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Usually the initial measurement is the minimal level of fluorescence, . This is the fluorescence in the absence of photosynthetic light.
To use measurements of chlorophyll fluorescence to analyse photosynthesis, researchers must distinguish between photochemical quenching and non-photochemical quenching (heat dissipation). This is achieved by stopping photochemistry, which allows researchers to measure fluorescence in the presence of non-photochemical quenching alone. To reduce photochemical quenching to negligible levels, a high intensity, short flash of light is applied to the leaf. This transiently closes all PSII reaction centres, which prevents energy of PSII being passed to downstream electron carriers. Non-photochemical quenching will not be affected if the flash is short. During the flash, the fluorescence reaches the level reached in the absence of any photochemical quenching, known as maximum fluorescence .
The efficiency of photochemical quenching (which is a proxy of the efficiency of PSII) can be estimated by comparing to the steady yield of fluorescence in the light and the yield of fluorescence in the absence of photosynthetic light .
The efficiency of non-photochemical quenching is altered by various internal and external factors. Alterations in heat dissipation mean changes in . Heat dissipation cannot be totally stopped, so the yield of chlorophyll fluorescence in the absence of non-photochemical quenching cannot be measured. Therefore, researchers use a dark-adapted point () with which to compare estimations of non-photochemical quenching. | 5 | Photochemistry |
In asymmetric trifluoromethylation the trifluoromethyl group is added to the substrate in an enantioselective way. Ruppert's reagent has been used for this purpose in an asymmetric induction approach to functionalise chiral amino acid derivates, saccharides, and steroids.
Because Ruppert's reagent requires a tetraalkylammonium fluoride, chiral ammonium fluorides have been employed in asymmetric catalysis.
In the field of electrophilic trifluoromethylation an early contribution involved reaction of a metal enolate with a trifluoromethyl chalcogen salt in presence of a chiral boron catalyst.
More recent examples of highly enantioselective methods for the α-trifluoromethylation of carbonyls are available through enamine catalysis of aldehydes (photoredox or iodonium), copper catalysis of β-ketoesters, and radical addition to zirconium enolates. | 0 | Organic Chemistry |
Because the previous synthesis had worked, photo-methionine is photo-reactive due to the diazirine ring. Once this ring has become exposed to UV light, nitrogen leaves as nitrogen gas (N) and forms the highly reactive intermediate carbene. Photo-activation of amino acids provide the ability of photo-cross-linking in proteins. This type of cross-linking has three major advantages; there is greater specificity for this cross linking due to the short lived intermediates and that this amino acid is functional, and most importantly; not toxic (meaning it should not disrupt the protein's function or structure dramatically). Research had found that this activation is the rate-limiting step; not the cross-linkage. | 5 | Photochemistry |
The Flippin-Lodge and Bürgi-Dunitz angles were central, practically, to the development of a clearer understanding of asymmetric induction during nucleophilic attack at hindered carbonyl centers in synthetic organic chemistry. It was in this area that was first defined by Heathcock, and has been primarily used. Larger substituents around the electrophilic center, such as tert-butyls, lead to higher stereoselectivities in asymmetric induction than smaller substituents like methyls. The trajectory of the nucleophile approaching a center flanked by two large substituents is more limited, i.e. the Flippin–Lodge angle is smaller. For example, in Mukaiyama aldol addition, the bulkier phenyl tert-butyl ketone has a higher selectivity for the syn isomer than the smaller phenyl methyl ketone. Likewise, if bulky a nucleophile, such as a t-butylmethylsilyl enolate, is used, the selectivity is higher than for a small nucleophile like a lithium enolate.
Given a reaction system of a given nucleophile with a carbonyl having the two substituents R and R, where substituent R is sterically small relative to substituent R (e.g., R = hydrogen atom, R = phenyl), the values that are inferred from the reaction outcomes and theoretical studies tend to be larger; alternatively, if the hydrocarbon substituents are nearer or equal in steric size, the inferred values diminish and may approach zero (e.g., R = tert-butyl, R = phenyl). Thus, from the perspective of simpler electrophile systems where only steric bulk come into play, the attack trajectories of the classes of nucleophiles studied makes clear that as the disparity in size between the substituent increase, there is a perturbation in the FL angle that can be used to provide higher stereoselectivities in designed reaction systems; while the patterns become more complex when factors other than steric bulk come into play (see section above on orbital contributions), Flippin, Lodge, and Heathcock were able to show that generalizations could be made that were useful to reaction design.
A surpassing area of application has been in studies of various aldol reactions, the addition of ketone-derived enol/enolate nucleophiles to electrophilic aldehydes, each with functional groups varying in size and group polarity; the way that features on the nucleophile and electrophile impact the stereochemistry seen in reaction products, and in particular, the diastereoselection exhibited, has been carefully mapped (see the steric and orbital description above, the aldol reaction article, and David Evans related Harvard teaching materials on the aldol). These studies have improved the chemists abilities to design enantioselective and diastereoselective reactions needed in the construction of complex molecules, such as the natural product spongistatins and modern drugs. It remains to be seen whether a particular range of values contributes similarly to the arrangement of functional groups within proteins and so to their conformational stabilities (as has been reported in relation to the BD trajectory), or to other BD-correlated stabilizations of conformation important to structure and reactivity. | 7 | Physical Chemistry |
A post-metallocene catalyst is a kind of catalyst for the polymerization of olefins, i.e., the industrial production of some of the most common plastics. "Post-metallocene" refers to a class of homogeneous catalysts that are not metallocenes. This area has attracted much attention because the market for polyethylene, polypropylene, and related copolymers is large. There is a corresponding intense market for new processes as indicated by the fact that, in the US alone, 50,000 patents were issued between 1991-2007 on polyethylene and polypropylene.
Many methods exist to polymerize alkenes, including the traditional routes using Philips catalyst and traditional heterogeneous Ziegler-Natta catalysts, which still are used to produce the bulk of polyethylene. | 7 | Physical Chemistry |
Thermally stimulated current (TSC) spectroscopy (not to be confused with thermally stimulated depolarization current) is an experimental technique which is used to study energy levels in semiconductors or insulators (organic or inorganic). Energy levels are first filled either by optical or electrical injection usually at a relatively low temperature, subsequently electrons or holes are emitted by heating to a higher temperature. A curve of emitted current will be recorded and plotted against temperature, resulting in a TSC spectrum. By analyzing TSC spectra, information can be obtained regarding energy levels in semiconductors or insulators.
A driving force is required for emitted carriers to flow when the sample temperature is being increased. This driving force can be an electric field or a temperature gradient. Usually, the driving force adopted is an electric field; however, electron traps and hole traps cannot be distinguished. If the driving force adopted is a temperature gradient, electron traps and hole traps can be distinguished by the sign of the current. TSC based on a temperature gradient is also known as "Thermoelectric Effect Spectroscopy" (TEES) according to 2 scientists (Santic and Desnica) from ex-Yugoslavia; they demonstrated their technique on semi-insulating gallium arsenide (GaAs). (Note: TSC based on a temperature gradient was invented before Santic and Desnica and applied to the study of organic plastic materials. However, Santic and Desnica applied TSC based on a temperature gradient to study a technologically important semiconductor material and coined a new name, TEES, for it.)
Historically, Frei and Groetzinger published a paper in German in 1936 with the title "Liberation of electrical energy during the fusion of electrets" (English translation of the original title in German). This may be the first paper on TSC. Before the invention of deep-level transient spectroscopy (DLTS), thermally stimulated current (TSC) spectroscopy was a popular technique to study traps in semiconductors. Nowadays, for traps in Schottky diodes or p-n junctions, DLTS is the standard method to study traps. However, there is an important shortcoming for DLTS: it cannot be used for an insulating material while TSC can be applied to such a situation. (Note: an insulator can be considered as a very large bandgap semiconductor.) In addition, the standard transient capacitance based DLTS method may not be very good for the study of traps in the i-region of a p-i-n diode while the transient current based DLTS (I-DLTS) may be more useful.
TSC has been used to study traps in semi-insulating gallium arsenide (GaAs) substrates. It has also been applied to materials used for particle detectors or semiconductor detectors used in nuclear research, for example, high-resistivity silicon, cadmium telluride (CdTe), etc. TSC has also been applied to various organic insulators. TSC is useful for electret research. More advanced modifications of TSC have been applied to study traps in ultrathin high-k dielectric thin films. W. S. Lau (Lau Wai Shing, Republic of Singapore) applied zero-bias thermally stimulated current or zero-temperature-gradient zero-bias thermally stimulated current to ultrathin tantalum pentoxide samples. For samples with some shallow traps which can be filled at low temperature and some deep traps which can be filled only at high temperature, a two-scan TSC may be useful as suggested by Lau in 2007. TSC has also been applied to hafnium oxide.
