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As a more complex example, the ionic strength of a mixed solution 0.050 M in NaSO and 0.020 M in KCl is: | 7 | Physical Chemistry |
Hexafluoroethane is used as a versatile etchant in semiconductor manufacturing. It can be used for selective etching of metal silicides and oxides versus their metal substrates and also for etching of silicon dioxide over silicon. The primary aluminium and the semiconductor manufacturing industries are the major emitters of hexafluoroethane using the Hall-Héroult process.
Together with trifluoromethane it is used in refrigerants R508A (61%) and R508B (54%).
It is used as a tamponade to assist in retinal reattachment following vitreoretinal surgery. | 2 | Environmental Chemistry |
The principal manuscripts are:
* The Lucca MS, Lucca, Biblioteca Capitolare Feliniana, Codex 490, the oldest witness, c. 800.
* The Sélestat MS, Sélestat, Bibliothèque Humaniste, MS 17. A very full yet old witness, early ninth century.
* The Codex Matritensis (Madrid codex), Madrid, Biblioteca Nacional, MS A.16 (Was: MS A.19), c. 1130.
* The Phillipps-Corning Manuscript, Corning Museum of Glass, MS 5, late twelfth century.
These are simply among the fullest witnesses - there are dozens more that preserve extracts. | 8 | Metallurgy |
C/EBPβ and δ are transiently induced during the early stages of adipocyte differentiation (adipogenesis), while C/EBPα is upregulated during the terminal stages of adipogenesis. In vitro and in vivo studies have demonstrated that each plays an important role in this process. For example, Murine Embryonic Fibroblasts (MEFs) from mice lacking both C/EBPβ and C/EBPδ show impaired adipocyte differentiation in response to adipogenic stimuli. In contrast, ectopic expression of C/EBPβ and δ in 3T3-L1 preadipocytes promotes adipogenesis, even in the absence of adipogenic stimuli. C/EBPβ and δ promote adipogenesis, at least in part by inducing the expression of the "master" adipogenic transcription factors C/EBPα and PPARγ.
C/EBPα is required both for adipogenesis and for normal adipocyte function. For example, mice lacking C/EBPα in all tissues except the liver (where it is needed to avoid postnatal lethality) show abnormal adipose tissue formation. Moreover, ectopic expression of C/EBPα in various fibroblast cell lines promotes adipogenesis. C/EBPα probably promotes adipogenesis by inducing the expression of PPARγ. | 1 | Biochemistry |
Transition metal alkyl complexes are coordination complexes that contain a bond between a transition metal and an alkyl ligand. Such complexes are not only pervasive but are of practical and theoretical interest. | 0 | Organic Chemistry |
Ion-exchange membranes are traditionally used in electrodialysis or diffusion dialysis by means of an electrical potential or concentration gradient, respectively, to selectively transport cationic and anionic species. When applied in an electrodialysis desalination process, anion- and cation-exchange membranes are typically arranged in an alternating pattern between two electrodes (an anode and a cathode) within the electrodialysis stack. A galvanic potential is supplied as a voltage generated at the electrodes.
A typical industrial electrodialysis stack consists of two chambers: a product-water chamber and a concentrate-reject chamber. During stack operation, salts are transferred from the product to the concentrate. As a result, the reject stream is concentrated up while the product stream is desalted.
Exemplary applications of ion-exchange membranes utilized in electrodialysis and EDR include seawater desalination, industrial wastewater treatment of highly scaling waters, food and beverage production, and other industrial wastewaters. | 3 | Analytical Chemistry |
A purge box is typically used so that absorption of THz radiation by gaseous water molecules is minimized. A dry air source is often used for this purpose, however, a nitrogen gas source may also be used.
Water is known to have many discrete absorptions in the THz region that are rotational modes of water molecules. Alternatively, nitrogen, as a diatomic molecule, has no electric dipole moment, and does not (for the purposes of typical THz-TDS) absorb THz radiation. Thus, a purge box may be filled with nitrogen gas so no unintended discrete absorptions in the THz frequency range occur. | 7 | Physical Chemistry |
At the spinal cord, cannabinoids suppress noxious-stimulus-evoked responses of neurons in the dorsal horn, possibly by modulating descending noradrenaline input from the brainstem. As many of these fibers are primarily GABAergic, cannabinoid stimulation in the spinal column results in disinhibition that should increase noradrenaline release and attenuation of noxious-stimuli-processing in the periphery and dorsal root ganglion.
The endocannabinoid most researched in pain is palmitoylethanolamide. Palmitoylethanolamide is a fatty amine related to anandamide, but saturated and although initially it was thought that palmitoylethanolamide would bind to the CB1 and the CB2 receptor, later it was found that the most important receptors are the PPAR-alpha receptor, the TRPV receptor and the GPR55 receptor. Palmitoylethanolamide has been evaluated for its analgesic actions in a great variety of pain indications and found to be safe and effective.
Modulation of the endocannabinoid system by metabolism to N-arachidinoyl-phenolamine (AM404), an endogenous cannabinoid neurotransmitter, has been discovered to be one mechanism for analgesia by acetaminophen (paracetamol).
Endocannabinoids are involved in placebo induced analgesia responses. | 1 | Biochemistry |
Specific dynamic action (SDA), also known as thermic effect of food (TEF) or dietary induced thermogenesis (DIT), is the amount of energy expenditure above the basal metabolic rate due to the cost of processing food for use and storage. Heat production by brown adipose tissue which is activated after consumption of a meal is an additional component of dietary induced thermogenesis. The thermic effect of food is one of the components of metabolism along with resting metabolic rate and the exercise component. A commonly used estimate of the thermic effect of food is about 10% of one's caloric intake, though the effect varies substantially for different food components. For example, dietary fat is very easy to process and has very little thermic effect, while protein is hard to process and has a much larger thermic effect. | 1 | Biochemistry |
In organic chemistry, a methylene bridge, methylene spacer, or methanediyl group is any part of a molecule with formula ; namely, a carbon atom bound to two hydrogen atoms and connected by single bonds to two other distinct atoms in the rest of the molecule. It is the repeating unit in the skeleton of the unbranched alkanes.
A methylene bridge can also act as a bidentate ligand joining two metals in a coordination compound, such as titanium and aluminum in Tebbe's reagent.
A methylene bridge is often called a methylene group or simply methylene, as in "methylene chloride" (dichloromethane ). As a bridge in other compounds, for example in cyclic compounds, it is given the name methano. However, the term methylidene group (not to be confused with the term methylene group, nor the carbene methylidene) properly applies to the group when it is connected to the rest of the molecule by a double bond (), giving it chemical properties very distinct from those of a bridging group. | 0 | Organic Chemistry |
Cereins are a group of bacteriocins produced by various strains of the bacterium Bacillus cereus. Although all cereins are by definition produced by B. cereus, it is possible that they are chemically quite different from one another. Cereins have been found to be active against other strains of B. cereus, as well as a broad range of other gram-positive bacteria. Like other bacteriocins, cereins are generally named after the strain in which their production was first discovered. Named cereins include cerein 7, cerein 7B, cerein 8A, and cerein MRX1. | 1 | Biochemistry |
The journal is abstracted and indexed in:
According to the Journal Citation Reports, the journal has a 2022 impact factor of 3.4. | 9 | Geochemistry |
The polyadenylation activity of GLD-2, as we previously mentioned, is stimulated by physical interaction with an RNA binding protein, GLD-3. To test whether GLD-3 might stimulate GLD-2 by recruiting it to RNA, some studies tethered C. elegans GLD-2 to mRNAs in Xenopus oocytes by using MS2 coat protein. Tethered GLD-2 adds poly(A) and stimulates translation of the mRNA, demonstrating that recruitment is sufficient to stimulate polyadenylation activity. PAP heterodimer in which GLD-2 contains the active site and GLD-3 provides RNA-binding specificity. MS2 coat protein was joined to GLD-2 to recruit it to an RNA.
Furthermore, GLD-2 activity is also important to maintain or up-regulate the abundance of many mRNAs, as the cytoplasmic polyadenylation has an essential role in activating maternal mRNA translation during early development. In vertebrates, the reaction requires CPEB, an RNA-binding protein and the poly(A) polymerase GLD-2.
The Xenopus enzyme, which exists in two closely related forms, polyadenylates RNAs to which it is tethered and enhances their translation. Likewise, it interacts with cytoplasmic polyadenylation factors, including Cleavage and polyadenylation specificity factor and CPEB, and with target mRNAs. These findings confirm and extend a recent report that a GLD-2 enzyme is the long-sought PAP responsible for cytoplasmic polyadenylation in oocytes.
In addition, the formation of long-term memory is believed to lack translational control of localized mRNAs. In mammals, dendrite mRNAs are kept in a repressed state and are activated upon repetitive stimulation. Several regulatory proteins required for translational control in early development are thought to be needed for memory formation, suggesting similar molecular mechanisms. In an experiment using Drosophila, it has been detected the enzyme responsible for poly(A) elongation in the brain and it has been demonstrated too that its activity is required specifically for long-term memory. These findings provide strong evidence that cytoplasmic polyadenylation is critical for memory formation, and that GLD2 is the responsible enzyme. | 1 | Biochemistry |
Note that
where m is the mass of particle i.
To prove this, we need to use two facts:
:*The square of a particle's four momentum is the square of its mass,
:*And conservation of four-momentum,
So, to begin,
Then adding the three while inserting squared masses leads to,
Then note that the last four terms add up to zero using conservation of four-momentum,
So finally, | 7 | Physical Chemistry |
As austenite cools, the carbon diffuses out of the austenite and forms carbon-rich iron-carbide (cementite) and leaves behind carbon-poor ferrite. Depending on alloy composition, a layering of ferrite and cementite, called pearlite, may form. If the rate of cooling is very swift, the carbon does not have sufficient time to diffuse, and the alloy may experience a large lattice distortion known as martensitic transformation in which it transforms into martensite, a body centered tetragonal structure (BCT). The rate of cooling determines the relative proportions of martensite, ferrite, and cementite, and therefore determines the mechanical properties of the resulting steel, such as hardness and tensile strength.
