties as anti-oxidants, and thus the protein may serve as a template for delivery of carotenoids for therapeutic purposes in human medicine.
Because of its high efficiency of fluorescence quenching, coupled to its low quantum yield of photoactivation by specific wavelengths of light, OCP has ideal properties as a photoswitch and has been proposed as a novel system for developing optogenetics technologies and may have other applications in optofluidics and biophotonics. | 5 | Photochemistry |
Few Ru(II) and Os(II) complexes react directly with arenes. Instead, arene complexes of these metals are typically prepared by treatment of M(III) precursors with cyclohexadienes. For example, heating alcohol solutions of 1,3- or 1,4-cyclohexadiene and ruthenium trichloride gives (benzene)ruthenium dichloride dimer. The conversion entails dehydrogenation of an intermediate diene complex. | 0 | Organic Chemistry |
In optics, two non-Lambertian sources that emit beamed energy can interact in a way that causes a shift in the spectral lines. It is analogous to a pair of tuning forks with similar frequencies (pitches), connected together mechanically with a sounding board; there is a strong coupling that results in the resonant frequencies getting "dragged down" in pitch. The Wolf Effect requires that the waves from the sources are partially coherent - the wavefronts being partially in phase. Laser light is coherent while candlelight is incoherent, each photon having random phase. It can produce either redshifts or blueshifts, depending on the observer's point of view, but is redshifted when the observer is head-on.
For two sources interacting while separated by a vacuum, the Wolf effect cannot produce shifts greater than the linewidth of the source spectral line, since it is a position-dependent change in the distribution of the source spectrum, not a method by which new frequencies may be generated. However, when interacting with a medium, in combination with effects such as Brillouin scattering it may produce distorted shifts greater than the linewidth of the source. | 7 | Physical Chemistry |
*2024: Humboldt Research Award
*2018: Madhuri and Jagdish N. Sheth International Alumni Award for Exceptional Achievement (University of Illinois)
*2015: Ho-Am Prize in Science (HOAM Foundation)
*2014: The World's Most Influential Scientific Minds (Thomson Reuters)
*2013: KCS Academic Achievement Award (Korean Chemical Society)
*2012: POSCO TJ Park Prize (POSCO TJ Park Foundation)
*2012: Korea's 100 Most Influential Person for Next 10 Years (DongA Daily News)
*2010: Inchon Prize (Inchon Memorial Foundation)
*2007: Song-Gok Science Prize (Korea Institute of Science and Technology)
*2004: KCS Award in Inorganic Chemistry (Korean Chemical Society)
*2002: Young Scientist Award, Korean Academy of Science and Technology
*2001: Wiley Young Chemist Award (Korean Chemical Society-Wiley & Sons) | 0 | Organic Chemistry |
Ribozymes are catalytic RNA molecules used to inhibit gene expression. These molecules work by cleaving mRNA molecules, essentially silencing the genes that produced them. Sidney Altman and Thomas Cech first discovered catalytic RNA molecules, RNase P and group II intron ribozymes, in 1989 and won the Nobel Prize for their discovery. Several types of ribozyme motifs exist, including hammerhead, hairpin, hepatitis delta virus, group I, group II, and RNase P ribozymes. Hammerhead, hairpin, and hepatitis delta virus (HDV) ribozyme motifs are generally found in viruses or viroid RNAs. These motifs are able to self-cleave a specific phosphodiester bond on an mRNA molecule. Lower eukaryotes and a few bacteria contain group I and group II ribozymes. These motifs can self-splice by cleaving and joining phosphodiester bonds. The last ribozyme motif, the RNase P ribozyme, is found in Escherichia coli and is known for its ability to cleave the phosphodiester bonds of several tRNA precursors when joined to a protein cofactor.