TSC technique is used to study dielectric materials and polymers. Different theories was made to describe the response curve for this technique in order to calculate the peak parameters which are, the activation energy and the relaxation time. | 7 | Physical Chemistry |
Following, the IMFP is employed to calculate the effective attenuation length (EAL), the mean escape depth (MED) and the information depth (ID). Besides, one can utilize the IMFP to make matrix corrections for the relative sensitivity factor in quantitative surface analysis. Moreover, the IMFP is an important parameter in Monte Carlo simulations of photoelectron transport in matter. | 7 | Physical Chemistry |
Carbonic anhydrase-related protein is a protein that in humans is encoded by the CA8 gene. The CA8 protein lacks the catalytic activity of other carbonic anhydrase enzymes. A rare, autosomal recessive form of cerebellar ataxia known as "cerebellar ataxia, mental retardation, and dysequilibrium syndrome 3" (CAMRQ3) is caused by mutations in the CA8 gene. | 1 | Biochemistry |
In humans, cAMP works by activating protein kinase A (PKA, cAMP-dependent protein kinase), one of the first few kinases discovered. It has four sub-units two catalytic and two regulatory. cAMP binds to the regulatory sub-units. It causes them to break apart from the catalytic sub-units. The catalytic sub-units make their way in to the nucleus to influence transcription. Further effects mainly depend on cAMP-dependent protein kinase, which vary based on the type of cell.
cAMP-dependent pathway is necessary for many living organisms and life processes. Many different cell responses are mediated by cAMP; these include increase in heart rate, cortisol secretion, and breakdown of glycogen and fat. cAMP is essential for the maintenance of memory in the brain, relaxation in the heart, and water absorbed in the kidney.
This pathway can activate enzymes and regulate gene expression. The activation of preexisting enzymes is a much faster process, whereas regulation of gene expression is much longer and can take up to hours. The cAMP pathway is studied through loss of function (inhibition) and gain of function (increase) of cAMP.
If cAMP-dependent pathway is not controlled, it can ultimately lead to hyper-proliferation, which may contribute to the development and/or progression of cancer. | 1 | Biochemistry |
Ca ion flow regulates several secondary messenger systems in neural adaptation for visual, auditory, and the olfactory system. It may often be bound to calmodulin such as in the olfactory system to either enhance or repress cation channels. Other times the calcium level change can actually release guanylyl cyclase from inhibition, like in the photoreception system. Ca ion can also determine the speed of adaptation in a neural system depending on the receptors and proteins that have varied affinity for detecting levels of calcium to open or close channels at high concentration and low concentration of calcium in the cell at that time. | 1 | Biochemistry |
Phosphorus is an essential nutrient for plants and animals. Phosphorus is a limiting nutrient for aquatic organisms. Phosphorus forms parts of important life-sustaining molecules that are very common in the biosphere. Phosphorus does enter the atmosphere in very small amounts when dust containing phosphorus is dissolved in rainwater and sea spray, but the element mainly remains on land and in rock and soil minerals. Phosphates which are found in fertilizers, sewage and detergents, can cause pollution in lakes and streams. Over-enrichment of phosphate in both fresh and inshore marine waters can lead to massive algae blooms. In fresh water, the death and decay of these blooms leads to eutrophication. An example of this is the Canadian Experimental Lakes Area.
Freshwater algal blooms are generally caused by excess phosphorus, while those that take place in saltwater tend to occur when excess nitrogen is added. However, it is possible for eutrophication to be due to a spike in phosphorus content in both freshwater and saltwater environments.
Phosphorus occurs most abundantly in nature as part of the orthophosphate ion (PO), consisting of a P atom and 4 oxygen atoms. On land most phosphorus is found in rocks and minerals. Phosphorus-rich deposits have generally formed in the ocean or from guano, and over time, geologic processes bring ocean sediments to land. Weathering of rocks and minerals release phosphorus in a soluble form where it is taken up by plants, and it is transformed into organic compounds. The plants may then be consumed by herbivores and the phosphorus is either incorporated into their tissues or excreted. After death, the animal or plant decays, and phosphorus is returned to the soil where a large part of the phosphorus is transformed into insoluble compounds. Runoff may carry a small part of the phosphorus back to the ocean. Generally with time (thousands of years) soils become deficient in phosphorus leading to ecosystem retrogression. | 9 | Geochemistry |
After passage of the Food Quality Protection Act (FQPA) of 1996, the U.S. EPA had established a tolerance level for apples at 10 ppm, and for meat and milk at 0 ppm. The tentative LOAEL was 10 mg/kg/day In 1997 EPA approved the reregistration of diphenylamine, and determined that recommended tolerances met the safety standards under FQPA and that "adequate data indicate that tolerances for residues in milk and meat could be increased from 0.0 ppm and established as separate tolerances set at 0.01 ppm". EPA has not reviewed diphenylamine since then. | 3 | Analytical Chemistry |
From Bjerrum plots, it is found that a decrease in the salinity of an aqueous fluid will act to increase the value of the carbon dioxide-carbonate system equilibrium constants, (pK*). This means that the relative proportion of carbonate with respect to carbon dioxide is higher in more saline fluids, e.g. seawater, than in fresher waters. Of crucial importance for paleoclimatology is the observation that an increase in salinity will thus reduce the solubility of carbon dioxide in the oceans. Since there is thought to have been a 120 m depression in sea level at the last glacial maximum due to the extensive formation of ice sheets (which are solely freshwater), this represents a significant fractionation towards saltier seas during glacial periods. Correspondingly, this will cause a net outgassing of carbon dioxide into the atmosphere because of its reduced solubility, acting to increase atmospheric carbon dioxide by 6.5‰. This is thought to partly offset the net decrease of 80-100‰ observed during glacial periods. | 9 | Geochemistry |
Samarium(II) iodide is a powerful reducing agent – for example it rapidly reduces water to hydrogen. It is available commercially as a dark blue 0.1 M solution in THF. Although used typically in superstoichiometric amounts, catalytic applications have been described. | 0 | Organic Chemistry |
The basic technique for the detection of RFLPs involves fragmenting a sample of DNA with the application of a restriction enzyme, which can selectively cleave a DNA molecule wherever a short, specific sequence is recognized in a process known as a restriction digest. The DNA fragments produced by the digest are then separated by length through a process known as agarose gel electrophoresis and transferred to a membrane via the Southern blot procedure. Hybridization of the membrane to a labeled DNA probe then determines the length of the fragments which are complementary to the probe. A restriction fragment length polymorphism is said to occur when the length of a detected fragment varies between individuals, indicating non-identical sequence homologies. Each fragment length is considered an allele, whether it actually contains a coding region or not, and can be used in subsequent genetic analysis. | 1 | Biochemistry |
An antagonist of a prostaglandin E2 receptor has been shown to serve as an affective contraceptive for female macaques while unaffecting their menstrual cyclicity as well as hormonal patterns. The exact reason behind the reduced amount of successful pregnancies of primates during the study is unclear due a number of possibilities that may affect such result.
Inhibition of the prostaglandin E2 EP receptor has been shown to inhibit tumor growth, angiogenesis, lymphangiogenesis, and metastasis. | 1 | Biochemistry |
Once particles have aggregated to several micrometers in diameter, they begin to accumulate bacteria, since there is sufficient site space for feeding and reproduction. At this size, it is large enough to undergo sinking. It also has the components necessary to fit the "aggregate spinning wheel hypothesis". Evidence for this has been found by Alldredge and Cohen (1987) who found evidence of both respiration and photosynthesis within aggregates, suggesting the presence of both autotrophic and heterotrophic organisms. During zooplankton's vertical migration, the abundances of aggregates increased while size distributions decreased. Aggregates were found in the abdomen in zooplankton indicating their grazing will fragment larger aggregates. | 9 | Geochemistry |
The hemin/G-Quadruplex DNAzyme consists of G-Quadruplex forming DNA that can bind the co-factor hemin (a.k.a. Fe(III)Protoporphyrin IX), forming a complex that can perform certain oxidation reaction in the presence of hydrogen peroxide. This DNAzyme can oxidize small molecules, such as dopamine and adenosine triphosphate, but can also be used for the modification of peptides and proteins by attaching small molecules. | 7 | Physical Chemistry |
Ocean acidification is the ongoing decrease in the pH of the Earth's ocean. Between 1950 and 2020, the average pH of the ocean surface fell from approximately 8.15 to 8.05. Carbon dioxide emissions from human activities are the primary cause of ocean acidification, with atmospheric carbon dioxide () levels exceeding 410 ppm (in 2020). from the atmosphere is absorbed by the oceans. This chemical reaction produces carbonic acid () which dissociates into a bicarbonate ion () and a hydrogen ion (). The presence of free hydrogen ions () lowers the pH of the ocean, increasing acidity (this does not mean that seawater is acidic yet; it is still alkaline, with a pH higher than 8). Marine calcifying organisms, such as mollusks and corals, are especially vulnerable because they rely on calcium carbonate to build shells and skeletons.
A change in pH by 0.1 represents a 26% increase in hydrogen ion concentration in the world's oceans (the pH scale is logarithmic, so a change of one in pH units is equivalent to a tenfold change in hydrogen ion concentration). Sea-surface pH and carbonate saturation states vary depending on ocean depth and location. Colder and higher latitude waters are capable of absorbing more . This can cause acidity to rise, lowering the pH and carbonate saturation levels in these areas. Other factors that influence the atmosphere-ocean exchange, and thus local ocean acidification, include: ocean currents and upwelling zones, proximity to large continental rivers, sea ice coverage, and atmospheric exchange with nitrogen and sulfur from fossil fuel burning and agriculture.
Decreased ocean pH has a range of potentially harmful effects for marine organisms. These include reduced calcification, depressed metabolic rates, lowered immune responses, and reduced energy for basic functions such as reproduction. The effects of ocean acidification are therefore impacting marine ecosystems that provide food, livelihoods, and other ecosystem services for a large portion of humanity. Some 1 billion people are wholly or partially dependent on the fishing, tourism, and coastal management services provided by coral reefs. Ongoing acidification of the oceans may therefore threaten food chains linked with the oceans.