A high cooling rate of thick sections will cause a steep thermal gradient in the material. The outer layers of the heat treated part will cool faster and shrink more, causing it to be under tension and thermal straining. At high cooling rates, the material will transform from austenite to martensite which is much harder and will generate cracks at much lower strains. The volume change (martensite is less dense than austenite) can generate stresses as well. The difference in strain rates of the inner and outer portion of the part may cause cracks to develop in the outer portion, compelling the use of slower quenching rates to avoid this. By alloying the steel with tungsten, the carbon diffusion is slowed and the transformation to BCT allotrope occurs at lower temperatures, thereby avoiding the cracking. Such a material is said to have its hardenability increased. Tempering following quenching will transform some of the brittle martensite into tempered martensite. If a low-hardenability steel is quenched, a significant amount of austenite will be retained in the microstructure, leaving the steel with internal stresses that leave the product prone to sudden fracture. | 8 | Metallurgy |
Iron levels in cells are maintained by translation regulation of many proteins involved in iron storage and metabolism. The 5′ UTR has the ability to form a hairpin loop secondary structure (known as the iron response element or IRE) that is recognized by iron-regulatory proteins (IRP1 and IRP2). In low levels of iron, the ORF of the target mRNA is blocked as a result of steric hindrance from the binding of IRP1 and IRP2 to the IRE. When iron is high, then the two iron-regulatory proteins do not bind as strongly and allow proteins to be expressed that have a role in iron concentration control. This function has gained some interest after it was revealed that the translation of amyloid precursor protein may be disrupted due to a single-nucleotide polymorphism to the IRE found in the 5′ UTR of its mRNA, leading to a spontaneous increased risk of Alzheimer's disease. | 1 | Biochemistry |
The Klein–Nishina formula was derived in 1928 by Oskar Klein and Yoshio Nishina, and was one of the first results obtained from the study of quantum electrodynamics. Consideration of relativistic and quantum mechanical effects allowed development of an accurate equation for the scattering of radiation from a target electron. Before this derivation, the electron cross section had been classically derived by the British physicist and discoverer of the electron, J.J. Thomson. However, scattering experiments showed significant deviations from the results predicted by the Thomson cross section. Further scattering experiments agreed perfectly with the predictions of the Klein–Nishina formula. | 7 | Physical Chemistry |
Although the exact route of vanillin biosynthesis in V. planifolia is currently unknown, several pathways are proposed for its biosynthesis. Vanillin biosynthesis is generally agreed to be part of the phenylpropanoid pathway starting with -phenylalanine, which is deaminated by phenylalanine ammonia lyase (PAL) to form t-cinnamic acid. The para position of the ring is then hydroxylated by the cytochrome P450 enzyme cinnamate 4-hydroxylase (C4H/P450) to create p-coumaric acid. Then, in the proposed ferulate pathway, 4-hydroxycinnamoyl-CoA ligase (4CL) attaches p-coumaric acid to coenzyme A (CoA) to create p-coumaroyl CoA. Hydroxycinnamoyl transferase (HCT) then converts p-coumaroyl CoA to 4-coumaroyl shikimate/quinate. This subsequently undergoes oxidation by the P450 enzyme coumaroyl ester 3’-hydroxylase (C3’H/P450) to give caffeoyl shikimate/quinate. HCT then exchanges the shikimate/quinate for CoA to create caffeoyl CoA, and 4CL removes CoA to afford caffeic acid. Caffeic acid then undergoes methylation by caffeic acid O-methyltransferase (COMT) to give ferulic acid. Finally, vanillin synthase hydratase/lyase (vp/VAN) catalyzes hydration of the double bond in ferulic acid followed by a retro-aldol elimination to afford vanillin. Vanillin can also be produced from vanilla glycoside with the additional final step of deglycosylation. In the past p-hydroxybenzaldehyde was speculated to be a precursor for vanillin biosynthesis. However, a 2014 study using radiolabelled precursor indicated that p-hydroxybenzaldehyde is not used to synthesise vanillin or vanillin glucoside in the vanilla orchids. | 0 | Organic Chemistry |
Serum ferritin levels are measured in medical laboratories as part of the iron studies workup for iron-deficiency anemia. They are measured in nanograms per milliliter (ng/mL) or micrograms per liter (μg/L); the two units are equivalent.
The ferritin levels measured usually have a direct correlation with the total amount of iron stored in the body. However, ferritin levels may be artificially high in cases of anemia of chronic disease, where ferritin is elevated in its capacity as an inflammatory acute phase protein and not as a marker for iron overload. | 1 | Biochemistry |
In the future, radioligand therapy may expand to include more α-emitter based treatments. Currently, β radioligand therapies are more commonly used in oncology. Clinical trials of α-emitters are underway due to their higher potency and ability to induce double-strand DNA breaks. There are multiple Actinium-225 based PSMA studies that will be launched in 2024. If these prove successful, there is potential for further studies and clinical trials to be done using α-emitters. Additionally, there is potential for the future use of radioligand therapy in patients with malignant brain tumors. Finally, there have been recent developments in diagnostic tracers using radioligands, as well as with radioligand-based imaging techniques and in the field of theranostics. | 1 | Biochemistry |
George W. Corner and Willard M. Allen discovered the hormonal action of progesterone in 1929. By 1931–1932, nearly pure crystalline material of high progestational activity had been isolated from the corpus luteum of animals, and by 1934, pure crystalline progesterone had been refined and obtained and the chemical structure of progesterone was determined. This was achieved by Adolf Butenandt at the Chemisches Institut of Technical University in Danzig, who extracted this new compound from several thousand liters of urine.
Chemical synthesis of progesterone from stigmasterol and pregnanediol was accomplished later that year. Up to this point, progesterone, known generically as corpus luteum hormone, had been being referred to by several groups by different names, including corporin, lutein, luteosterone, and progestin. In 1935, at the time of the Second International Conference on the Standardization of Sex Hormones in London, England, a compromise was made between the groups and the name progesterone (progestational steroidal ketone) was created. | 0 | Organic Chemistry |
Z-HIT is a special case of the Hilbert transform and through restriction by the Kramers–Kronig relations it can be derived for one-Port-systems. The frequency-dependent relationship between impedance and phase angle can be observed in the Bode plot of an impedance spectrum. Equation (1) is obtained as a general solution of the correlation between impedance modulus and phase shift.
Equation (1) indicates that the logarithm of the impedance () at a specific frequency can be calculated up to a constant value of (), if the phase shift is integrated up to the frequency point of interest , while the starting value of the integral can be freely chosen. As an additional contribution to the calculation of , the odd-numbered derivatives of the phase shift at the point have to be added, weighted with the factors .
The factors can be calculated according to equation (2), whereat represents the Riemann ζ-function.
The practically applied Z-HIT approximation is obtained from equation (1) by limitation to the first derivative of the phase shift neglecting higher derivatives (equation (3)), where C represents a constant.
The free choice of the integration boundaries in the ZHIT algorithm is a fundamental difference concerning the Kramers-Kronig relations; in ZHIT the integration boundaries are
and .
The greatest advantage of the ZHIT results from the fact, that both integration boundaries can be chosen within the measured spectrum, and thus does not require extrapolation to frequencies 0 and , as with the Kramers-Kronig relations. | 7 | Physical Chemistry |
There are a number of types of mechanical screening equipment that cause segregation. These types are based on the motion of the machine through its motor drive.
*Circle-throw vibrating equipment - This type of equipment has an eccentric shaft that causes the frame of the shaker to lurch at a given angle. This lurching action literally throws the material forward and up. As the machine returns to its base state the material falls by gravity to physically lower level. This type of screening is used also in mining operations for large material with sizes that range from six inches to +20 mesh.
*High frequency vibrating equipment - This type of equipment drives the screen cloth only. Unlike above the frame of the equipment is fixed and only the screen vibrates. However, this equipment is similar to the above such that it still throws material off of it and allows the particles to cascade down the screen cloth. These screens are for sizes smaller than 1/8 of an inch to +150 mesh.
*Gyratory equipment - This type of equipment differs from the above two such that the machine gyrates in a circular motion at a near level plane at low angles. The drive is an eccentric gear box or eccentric weights.
*Trommel screens - Does not require vibration. Instead, material is fed into a horizontal rotating drum with screen panels around the diameter of the drum. | 8 | Metallurgy |
Intravenous dexmedetomidine exhibits linear pharmacokinetics with a rapid distribution half-life of approximately 6 minutes in healthy volunteers, and a longer and more variable distribution half-life in ICU patients. The terminal elimination half-life of intravenous dexmedetomidine ranged 2.1 to 3.1 hours in healthy adults and 2.2 to 3.7 hours in ICU patients. Plasma protein binding of dexmedetomidine is about 94% (mostly albumin).
Dexmedetomidine is metabolized by the liver, largely by glucuronidation (34%) as well as by oxidation via CYP2A6 and other Cytochrome P450 enzymes. As such, it should be used with caution in people with liver disease.
The majority of metabolized dexmedetomidine is excreted in the urine (~95%).
It can be absorbed sublingually. | 4 | Stereochemistry |
Unhindered settling is a process that removes the discrete particles in a very low concentration without interference from nearby particles. In general, if the concentration of the solutions is lower than 500 mg/L total suspended solids, sedimentation will be considered discrete. Concentrations of raceway effluent total suspended solids (TSS) in the west are usually less than 5 mg/L net. TSS concentrations of off-line settling basin effluent are less than 100 mg/L net. The particles keep their size and shape during discrete settling, with an independent velocity. With such low concentrations of suspended particles, the probability of particle collisions is very low and consequently the rate of flocculation is small enough to be neglected for most calculations. Thus the surface area of the settling basin becomes the main factor of sedimentation rate. All continuous flow settling basins are divided into four parts: inlet zone, settling zone, sludge zone and outlet zone (Figure 2).
In the inlet zone, flow is established in a same forward direction. Sedimentation occurs in the settling zone as the water flow towards to outlet zone. The clarified liquid is then flow out from outlet zone.
Sludge zone: settled will be collected here and usually we assume that it is removed from water flow once the particles arrives the sludge zone.
In an ideal rectangular sedimentation tank, in the settling zone, the critical particle enters at the top of the settling zone, and the settle velocity would be the smallest value to reach the sludge zone, and at the end of outlet zone, the velocity component of this critical particle are the settling velocity in vertical direction (v) and in horizontal direction (v).
From Figure 1, the time needed for the particle to settle;
:t =H/v=L/v (3)
Since the surface area of the tank is WL, and v = Q/WL, v = Q/WH, where Q is the flow rate and W, L, H is the width, length, depth of the tank.
According to Eq. 1, this also is a basic factor that can control the sedimentation tank performance which called overflow rate.
Eq. 2 also shows that the depth of sedimentation tank is independent to the sedimentation efficiency, only if the forward velocity is low enough to make sure the settled mass would not suspended again from the tank floor. | 3 | Analytical Chemistry |
Biophysical organic chemistry is a term used when attempting to describe intimate details of molecular recognition by bioorganic chemistry.
Natural product chemistry is the process of Identifying compounds found in nature to determine their properties. Compound discoveries have and often lead to medicinal uses, development of herbicides and insecticides. | 1 | Biochemistry |
AR STAT2 deficiency was first time observed in 2 siblings. After routine immunization with measles-mump-rubella, one sibling developed disseminated vaccine-strain measles (MMR) but recovered and second sibling died in infancy from a viral infection due to primary immunodeficiency disorder. Later, the results showed that siblings were homozygous for absent expression of gene for STAT2. Patients with AR STAT2 deficiency have mutations which bring substitutions at important splice sites what leads to defected splicing and premature stop codons leading to a loss of expression of an interferon-stimulated gene. The typical clinical phenotype is disseminated infection after immunization with the live attenuated MMR vaccine. Some patients had also an onset of severe disease in infancy like infection with RSV, norovirus, coxsackievirus, adenovirus or enterovirus. One of the patients had CNS disease after the primary infection with EBV. EBV suppression was delayed in peripheral blood and cerebrospinal fluid as type I interferon signalling plays important role in the initial immune response against EBV. During next 3 years, PCR test showed persistent EBV presence in blood as well as in cerebrospinal fluid despite anti-EBV IgG. CMV and VZV infections were severe as well in few patients. The virus infection was treated by high-dose of intravenous immunoglobulin (IVIG) after which patients recovered and became afebrile within 24 hours. IVIG has anti-inflammatory effect and suggests that the passive immunization could help to control the ongoing viral infections. Therefore, the monthly IgG therapy could be beneficial for patients with STAT2 deficiency during childhood, until their adaptive immune system has sufficiently developed. From the age 5 years, the frequency and severity of viral infections decreased and the age of 10 years the patients were mostly off all medication. In general, the patients with STAT2 deficiency are relatively healthy with no specific defects in their adaptive immunity or developmental abnormalities. These findings show that type I IFN signaling trough ISGF3 is not essential for host defense against the majority of common childhood viral pathogens. Despite a profoundly defective innate IFN response and evident susceptibility to some viral infections, STAT2-deficient individuals can live a relatively healthy life.