The general catalytic mechanism used by ribozymes is similar to the mechanism used by protein ribonucleases. These catalytic RNA molecules bind to a specific site and attack the neighboring phosphate in the RNA backbone with their 2 oxygen, which acts as a nucleophile, resulting in the formation of cleaved products with a 23-cyclic phosphate and a 5 hydroxyl terminal end. This catalytic mechanism has been increasingly used by scientists to perform sequence-specific cleavage of target mRNA molecules. In addition, attempts are being made to use ribozymes to produce gene silencing therapeutics, which would silence genes that are responsible for causing diseases. | 1 | Biochemistry |
All pharmaceuticals are derived from petroleum, albeit via mutlistep processes. Modern medicine depends on petroleum as a source of building blocks, reagents, and solvents. Similarly, virtually all pesticides - insecticides, herbicides, etc. - are derived from petroleum. Pesticides have profoundly affected life expectancies by controlling disease vectors and by increasing yields of crops. Like pharmaceuticals, pesticides are in essence petrochemicals. Virtually all plastics and synthetic polymers are derived from petroleum, which is the source of monomers. Alkenes (olefins) are one important class of these precursor molecules. | 7 | Physical Chemistry |
The mouse sperm genome is 80–90% methylated at its CpG sites in DNA, amounting to about 20 million methylated sites. After fertilization, the paternal chromosome is almost completely demethylated in six hours by an active process, before DNA replication (blue line in Figure).
Demethylation of the maternal genome occurs by a different process. In the mature oocyte, about 40% of its CpG sites in DNA are methylated. While somatic cells of mammals have three main DNA methyltransferases (which add methyl groups to cytosines at CpG sites), DNMT1, DNMT3A, and DNMT3B, in the pre-implantation embryo up to the blastocyst stage (see Figure), the only methyltransferase present is an isoform of DNMT1 designated DNMT1o. DNMT1o has an alternative oocyte-specific promoter and first exon (exon 1o) located 5' of the somatic and spermatocyte promoters. As reviewed by Howell et al., DNMT1o is sequestered in the cytoplasm of mature oocytes and in 2-cell and 4-cell embryos, but at the 8-cell stage is only present in the nucleus. At the 16 cell stage (the morula) DNMT1o is again found only in the cytoplasm. It appears that demethylation of the maternal chromosomes largely takes place by blockage of the methylating enzyme DNMT1o from entering the nucleus except briefly at the 8 cell stage. The maternal-origin DNA thus undergoes passive demethylation by dilution of the methylated maternal DNA during replication (red line in Figure). The morula (at the 16 cell stage), has only a small amount of DNA methylation (black line in Figure).
DNMT3b begins to be expressed in the blastocyst. Methylation begins to increase at 3.5 days after fertilization in the blastocyst, and a large wave of methylation then occurs on days 4.5 to 5.5 in the epiblast, going from 12% to 62% methylation, and reaching maximum level after implantation in the uterus. By day seven after fertilization, the newly formed primordial germ cells (PGC) in the implanted embryo segregate from the remaining somatic cells. At this point the PGCs have about the same level of methylation as the somatic cells. | 1 | Biochemistry |
In recent years, benzene is generally depicted as a hexagon with alternating single and double bonds, much like the structure Kekulé originally proposed in 1872. As mentioned above, the alternating single and double bonds of "1,3,5-cyclohexatriene" are understood to be a drawing of one of the two equivalent canonical forms of benzene (the one explicitly shown and the one with the opposite pattern of formal single and double bonds), in which all carbon–carbon bonds are of equivalent length and have a bond order of exactly 1.5. For aryl rings in general, the two analogous canonical forms are almost always the primary contributors to the structure, but they are nonequivalent, so one structure may make a slightly greater contribution than the other, and bond orders may differ somewhat from 1.5.