The United Nations Sustainable Development Goal 14 ("Life below Water") has a target to "minimize and address the impacts of ocean acidification". Reducing carbon dioxide emissions (i.e., climate change mitigation measures) is the only solution that addresses the root cause of ocean acidification. Mitigation measures which achieve carbon dioxide removal from the atmosphere would help to reverse ocean acidification. The more specific ocean-based mitigation methods (e.g. ocean alkalinity enhancement, enhanced weathering) could also reduce ocean acidification. These strategies are being researched, but generally have a low technology readiness level and many risks.
Ocean acidification has occurred previously in Earth's history. The resulting ecological collapse in the oceans had long-lasting effects on the global carbon cycle and climate. | 9 | Geochemistry |
These predicted editing sites result in the translation of an Arginine instead of a Glutamine at the Q/R site and an Alanine instead of a Threonine at the T/A site. These codon changes are nonsynomonous. Since the editing sites are located just before a collagen like trimerization domain, editing may effect protein oligomerization. This region is also likely to be a protease domain. It is not known if the amino acid changes caused by editing could have an effect on these domains. | 1 | Biochemistry |
Chemist Walter Reppe pioneered catalytic, industrial-scale ethynylations using acetylene with alkali metal and copper(I) acetylides:
These reactions are used to manufacture propargyl alcohol and butynediol. Alkali metal acetylides, which are often more effective for ketone additions, are used to produce 2-methyl-3-butyn-2-ol from acetylene and acetone. | 0 | Organic Chemistry |
Environmental water quality, also called ambient water quality, relates to water bodies such as lakes, rivers, and oceans. Water quality standards for surface waters vary significantly due to different environmental conditions, ecosystems, and intended human uses. Toxic substances and high populations of certain microorganisms can present a health hazard for non-drinking purposes such as irrigation, swimming, fishing, rafting, boating, and industrial uses. These conditions may also affect wildlife, which use the water for drinking or as a habitat. According to the EPA, water quality laws generally specify protection of fisheries and recreational use and require, as a minimum, retention of current quality standards. In some locations, desired water quality conditions include high dissolved oxygen concentrations, low chlorophyll-a concentrations, and high water clarity.
There is some desire among the public to return water bodies to pristine, or pre-industrial conditions. Most current environmental laws focus on the designation of particular uses of a water body. In some countries these designations allow for some water contamination as long as the particular type of contamination is not harmful to the designated uses. Given the landscape changes (e.g., land development, urbanization, clearcutting in forested areas) in the watersheds of many freshwater bodies, returning to pristine conditions would be a significant challenge. In these cases, environmental scientists focus on achieving goals for maintaining healthy ecosystems and may concentrate on the protection of populations of endangered species and protecting human health. | 3 | Analytical Chemistry |
Triflic acid reacts with acyl halides to give mixed triflate anhydrides, which are strong acylating agents, e.g. in Friedel–Crafts reactions.
Triflic acid catalyzes the reaction of aromatic compounds with sulfonyl chlorides, probably also through the intermediacy of a mixed anhydride of the sulfonic acid.
Triflic acid promotes other Friedel–Crafts-like reactions including the cracking of alkanes and alkylation of alkenes, which are very important to the petroleum industry. These triflic acid derivative catalysts are very effective in isomerizing straight chain or slightly branched hydrocarbons that can increase the octane rating of a particular petroleum-based fuel.
Triflic acid reacts exothermically with alcohols to produce ethers and olefins.
Dehydration gives the acid anhydride, trifluoromethanesulfonic anhydride, (CFSO)O. | 0 | Organic Chemistry |
mRNA methylation is important throughout the entire life-cycle of the mRNA, starting with the alternative polyadenylation (APA) of some transcripts. mA sites are often located in the last exon, mostly in the 3’ untranslated region (3-UTR). The presence of mA in the 3’-UTR promotes the use of the proximal APA site, resulting in a shorter 3’-UTR. Splicing of the pre-mRNA transcripts may be influenced by mA, although this effect can vary across different biological systems. Furthermore, nuclear export of mature mRNAs depends on mA; when the mA "writers" are inhibited, there is a delay in the export of the mature mRNAs. However, normal nuclear export does not solely depend on mA, other mRNA marks such as 5-methylcytosine (mC) are also involved.
The mA mark has a notable effect on translational dynamics. There are various ways in which mA is involved in translational efficiency. For instance, this modification modulates multiple steps in the process of tRNA incorporation. On the one hand, it slows down GTP hydrolysis by EF-Tu by 12-fold and the peptidyl transfer reaction by two-fold. It also causes a 1.5-fold increase in the amount of GTP hydrolyzed per peptidyl transfer, which indicates that a lot of proofreading is required. Moreover, because it is just a modified adenosine base, mA base-pairs with uridine during decoding. However, the adenosine's methylation hinders tRNA accommodation and translation elongation. When a mA-modified codon interacts with its cognate tRNA (the tRNA with the anticodon that is complementary to a particular codon), it acts more like a near-cognate codon interaction instead of the cognate codon interaction. This can be seen in the delay in the tRNA accommodation, which is dependent upon both the position of the mA in the mRNA codons and on how accurate the translation is. Overall, this mA modification leads to a kinetic loss of a factor of 18. To summarize, translation-elongation dynamics are slower for codons with mA and different locations of these modified nucleotides in the mRNA codons affect decoding dynamics in different ways.
However, this mark can also increase translational efficiency. The mA "reader" YTHDF1 induces the association of the modified mRNA with the ribosome. Furthermore, it also recruits the translation initiation factor eIF3 to the mRNA independently of METTL3. Additionally, eIF3 also acts as a "reader" of a mA located in the 5’-UTR of the mRNA, which results in recruitment of the 40S translational preinitiation complex. This interaction is involved in cap-independent translation, which happens during the cellular response to heat shock stress.
mA methylation also modulates mRNA stability. The "reader" YTHDF2 binds to mA-containing mRNAs and decreases their stability by recruiting them to P-bodies, in a process called methylation-dependent mRNA decay. This process is needed to rapidly degrade pluripotency transcription factor transcripts, to enable the commitment of a pluripotent stem cell to a specific cell lineage. Reduced levels of mA in mice embryos lead to embryonic lethality during the early stages of development. | 1 | Biochemistry |
*Multi-parametric surface plasmon resonance
*Dual-polarization interferometry
*Quartz crystal microbalance with dissipation monitoring (QCM-D) | 1 | Biochemistry |
Staff at BRM began work on an alternative to the conventional reverberatory cupellation furnace in the early 1980s. This included a review of the available technology, including the top-blown rotary converter ("TBRC"), on which test work was undertaken.
One of the first areas investigated was the use of oxygen-enriched blast air in the reverberatory furnace. This was “found to be of marginal benefit and not economically viable."
The BRM staff subsequently tried to increase the oxygen transfer rate by using lances submerged in the bath of the reverberatory furnace and found that there was some benefit in doing this. However, the wear rate of the lances was excessive and it was realized that the basic design of the furnace, with its shallow bath, was not conducive to the development of a high-intensity reactor.
The concept then evolved into a new furnace design, one that had a deep bath, in contrast to the reverberatory furnace design.
Initial tests of the bottom injection of oxygen were carried out on a small scale at Imperial College, London, using a nitrogen-shrouded tuyere. These showed that under certain conditions a protective accretion would form at the tip of the injector, and that oxygen utilization was high, with the oxidation reactions generating sufficient heat to keep the furnace hot until the final stages of refining when the impurity levels were low.
Additionally, the test work on the TBRC had shown that it had a high rate of refractory wear, due to the washing action of the slag caused by the rotation of the furnace, which provided additional pressure to develop an alternate process. The TBRC test work also resulted in low oxygen utilization (about 60%).
Based on the success of the small-scale tests, and with calculations indicating that the new design would have significant energy savings over the reverberatory furnace, the BRM staff built a 1.5 t pilot plant with a working volume of 150 liters (“L”). The oxygen injector was a fixed tuyere, located at corner of the base with the side wall, with an annular nitrogen shroud.
The initial pilot plant tests showed that it was difficult to maintain the protective accretion that had been generated in the small-scale tests, due to the variation in temperature and bullion composition that occurred throughout the cupelling cycle. Without the accretion, the nitrogen shroud could not provide sufficient protection to the injector, and it burned back to the level of the refractory lining, which resulted in damage to the lining.
The solution eventually developed was the concept of the moveable lance system in place of the fixed tuyere that had been used initially. The lance was pushed further into the furnace as its tip was worn away.
The initial lance advancing system was manual, but the current automated system was subsequently developed.
Once a sustainable system had been developed in the pilot plant, and after three years of pilot plant development, a commercial, 3 t-scale BBOC was commissioned at BRM in 1986. Its use reduced the fuel consumption per tonne of silver by 85%, from 30 gigajoules per tonne (“GJ/t”) to 4.5 GJ/t and the exhaust gas volume from 32 000 Nm/h to 7500 Nm/h. | 8 | Metallurgy |
For each entry, cross-references are maintained to [http://www.ensembl.org EnsEMBL], [https://www.ncbi.nlm.nih.gov/projects/SNP/ dbSNP], [https://www.ncbi.nlm.nih.gov/entrez/query.fcgi?DB=gene Entrez Gene], [https://www.ncbi.nlm.nih.gov/entrez/query.fcgi?CMD=search&DB=taxonomy the NCBI Taxonomy database] and [https://web.archive.org/web/20150213023323/http://www.pubmed.com/ PubMed]. The information within ORegAnno is regularly mapped and provided as a [http://genome.ucsc.edu/cgi-bin/hgTrackUi?org=Human&g=oreganno UCSC Genome Browser] track. Furthermore, each entry is associated with its experimental evidence, embedded as an [http://www.oreganno.org/oregano/evidenceview.action Evidence Ontology] within ORegAnno. This allows the researcher to analyze regulatory data using their own conditions as to the suitability of the supporting evidence. | 1 | Biochemistry |
Hydrogenated MDI (HMDI or 4,4′-diisocyanato dicyclohexylmethane) is an organic compound in the class known as isocyanates. More specifically, it is an aliphatic diisocyanate. It is a water white liquid at room temperature and is manufactured in relatively small quantities. It is also known as 4,4'-methylenedi(cyclohexyl isocyanate) or methylene bis(4-cyclohexylisocyanate) and has the formula CH[(CH)NCO]. | 0 | Organic Chemistry |
* A well-known electrosynthesis is the Kolbe electrolysis, in which two carboxylic acids decarboxylate, and the remaining structures bond together:
* A variation is called the non-Kolbe reaction when a heteroatom (nitrogen or oxygen) is present at the α-position. The intermediate oxonium ion is trapped by a nucleophile, usually solvent.