It was also reported a homozygous STAT2 missense mutation (R148W/Q) which results to a STAT2 gain of function underlying fatal early-onset autoinflammation in three patients. This mutation leads to a persistent type I IFN response due to defective binding of the mutated STAT2 to ubiquitin specific peptidase 1 (USP18) which is an essential in the negative autofeedback loop where USP18 sterically hinders the binding of JAK1 to IFNAR1. Therefore complete AR STAT2 deficiency usually causes disseminated LAV infection and recurrent natural viral infections. Penetrance is not complete for several viral infections and for complicated live measles vaccine disease. These observation suggest that the phenotype of AR STAT2 deficiency could range from asymptomatic (the healthy adult) to fatal (childhood death from a crushing viral disease). The phenotype is less severe than human complete AR STAT1 deficiency but more severe than IFNAR1 or IFNAR2 deficiency. The human phenotype is less severe than in mice. | 1 | Biochemistry |
Organoniobium chemistry is the chemistry of compounds containing niobium-carbon (Nb-C) bonds. Compared to the other group 5 transition metal organometallics, the chemistry of organoniobium compounds most closely resembles that of organotantalum compounds. Organoniobium compounds of oxidation states +5, +4, +3, +2, +1, 0, -1, and -3 have been prepared, with the +5 oxidation state being the most common. | 0 | Organic Chemistry |
These properties of the genetic code make it more fault-tolerant for point mutations. For example, in theory, fourfold degenerate codons can tolerate any point mutation at the third position, although codon usage bias restricts this in practice in many organisms; twofold degenerate codons can withstand silence mutation rather than Missense or Nonsense point mutations at the third position. Since transition mutations (purine to purine or pyrimidine to pyrimidine mutations) are more likely than transversion (purine to pyrimidine or vice versa) mutations, the equivalence of purines or that of pyrimidines at twofold degenerate sites adds a further fault-tolerance.
A practical consequence of redundancy is that some errors in the genetic code cause only a synonymous mutation, or an error that would not affect the protein because the hydrophilicity or hydrophobicity is maintained by equivalent substitution of amino acids (conservative mutation). For example, a codon of NUN (where N = any nucleotide) tends to code for hydrophobic amino acids, NCN yields amino acid residues that are small in size and moderate in hydropathy, and NAN encodes average size hydrophilic residues. These tendencies may result from the shared ancestry of the aminoacyl tRNA synthetases related to these codons.
These variable codes for amino acids are allowed because of modified bases in the first base of the anticodon of the tRNA, and the base-pair formed is called a wobble base pair. The modified bases include inosine and the Non-Watson-Crick U-G basepair. | 1 | Biochemistry |
The split gene theory implies that structural features of split genes predicted from computer-simulated random sequences occur in eukaryotic split genes. This is borne out in most known split genes. The sequences exhibit a nearly perfect negative exponential distribution of ORF lengths. With rare exceptions, eukaryotic gene exons fall within the predicted 600 base maximum.
The theory correctly predicts that exons are delimited by stop codons, especially at the 3’ ends of exons. Actually they are precisely delimited more strongly at the 3’ ends of exons and less strongly at the 5’ ends in most known genes, as predicted. These stop codons are the most important functional parts of both splice junctions. The theory thus provides an explanation for the “conserved” splice junctions at the ends of exons and for the loss of these stop codons along with introns when they are spliced out. The theory correctly predicts that splice junctions are randomly distributed in eukaryotic DNA sequences. The theory correctly predicts that splice junctions present in transfer RNA genes and ribosomal RNA genes, do not contain stop codons. The lariat signal, another sequence involved in the splicing process, also contains stop codons.
The theory correctly predicts that introns are non-coding and that they are mostly non-functional. Except for some intron sequences including the donor and acceptor splice signal sequences and branch point sequences, and possibly the intron splice enhancers that occur at the ends of introns, which aid in the removal of introns, the vast majority of introns are devoid of any functions. The theory does not exclude rare sequences within introns that could be used by the genome and the cell, especially because introns are so long.
Thus, the theory's predictions are precisely corroborated by the major elements in modern eukaryotic genomes.
Comparative analysis of the modern genome data from several living organisms found that the characteristics of split genes trace back to the earliest organisms. These organisms could have contained the split genes and complex proteins that occur in today's living organisms.
Studies employing maximum likelihood analysis found that the earliest eukaryotic organisms contained the same genes as modern organisms with yet a higher intron density. Comparative genomics of many organisms including basal eukaryotes (considered to be primitive eukaryotic organisms such as Amoeboflagellata, Diplomonadida, and Parabasalia) showed that intron-rich split genes accompanied and spliceosome from modern organisms were present in their earliest forebears, and that the earliest organisms came with all the eukaryotic cellular components. | 1 | Biochemistry |
Isozymes (and allozymes) are variants of the same enzyme. Unless they are identical in their biochemical properties, for example their substrates and enzyme kinetics, they may be distinguished by a biochemical assay. However, such differences are usually subtle, particularly between allozymes which are often neutral variants. This subtlety is to be expected, because two enzymes that differ significantly in their function are unlikely to have been identified as isozymes.
While isozymes may be almost identical in function, they may differ in other ways. In particular, amino acid substitutions that change the electric charge of the enzyme are simple to identify by gel electrophoresis, and this forms the basis for the use of isozymes as molecular markers. To identify isozymes, a crude protein extract is made by grinding animal or plant tissue with an extraction buffer, and the components of extract are separated according to their charge by gel electrophoresis. Historically, this has usually been done using gels made from potato starch, but acrylamide gels provide better resolution.
All the proteins from the tissue are present in the gel, so that individual enzymes must be identified using an assay that links their function to a staining reaction. For example, detection can be based on the localised precipitation of soluble indicator dyes such as tetrazolium salts which become insoluble when they are reduced by cofactors such as NAD or NADP, which generated in zones of enzyme activity. This assay method requires that the enzymes are still functional after separation (native gel electrophoresis), and provides the greatest challenge to using isozymes as a laboratory technique.
Isoenzymes differ in kinetics (they have different K and V values). | 1 | Biochemistry |
Perhaps the simplest definition of electronegativity is that of Leland C. Allen, who has proposed that it is related to the average energy of the valence electrons in a free atom,
where ε are the one-electron energies of s- and p-electrons in the free atom and n are the number of s- and p-electrons in the valence shell. It is usual to apply a scaling factor, 1.75×10 for energies expressed in kilojoules per mole or 0.169 for energies measured in electronvolts, to give values that are numerically similar to Pauling electronegativities.
The one-electron energies can be determined directly from spectroscopic data, and so electronegativities calculated by this method are sometimes referred to as spectroscopic electronegativities. The necessary data are available for almost all elements, and this method allows the estimation of electronegativities for elements that cannot be treated by the other methods, e.g. francium, which has an Allen electronegativity of 0.67. However, it is not clear what should be considered to be valence electrons for the d- and f-block elements, which leads to an ambiguity for their electronegativities calculated by the Allen method.
On this scale, neon has the highest electronegativity of all elements, followed by fluorine, helium, and oxygen. | 3 | Analytical Chemistry |
Numerous reports have been published indicating that the glutamate/GABA–glutamine cycle is compromised in a variety of neurological disorders and conditions. Biopsies of sclerotic hippocampus tissue from human subjects with epilepsy have shown decreased glutamate–glutamine cycling. Another pathology in which the glutamate/GABA–glutamine cycle might be compromised is Alzheimers disease; NMR spectroscopy showed decreased glutamate neurotransmission activity and TCA cycling rate in patients with Alzheimers disease. Hyperammonemia in the brain, typically occurring as a secondary complication of primary liver disease and known as hepatic encephalopathy, is a condition that affects glutamate/GABA–glutamine cycling in the brain. Current research into autism also indicates potential roles for glutamate, glutamine, and/or GABA in autistic spectrum disorders. | 1 | Biochemistry |
SIR4 is involved in scaffolding the assembly of silenced chromatin. It binds to DNA with high affinity, but low specificity. It is most stable when co-expressed with SIR2, but neither SIR2 nor SIR3 are required for it to operate at the telomeres. Each half of the SIR4 protein has distinct responsibilities in heterochromatin spreading. SIR4s N-terminus is required for telomeric silencing, but not for homothallic mating-type (HM) silencing. Conversely, its C-terminus supports HM but not telomeric repression. The N-terminus is positively charged and can be recruited to the telomeric repression site by SIR1 and YKU80. The C-terminus contains the coiled-coil region, which interacts with SIR3 in the heterotrimeric SIR complex and can also interact with RAP1 and YKU70 for recruitment to the telomeric region of the chromosome. The C-terminus also contains the SIR2-interacting domain (SID), where SIR4 can bind to the extended N-terminus of SIR2. SIR2 can catalyze reactions without being bound to SIR4, but SIR2s catalytic activity is enhanced when interacting with SIR4. | 1 | Biochemistry |
H can interfere with the removal of methane from the atmosphere, a greenhouse gas. Typically, atmospheric CH is oxidized by hydroxyl radicals (OH), but H can also react with OH to reduce it to HO.
# CH + OH → CH + HO
# H + OH → H + HO | 1 | Biochemistry |
Monocytes, activated dendritic cells (DC) and macrophages stimulate the accumulation of IL-23 after exposure to molecules of Gram-positive/negative bacteria or viruses. Receptor for IL-23 contains IL12β and IL23R subunits, which upon binding of IL-23 promotes the phosphorylation STAT4. The presence of IL12β enables similar, although weaker downstream activity as compared to IL-12. During chronic inflammation, IL-23/STAT4 signalling pathway is involved in the induction of differentiation and expansion of Th17 pro-inflammatory T helper cells.
Additionally, other cytokines like IL2, IL 27, IL35, IL18 and IL21 are known to activate STAT4. | 1 | Biochemistry |
The formose reaction is of importance to the question of the origin of life, as it leads from simple formaldehyde to complex sugars like ribose, a building block of RNA. In one experiment simulating early Earth conditions, pentoses formed from mixtures of formaldehyde, glyceraldehyde, and borate minerals such as colemanite (CaBO5HO) or kernite (NaBO). However, issues remain with both the thermodynamic and kinetic feasibility of binding pre-made sugars to a pre-made nucleobase, as well as a method to selectively employ ribose from the mixture. Both formaldehyde and glycolaldehyde have been observed spectroscopically in outer space, making the formose reaction of particular interest to the field of astrobiology. | 0 | Organic Chemistry |
The main benefit of electrodialysis is the high recovery, especially in the water recovery. Another advantage is the fact that not high pressure is applied which implies that the effect fouling is not significant and consequently no chemicals are required to fight against them. Moreover, the fouling layer is not compact which leads to a higher recovery and to a long membrane life. It is also important that the treatments are for concentrations higher than 70,000 ppm eliminating the concentration limit. Finally, the energy required to operate is low due to the non-phase change. In fact, it is lower in comparison with the needed in the multi effect distillation (MED) and mechanical vapour compression (MVC) processes.
The main drawback of electrodialysis is the current density limit, the process must be operated at a lower current density than the maximum allowed. The fact is that at certain voltage applied the diffusion of ions through the membrane are not linear leading to water dissociation, which would reduce the efficiency of the operation. Another aspect to take into account is that although low energy is required to operate, the higher the salt feed concentration is, the higher the energy needed will be. Finally, in the case of some products, it must be considered that electrodialysis does not remove microorganisms and organic contaminants, therefore a post-treatment is necessary. | 1 | Biochemistry |
In-Methylcyclophanes are organic compounds and members of a larger family of cyclophanes. These compounds are used to study how chemical bonds in molecules adapt to strain. In-methylcyclophanes in particular have a methyl group in proximity to a benzene ring. This is only possible when both methyl group and ring are attached to the same rigid scaffold. In one In-methylcyclophane molecule this is accomplished with a triptycene frame.
This particular compound is synthesed starting from anthracene with a methyl group added to each arene ring (1,8,9-trimethylanthracene). A triptycene compound is formed from a reaction of this anthracene compound with an aryne in a Diels-Alder reaction in isoamyl nitrite. In this synthesis the precursor to the reactive aryne is 2-amino-6-methylbenzoic acid. Next the methyl substituents are functionalized with bromine groups by the photochemical reaction with N-bromosuccinimide or NBS. The final cyclophane is put together by reaction with 1,3,5-tris(mercaptomethyl)benzene with nucleophilic sulfhydryl groups and electrophilic alkyl bromides in a nucleophilic aliphatic Substitution.