An alternate representation that emphasizes this delocalization uses a circle, drawn inside the hexagon of single bonds, to represent the delocalized pi orbital. This style, based on one proposed by Johannes Thiele, used to be very common in introductory organic chemistry textbooks and is still frequently used in informal settings. However, because this depiction does not keep track of electron pairs and is unable to show the precise movement of electrons, it has largely been superseded by the Kekuléan depiction in pedagogical and formal academic contexts. | 0 | Organic Chemistry |
Antiretroviral drugs are medications for the treatment of infection by retroviruses, primarily HIV. Different classes of antiretroviral drugs act on different stages of the HIV life cycle. Combination of several (typically three or four) antiretroviral drugs is known as highly active antiretroviral therapy (HAART). | 1 | Biochemistry |
In mathematics, a Meyer set or almost lattice is a relatively dense set X of points in the Euclidean plane or a higher-dimensional Euclidean space such that its Minkowski difference with itself is uniformly discrete. Meyer sets have several equivalent characterizations; they are named after Yves Meyer, who introduced and studied them in the context of diophantine approximation. Nowadays Meyer sets are best known as mathematical model for quasicrystals. However, Meyer's work precedes the discovery of quasicrystals by more than a decade and was entirely motivated by number theoretic questions. | 3 | Analytical Chemistry |
RNA replication is the copying of one RNA to another. Many viruses replicate this way. The enzymes that copy RNA to new RNA, called RNA-dependent RNA polymerases, are also found in many eukaryotes where they are involved in RNA silencing.
RNA editing, in which an RNA sequence is altered by a complex of proteins and a "guide RNA", could also be seen as an RNA-to-RNA transfer. | 1 | Biochemistry |
The increasing amount of bacterial genomic data provides new opportunities for understanding the genetic and molecular bases of the degradation of organic pollutants. Aromatic compounds are among the most persistent of these pollutants and lessons can be learned from the recent genomic studies of Burkholderia xenovorans LB400 and Rhodococcus sp. strain RHA1, two of the largest bacterial genomes completely sequenced to date. These studies have helped expand our understanding of bacterial catabolism, non-catabolic physiological adaptation to organic compounds, and the evolution of large bacterial genomes. First, the metabolic pathways from phylogenetically diverse isolates are very similar with respect to overall organization. Thus, as originally noted in pseudomonads, a large number of "peripheral aromatic" pathways funnel a range of natural and xenobiotic compounds into a restricted number of "central aromatic" pathways. Nevertheless, these pathways are genetically organized in genus-specific fashions, as exemplified by the b-ketoadipate and Paa pathways. Comparative genomic studies further reveal that some pathways are more widespread than initially thought. Thus, the Box and Paa pathways illustrate the prevalence of non-oxygenolytic ring-cleavage strategies in aerobic aromatic degradation processes. Functional genomic studies have been useful in establishing that even organisms harboring high numbers of homologous enzymes seem to contain few examples of true redundancy. For example, the multiplicity of ring-cleaving dioxygenases in certain rhodococcal isolates may be attributed to the cryptic aromatic catabolism of different terpenoids and steroids. Finally, analyses have indicated that recent genetic flux appears to have played a more significant role in the evolution of some large genomes, such as LB400's, than others. However, the emerging trend is that the large gene repertoires of potent pollutant degraders such as LB400 and RHA1 have evolved principally through more ancient processes. That this is true in such phylogenetically diverse species is remarkable and further suggests the ancient origin of this catabolic capacity. | 2 | Environmental Chemistry |
BOP (benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate) reagent is a reagent commonly used in the synthesis of peptides. Its use is discouraged because coupling using BOP liberates HMPA which is carcinogenic, although for small scale use in an organic laboratory this is not a great disadvantage as it is in large scale industrial usage.
BOP has been used for peptide coupling, synthesis of esters, esterification of carboxylic acids, or as a catalyst. This reagent is advantageous in peptide coupling to other derived reagents because there are no side reactions from the dehydration of asparagine or glutamine. In peptide coupling the BOP reagent works well because it forms reactive intermediates which allow for the amines to bond together with little energy loss. In the reduction of carboxylic acids, using the BOP reagent with NaBH resulted in high percent yields.