* Anodic electrosynthesis oxidize primary aliphatic amine to nitrile.
* Amides can be oxidized to N-acyliminium ions, which can be captured by various nucleophiles, for example:
:This reaction type is called a Shono oxidation. An example is the α-methoxylation of N-carbomethoxypyrrolidine
* Oxidation of a carbanion can lead to a coupling reaction for instance in the electrosynthesis of the tetramethyl ester of ethanetetracarboxylic acid from the corresponding malonate ester
* α-amino acids form nitriles and carbon dioxide via oxidative decarboxylation at AgO anodes (the latter is formed in-situ by oxidation of AgO):
* Cyanoacetic acid from cathodic reduction of carbon dioxide and anodic oxidation of acetonitrile.
* Propiolic acid is prepared commercially by oxidizing propargyl alcohol at a lead electrode.. | 7 | Physical Chemistry |
The water content of most compounds can be determined with a knowledge of its formula. An unknown sample can be determined through thermogravimetric analysis (TGA) where the sample is heated strongly, and the accurate weight of a sample is plotted against the temperature. The amount of water driven off is then divided by the molar mass of water to obtain the number of molecules of water bound to the salt. | 3 | Analytical Chemistry |
IP is an organic molecule with a molecular mass of 420.10 g/mol. Its empirical formula is CHOP. It is composed of an inositol ring with three phosphate groups bound at the 1, 4, and 5 carbon positions, and three hydroxyl groups bound at positions 2, 3, and 6. | 1 | Biochemistry |
Tacticity (from , "relating to arrangement or order") is the relative stereochemistry of adjacent chiral centers within a macromolecule. The practical significance of tacticity rests on the effects on the physical properties of the polymer. The regularity of the macromolecular structure influences the degree to which it has rigid, crystalline long range order or flexible, amorphous long range disorder. Precise knowledge of tacticity of a polymer also helps understanding at what temperature a polymer melts, how soluble it is in a solvent and its mechanical properties.
A tactic macromolecule in the IUPAC definition is a macromolecule in which essentially all the configurational (repeating) units are identical. Tacticity is particularly significant in vinyl polymers of the type - where each repeating unit with a substituent R on one side of the polymer backbone is followed by the next repeating unit with the substituent on the same side as the previous one, the other side as the previous one or positioned randomly with respect to the previous one. In a hydrocarbon macromolecule with all carbon atoms making up the backbone in a tetrahedral molecular geometry, the zigzag backbone is in the paper plane with the substituents either sticking out of the paper or retreating into the paper. This projection is called the Natta projection after Giulio Natta. Monotactic macromolecules have one stereoisomeric atom per repeat unit, ditactic to n-tactic macromolecules have more than one stereoisomeric atom per unit. | 4 | Stereochemistry |
Rovibronic coupling, also known as rotation/vibration-electron coupling, denotes the simultaneous interactions between rotational, vibrational, and electronic degrees of freedom in a molecule. When a rovibronic transition occurs, the rotational, vibrational, and electronic states change simultaneously, unlike in rovibrational coupling. The coupling can be observed using spectroscopy, and is most easily seen in the Renner–Teller effect in which a linear polyatomic molecule is in a degenerate electronic state and bending vibrations will cause a large rovibronic coupling. | 7 | Physical Chemistry |
Magic numbers are connected with the number of metal atoms in those thiolate-protected clusters which display an outstanding stability. Such clusters can be synthesized monodispersely and are end products of the etching procedure after an addition of excess thiols does not lead to further metal dissolution. Some important clusters with magic numbers are (SG:Glutathione): Au(SG), Au(SG), Au(SG), Au(SG), Au(SG), Au(SG), Au(SG), Au(SG), and Au(SG).
Au(SCHPh) is also well-known. It was greater than representatives Au(p-MBA) with the para-mercaptobenzoice (para-mercapto-benzoic acid, p-MBA) produced ligand. | 7 | Physical Chemistry |
Sensitizers (denoted "Sens") are compounds, such as fluorescein dyes, methylene blue, and polycyclic aromatic hydrocarbons, which are able to absorb electromagnetic radiation (usually in the visible range of the spectrum) and eventually transfer that energy to molecular oxygen or the substrate of photooxygenation process. Many sensitizers, both naturally occurring and synthetic, rely on extensive aromatic systems to absorb light in the visible spectrum. When sensitizers are excited by light, they reach a singlet state, Sens*. This singlet is then converted into a triplet state (which is more stable), Sens*, via intersystem crossing. The Sens* is what reacts with either the substrate or O in the three types of photooxygenation reactions. | 5 | Photochemistry |
Retinal is a conjugated chromophore. In the human eye, retinal begins in an 11-cis-retinal configuration, which — upon capturing a photon of the correct wavelength — straightens out into an all-trans-retinal configuration. This configuration change pushes against an opsin protein in the retina, which triggers a chemical signaling cascade, which results in perception of light or images by the human brain. The absorbance spectrum of the chromophore depends on its interactions with the opsin protein to which it is bound, so that different retinal-opsin complexes will absorb photons of different wavelengths (i.e., different colors of light). | 1 | Biochemistry |
A nuclear chain reaction was proposed by Leo Szilard in 1933, shortly after the neutron was discovered, yet more than five years before nuclear fission was first discovered. Szilárd knew of chemical chain reactions, and he had been reading about an energy-producing nuclear reaction involving high-energy protons bombarding lithium, demonstrated by John Cockcroft and Ernest Walton, in 1932. Now, Szilárd proposed to use neutrons theoretically produced from certain nuclear reactions in lighter isotopes, to induce further reactions in light isotopes that produced more neutrons. This would in theory produce a chain reaction at the level of the nucleus. He did not envision fission as one of these neutron-producing reactions, since this reaction was not known at the time. Experiments he proposed using beryllium and indium failed.
Later, after fission was discovered in 1938, Szilárd immediately realized the possibility of using neutron-induced fission as the particular nuclear reaction necessary to create a chain-reaction, so long as fission also produced neutrons. In 1939, with Enrico Fermi, Szilárd proved this neutron-multiplying reaction in uranium. In this reaction, a neutron plus a fissionable atom causes a fission resulting in a larger number of neutrons than the single one that was consumed in the initial reaction. Thus was born the practical nuclear chain reaction by the mechanism of neutron-induced nuclear fission.
Specifically, if one or more of the produced neutrons themselves interact with other fissionable nuclei, and these also undergo fission, then there is a possibility that the macroscopic overall fission reaction will not stop, but continue throughout the reaction material. This is then a self-propagating and thus self-sustaining chain reaction. This is the principle for nuclear reactors and atomic bombs.
Demonstration of a self-sustaining nuclear chain reaction was accomplished by Enrico Fermi and others, in the successful operation of Chicago Pile-1, the first artificial nuclear reactor, in late 1942. | 7 | Physical Chemistry |
There is an important distinction between thermal and thermodynamic equilibrium. According to Münster (1970), in states of thermodynamic equilibrium, the state variables of a system do not change at a measurable rate. Moreover, "The proviso at a measurable rate implies that we can consider an equilibrium only with respect to specified processes and defined experimental conditions." Also, a state of thermodynamic equilibrium can be described by fewer macroscopic variables than any other state of a given body of matter. A single isolated body can start in a state which is not one of thermodynamic equilibrium, and can change till thermodynamic equilibrium is reached. Thermal equilibrium is a relation between two bodies or closed systems, in which transfers are allowed only of energy and take place through a partition permeable to heat, and in which the transfers have proceeded till the states of the bodies cease to change.
An explicit distinction between thermal equilibrium and thermodynamic equilibrium is made by C.J. Adkins. He allows that two systems might be allowed to exchange heat but be constrained from exchanging work; they will naturally exchange heat till they have equal temperatures, and reach thermal equilibrium, but in general, will not be in thermodynamic equilibrium. They can reach thermodynamic equilibrium when they are allowed also to exchange work.
Another explicit distinction between thermal equilibrium and thermodynamic equilibrium is made by B. C. Eu. He considers two systems in thermal contact, one a thermometer, the other a system in which several irreversible processes are occurring. He considers the case in which, over the time scale of interest, it happens that both the thermometer reading and the irreversible processes are steady. Then there is thermal equilibrium without thermodynamic equilibrium. Eu proposes consequently that the zeroth law of thermodynamics can be considered to apply even when thermodynamic equilibrium is not present; also he proposes that if changes are occurring so fast that a steady temperature cannot be defined, then "it is no longer possible to describe the process by means of a thermodynamic formalism. In other words, thermodynamics has no meaning for such a process." | 7 | Physical Chemistry |
Triflic acid is one of the strongest acids. Contact with skin causes severe burns with delayed tissue destruction. On inhalation it causes fatal spasms, inflammation and edema.