X-ray crystallography of the tri-sulfone derivative of this cyclophane shows that the methyl group located 289.6 picometers from the center of the benzene ring. The carbon-to-carbon bond linking the methyl group to the triptycene frame is actually shortened and measures 147.5 to 149.5 pm. The similar bond in the triptycene precursor is 154 pm. Proton NMR analysis shows a chemical shift of 2.52 ppm for the methyl protons compared to that of 3.16 to 3.85 in the anthracene compound. The reason for this anomaly is that the methyl protons are in line with the aromatic ring current of the benzene ring and are therefore severely shielded, an effect similar to the nucleus-independent chemical shift method of analyzing aromaticity. | 0 | Organic Chemistry |
Outdoors, DLI values vary depending on latitude, time of year, and cloud cover. Occasionally, values over 70 mol·m·d can be reached at bright summer days at some locations. Monthly-averaged DLI values range between 20-40 in the tropics, 15-60 at 30° latitude and 1-40 at 60° latitude. For plants growing in the shade of taller plants, such as on the forest floor, DLI may be less than 1 mol·m·d, even in summer.
In greenhouses, 30-70% of the outside light will be absorbed or reflected by the glass and other greenhouse structures. DLI levels in greenhouses therefore rarely exceed 30 mol·m·d. In growth chambers, values between 10 and 30 mol·m·d are most common. New light modules are now available for the horticultural industry, where light intensity of the lamps used in glasshouses is regulated such that plants receive a set value of DLI, independent of outside weather conditions. | 5 | Photochemistry |
Bioceramics properties of being anticorrosive, biocompatible, and aesthetic make them quite suitable for medical usage. Zirconia ceramic has bioinertness and noncytotoxicity. Carbon is another alternative with similar mechanical properties to bone, and it also features blood compatibility, no tissue reaction, and non-toxicity to cells. Bioinert ceramics do not exhibit bonding with the bone, known as osseointegration. However, bioactivity of bioinert ceramics can be achieved by forming composites with bioactive ceramics. Bioactive ceramics, including bioglasses must be non-toxic, and form a bond with bone. In bone repair applications, i.e. scaffolds for bone regeneration, the solubility of bioceramics is an important parameter, and the slow dissolution rate of most bioceramics relative to bone growth rates remains a challenge in their remedial usage. Unsurprisingly, much focus is placed on improving dissolution characteristics of bioceramics while maintaining or improving their mechanical properties. Glass ceramics elicit osteoinductive properties, with higher dissolution rates relative to crystalline materials, while crystalline calcium phosphate ceramics also exhibit non-toxicity to tissues and bioresorption. The ceramic particulate reinforcement has led to the choice of more materials for implant applications that include ceramic/ceramic, ceramic/polymer, and ceramic/metal composites. Among these composites ceramic/polymer composites have been found to release toxic elements into the surrounding tissues. Metals face corrosion related problems, and ceramic coatings on metallic implants degrade over time during lengthy applications. Ceramic/ceramic composites enjoy superiority due to similarity to bone minerals, exhibiting biocompatibility and a readiness to be shaped. The biological activity of bioceramics has to be considered under various in vitro and in vivo' studies. Performance needs must be considered in accordance with the particular site of implantation. | 7 | Physical Chemistry |
REMS scans on femur and spine last 40 and 80 seconds, respectively, allowing the acquisition of several thousands of ultrasound signals related to the skeletal site under examination. The patented algorithm (see for more details) automatically processes these signals on the basis of their spectral features; each signal can be classified as reliable and included in the pipeline for the computation of the diagnostic parameters or, alternatively, classified as unreliable and discarded. During the analysis phase, the acquired spectra are compared to the spectral models stored in the database; afterwards, the values obtained by each comparison are averaged, leading to a precise and repeatable estimation of the diagnostic parameters of interest. | 7 | Physical Chemistry |
Although less commonly used, activation energy also applies to nuclear reactions and various other physical phenomena. | 7 | Physical Chemistry |
Dry basis is an expression of a calculation in chemistry, chemical engineering and related subjects, in which the presence of water (HO) (and/or other solvents) is neglected for the purposes of the calculation. Water (and/or other solvents) is neglected because addition and removal of water (and/or other solvents) are common processing steps, and also happen naturally through evaporation and condensation; it is frequently useful to express compositions on a dry basis to remove these effects.
In food science and pharmacy, dry basis also refers to a ratio of the weight of water to the weight of a completely dry material, as opposed to the wet basis ratio of water to a material under normal conditions that contains a measurable amount of moisture. | 3 | Analytical Chemistry |
According to Ohta (1994, pp. 90–91) the ranking and scientific analysis of energy quality was first proposed in 1851 by William Thomson under the concept of "availability". This concept was continued in Germany by Z. Rant, who developed it under the title, "die Exergie" (the exergy). It was later continued and standardised in Japan. Exergy analysis now forms a common part of many industrial and ecological energy analyses. For example, I.Dincer and Y.A. Cengel (2001, p. 132) state that energy forms of different qualities are now commonly dealt with in steam power engineering industry. Here the "quality index" is the relation of exergy to the energy content (Ibid.). However energy engineers were aware that the notion of heat quality involved the notion of value – for example A. Thumann wrote, "The essential quality of heat is not the amount but rather its value" (1984, p. 113) – which brings into play the question of teleology and wider, or ecological-scale goal functions. In an ecological context S.E. Jorgensen and G.Bendoricchio say that exergy is used as a goal function in ecological models, and expresses energy "with a built-in measure of quality like energy" (2001, p. 392). | 7 | Physical Chemistry |
Volatility is an important consideration when crafting perfumes. Humans detect odors when aromatic vapors come in contact with receptors in the nose. Ingredients that vaporize quickly after being applied will produce fragrant vapors for a short time before the oils evaporate. Slow-evaporating ingredients can stay on the skin for weeks or even months, but may not produce enough vapors to produce a strong aroma. To prevent these problems, perfume designers carefully consider the volatility of essential oils and other ingredients in their perfumes. Appropriate evaporation rates are achieved by modifying the amount of highly volatile and non-volatile ingredients used. | 7 | Physical Chemistry |
In atomic physics, exoelectron emission (EE) is a weak electron emission, appearing only from pretreated (irradiated, deformed etc.) objects. The pretreatment ("excitation") turns the objects into an unequilibrial state. EE accompanies the relaxation of these unequilibria. The relaxation can be stimulated e.g. by slight heating or longwave illumination, not causing emission from untreated samples. Accordingly, thermo- and photostimulated EE (TSEE, PSEE) are distinguished. Thus, EE is an electron emission analogue of such optical phenomena as phosphorescence, thermo- and photostimulated luminescence. | 7 | Physical Chemistry |
In ultraviolet (UV) methods there is no visible color change but the principle is exactly the same, i.e. the measurement of a change in the absorbance of the solution. UV methods usually measure the difference in absorbance at 340 nm wavelength between nicotinamide adenine dinucleotide (NAD) and its reduced form (NADH). | 3 | Analytical Chemistry |
Hexaferrum and epsilon iron (ε-Fe) are synonyms for the hexagonal close-packed (HCP) phase of iron that is stable only at extremely high pressure.
A 1964 study at the University of Rochester mixed 99.8% pure α-iron powder with sodium chloride, and pressed a 0.5-mm diameter pellet between the flat faces of two diamond anvils. The deformation of the NaCl lattice, as measured by x-ray diffraction (XRD), served as a pressure indicator. At a pressure of 13 GPa and room temperature, the body-centered cubic (BCC) ferrite powder transformed to the HCP phase in Figure 1. When the pressure was lowered, ε-Fe transformed back to ferrite (α-Fe) rapidly. A specific volume change of −0.20 cm/mole ± 0.03 was measured. Hexaferrum, much like austenite, is more dense than ferrite at the phase boundary. A shock wave experiment confirmed the diamond anvil results. Epsilon was chosen for the new phase to correspond with the HCP form of cobalt.
The triple point between the alpha, gamma and epsilon phases in the unary phase diagram of iron has been calculated as T = 770 K and P = 11 GPa, although it was determined at a lower temperature of T = 750 K (477 °C) in Figure 1. The Pearson symbol for hexaferrum is hP2 and its space group is P6/mmc.
Another study concerning the ferrite-hexaferrum transformation metallographically determined that it is a martensitic rather than equilibrium transformation.
While hexaferrum is purely academic in metallurgical engineering, it may have significance in geology. The pressure and temperature of Earths iron core are on the order of 150–350 GPa and 3000 ± 1000 °C. An extrapolation of the austenite-hexaferrum phase boundary in Figure 1 suggests hexaferrum could be stable or metastable in Earths core. For this reason, many experimental studies have investigated the properties of HCP iron under extreme pressures and temperatures. Figure 2 shows the compressional behaviour of ε-iron at room temperature up to a pressure as would be encountered halfway through the outer core of the Earth; there are no points at pressures lower than approximately 6 GPa, because this allotrope is not thermodynamically stable at low pressures but will slowly transform into α-iron. | 8 | Metallurgy |
A nuclear localization signal (NLS) is a target peptide that directs proteins to the nucleus and is often a unit consisting of five basic, positively charged amino acids. The NLS normally is located anywhere on the peptide chain.
A nuclear export signal (NES) is a target peptide that directs proteins from the nucleus back to the cytosol. It often consists of several hydrophobic amino acids (often leucine) interspaced by 2-3 other amino acids.
Many proteins are known to constantly shuttle between the cytosol and nucleus and these contain both NESs and NLSs. | 1 | Biochemistry |
Electropositive metals such as sodium, potassium, magnesium, zinc, etc. can insert into alkyl halides, breaking the carbon-halide bond
( halide could be chlorine, bromine, iodine ) and forming a carbon-metal bond. This reaction happens via a SET mechanism ( single-electron-transfer mechanism ). If magnesium reacts with an alkyl halide, it forms a Grignard reagent, or if lithium reacts, an organolithium reagent is formed. Thus, this type of insertion reactions has important applications in chemical synthesis. | 0 | Organic Chemistry |
Medium-carbon steel has approximately 0.3–0.5% carbon content. It balances ductility and strength and has good wear resistance. It is used for large parts, forging and automotive components. | 8 | Metallurgy |
The main advantages for SRCD over lab-based cCD machines arise from the use of the synchrotron light emission as the source. A number of biologically interesting absorption bands are found in the region between ~170 nm and ~350 nm. For proteins these come from their secondary and tertiary structures, while structural bands for nucleic acids, (DNA and RNA), and saccharides are also located in this region. However, for cCD machines the photon flux from the source reduces by around two orders of magnitude in the wavelength range from 250 nm down to 180 nm, exactly in the region of most significance for these biological molecules. By contrast, typically, the photon flux for an SRCD beamline in this region is at least three orders of magnitude higher than a cCD machine, retaining that level down to ~150 nm. The increased flux means the measured signals from the sample will be increased relative to the background noise, so there is a significant improvement in the signal-to-noise ratio of the sample. This will improve the accuracy of the data recorded meaning interpretation can be undertaken with more confidence in the results. A further advantage of the increased flux is that the concentration of the sample can be reduced while still retaining a significant increase in signal strength, so samples that are difficult to produce in quantity have more chance of producing usable CD data from SRCD rather than a cCD machine. Increasing the lower wavelength range provides more spectral data for analysis which means there is more information content available in that data, meaning that more parameters, here secondary structure features in the protein structure, can be accurately determined. | 7 | Physical Chemistry |
When the modeling phase is complete, selected systems are validated using a professional third party to provide oversight and to determine how closely the model is able to predict the reality of system performance. System validation uses non-pathogenic surrogates such as MS 2 phage or Bacillus subtilis to determine the Reduction Equivalent Dose within an envelope of flow and transmittance.