<br /> | 1 | Biochemistry |
The biosynthesis of trabectedin in Candidatus Endoecteinascidia frumentensis starts with a fatty acid loading onto the acyl-ligase domain of the EtuA3 module. A cysteine and glycine are then loaded as canonical NRPS amino acids. A tyrosine residue is modified by the enzymes EtuH, EtuM1, and EtuM2 to add a hydroxyl at the meta position of the phenol, and adding two methyl groups at the para-hydroxyl and the meta carbon position. This modified tyrosine reacts with the original substrate via a Pictet-Spengler reaction, where the amine group is converted to an imine by deprotonation, then attacks the free aldehyde to form a carbocation that is quenched by electrons from the methyl-phenol ring. This is done in the EtuA2 T-domain. This reaction is done a second time to yield a dimer of modified tyrosine residues that have been further cyclized via Pictet-Spengler reaction, yielding a bicyclic ring moiety. The EtuO and EtuF3 enzymes continue to post-translationally modify the molecule, adding several functional groups and making a sulfide bridge between the original cysteine residue and the beta-carbon of the first tyrosine to form ET-583, ET-597, ET-596, and ET-594 which have been previously isolated. A third O-methylated tyrosine is added and cyclized via Pictet-Spengler to yield the final product. | 0 | Organic Chemistry |
A non-profit research and testing organization, the Instrumentation Testing Association (ITA) can provide results of field testing online TOC analysers in an industrial wastewater application. Gulf Coast Waste Disposal Authority (GCWDA), Bayport Industrial Wastewater Treatment Plant in Pasadena, Texas sponsored and conducted this test in 2011. The GCWDA Bayport facility treats approximately 30 mgd of industrial waste received from approximately 65 customers (primarily petrochemical). Field tests consisted of operating online TOC analysers at the influent of the Bayport facility in which TOC concentrations can range from 490 to 1020 mg/L with an average of 870 mg/L. GCWDA conducts approximately 102 TOC analyses in their laboratory per day at their Bayport treatment facility and use TOC measurements for process control and billing purposes. GCWDA plans to use online TOC analysers for process control, detecting influent slug loads from industries and to potentially use online TOC analysers to detect and monitor volatiles of the incoming stream. Field tests were conducted for a period of 90-days and used laboratory conformance measurements once per day to compare with analyser output to demonstrate the instrument's overall accuracy when subjected to many simultaneously changing parameters as experienced in real-time monitoring conditions. Field test results can provide information regarding instrument design, operation and maintenance requirements which influence the performance of the instruments in field applications. The field test report includes evaluations of online TOC analysers utilizing the following technologies: High temperature combustion (HTC), high temperature catalytic/combustion oxidation (HTCO), supercritical water oxidation (SCWO), and two-stage advanced oxidation (TSAO). | 3 | Analytical Chemistry |
The atmosphere of Early Earth is widely speculated to have been reducing. The Miller–Urey experiment, related to some hypotheses for the origin of life, entailed reactions in a reducing atmosphere composed of a mixed atmosphere of methane, ammonia and hydrogen sulfide. Some hypotheses for the origin of life invoke a reducing atmosphere consisting of hydrogen cyanide (HCN). Experiments show that HCN can polymerize in the presence of ammonia to give a variety of products including amino acids. The same principle applies to Mars, Venus and Titan.
Cyanobacteria are suspected to be the first photoautotrophs that evolved oxygenic photosynthesis, which over the latter half of the Archaen eon eventually depleted all reductants in the Earth's oceans, terrestrial surface and atmsophere, gradually increasing the oxygen concentration in the atmosphere, changing it to what is known as an oxidizing atmosphere. This rising oxygen initially led to a 300 million-year-long ice age that devastated the then-mostly anaerobe-dominated biosphere, forcing the surviving anaerobic colonies to evolve into symbiotic microbial mats with the newly evolved aerobes. Some aerobic bacteria eventually became endosymbiont within other anaerobes (likely archaea), and the resultant symbiogenesis led to the evolution of a completely new lineage of life — the eukaryotes, who took advantage of mitochondrial aerobic respiration to power their cellular activities, allowing life to thrive and evolve into ever more complex forms. The increased oxygen in the atmosphere also eventually created the ozone layer, which shielded away harmful ionizing ultraviolet radiation that otherwise would have photodissociated away surface water and rendered life impossible on land and the ocean surface.