Like sulfuric acid, triflic acid must be slowly added to polar solvents to prevent thermal runaway. | 0 | Organic Chemistry |
Agostic interactions serve a key function in alkene polymerization and stereochemistry, as well as migratory insertion. | 0 | Organic Chemistry |
In the mid-2000s, Dr. Ferrara was diagnosed with early-stage lung cancer. Several years after the initial lung surgery, it was discovered that the cancer had spread.
Dr. Ferrara died on May 30, 2011, of brain cancer at the age of 68.
Upon approval of Governor McDonnell, the DFS Central Laboratory building was renamed the Paul B. Ferrara Building, in honor of the late department director who died in May 2011. A ceremony and reception was held at the Central Laboratory on November 18, 2011, to unveil the signage displaying the new building name. | 0 | Organic Chemistry |
Not all cells in a multicellular plant contain chloroplasts. All green parts of a plant contain chloroplasts—the chloroplasts, or more specifically, the chlorophyll in them are what make the photosynthetic parts of a plant green. The plant cells which contain chloroplasts are usually parenchyma cells, though chloroplasts can also be found in collenchyma tissue. A plant cell which contains chloroplasts is known as a chlorenchyma cell. A typical chlorenchyma cell of a land plant contains about 10 to 100 chloroplasts.
In some plants such as cacti, chloroplasts are found in the stems, though in most plants, chloroplasts are concentrated in the leaves. One square millimeter of leaf tissue can contain half a million chloroplasts. Within a leaf, chloroplasts are mainly found in the mesophyll layers of a leaf, and the guard cells of stomata. Palisade mesophyll cells can contain 30–70 chloroplasts per cell, while stomatal guard cells contain only around 8–15 per cell, as well as much less chlorophyll. Chloroplasts can also be found in the bundle sheath cells of a leaf, especially in C plants, which carry out the Calvin cycle in their bundle sheath cells. They are often absent from the epidermis of a leaf. | 5 | Photochemistry |
Igor V. Komarov was a coordinator of scientific projects financed by the Ministry of Education and Science of the Ukraine (three applied projects devoted to design of therapeutic peptides, including photocontrolled [http://science.univ.kiev.ua/research/theme/themefund/ ]), Alexander von Humboldt Foundation (Institute Partnershaft and Research Linkage Programs, in collaboration with Karlsruhe University (Karlsruhe, Germany)[http://www.ibg.kit.edu/nmr/english/26.php ] and Leibniz Institute of Molecular Pharmacology (Berlin, Germany)[http://www.leibniz-fmp.de/de/research/chemical-biology/res-groups-chembio/dathe-oehlke/projectspeptidelipidinteractio.html ]), private companies Degussa (the project was devoted to development of large-scale production of a ligand for Rhodium-based catalysts of asymmetric hydrogenation) and Enamine (six medicinal chemistry projects, lead discovery and lead optimization). He is currently a coordinator of a European Horizon2020 Research and Innovation Staff Exchange (RISE) Programme (2016–2019) Grant Agreement number: 690973 [http://pelico.org/ ], the title of the project – “Peptidomimetics with Photocontrolled Biological Activity”. | 0 | Organic Chemistry |
Initial scientific discoveries towards modern-day laser peening began in the early 1960s as pulsed-laser technology began to proliferate around the world. In an early investigation of the laser interaction with materials by Gurgen Askaryan and E.M. Moroz, they documented pressure measurements on a targeted surface using a pulsed laser. The pressures observed were much larger than could be created by the force of the laser beam alone. Research into the phenomenon indicated the high-pressure resulted from a momentum impulse generated by material vaporization at the target surface when rapidly heated by the laser pulse. Throughout the 1960s, a number of investigators further defined and modeled the laser beam pulse interaction with materials and the subsequent generation of stress waves. These, and other studies, observed that stress waves in the material were generated from the rapidly expanding plasma created when the pulsed laser beam struck the target. Subsequently, this led to interest in achieving higher pressures to increase the stress wave intensity. To generate higher pressures it was necessary to increase the power density and focus the laser beam (concentrate the energy), requiring that the laser beam-material interaction occur in a vacuum chamber to avoid dielectric breakdown within the beam in air. These constraints limited study of high-intensity pulsed laser–material interactions to a select group of researchers with high-energy pulsed lasers.
In the late 1960s a major breakthrough occurred when N.C. Anderholm discovered that much higher plasma pressures could be achieved by confining the expanding plasma against the target surface. Anderholm confined the plasma by placing a quartz overlay, transparent to the laser beam, firmly against the target surface. With the overlay in place, the laser beam passed through the quartz before interacting with the target surface. The rapidly expanding plasma was now confined within the interface between the quartz overlay and the target surface. This method of confining the plasma greatly increased the resulting pressure, generating pressure peaks of , over an order of magnitude greater than unconfined plasma pressure measurements. The significance of Anderholm's discovery to laser peening was the demonstration that pulsed laser–material interactions to develop high-pressure stress waves could be performed in air, not constrained to a vacuum chamber. | 8 | Metallurgy |
ISO REMCO, the ISO committee responsible for guidance on reference materials within ISO, defines the following classes of reference material:
; Reference Material: Material, sufficiently homogeneous and stable with respect to one or more specified properties, which has been established to be fit for its intended use in a measurement process.
; Certified Reference Material: Reference material characterized by a metrologically valid procedure for one or more specified properties, accompanied by a certificate that provides the value of the specified property, its associated uncertainty, and a statement of metrological traceability. | 3 | Analytical Chemistry |
Electrolysis in an aqueous solution is a similar process as mentioned in electrolysis of water. However, it is considered to be a complex process because the contents in solution have to be analyzed in half reactions, whether reduced or oxidized. | 7 | Physical Chemistry |
Prime editing efficiency can be increased with the use of engineered pegRNAs (epegRNAs). One common issue with traditional pegRNAs is degradation of the 3 end, leading to decreased PE efficiency. epegRNAs have a structured RNA motif added to their 3 end to prevent degradation. | 1 | Biochemistry |
In the early days, chromosome walking from genetically linked DNA markers was used to identify and clone disease genes. However, the large molecular distance between known markers and the gene of interest was complicating the cloning process. In 1987, a human chromosome jumping library was constructed to clone the cystic fibrosis gene. Cystic fibrosis is an autosomal recessive disease affecting 1 in 2000 Caucasians. This was the first disease in which the usefulness of the jumping libraries was demonstrated. Met oncogene was a marker tightly linked to the cystic fibrosis gene on human chromosome 7, and the library was screened for a jumping clone starting at this marker. The cystic fibrosis gene was determined to localize 240kb downstream of the met gene. Chromosome jumping helped reduce the mapping "steps" and bypass the highly repetitive regions in the mammalian genome. Chromosome jumping also allowed the production of probes required for faster diagnosis of this and other diseases. | 1 | Biochemistry |
Inner sphere electron transfer (IS ET) or bonded electron transfer is a redox chemical reaction that proceeds via a covalent linkage—a strong electronic interaction—between the oxidant and the reductant reactants. In inner sphere electron transfer, a ligand bridges the two metal redox centers during the electron transfer event. Inner sphere reactions are inhibited by large ligands, which prevent the formation of the crucial bridged intermediate. Thus, inner sphere ET is rare in biological systems, where redox sites are often shielded by bulky proteins. Inner sphere ET is usually used to describe reactions involving transition metal complexes and most of this article is written from this perspective. However, redox centers can consist of organic groups rather than metal centers.
The bridging ligand could be virtually any entity that can convey electrons. Typically, such a ligand has more than one lone electron pair, such that it can serve as an electron donor to both the reductant and the oxidant. Common bridging ligands include the halides and the pseudohalides such as hydroxide and thiocyanate. More complex bridging ligands are also well known including oxalate, malonate, and pyrazine. Prior to ET, the bridged complex must form, and such processes are often highly reversible. Electron transfer occurs through the bridge once it is established. In some cases, the stable bridged structure may exist in the ground state; in other cases, the bridged structure may be a transiently-formed intermediate, or else as a transition state during the reaction.
The alternative to inner sphere electron transfer is outer sphere electron transfer. In any transition metal redox process, the mechanism can be assumed to be outer sphere unless the conditions of the inner sphere are met. Inner sphere electron transfer is generally enthalpically more favorable than outer sphere electron transfer due to a larger degree of interaction between the metal centers involved, however, inner sphere electron transfer is usually entropically less favorable since the two sites involved must become more ordered (come together via a bridge) than in outer sphere electron transfer. | 7 | Physical Chemistry |
The longer tag sequence confers a higher specificity than the classical SAGE tag of 9–10 bp. The level of unique gene expression is represented by the count of transcripts present per million molecules, similar to SAGE output. A significant advantage is the larger library size compared with SAGE. An MPSS library typically holds 1 million signature tags, which is roughly 20 times the size of a SAGE library. Some of the disadvantages related to SAGE apply to MPSS as well, such as loss of certain transcripts due to lack of restriction enzyme recognition site and ambiguity in tag annotation. The high sensitivity and absolute gene expression certainly favors MPSS. However, the technology is only available through Lynxgen Therapeutics, Inc. (then Solexa Inc till 2006 and then Illumina). | 1 | Biochemistry |
The reactions included in the calculation are only those that actually occur under the given conditions, and not those that might occur under different conditions such as higher temperature or the presence of a catalyst. For example, the dissociation of water into its elements does not occur at ordinary temperature, so a system of water, hydrogen and oxygen at 25 °C has 3 independent components. | 7 | Physical Chemistry |
Ashe was awarded the Metlife Foundation Award for Medical Research in Alzheimers Disease in 2005. Ashe also earned the Potamkin Prize in 2006 for her Alzheimers research, shortly after the publication of the 2006 Nature paper.