To validate effectiveness in drinking water systems, the method described in the EPA UV guidance manual is typically used by US water utilities, whilst Europe has adopted Germany's DVGW 294 standard. For wastewater systems, the NWRI/AwwaRF Ultraviolet Disinfection Guidelines for Drinking Water and Water Reuse protocols are typically used, especially in wastewater reuse applications. | 5 | Photochemistry |
Two-component signal transduction systems enable bacteria to sense, respond, and adapt to a wide range of environments, stressors, and growth conditions. These pathways have been adapted to respond to a wide variety of stimuli, including nutrients, cellular redox state, changes in osmolarity, quorum signals, antibiotics, temperature, chemoattractants, pH and more. The average number of two-component systems in a bacterial genome has been estimated as around 30, or about 1–2% of a prokaryotes genome. A few bacteria have none at all – typically endosymbionts and pathogens – and others contain over 200. All such systems must be closely regulated to prevent cross-talk, which is rare in vivo'.
In Escherichia coli, the osmoregulatory EnvZ/OmpR two-component system controls the differential expression of the outer membrane porin proteins OmpF and OmpC. The KdpD sensor kinase proteins regulate the kdpFABC operon responsible for potassium transport in bacteria including E. coli and Clostridium acetobutylicum. The N-terminal domain of this protein forms part of the cytoplasmic region of the protein, which may be the sensor domain responsible for sensing turgor pressure. | 1 | Biochemistry |
The microprocessor complex is a protein complex involved in the early stages of processing microRNA (miRNA) and RNA interference (RNAi) in animal cells. The complex is minimally composed of the ribonuclease enzyme Drosha and the dimeric RNA-binding protein DGCR8 (also known as Pasha in non-human animals), and cleaves primary miRNA substrates to pre-miRNA in the cell nucleus. Microprocessor is also the smaller of the two multi-protein complexes that contain human Drosha. | 1 | Biochemistry |
The toxicity of metal carbonyls is due to toxicity of carbon monoxide, the metal, and because of the volatility and instability of the complexes, any inherent toxicity of the metal is generally made much more severe due to ease of exposure. Exposure occurs by inhalation, or for liquid metal carbonyls by ingestion or due to the good fat solubility by skin resorption. Most clinical experience were gained from toxicological poisoning with nickel tetracarbonyl and iron pentacarbonyl due to their use in industry. Nickel tetracarbonyl is considered as one of the strongest inhalation poisons.
Inhalation of nickel tetracarbonyl causes acute non-specific symptoms similar to a carbon monoxide poisoning, such as nausea, cough, headache, fever, and dizziness. After some time, severe pulmonary symptoms such as cough, tachycardia, and cyanosis, or problems in the gastrointestinal tract occur. In addition to pathological alterations of the lung, such as by metalation of the alveoli, damages are observed in the brain, liver, kidneys, adrenal glands, and spleen. A metal carbonyl poisoning often necessitates a lengthy recovery.
Chronic exposure by inhalation of low concentrations of nickel tetracarbonyl can cause neurological symptoms such as insomnia, headaches, dizziness and memory loss. Nickel tetracarbonyl is considered carcinogenic, but it can take 20 to 30 years from the start of exposure to the clinical manifestation of cancer. | 0 | Organic Chemistry |
Low levels of vitamin D in pregnancy are associated with gestational diabetes, pre-eclampsia, and small (for gestational age) infants. Although taking vitamin D supplements during pregnancy raises blood levels of vitamin D in the mother at term, the full extent of benefits for the mother or baby is unclear. Pregnant women who take an adequate amount of vitamin D during gestation may experience a lower risk of pre-eclampsia and positive immune effects. Vitamin D supplementation is also likely to reduce the risk of gestational diabetes, undersized babies and of their poor rate of growth. Pregnant women often do not take the recommended amount of vitamin D. | 1 | Biochemistry |
Supramolecular equivalent of step-growth mechanism is commonly known as isodesmic or equal-K model (K represents the total binding interaction between two neighboring monomers). In isodesmic supramolecular polymerization, no critical temperature or concentration of monomers is required for the polymerization to occur and the association constant between polymer and monomer is independent of the polymer chain length. Instead, the length of the supramolecular polymer chains rises as the concentration of monomers in the solution increases, or as the temperature decreases. In conventional polycondensation, the association constant is usually large that leads to a high degree of polymerization; however, a byproduct is observed. In isodesmic supramolecular polymerization, due to non-covalent bonding, the association between monomeric units is weak, and the degree of polymerization strongly depends on the strength of interaction, i.e. multivalent interaction between monomeric units. For instance, supramolecular polymers consisting of bifunctional monomers having single hydrogen bonding donor/acceptor at their termini usually end up with low degree of polymerization, however those with quadrupole hydrogen bonding, as in the case of ureidopyrimidinone motifs, result in a high degree of polymerization. In ureidopyrimidinone-based supramolecular polymer, the experimentally observed molecular weight at semi-dilute concentrations is in the order of 10 Dalton and the molecular weight of the polymer can be controlled by adding mono-functional chain-cappers. | 6 | Supramolecular Chemistry |
The amount of material available for assimilating into organismal cells controls the rate of metabolism at the cellular to lake ecosystem level. In lakes, phosphorus and nitrogen are the most common limiting nutrients of primary production and ecosystem respiration. Foundational work on the positive relationship between phosphorus concentration and lake eutrophication resulted in legislation that limited the amount of phosphorus in laundry detergents, among other regulations. Although phosphorus is often used as a predictor of lake ecosystem productivity and excess phosphorus as an indicator of eutrophication, many studies show that metabolism is co-limited by phosphorus and nitrogen or nitrogen alone. The balance between phosphorus, nitrogen, and other nutrients, termed ecological stoichiometry, can dictate rates of organismal growth and whole-lake metabolism through cellular requirements of these essential nutrients mediated by life-history traits. For example, fast-growing cladocerans have a much lower nitrogen to phosphorus ratio (N:P) than copepods, mostly due to the high amount of phosphorus-rich RNA in their cells used for rapid growth. Cladocerans residing in lakes with high N:P ratios relative to cladoceran body stoichiometry will be limited in growth and metabolism, having effects on whole-lake metabolism. Furthermore, cascading effects from food web manipulations can cause changes in productivity from changes to nutrient stoichiometry. For example, piscivore addition can reduce predation pressure on fast-growing, low N:P cladocerans which increase in population rapidly, retain phosphorus in their cells, and can cause a lake to become phosphorus limited, consequently reducing whole-lake primary productivity. | 1 | Biochemistry |
Also called Kharasch effect (named after Morris S. Kharasch), these reactions that do not involve a carbocation intermediate may react through other mechanisms that have regioselectivities not dictated by Markovnikov's rule, such as free radical addition. Such reactions are said to be anti-Markovnikov, since the halogen adds to the less substituted carbon, the opposite of a Markovnikov reaction.
The anti-Markovnikov rule can be illustrated using the addition of hydrogen bromide to isobutylene in the presence of benzoyl peroxide or hydrogen peroxide. The reaction of HBr with substituted alkenes was prototypical in the study of free-radical additions. Early chemists discovered that the reason for the variability in the ratio of Markovnikov to anti-Markovnikov reaction products was due to the unexpected presence of free radical ionizing substances such as peroxides. The explanation is that the O-O bond in peroxides is relatively weak. With the aid of light, heat, or sometimes even just acting on its own, the O-O bond can split to form 2 radicals. The radical groups can then interact with HBr to produce a Br radical, which then reacts with the double bond. Since the bromine atom is relatively large, it is more likely to encounter and react with the least substituted carbon since this interaction produces less static interactions between the carbon and the bromine radical. Furthermore, similar to a positive charged species, the radical species is most stable when the unpaired electron is in the more substituted position. The radical intermediate is stabilized by hyperconjugation. In the more substituted position, more carbon-hydrogen bonds are aligned with the radical's electron deficient molecular orbital. This means that there are greater hyperconjugation effects, so that position is more favorable. In this case, the terminal carbon is a reactant that produces a primary addition product instead of a secondary addition product.
A new method of anti-Markovnikov addition has been described by Hamilton and Nicewicz, who utilize aromatic molecules and light energy from a low-energy diode to turn the alkene into a cation radical.
Anti-Markovnikov behaviour extends to more chemical reactions than additions to alkenes. Anti-Markovnikov behaviour is observed in the hydration of phenylacetylene by auric catalysis, which gives acetophenone; although with a special ruthenium catalyst it provides the other regioisomer 2-phenylacetaldehyde:
Anti-Markovnikov behavior can also manifest itself in certain rearrangement reactions. In a titanium(IV) chloride-catalyzed formal nucleophilic substitution at enantiopure 1 in the scheme below, two products are formed – 2a and 2b Due to the two chiral centers in the target molecule, the carbon carrying chlorine and the carbon carrying the methyl and acetoxyethyl group, four different compounds are to be formed: 1R,2R- (drawn as 2b) 1R,2S- 1S,2R- (drawn as 2a) and 1S,2S- . Therefore, both of the depicted structures will exist in a D- and an L-form. :
This product distribution can be rationalized by assuming that loss of the hydroxy group in 1 gives the tertiary carbocation A, which rearranges to the seemingly less stable secondary carbocation B. Chlorine can approach this center from two faces leading to the observed mixture of isomers.
Another notable example of anti-Markovnikov addition is hydroboration. | 7 | Physical Chemistry |
Acetyl-CoA is formed into malonyl-CoA by acetyl-CoA carboxylase, at which point malonyl-CoA is destined to feed into the fatty acid synthesis pathway. Acetyl-CoA carboxylase is the point of regulation in saturated straight-chain fatty acid synthesis, and is subject to both phosphorylation and allosteric regulation. Regulation by phosphorylation occurs mostly in mammals, while allosteric regulation occurs in most organisms. Allosteric control occurs as feedback inhibition by palmitoyl-CoA and activation by citrate. When there are high levels of palmitoyl-CoA, the final product of saturated fatty acid synthesis, it allosterically inactivates acetyl-CoA carboxylase to prevent a build-up of fatty acids in cells. Citrate acts to activate acetyl-CoA carboxylase under high levels, because high levels indicate that there is enough acetyl-CoA to feed into the Krebs cycle and produce energy.
High plasma levels of insulin in the blood plasma (e.g. after meals) cause the dephosphorylation and activation of acetyl-CoA carboxylase, thus promoting the formation of malonyl-CoA from acetyl-CoA, and consequently the conversion of carbohydrates into fatty acids, while epinephrine and glucagon (released into the blood during starvation and exercise) cause the phosphorylation of this enzyme, inhibiting lipogenesis in favor of fatty acid oxidation via beta-oxidation. | 1 | Biochemistry |
Alloying elements are added to a base metal, to induce hardness, toughness, ductility, or other desired properties. Most metals and alloys can be work hardened by creating defects in their crystal structure. These defects are created during plastic deformation by hammering, bending, extruding, et cetera, and are permanent unless the metal is recrystallized. Otherwise, some alloys can also have their properties altered by heat treatment. Nearly all metals can be softened by annealing, which recrystallizes the alloy and repairs the defects, but not as many can be hardened by controlled heating and cooling. Many alloys of aluminium, copper, magnesium, titanium, and nickel can be strengthened to some degree by some method of heat treatment, but few respond to this to the same degree as does steel.