In contrast to the hypothesized early reducing atmosphere, evidence exists that Hadean atmospheric oxygen levels were similar to those of today. These results suggests prebiotic building blocks were delivered from elsewhere in the galaxy. The results however do not run contrary to existing theories on life's journey from anaerobic to aerobic organisms. The results quantify the nature of gas molecules containing carbon, hydrogen, and sulphur in the earliest atmosphere, but they shed no light on the much later rise of free oxygen in the air. | 8 | Metallurgy |
The Lemberg Medal, named after Max Rudolf Lemberg, the first president of the Australian Society for Biochemistry and Molecular Biology (ASBMB), is awarded annually to a scientist who has been a member for five or more years and who has "demonstrated excellence in Biochemistry and Molecular Biology and who has made significant contributions to the scientific community". The winner presents the Lemberg Lecture at the following ASBMB annual conference. | 1 | Biochemistry |
In the late 1990s it was discovered that very distant supernovae were dimmer than expected suggesting that the universes expansion was accelerating rather than slowing down. This revived discussion that Einsteins cosmological constant, long disregarded by physicists as being equal to zero, was in fact some small positive value. This would indicate empty space exerted some form of negative pressure or energy.
There is no natural candidate for what might cause what has been called dark energy but the current best guess is that it is the zero-point energy of the vacuum. One difficulty with this assumption is that the zero-point energy of the vacuum is absurdly large compared to the observed cosmological constant. This issue, called the cosmological constant problem, is one of the greatest unsolved mysteries in physics.
The European Space Agencys Euclid telescope, launched on 1 July 2023, will map galaxies up to 10 billion light years away. By seeing how dark energy influences their arrangement and shape, the mission will allow scientists to see if the strength of dark energy has changed. If dark energy is found to vary throughout time it would indicate it is due to quintessence, where observed acceleration is due to the energy of a scalar field, rather than the cosmological constant. No evidence of quintessence is yet available, but it has not been ruled out either. It generally predicts a slightly slower acceleration of the expansion of the universe than the cosmological constant. Some scientists think that the best evidence for quintessence would come from violations of Einsteins equivalence principle and variation of the fundamental constants in space or time. Scalar fields are predicted by the Standard Model of particle physics and string theory, but an analogous problem to the cosmological constant problem (or the problem of constructing models of cosmological inflation) occurs: renormalization theory predicts that scalar fields should acquire large masses again due to zero-point energy. | 7 | Physical Chemistry |
It was not until after the observations of certain molecular phenomena that stereochemical principles were developed. In 1815, Jean-Baptiste Biots observation of optical activity marked the beginning of organic stereochemistry history. He observed that organic molecules were able to rotate the plane of polarized light in a solution or in the gaseous phase. Despite Biots discoveries, Louis Pasteur is commonly described as the first stereochemist, having observed in 1842 that salts of tartaric acid collected from wine production vessels could rotate the plane of polarized light, but that salts from other sources did not. This property, the only physical property in which the two types of tartrate salts differed, is due to optical isomerism. In 1874, Jacobus Henricus van t Hoff and Joseph Le Bel explained optical activity in terms of the tetrahedral arrangement of the atoms bound to carbon. Kekulé used tetrahedral models earlier in 1862 but never published these; Emanuele Paternò probably knew of these but was the first to draw and discuss three dimensional structures, such as of 1,2-dibromoethane in the Giornale di Scienze Naturali ed Economiche' in 1869. The term "chiral" was introduced by Lord Kelvin in 1904. Arthur Robertson Cushny, Scottish Pharmacologist, in 1908, first offered a definite example of a bioactivity difference between enantiomers of a chiral molecule viz. (-)-Adrenaline is two times more potent than the (±)- form as a vasoconstrictor and in 1926 laid the foundation for chiral pharmacology/stereo-pharmacology (biological relations of optically isomeric substances). Later in 1966, the Cahn-Ingold-Prelog nomenclature or Sequence rule was devised to assign absolute configuration to stereogenic/chiral center (R- and S- notation) and extended to be applied across olefinic bonds (E- and Z- notation). | 4 | Stereochemistry |
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