In 2009, Ashe was elected to the National Academy of Medicine for her achievements in medicine. | 1 | Biochemistry |
Bridging carbido ligands can be subdivided into three classes:
*cumulenic ,
*metallocarbyne , and
*polar covalent .
Cumulenic compounds generally bridge two metal atoms of the same element and are symmetrical. However, there are exceptions to this.
In contrast, metallocarbyne compounds are generally constitutionally heterobimetallic, with complexes containing varying coordination geometries being common. These moieties have been able to serve as precursors to elaborate molecular scaffolds such as porphyrin derivatives.
The polar covalent class is distinguished from metallocarbynes by a very fine line. This carbide-metal interaction is considered labile in nature. Carbon here can be understood fundamentally as being similar to CO ligands, that is, dative (L-type). Although, this class has also been described to some extent being analogous to the behavior of Lewis acid adduct-forming terminal nitrido and oxo complexes e.g. (PMePh)Cl-Re≡N-BCl and tBu(CH)(Br)W=O-AlBr. | 0 | Organic Chemistry |
Graft copolymers are generated by attaching chains of one monomer to the main chain of another polymer; a branched block copolymer is formed. Furthermore, end groups play an important role in the process of initiation, propagation and termination of graft polymers. Graft polymers can be achieved by either "grafting from" or "grafting to"; these different methods are able to produce a vast array of different polymer structures, which can be tailored to the application in question. The "grafting from" approach involves, for example, generation of radicals along a polymer chain, which can then be reacted with monomers to grow a new polymer from the backbone of another. In "grafting from," the initiation sites on the backbone of the first polymer can be part of the backbone structure originally or generated in situ. The "grafting to" approach involves the reaction of functionalized monomers to a polymer backbone. In graft polymers, end groups play an important role, for example, in the "grafting to" technique the generation of the reactive functionalized monomers occurs at the end group, which is then tethered to the polymer chain. There are various methods to synthesize graft polymers some of the more common include redox reaction to produce free radicals, by free radical polymerization techniques avoiding chain termination (ATRP, RAFT, nitroxide mediated, for example) and step-growth polymerization. A schematic of "grafting from" and "grafting to" is illustrated in the figure below.
The "grafting from" technique involves the generation of radicals along the polymer backbone from an abstraction of a halogen, from either the backbone or a functional group along the backbone. Monomers are reacted with the radicals along the backbone and subsequently generate polymers which are grafted from the backbone of the first polymer. The schematic for "grafting to" shows an example using anionic polymerizations, the polymer containing the carbonyl functionalities gets attacked by the activated polymer chain and generates a polymer attached to the associated carbon along with an alcohol group, in this example. These examples show us the potential of fine tuning end groups of polymer chains to target certain copolymer structures. | 7 | Physical Chemistry |
Except their abilities in catalyzing organic reactions, palladacycles have also shown their potential in medicinal and biological chemistry after the success of cis-Pt(NH)Cl as an anticancer agent. Additionally, they can also be used in CO/SCN- sensing. | 0 | Organic Chemistry |
The uses of bioluminescence and its biological and ecological significance for animals, including host organisms for bacteria symbiosis, have been widely studied. The biological role and evolutionary history for specifically bioluminescent bacteria still remains quite mysterious and unclear. However, there are continually new studies being done to determine the impacts that bacterial bioluminescence can have on our constantly changing environment and society. Aside from the many scientific and medical uses, scientists have also recently begun to come together with artists and designers to explore new ways of incorporating bioluminescent bacteria, as well as bioluminescent plants, into urban light sources to reduce the need for electricity. They have also begun to use bioluminescent bacteria as a form of art and urban design for the wonder and enjoyment of human society.
One explanation for the role of bacterial bioluminescence is from the biochemical aspect. Several studies have shown the biochemical roles of the luminescence pathway. It can function as an alternate pathway for electron flow under low oxygen concentration, which can be advantageous when no fermentable substrate is available. In this process, light emission is a side product of the metabolism.
Evidence also suggests that bacterial luciferase contributes to the resistance of oxidative stress. In laboratory culture, luxA and luxB mutants of Vibrio harveyi, which lacked luciferase activity, showed impairment of growth under high oxidative stress compared to wild type. The luxD mutants, which had an unaffected luciferase but were unable to produce luminescence, showed little or no difference. This suggests that luciferase mediates the detoxification of reactive oxygen.
Bacterial bioluminescence has also been proposed to be a source of internal light in photoreactivation, a DNA repair process carried out by photolyase. Experiments have shown that non-luminescent V. harveyi mutants are more sensitive to UV irradiation, suggesting the existence of a bioluminescent-mediated DNA repair system.
Another hypothesis, called the "bait hypothesis", is that bacterial bioluminescence attracts predators who will assist in their dispersal. They are either directly ingested by fish or indirectly ingested by zooplankton that will eventually be consumed by higher trophic levels. Ultimately, this may allow passage into the fish gut, a nutrient-rich environment where the bacteria can divide, be excreted, and continue their cycle. Experiments using luminescent Photobacterium leiognathi and non-luminescent mutants have shown that luminescence attracts zooplankton and fish, thus supporting this hypothesis. | 1 | Biochemistry |
Fischer–Tropsch plants associated with biomass or coal or related solid feedstocks (sources of carbon) must first convert the solid fuel into gases. These gases include CO, H, and alkanes. This conversion is called gasification. Synthesis gas ("syngas") is obtained from biomass/coal gasification is a mixture of hydrogen and carbon monoxide. The H:CO ratio is adjusted using the water-gas shift reaction. Coal-based FT plants produce varying amounts of CO, depending upon the energy source of the gasification process. However, most coal-based plants rely on the feed coal to supply all the energy requirements of the process. | 0 | Organic Chemistry |
The negative charge of its phosphate backbone moves the DNA towards the positively charged anode during electrophoresis. However, the migration of DNA molecules in solution, in the absence of a gel matrix, is independent of molecular weight during electrophoresis. The gel matrix is therefore responsible for the separation of DNA by size during electrophoresis, and a number of models exist to explain the mechanism of separation of biomolecules in gel matrix. A widely accepted one is the Ogston model which treats the polymer matrix as a sieve. A globular protein or a random coil DNA moves through the interconnected pores, and the movement of larger molecules is more likely to be impeded and slowed down by collisions with the gel matrix, and the molecules of different sizes can therefore be separated in this sieving process.
The Ogston model however breaks down for large molecules whereby the pores are significantly smaller than size of the molecule. For DNA molecules of size greater than 1 kb, a reptation model (or its variants) is most commonly used. This model assumes that the DNA can crawl in a "snake-like" fashion (hence "reptation") through the pores as an elongated molecule. A biased reptation model applies at higher electric field strength, whereby the leading end of the molecule become strongly biased in the forward direction and pulls the rest of the molecule along. Real-time fluorescence microscopy of stained molecules, however, showed more subtle dynamics during electrophoresis, with the DNA showing considerable elasticity as it alternately stretching in the direction of the applied field and then contracting into a ball, or becoming hooked into a U-shape when it gets caught on the polymer fibres. | 1 | Biochemistry |
A wide variety of divinylcyclopropanes undergo the titular reaction. These precursors have been generated by a variety of methods, including the addition of cyclopropyl nucleophiles (salts of lithium, or copper) to activated double or triple bonds, elimination of bis(2-haloethyl)cyclopropanes and cyclopropanation.
In the example below, cuprate addition-elimination generates the transient enone 1, which rearranges to spirocycle 2.
Organolithiums can be employed in a similar role, but add in a direct fashion to carbonyls. Products with fused topology result.
Rearrangement after elimination of ditosylates has been observed; the chlorinated cycloheptadiene thus produced isomerizes to conjugated heptadiene 3 during the reaction.
Cyclopropanation with conjugated diazo compounds produces divinylcyclopropanes that then undergo rearrangement. When cyclic starting materials are used, bridged products result.
Substrates containing three-membered heterocyclic rings can also undergo the reaction. cis-Divinylepoxides give oxepines at elevated temperatures (100 °C). trans Isomers undergo an interesting competitive rearrangement to dihydrofurans through the intermediacy of a carbonyl ylide and the same ylide intermediate has been proposed as the direct precursor to the oxepine product 4. Conjugated dienyl epoxides form similar products, lending support to the existence of an ylide intermediate.