The base metal iron of the iron-carbon alloy known as steel, undergoes a change in the arrangement (allotropy) of the atoms of its crystal matrix at a certain temperature (usually between and , depending on carbon content). This allows the smaller carbon atoms to enter the interstices of the iron crystal. When this diffusion happens, the carbon atoms are said to be in solution in the iron, forming a particular single, homogeneous, crystalline phase called austenite. If the steel is cooled slowly, the carbon can diffuse out of the iron and it will gradually revert to its low temperature allotrope. During slow cooling, the carbon atoms will no longer be as soluble with the iron, and will be forced to precipitate out of solution, nucleating into a more concentrated form of iron carbide (FeC) in the spaces between the pure iron crystals. The steel then becomes heterogeneous, as it is formed of two phases, the iron-carbon phase called cementite (or carbide), and pure iron ferrite. Such a heat treatment produces a steel that is rather soft. If the steel is cooled quickly, however, the carbon atoms will not have time to diffuse and precipitate out as carbide, but will be trapped within the iron crystals. When rapidly cooled, a diffusionless (martensite) transformation occurs, in which the carbon atoms become trapped in solution. This causes the iron crystals to deform as the crystal structure tries to change to its low temperature state, leaving those crystals very hard but much less ductile (more brittle).
While the high strength of steel results when diffusion and precipitation is prevented (forming martensite), most heat-treatable alloys are precipitation hardening alloys, that depend on the diffusion of alloying elements to achieve their strength. When heated to form a solution and then cooled quickly, these alloys become much softer than normal, during the diffusionless transformation, but then harden as they age. The solutes in these alloys will precipitate over time, forming intermetallic phases, which are difficult to discern from the base metal. Unlike steel, in which the solid solution separates into different crystal phases (carbide and ferrite), precipitation hardening alloys form different phases within the same crystal. These intermetallic alloys appear homogeneous in crystal structure, but tend to behave heterogeneously, becoming hard and somewhat brittle.
In 1906, precipitation hardening alloys were discovered by Alfred Wilm. Precipitation hardening alloys, such as certain alloys of aluminium, titanium, and copper, are heat-treatable alloys that soften when quenched (cooled quickly), and then harden over time. Wilm had been searching for a way to harden aluminium alloys for use in machine-gun cartridge cases. Knowing that aluminium-copper alloys were heat-treatable to some degree, Wilm tried quenching a ternary alloy of aluminium, copper, and the addition of magnesium, but was initially disappointed with the results. However, when Wilm retested it the next day he discovered that the alloy increased in hardness when left to age at room temperature, and far exceeded his expectations. Although an explanation for the phenomenon was not provided until 1919, duralumin was one of the first "age hardening" alloys used, becoming the primary building material for the first Zeppelins, and was soon followed by many others. Because they often exhibit a combination of high strength and low weight, these alloys became widely used in many forms of industry, including the construction of modern aircraft. | 8 | Metallurgy |
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* Banyasz, A.; Vay, I.; Changenet-Barret, P.; Gustavsson, T.; Douki, T.; Markovitsi, D. Base-pairing enhances fluorescence and favors cyclobutane dimer formation induced upon absorption of UVA radiation by DNA. J. Am. Chem. Soc. 2011, 133, 5163-5165.
* Ecoffet, C.; Markovitsi, D.; Millie, P.; Lemaistre, J. Electronic excitations in organized molecular systems. A model for columnar aggregates of ionic compounds. Chem. Phys. 1993, 177, 629-643. | 5 | Photochemistry |
The structure of β-rhombohedral boron is complicated by the presence of partial occupancies and vacancies. The idealized unit cell, has been shown to be electron-deficient and hence metallic according to theoretical studies, but β-boron is a semiconductor. Application of the Jemmis rule shows that the partial occupancies and vacancies are necessary for electron sufficiency.
can be conceptually divided into a fragment and a () fragment. According to Wades rule, the fragment requires 8 electrons (the icosahedron at the centre (green) requires 2 electrons; each of the six pentagonal pyramids (black and red) completes an icosahedron in the extended structure; as such the electronic requirement for each of them is 1). The or is formed by the condensation of 6 icosahedra and two trigonal bipyramids. Here, m + n + o + p − q' = 8 + 57 + 1 + 0 − 0 = 66 pairs required for stability, but are available. Therefore the fragment has 3 excess electrons and the idealized is missing 5 electrons. The 3 excess electrons in the fragment can be removed by removing one B atom, which leads to (). The requirement of 8 electrons by the fragment can be satisfied by boron atoms and the unit cell contains 48 + 56 + = , which is very close to the experimental result. | 7 | Physical Chemistry |
* In non-homogeneous media, the diffusion coefficient varies in space, . This dependence does not affect Fick's first law but the second law changes:
* In anisotropic media, the diffusion coefficient depends on the direction. It is a symmetric tensor . Fick's first law changes to it is the product of a tensor and a vector: For the diffusion equation this formula gives The symmetric matrix of diffusion coefficients should be positive definite. It is needed to make the right hand side operator elliptic.
* For inhomogeneous anisotropic media these two forms of the diffusion equation should be combined in
* The approach based on Einsteins mobility and Teorell formula gives the following generalization of Ficks equation for the multicomponent diffusion of the perfect components: where are concentrations of the components and is the matrix of coefficients. Here, indices and are related to the various components and not to the space coordinates.
The Chapman–Enskog formulae for diffusion in gases include exactly the same terms. These physical models of diffusion are different from the test models which are valid for very small deviations from the uniform equilibrium. Earlier, such terms were introduced in the Maxwell–Stefan diffusion equation.
For anisotropic multicomponent diffusion coefficients one needs a rank-four tensor, for example , where refer to the components and correspond to the space coordinates. | 7 | Physical Chemistry |
Methylglyoxal is a component of some kinds of honey, including manuka honey; it appears to have activity against E. coli and S. aureus and may help prevent formation of biofilms formed by P. aeruginosa.
Research suggests that methylglyoxal contained in honey does not cause an increased formation of advanced glycation end products (AGEs) in healthy persons. | 1 | Biochemistry |
Three types of spectra can be collected from a PIXE experiment:
# X-ray emission spectrum.
# Rutherford backscattering spectrum.
# Proton transmission spectrum. | 7 | Physical Chemistry |
The Renner-Teller effect is a phenomenon in molecular spectroscopy where a pair of electronic states that become degenerate at linearity are coupled by rovibrational motion.
The Renner-Teller effect is observed in the spectra of molecules that have electronic states that allow vibration through a linear configuration. For such molecules electronic states that are doubly degenerate at linearity (Π, Δ, ..., etc.) will split into two close-lying nondegenerate states for non-linear configurations. As part of the Renner–Teller effect, the rovibronic levels of such a pair of states will be strongly Coriolis coupled by the rotational kinetic energy operator causing a breakdown of the Born–Oppenheimer approximation. This is to be contrasted with the Jahn–Teller effect which occurs for polyatomic molecules in electronic states that allow vibration through a symmetric nonlinear configuration, where the electronic state is degenerate, and which further involves a breakdown of the Born-Oppenheimer approximation but here caused by the vibrational kinetic energy operator.
In its original formulation, the Renner–Teller effect was discussed for a triatomic molecule in an electronic state that is a linear Π-state at equilibrium. The 1934 article by Rudolf Renner was one of the first that considered dynamic effects that go beyond the Born–Oppenheimer approximation, in which the nuclear and electronic motions in a molecule are uncoupled. Renner chose an electronically excited state of the carbon dioxide molecule (CO) that is a linear Π-state at equilibrium for his studies. The products of purely electronic and purely nuclear rovibrational states served as the zeroth-order (no rovibronic coupling) wave functions in Renner's study. The rovibronic coupling acts as a perturbation.
Renner is the only author of the 1934 paper that first described the effect, so it can be called simply the Renner effect. Renner did this work as a PhD student under the supervision of Edward Teller and presumably Teller was perfectly happy not to be a coauthor. However, in 1933 Gerhard Herzberg and Teller had recognized that the potential of a triatomic linear molecule in a degenerate electronic state at linearity splits into two when the molecule is bent. A year later this effect was worked out in detail by Renner. Herzberg refers to this as the "Renner–Teller" effect in one of his influential books, and this name is most commonly used.
While Renner's theoretical study concerns an excited electronic state of carbon dioxide that is linear at equilibrium, the first observation of the Renner–Teller effect was in an electronic state of the NH molecule that is bent at equilibrium.
Much has been published about the Renner–Teller effect since its first experimental observation in 1959; see the bibliography on pages 412-413 of the textbook by Bunker and Jensen. Section 13.4 of this textbook discusses both the Renner–Teller effect (called the Renner effect) and the Jahn–Teller effect. | 7 | Physical Chemistry |
In 1643, the Italian physicist and mathematician, Evangelista Torricelli, who for a few months had acted as Galileos secretary, conducted a celebrated experiment in Florence. He demonstrated that a column of mercury in an inverted tube can be supported by the pressure of air outside of the tube, with the creation of a small section of vacuum above the mercury. This experiment essentially paved the way towards the invention of the barometer, as well as drawing the attention of Robert Boyle, then a "skeptical" scientist working in England. Boyle was inspired by Torricellis experiment to investigate how the elasticity of air responds to varying pressure, and he did this through a series of experiments with a setup reminiscent of that used by Torricelli. Boyle published his results in 1662.
Later on, in 1676, the French physicist Edme Mariotte, independently arrived at the same conclusions of Boyle, while also noting some dependency of air volume on temperature. However it took another century and a half for the development of thermometry and recognition of the absolute zero temperature scale, which eventually allowed the discovery of temperature-dependent gas laws. | 7 | Physical Chemistry |
Pertussis toxin (PT) is a protein-based AB-type exotoxin produced by the bacterium Bordetella pertussis, which causes whooping cough. PT is involved in the colonization of the respiratory tract and the establishment of infection. Research suggests PT may have a therapeutic role in treating a number of common human ailments, including hypertension, viral infection, and autoimmunity. | 1 | Biochemistry |
The Journal of Physical Chemistry B is a peer-reviewed scientific journal that covers research on several fields of material chemistry (macromolecules, soft matter, and surfactants) as well as statistical mechanics, thermodynamics, and biophysical chemistry. It has been published weekly since 1997 by the American Chemical Society. According to the Journal Citation Reports, the journal had an impact factor of 3.5 for 2023.
Due to the growing amount of research in the fields it covers, the journal was split into two at the beginning of 2007, with The Journal of Physical Chemistry C specializing in nanostructures, the structures and properties of surfaces and interfaces, electronics, and related topics. | 7 | Physical Chemistry |
Racemic malic acid is produced industrially by the double hydration of maleic anhydride. In 2000, American production capacity was 5,000 tons per year. The enantiomers may be separated by chiral resolution of the racemic mixture. S-Malic acid is obtained by fermentation of fumaric acid.
Self-condensation of malic acid in the presence of fuming sulfuric acid gives the pyrone coumalic acid:
Carbon monoxide and water are liberated during this reaction.
Malic acid was important in the discovery of the Walden inversion and the Walden cycle, in which (−)-malic acid first is converted into (+)-chlorosuccinic acid by action of phosphorus pentachloride. Wet silver oxide then converts the chlorine compound to (+)-malic acid, which then reacts with PCl to the (−)-chlorosuccinic acid. The cycle is completed when silver oxide takes this compound back to (−)-malic acid.