Divinyl aziridines undergo a similar suite of reactions providing azepines or vinyl pyrrolines depending on the relative configuration of the aziridine starting material. Divinyl thiiranes can provide thiepines or dihydrothiophenes, although these reactions are slower than those of the corresponding nitrogen- and oxygen-containing compounds. | 0 | Organic Chemistry |
The precipitation of calcium carbonate is important as it results in a loss of alkalinity as well as a release of CO (Equation 4), and therefore a change in the rate of preservation of calcium carbonate can alter the partial pressure of CO in Earths atmosphere. CaCO is supersatured in the great majority of ocean surface waters and undersaturated at depth, meaning the shells are more likely to dissolve as they sink to ocean depths. CaCO can also be dissolved through metabolic dissolution (i.e. can be used as food and excreted) and thus deep ocean sediments have very little calcium carbonate. The precipitation and burial of calcium carbonate in the ocean removes particulate inorganic carbon from the ocean and ultimately forms limestone. On time scales greater than 500,000 years Earths climate is moderated by the flux of carbon in and out of the lithosphere. Rocks formed in the ocean seafloor are recycled through plate tectonics back to the surface and weathered or subducted into the mantle, the carbon outgassed by volcanoes. | 9 | Geochemistry |
Amatoxins and phallotoxins are 8- and 7-membered natural products, respectively, characterized by N-to-C cyclization in addition to a tryptathionine motif derived from the crosslinking of Cys and Trp. The amatoxins and phallotoxins also differ from other RiPPs based on the presence of a C-terminal recognition sequence in addition to the N-terminal leader peptide. α-Amanitin, an amatoxin, has a number of posttranslational modifications in addition to macrocyclization and formation of the tryptathionine bridge: oxidation of the tryptathionine leads to the presence of a sulfoxide, and numerous hydroxylations decorate the natural product. As an amatoxin, α-amanitin is an inhibitor of RNA polymerase II. | 1 | Biochemistry |
The first scientific concept of acids and bases was provided by Lavoisier in around 1776. Since Lavoisiers knowledge of strong acids was mainly restricted to oxoacids, such as (nitric acid) and (sulfuric acid), which tend to contain central atoms in high oxidation states surrounded by oxygen, and since he was not aware of the true composition of the hydrohalic acids (HF, HCl, HBr, and HI), he defined acids in terms of their containing oxygen', which in fact he named from Greek words meaning "acid-former" (). The Lavoisier definition held for over 30 years, until the 1810 article and subsequent lectures by Sir Humphry Davy in which he proved the lack of oxygen in hydrogen sulfide (), hydrogen telluride (), and the hydrohalic acids. However, Davy failed to develop a new theory, concluding that "acidity does not depend upon any particular elementary substance, but upon peculiar arrangement of various substances". One notable modification of oxygen theory was provided by Jöns Jacob Berzelius, who stated that acids are oxides of nonmetals while bases are oxides of metals. | 7 | Physical Chemistry |
Sulfur isotopes of sediments are often measured for studying environments in the Earth's past (Paleoenvironment). Disproportionation of sulfur intermediates, being one of the processes affecting sulfur isotopes of sediments, has drawn attention from geoscientists for studying the redox conditions in the oceans in the past.
Sulfate-reducing bacteria fractionate sulfur isotopes as they take in sulfate and produce sulfide. Prior to 2010s, it was thought that sulfate reduction could fractionate sulfur isotopes up to 46 permil and fractionation larger than 46 permil recorded in sediments must be due to disproportionation of sulfur intermediates in the sediment. This view has changed since the 2010s. As substrates for disproportionation are limited by the product of sulfate reduction, the isotopic effect of disproportionation should be less than 16 permil in most sedimentary settings.
Disproportionation can be carried out by microorganisms obligated to disproportionation or microorganisms that can carry out sulfate reduction as well. Common substrates for disproportionation include elemental sulfur, thiosulfate and sulfite. | 0 | Organic Chemistry |
The principle of minimum energy is essentially a restatement of the second law of thermodynamics. It states that for a closed system, with constant external parameters and entropy, the internal energy will decrease and approach a minimum value at equilibrium. External parameters generally means the volume, but may include other parameters which are specified externally, such as a constant magnetic field.
In contrast, for isolated systems (and fixed external parameters), the second law states that the entropy will increase to a maximum value at equilibrium. An isolated system has a fixed total energy and mass. A closed system, on the other hand, is a system which is connected to another, and cannot exchange matter (i.e. particles), but can transfer other forms of energy (e.g. heat), to or from the other system. If, rather than an isolated system, we have a closed system, in which the entropy rather than the energy remains constant, then it follows from the first and second laws of thermodynamics that the energy of that system will drop to a minimum value at equilibrium, transferring its energy to the other system. To restate:
* The maximum entropy principle: For a closed system with fixed internal energy (i.e. an isolated system), the entropy is maximized at equilibrium.
* The minimum energy principle: For a closed system with fixed entropy, the total energy is minimized at equilibrium. | 7 | Physical Chemistry |
A: α-naphthol – 5 g
*Absolute ethyl alcohol – 100 mL – 0.6 mL – 3 parts
*B: KOH – 40 g
*Distilled water – 100 mL – 0.2 mL – 1 part | 3 | Analytical Chemistry |
Fellutanine A, B, C and D are bio-active diketopiperazine alkaloids isolated from the cultures of Penicillium fellutanum, that belongs to a class of naturally occurring 2,5-diketopiperazines. Originally they were thought to be based on the "trans" cyclic dipetide cyclo(L-Trp-D-Trp) but were later shown to be based on the "cis" cyclic dipetide cyclo(L-Trp-L-Trp). This was also confirmed when fellutanine A, B and C were isolated from Penicillium simplicissimum. The fellutanines A−C, are non-annulated analogues of cyclo(L-Trp-L-Trp), but unlike their diannulated analogue fellutanine D are not cytotoxic. | 0 | Organic Chemistry |
The main advantages of excimer lamps over other sources of UV and VUV radiation are as follows:
* high average specific power of UV radiation (up to 1 Watt per cubic centimeter of active medium);
* high energy of an emitted photon (from 3.5 to 11.5 eV);
* quasimonochromatic radiation with the spectral full-width at half maximum from 2 to 15 nm;
* high power spectral density of UV radiation;
* choice of the wavelength of the spectral maximum of UV radiation for specific purposes (see table);
* availability of multi-wave UV radiation owing to simultaneous excitation of several kinds of working excimer molecules;
* absence of visible and IR radiation;
* instant achievement of the operating mode;
* low heating of radiating surface;
* absence of mercury. | 5 | Photochemistry |
Some authors define stereographic projection from the north pole (0, 0, 1) onto the plane , which is tangent to the unit sphere at the south pole (0, 0, −1). This can be described as a composition of a projection onto the equatorial plane described above, and a homothety from it to the polar plane. The homothety scales the image by a factor of 2 (a ratio of a diameter to a radius of the sphere), hence the values and produced by this projection are exactly twice those produced by the equatorial projection described in the preceding section. For example, this projection sends the equator to the circle of radius 2 centered at the origin. While the equatorial projection produces no infinitesimal area distortion along the equator, this pole-tangent projection instead produces no infinitesimal area distortion at the south pole.
Other authors use a sphere of radius and the plane . In this case the formulae become
In general, one can define a stereographic projection from any point on the sphere onto any plane such that
* is perpendicular to the diameter through , and
* does not contain .
As long as meets these conditions, then for any point other than the line through and meets in exactly one point , which is defined to be the stereographic projection of P onto E. | 3 | Analytical Chemistry |
Nicotinamide adenine dinucleotide (NAD) is a coenzyme central to metabolism. Found in all living cells, NAD is called a dinucleotide because it consists of two nucleotides joined through their phosphate groups. One nucleotide contains an adenine nucleobase and the other, nicotinamide. NAD exists in two forms: an oxidized and reduced form, abbreviated as NAD and NADH (H for hydrogen), respectively.
In cellular metabolism, NAD is involved in redox reactions, carrying electrons from one reaction to another, so it is found in two forms: NAD is an oxidizing agent, accepting electrons from other molecules and becoming reduced; with H, this reaction forms NADH, which can be used as a reducing agent to donate electrons. These electron transfer reactions are the main function of NAD. It is also used in other cellular processes, most notably as a substrate of enzymes in adding or removing chemical groups to or from proteins, in posttranslational modifications. Because of the importance of these functions, the enzymes involved in NAD metabolism are targets for drug discovery.
In organisms, NAD can be synthesized from simple building-blocks (de novo) from either tryptophan or aspartic acid, each a case of an amino acid. Alternatively, more complex components of the coenzymes are taken up from nutritive compounds such as niacin; similar compounds are produced by reactions that break down the structure of NAD, providing a salvage pathway that recycles them back into their respective active form.
Some NAD is converted into the coenzyme nicotinamide adenine dinucleotide phosphate (NADP), whose chemistry largely parallels that of NAD, though its predominant role is as a coenzyme in anabolic metabolism.
In the name NAD, the superscripted plus sign indicates the positive formal charge on one of its nitrogen atoms. | 5 | Photochemistry |
Myosins are a superfamily of actin motor proteins that convert chemical energy in the form of ATP to mechanical energy, thus generating force and movement. The first identified myosin, myosin II, is responsible for generating muscle contraction. Myosin II is an elongated protein that is formed from two heavy chains with motor heads and two light chains. Each myosin head contains actin and ATP binding site. The myosin heads bind and hydrolyze ATP, which provides the energy to walk toward the plus end of an actin filament. Myosin II are also vital in the process of cell division. For example, non-muscle myosin II bipolar thick filaments provide the force of contraction needed to divide the cell into two daughter cells during cytokinesis. In addition to myosin II, many other myosin types are responsible for variety of movement of non-muscle cells. For example, myosin is involved in intracellular organization and the protrusion of actin-rich structures at the cell surface. Myosin V is involved in vesicle and organelle transport. Myosin XI is involved in cytoplasmic streaming, wherein movement along microfilament networks in the cell allows organelles and cytoplasm to stream in a particular direction. Eighteen different classes of myosins are known.