-malic acid is used to resolve α-phenylethylamine, a versatile resolving agent in its own right. | 1 | Biochemistry |
GaN is another option, because metal nitrides usually have a narrow band gap that could encompass almost the entire solar spectrum. GaN has a narrower band gap than but is still large enough to allow water splitting to occur at the surface. GaN nanowires exhibited better performance than GaN thin films, because they have a larger surface area and have a high single crystallinity which allows longer electron-hole pair lifetimes. Meanwhile, other non-oxide semiconductors such as GaAs, Molybdenum disulfide|, and are used as n-type electrode, due to their stability in chemical and electrochemical steps in the photocorrosion reactions. | 5 | Photochemistry |
*PSMA1 NM_002786
*PSMA2 NM_002787
*PSMA3 NM_002788
*PSMA4 NM_002789
*PSMA5 NM_002790
*PSMA6 NM_002791
*PSMA7 NM_002792 Homo sapiens proteasome (prosome, macropain) subunit, alpha type, 7 (PSMA7),
*PSMB1 NM_002793 Homo sapiens proteasome (prosome, macropain) subunit, beta type, 1 (PSMB1), mRNA
*PSMB2 NM_002794 Homo sapiens proteasome (prosome, macropain) subunit, beta type, 2 (PSMB2), mRNA
*PSMB3 NM_002795
*PSMB4 NM_002796 Homo sapiens proteasome (prosome, macropain) subunit, beta type, 4 (PSMB4), mRNA
*PSMB5 NM_002797
*PSMB6 NM_002798
*PSMB7 NM_002799 Homo sapiens proteasome (prosome, macropain) subunit, beta type, 7 (PSMB7), mRNA
*PSMC2 NM_002803
*PSMC3 NM_002804
*PSMC4 NM_006503
*PSMC5 NM_002805
*PSMC6 NM_002806
*PSMD1 NM_002807
*PSMD10 NM_002814
*PSMD11 NM_002815 Homo sapiens proteasome (prosome, macropain) 26S subunit, non-ATPase, 11
*PSMD12 NM_002816
*PSMD13 NM_002817
*PSMD14 NM_005805
*PSMD2 NM_002808
*PSMD3 NM_002809
*PSMD4 NM_002810
*PSMD5 NM_005047
*PSMD6 NM_014814
*PSMD7 NM_002811
*PSMD8 NM_002812 Homo sapiens proteasome (prosome, macropain) 26S subunit, non-ATPase, 8 (PSMD8),
*PSMD9 NM_002813
*PSME2 NM_002818 Homo sapiens proteasome (prosome, macropain) activator subunit 2 (PA28 beta)
*PSME3 NM_005789
*PSMF1 NM_006814
*PSMG2 NM_020232
*PSMG3 NM_032302
*PSMG4 NM_001128591
*UBA1 NM_003334 Homo sapiens ubiquitin-activating enzyme E1 (A1S9T and BN75 temperature
*UBA2 NM_005499
*UBA3 NM_003968
*UBA5 NM_024818
*UBA52 NM_003333
*UBAC2 NM_177967
*UBALD1 NM_145253
*UBAP1 NM_016525
*UBAP2L NM_014847
*UBB NM_018955 Homo sapiens ubiquitin B (UBB), mRNA
*UBC NM_021009 Homo sapiens ubiquitin C (UBC), mRNA
*UBE2A NM_003336
*UBE2B NM_003337
*UBE2D2 NM_003339 Homo sapiens ubiquitin-conjugating enzyme E2D 2 (UBC4/5 homolog, yeast)
*UBE2D3 NM_003340
*UBE2D4 NM_015983
*UBE2E1 NM_003341
*UBE2E2 NM_152653
*UBE2E3 NM_006357
*UBE2F NM_080678
*UBE2G2 NM_003343
*UBE2H NM_003344
*UBE2I NM_003345 Homo sapiens ubiquitin-conjugating enzyme E2I (UBC9 homolog, yeast) (UBE2I),
*UBE2J1 NM_016021
*UBE2J2 NM_058167
*UBE2K NM_005339
*UBE2L3 NM_003347
*UBE2M NM_003969 Homo sapiens ubiquitin-conjugating enzyme E2M (UBC12 homolog, yeast) (UBE2M),
*UBE2N NM_003348
*UBE2NL NM_001012989
*UBE2Q1 NM_017582
*UBE2R2 NM_017811
*UBE2V1 NM_021988
*UBE2V2 NM_003350
*UBE2W NM_018299
*UBE2Z NM_023079
*UBE3A NM_000462
*UBE3B NM_130466
*UBE3C NM_014671
*UBE4A NM_004788
*UBE4B NM_006048
*USP10 NM_005153
*USP14 NM_005151
*USP16 NM_006447
*USP19 NM_006677
*USP22 NM_015276
*USP25 NM_013396
*USP27X NM_001145073
*USP33 NM_015017
*USP38 NM_032557
*USP39 NM_006590
*USP4 NM_003363
*USP47 NM_017944
*USP5 NM_003481
*USP7 NM_003470
*USP8 NM_005154
*USP9X NM_001039590 | 1 | Biochemistry |
Eutrophication is a general term describing a process in which nutrients accumulate in a body of water, resulting in an increased growth of microorganisms that may deplete the water of oxygen. Although eutrophication is a natural process, manmade or cultural eutrophication is far more common and is a rapid process caused by a variety of polluting inputs including poorly treated sewage, industrial wastewater, and fertilizer runoff. Such nutrient pollution usually causes algal blooms and bacterial growth, resulting in the depletion of dissolved oxygen in water and causing substantial environmental degradation.
Approaches for prevention and reversal of eutrophication include minimizing point source pollution from sewage and agriculture as well as other nonpoint pollution sources. Additionally, the introducution of bacteria and algae-inhibiting organisms such as shellfish and seaweed can also help reduce nitrogen pollution, which in turn controls the growth of cyanobacteria, the main source of harmful algae blooms. | 2 | Environmental Chemistry |
The huge amount of Pre-Hispanic silver adornments known especially from Perú, Bolivia and Ecuador raises the question whether the pre-Hispanic civilizations obtained the raw material from native ores or from argentiferous-lead ores. Although native silver may be available in America, it is as rare as in the Old World. From colonial texts it is known that silver mines were open in colonial times by the Spaniards from Mexico to Argentina, the main ones being those of Tasco, Mexico, and Potosí in Bolivia.
Some kind of blast furnaces called huayrachinas were described in colonial texts, as native technology furnaces used in Perú and Bolivia to smelt the ores that come from the silver mines owned by the Spaniards. Although it is not conclusive, it is believed that these kinds of furnaces were used before the Spanish Conquest. Ethnoarchaeological and archaeological work in Porco Municipality, Potosí, Bolivia, has suggested pre-European use of huayrachinas.
There are no specific archaeological accounts about silver smelting or mining in the Andes prior to the Incas. Silver and lead artefacts have been found in the Peruvian central highlands dated in the pre-Inca and Inca periods. From the presence of lead in silver artefacts, archaeologists suggest that cupellation occurred there. | 8 | Metallurgy |
While the cytosolic fermentation pathway of lactate is well established, a novel feature of the lactate shuttle hypothesis is the oxidation of lactate in the mitochondria. Baba and Sherma (1971) were the first to identify the enzyme lactate dehydrogenase (LDH) in the mitochondrial inner membrane and matrix of rat skeletal and cardiac muscle. Subsequently, LDH was found in the rat liver, kidney, and heart mitochondria. It was also found that lactate could be oxidized as quickly as pyruvate in rat liver mitochondria. Because lactate can either be oxidized in the mitochondria (back to pyruvate for entry into the Krebs’ cycle, generating NADH in the process), or serve as a gluconeogenic precursor, the intracellular lactate shuttle has been proposed to account for the majority of lactate turnover in the human body (as evidenced by the slight increases in arterial lactate concentration). Brooks et al. confirmed this in 1999, when they found that lactate oxidation exceeded that of pyruvate by 10-40% in rat liver, skeletal, and cardiac muscle.
In 1990, Roth and Brooks found evidence for the facilitated transporter of lactate, monocarboxylate transport protein (MCT), in the sarcolemma vesicles of rat skeletal muscle. Later, MCT1 was the first of the MCT super family to be identified. The first four MCT isoforms are responsible for pyruvate/lactate transport. MCT1 was found to be the predominant isoform in many tissues including skeletal muscle, neurons, erythrocytes, and sperm. In skeletal muscle, MCT1 is found in the membranes of the sarcolemma, peroxisome, and mitochondria. Because of the mitochondrial localization of MCT (to transport lactate into the mitochondria), LDH (to oxidize the lactate back to pyruvate), and COX (cytochrome c oxidase, the terminal element of the electron transport chain), Brooks et al. proposed the possibility of a mitochondrial lactate oxidation complex in 2006. This is supported by the observation that the ability of muscle cells to oxidize lactate was related to the density of mitochondria. Furthermore, it was shown that training increases MCT1 protein levels in skeletal muscle mitochondria, and that corresponded with an increase in the ability of muscle to clear lactate from the body during exercise. The affinity of MCT for pyruvate is greater than lactate, however two reactions will ensure that lactate will be present in concentrations that are orders of magnitude greater than pyruvate: first, the equilibrium constant of LDH(3.6 x 104) greatly favors the formation of lactate. Secondly, the immediate removal of pyruvate from the mitochondria (either via the Krebs’ cycle or gluconeogenesis) ensures that pyruvate is not present in great concentrations within the cell.
LDH isoenzyme expression is tissue-dependent. It was found that in rats, LDH-1 was the predominant form in the mitochondria of myocardium, but LDH-5 was predominant in the liver mitochondria. It is suspected that this difference in isoenzyme is due to the predominant pathway the lactate will take - in liver it is more likely to be gluconeogenesis, whereas in the myocardium it is more likely to be oxidation. Despite these differences, it is thought that the redox state of the mitochondria dictates the ability of the tissues to oxidize lactate, not the particular LDH isoform. | 1 | Biochemistry |
A common way to define a Henry volatility is dividing the partial pressure by the aqueous-phase concentration:
The SI unit for is Pa·m/mol. | 7 | Physical Chemistry |
The case to be heard at the High Court in 2009 represented 18 young people who alleged that toxic waste dumped by Corby Borough Council between 1984 and 1999 was the cause of their deformities. All had serious disabilities, including missing or underdeveloped fingers and deformities of their feet. They alleged that their mothers ingested or inhaled the toxic substances that affected the development of their limbs while they were still in the womb. All of their mothers either lived in or regularly visited Corby between 1984 and 1999 when the work was carried out across the town.
The case had taken ten years to reach this point largely because of the difficulties encountered in obtaining disclosure of information from Corby Borough Council. | 2 | Environmental Chemistry |
The GTEx project is a human genetics project aimed at understanding the role of genetic variation in shaping variation in the transcriptome across tissues. The project has collected a variety of tissue samples (> 50 different tissues) from more than 700 post-mortem donors. This has resulted in the collection of >11,000 samples. GTEx has helped understand the tissue-sharing and tissue-specificity of eQTLs. The genomic resource was developed to "enrich our understanding of how differences in our DNA sequence contribute to health and disease." | 1 | Biochemistry |
In many cases, the splicing process can create a range of unique proteins by varying the exon composition of the same mRNA. This phenomenon is then called alternative splicing. Alternative splicing can occur in many ways. Exons can be extended or skipped, or introns can be retained. It is estimated that 95% of transcripts from multiexon genes undergo alternative splicing, some instances of which occur in a tissue-specific manner and/or under specific cellular conditions. Development of high throughput mRNA sequencing technology can help quantify the expression levels of alternatively spliced isoforms. Differential expression levels across tissues and cell lineages allowed computational approaches to be developed to predict the functions of these isoforms.
Given this complexity, alternative splicing of pre-mRNA transcripts is regulated by a system of trans-acting proteins (activators and repressors) that bind to cis-acting sites or "elements" (enhancers and silencers) on the pre-mRNA transcript itself. These proteins and their respective binding elements promote or reduce the usage of a particular splice site. The binding specificity comes from the sequence and structure of the cis-elements, e.g. in HIV-1 there are many donor and acceptor splice sites. Among the various splice sites, ssA7, which is 3' acceptor site, folds into three stem loop structures, i.e. Intronic splicing silencer (ISS), Exonic splicing enhancer (ESE), and Exonic splicing silencer (ESSE3). Solution structure of Intronic splicing silencer and its interaction to host protein hnRNPA1 give insight into specific recognition. However, adding to the complexity of alternative splicing, it is noted that the effects of regulatory factors are many times position-dependent. For example, a splicing factor that serves as a splicing activator when bound to an intronic enhancer element may serve as a repressor when bound to its splicing element in the context of an exon, and vice versa. In addition to the position-dependent effects of enhancer and silencer elements, the location of the branchpoint (i.e., distance upstream of the nearest 3’ acceptor site) also affects splicing. The secondary structure of the pre-mRNA transcript also plays a role in regulating splicing, such as by bringing together splicing elements or by masking a sequence that would otherwise serve as a binding element for a splicing factor. | 1 | Biochemistry |
Methyl fluoroacetate (MFA) is an organic compound with the chemical formula . It is an extremely toxic methyl ester of fluoroacetic acid. It is a colorless, odorless liquid at room temperature. It is used as a laboratory chemical and as a rodenticide. Because of its extreme toxicity, MFA was studied for potential use as a chemical weapon.
The general population is not likely to be exposed to methyl fluoroacetate. People who use MFA for work, however, can breathe in or have direct skin contact with the substance. | 1 | Biochemistry |
There are a number of physical processes which may cause contraction with increasing temperature, including transverse vibrational modes, rigid unit modes and phase transitions.
In 2011, Liu et al. showed that the NTE phenomenon originates from the existence of high pressure, small volume configurations with higher entropy, with their configurations present in the stable phase matrix through thermal fluctuations. They were able to predict both the colossal positive thermal expansion (In cerium) and zero and infinite negative thermal expansion (in ).
Alternatively, large negative and positive thermal expansion may result from the design of internal microstructure. | 7 | Physical Chemistry |
The foundations of the oxy-hydrogen blowpipe were laid down by Carl Wilhelm Scheele and Joseph Priestley around the last quarter of the eighteenth century. The oxy-hydrogen blowpipe itself was developed by the Frenchman Bochard-de-Saron, the English mineralogist Edward Daniel Clarke and the American chemist Robert Hare in the late 18th and early 19th centuries. It produced a flame hot enough to melt such refractory materials as platinum, porcelain, fire brick, and corundum, and was a valuable tool in several fields of science. It is used in the Verneuil process to produce synthetic corundum. | 7 | Physical Chemistry |
S has been positively correlated with the magnitude of carbon isotope fractionation (represented by ΔC), with larger values of S corresponding with a larger values of ΔC. It has been theorized that because increasing S means the transition state is more like the product, the OC---C-2 bond will be shorter, resulting in a higher overall potential energy & vibrational energy. This creates a higher energy transition state, which makes it even harder for CO (lower in the potential energy well than CO) to overcome the required activation energy. The RuBisCOs used by varying photosynthetic organisms vary slightly in their enzyme structure, and this enzyme structure results in varying transition states. This diversity in enzyme structure is reflected in the resulting ΔC values measured from different photosynthetic organisms. However, overlap exists between the ΔC values of different groups because the carbon isotope values measured are generally of the entire organism, and not just its RuBisCO enzyme. Many other factors, including growth rate and the isotopic composition of the starting substrate, can affect the carbon isotope values of whole organism and cause the spread seen in C isotope measurements. | 7 | Physical Chemistry |
Lotka said (1922b: 151):
Gilliland noted that these difficulties in analysis in turn required some new theory to adequately explain the interactions and transactions of these different energies (different concentrations of fuels, labour and environmental forces). Gilliland (Gilliland 1978, p. 101) suggested that Odum's statement of the maximum power principle (H.T.Odum 1978, pp. 54–87) was, perhaps, an adequate expression of the requisite theory:
This theory Odum called maximum power theory. In order to formulate maximum power theory Gilliland observed that Odum had added another law (the maximum power principle) to the already well established laws of thermodynamics. In 1978 Gilliland wrote that Odum's new law had not yet been validated (Gilliland 1978, p. 101). Gilliland stated that in maximum power theory the second law efficiency of thermodynamics required an additional physical concept: "the concept of second law efficiency under maximum power" (Gilliland 1978, p. 101):
In this way the concept of maximum power was being used as a principle to quantitatively describe the selective law of biological evolution. Perhaps H.T.Odum's most concise statement of this view was (1970, p. 62):
The Odum–Pinkerton approach to Lotkas proposal was to apply Ohms law – and the associated maximum power theorem (a result in electrical power systems) – to ecological systems. Odum and Pinkerton defined "power" in electronic terms as the rate of work, where Work is understood as a "useful energy transformation". The concept of maximum power can therefore be defined as the maximum rate of useful energy transformation. Hence the underlying philosophy aims to unify the theories and associated laws of electronic and thermodynamic systems with biological systems. This approach presupposed an analogical view which sees the world as an ecological-electronic-economic engine. | 7 | Physical Chemistry |
Many flavin-dependent enzymes are capable of oxidizing aliphatic nitro compounds to less-toxic aldehydes and ketones. Nitroalkane oxidase and 3-nitropropionate oxidase oxidize aliphatic nitro compounds exclusively, whereas other enzymes such as glucose oxidase have other physiological substrates. | 0 | Organic Chemistry |
The level of nucleotides remaining in the cell after storage was thought by Warnick to be important in determining whether the cell would be able to re-synthesize ATP and recover after rewarming. Frequent changing of the perfusate or the use of a large volume of perfusate has the theoretical disadvantage that broken down adenine nucleotides may be washed out of the cells and so not be available for re-synthesis into ATP when the kidney is rewarmed. | 1 | Biochemistry |
In molecular biology, treadmilling is a phenomenon observed within protein filaments of the cytoskeletons of many cells, especially in actin filaments and microtubules. It occurs when one end of a filament grows in length while the other end shrinks, resulting in a section of filament seemingly "moving" across a stratum or the cytosol. This is due to the constant removal of the protein subunits from these filaments at one end of the filament, while protein subunits are constantly added at the other end. Treadmilling was discovered by Wegner, who defined the thermodynamic and kinetic constraints. Wegner recognized that: “The equilibrium constant (K) for association of a monomer with a polymer is the same at both ends, since the addition of a monomer to each end leads to the same polymer.”; a simple reversible polymer can’t treadmill; ATP hydrolysis is required. GTP is hydrolyzed for microtubule treadmilling. | 1 | Biochemistry |
Ferroelectricity is a characteristic of certain materials that have a spontaneous electric polarization that can be reversed by the application of an external electric field. All ferroelectrics are also piezoelectric and pyroelectric, with the additional property that their natural electrical polarization is reversible. The term is used in analogy to ferromagnetism, in which a material exhibits a permanent magnetic moment. Ferromagnetism was already known when ferroelectricity was discovered in 1920 in Rochelle salt by Joseph Valasek. Thus, the prefix ferro, meaning iron, was used to describe the property despite the fact that most ferroelectric materials do not contain iron. Materials that are both ferroelectric and ferromagnetic are known as multiferroics. | 7 | Physical Chemistry |
Spontaneous deamination of 5-methylcytosine results in thymine and ammonia. This is the most common single nucleotide mutation. In DNA, this reaction, if detected prior to passage of the replication fork, can be corrected by the enzyme thymine-DNA glycosylase, which removes the thymine base in a G/T mismatch. This leaves an abasic site that is repaired by AP endonucleases and polymerase, as with uracil-DNA glycosylase. | 1 | Biochemistry |
Chemical mimicry of an organism's pheromones allows predators with this ability to draw select prey to them, rather than spend their energy finding and attempting to capture these organisms with varied success. The pheromones are typically used by the prey species to attract members of their own species as potential mates. In the case of predatory chemical mimicry, the predator has evolved to emit chemicals that are structurally similar and will cause the same behavioural reactions to be displayed by the prey. However, the mimicked pheromones will draw the animal toward the predator rather than a potential mate.
One group of organisms that use this method are Bolas spiders (genus: Mastophora). Bolas spiders emit chemicals that attract their prey, noctuid moths. These spiders have replaced the need to spin elaborate webs to capture prey by mimicking the pheromones emitted by female moths to attract males of the species effectively. In studies conducted on this spider it has been found that the moths only approach from downwind of the spider and that all of the moths captured were, in fact, male. | 1 | Biochemistry |
Simply add the name of the attached halide to the end of the acyl group. For example, is ethanoyl chloride. An alternate suffix is "-carbonyl halide" as opposed to "-oyl halide". The prefix form is "halocarbonyl-". | 0 | Organic Chemistry |
Yeast artificial chromosome or YAC is a DNA molecule that is developed by humans to take the DNA sequences that belong to yeast cells and clone them. Yeast artificial chromosomes can be inserted with fragments of DNA from the organism of interest. Yeast cells will then assimilate the yeast artificial chromosome that contains the DNA from the organism of interest. The yeast cells then multiply in number and this brings about the amplification of the DNA that has been incorporated into it which is then isolated for the purpose of things like sequencing and mapping of the DNA desired i.e. the DNA originally inserted into the yeast artificial chromosome. Vectorette PCR helps with this process by bringing about not only the isolation of the yeast artificial chromosome’s ends but also the amplification of the ends. | 1 | Biochemistry |
Similar to the polar sensitivity factor, the steric sensitivity factor δ for a new reaction series will describe to what magnitude the reaction rate is influenced by steric effects. When a reaction series is not significantly influenced by polar effects, the Taft equation reduces to:
A plot of the ratio of the rates versus the E value for the substituent will give a straight line with a slope equal to δ. Similarly to the Hammett ρ value, the magnitude of δ will reflect to what extent a reaction is influenced by steric effects:
*A very steep slope will correspond to high steric sensitivity, while a shallow slope will correspond to little to no sensitivity.
Since E values are large and negative for bulkier substituents, it follows that:
*If δ is positive, increasing steric bulk decreases the reaction rate and steric effects are greater in the transition state.
*If δ is negative, increasing steric bulk increases the reaction rate and steric effects are lessened in the transition state. | 7 | Physical Chemistry |
Knowles was awarded a Fellowship of the Institute of Materials, Minerals and Mining (FIMMM) in 2004 in recognition of his contributions to the field of materials science. In 2015, he was also made Fellow of the Royal Academy of Engineering (FREng). He holds two European patents and has authored over 100 academic papers - five of which have been cited over 100 times - and he has also given a number of invited lectures and conference keynotes | 8 | Metallurgy |
The original example proceeded via sequential loss of two equivalents of H from decamethyltungstocene dihydride, Cp*WH. The first dehydrogenation step affords a simple tuck-in complex:
:(CMe)WH → (CMe)(η-CMeCH)WH + H
The second dehydrogenation step affords a double tuck-in complex:
:(CMe)(η-CMeCH)WH → (CMe)(η-CMe(CH))W + H
In organouranium chemistry, both tuck-in and tuck-over complexes are recognized, for example in the dihydrido diuranium complex [Cp*(η-CMe(CH))UH]. In this complex the two methylene groups bind to different uranium centers. The tuck-over mode is binding of the Cp* methylene to a metal center elsewhere in the molecule rather than the one coordinated to that Cp* ligand. | 0 | Organic Chemistry |
Like Pfitzner–Moffatt oxidation and Swern oxidation, with DMSO, MsO can oxidize primary and secondary alcohols to aldehydes and ketones, respectively, in HMPA. This method applies to benzylic alcohol. HMPA may be substituted by dichloromethane but may result in more side-products. | 0 | Organic Chemistry |
Esomeprazole is a competitive inhibitor of the enzyme CYP2C19, and may therefore interact with drugs that depend on it for metabolism, such as diazepam and warfarin; the concentrations of these drugs may increase if they are used concomitantly with esomeprazole. Conversely, clopidogrel (Plavix) is an inactive prodrug that partially depends on CYP2C19 for conversion to its active form; inhibition of CYP2C19 blocks the activation of clopidogrel, thus reducing its effects.
Drugs that depend on stomach pH for absorption may interact with esomeprazole; drugs that depend on an acidic environment (such as ketoconazole or atazanavir) will be poorly absorbed, whereas drugs that are broken down in acidic environments (such as erythromycin) will be absorbed to a greater extent than normal. | 4 | Stereochemistry |
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