Genomic representation of myosin motors:
* Fungi (yeast): 5
* Plants (Arabidopsis): 17
* Insects (Drosophila): 13
* Mammals (human): 40
* Chromadorea ( nematode C. elegans): 15 | 6 | Supramolecular Chemistry |
Activated carbon has strong affinity for many gases and has an adsorption cross section of 0.162 nm for nitrogen adsorption at liquid-nitrogen temperature (77 K). BET theory can be applied to estimate the specific surface area of activated carbon from experimental data, demonstrating a large specific surface area, even around 3000 m/g. However, this surface area is largely overestimated due to enhanced adsorption in micropores, and more realistic methods should be used for its estimation, such as the subtracting pore effect (SPE) method. | 7 | Physical Chemistry |
The preinitiation complex, which contains a mediator, transcription factors, a nucleosome and RNA polymerase II, is important to position the polymerase for the start of transcription. Before RNA synthesis can occur, the polymerase must dissociate from mediator. This appears to be accomplished by phosphorylation of part of the polymerase by a kinase. Importantly, mediator and transcription factors do not dissociate from the DNA at the time polymerase begins transcription. Rather, the complex remains at the promoter to recruit another RNA polymerase to begin another round of transcription.
There is some evidence to suggest that mediator in a yeast is involved in regulating RNA polymerase III (Pol III) transcripts of tRNAs In support of that evidence, an independent report showed specific association of mediator with Pol III in Saccharomyces cerevisiae. Those authors also reported specific associations with RNA polymerase I and proteins involved in transcription elongation and RNA processing, supporting other evidence of mediator's involvement in elongation and processing. | 1 | Biochemistry |
In biochemistry, glycoside hydrolases (also called glycosidases or glycosyl hydrolases) are a class of enzymes which catalyze the hydrolysis of glycosidic bonds in complex sugars. They are extremely common enzymes, with roles in nature including degradation of biomass such as cellulose (cellulase), hemicellulose, and starch (amylase), in anti-bacterial defense strategies (e.g., lysozyme), in pathogenesis mechanisms (e.g., viral neuraminidases) and in normal cellular function (e.g., trimming mannosidases involved in N-linked glycoprotein biosynthesis). Together with glycosyltransferases, glycosidases form the major catalytic machinery for the synthesis and breakage of glycosidic bonds. | 0 | Organic Chemistry |
Sum frequency generation spectroscopy (SFG) is a nonlinear laser spectroscopy technique used to analyze surfaces and interfaces. It can be expressed as a sum of a series of Lorentz oscillators. In a typical SFG setup, two laser beams mix at an interface and generate an output beam with a frequency equal to the sum of the two input frequencies, traveling in a direction allegedly given by the sum of the incident beams' wavevectors. The technique was developed in 1987 by Yuen-Ron Shen and his students as an extension of second harmonic generation spectroscopy and rapidly applied to deduce the composition, orientation distributions, and structural information of molecules at gas–solid, gas–liquid and liquid–solid interfaces. Soon after its invention, Philippe Guyot-Sionnest extended the technique to obtain the first measurements of electronic and vibrational dynamics at surfaces. SFG has advantages in its ability to be monolayer surface sensitive, ability to be performed in situ (for example aqueous surfaces and in gases), and its capability to provide ultrafast time resolution. SFG gives information complementary to infrared and Raman spectroscopy. | 7 | Physical Chemistry |
Electroplating is a chemical surface-treatment technique. It involves bonding a thin layer of another metal such as gold, silver, chromium or zinc to the surface of the product. This is done by selecting the coating material electrolyte solution, which is the material that is going to coat the workpiece (gold, silver, zinc). There needs to be two electrodes of different materials: one the same material as the coating material and one that is receiving the coating material. Two electrodes are electrically charged and the coating material is stuck to the work piece. It is used to reduce corrosion as well as to improve the product's aesthetic appearance. It is also used to make inexpensive metals look like the more expensive ones (gold, silver). | 8 | Metallurgy |
For many surface/adsorbate configurations, surface energy data and experimental observations are unavailable. As wetting interactions are of great importance in various applications, it is often desired to predict and compare the wetting behavior of various material surfaces with particular crystallographic orientations, with relation to water or other adsorbates. This can be done from an atomistic perspective with tools including molecular dynamics and density functional theory. In the theoretical prediction of wetting by ab initio approaches such as DFT, ice is commonly substituted for water. This is because DFT calculations are generally conducted assuming conditions of zero thermal movement of atoms, essentially meaning the simulation is conducted at absolute zero. This simplification nevertheless yields results that are relevant for the adsorption of water under realistic conditions and the use of ice for the theoretical simulation of wetting is commonplace. | 7 | Physical Chemistry |
In addition to the traditional line-by-line spectroscopic absorption parameters, the HITRAN database contains information on absorption cross-sections where the line-by-line parameters are absent or incomplete. Typically HITRAN includes absorption cross-sections for heavy polyatomic molecules (with low-lying vibrational modes) which are difficult for detailed analysis due to the high density of the spectral bands/lines, broadening effects, isomerization, and overall modeling complexity. There are 327 molecular species in the current edition of the database provided as cross-section files. The cross-section files are provided in the HITRAN format described on the official HITRAN website (http://hitran.org/docs/cross-sections-definitions/). | 7 | Physical Chemistry |
Sarcalumenin is a protein that in humans is encoded by the SRL gene.
Sarcalumenin is a calcium-binding protein that can be found in the sarcoplasmic reticulum of striated muscle. Sarcalumenin is partially responsible for calcium buffering in the lumen of the sarcoplasmic reticulum and helps out calcium pump proteins. Additionally, sarcalumenin is necessary for keeping a normal sinus rhythm during both aerobic and anaerobic exercise activity. Sarcalumenin is a calcium-binding glycoprotein composed of 473 acidic amino acids with a molecular weight of 160 KDa. Together along with other luminal calcium buffer proteins, sarcalumenin plays an important role in regulation of calcium uptake and release during excitation-contraction coupling (ECC) in muscle fibers. | 1 | Biochemistry |
DGGE was invented by Leonard Lerman, while he was a professor at SUNY Albany.
The same equipment can be used for analysis of protein, which was first done by Thomas E. Creighton of the MRC Laboratory of Molecular Biology, Cambridge, England. Similar looking patterns are produced by proteins and nucleic acids, but the fundamental principles are quite different.
TGGE was first described by Thatcher and Hodson and by Roger Wartell of Georgia Tech. Extensive work was done by the group of Riesner in Germany. Commercial equipment for DGGE is available from Bio-Rad, INGENY and CBS Scientific; a system for TGGE is available from Biometra. | 1 | Biochemistry |
After an eight-year project involving the use of a pioneering cloning technique, Japanese researchers created 25 generations of healthy cloned mice with normal lifespans, demonstrating that clones are not intrinsically shorter-lived than naturally born animals. Other sources have noted that the offspring of clones tend to be healthier than the original clones and indistinguishable from animals produced naturally.
Some posited that Dolly the sheep may have aged more quickly than naturally born animals, as she died relatively early for a sheep at the age of six. Ultimately, her death was attributed to a respiratory illness, and the "advanced aging" theory is disputed.
A detailed study released in 2016 and less detailed studies by others suggest that once cloned animals get past the first month or two of life they are generally healthy. However, early pregnancy loss and neonatal losses are still greater with cloning than natural conception or assisted reproduction (IVF). Current research is attempting to overcome these problems. | 1 | Biochemistry |
In quantum chemistry, the Dunham expansion is an expression for the rotational-vibrational energy levels of a diatomic molecule:
where and are the vibrational and rotational quantum numbers, and is the projection of along the internuclear axis in the body-fixed frame.
The constant coefficients are called Dunham parameters with representing the electronic energy. The expression derives from a semiclassical treatment of a perturbational approach to deriving the energy levels. The Dunham parameters are typically calculated by a least-squares fitting procedure of energy levels with the quantum numbers. | 7 | Physical Chemistry |
Under physiological conditions, ptaquiloside readily liberates glucose to produce the ptaquilodienone. The alkylation of amino acids with the dienone mostly takes place at the thiol group in cysteine, glutathione and methionine. The alkylation at the carboxylate group of each amino acid, forming the corresponding ester, is also observed to a small extent based on the previously reported literature. The dienone reacts with both adenine (majorly at N-3) and guanine (majorly at N-7) residues of DNA to form the DNA adducts. The alkylation induces spontaneous depurination and cleavage of DNA at adenine base site. In a model reaction with a deoxytetranucleotide (as shown on the right), a covalent adduct is found at a guanine residue and the N-glycosidic bond breaks to release the adduct. In 1998, Prakash, Smith and co-workers showed that the alkylation of adenine by ptaquiloside in codon 61 followed by depurination and error in the DNA synthesis resulted in the activation of H-ras proto-oncogene in the ileum of calves fed bracken. | 0 | Organic Chemistry |
Lichenin, also known as lichenan or moss starch, is a complex glucan occurring in certain species of lichens. It can be extracted from Cetraria islandica (Iceland moss). It has been studied since about 1957. | 1 | Biochemistry |
The dry distillation of calcium acetate to give acetone was reported by Charles Friedel in 1858 and until World War I ketonization was the premier commercial method for its production.
Ketonic decarboxylation of propanoic acid over a manganese(II) oxide catalyst in a tube furnace affords 3-pentanone. Of commercial interest are related ketonizations using cerium(IV) oxide and manganese dioxide on alumina as the catalysts. 5-Nonanone, which is potentially of interest as a diesel fuel, can be produced from valeric acid. Stearone is prepared by heating magnesium stearate.
An example of intramolecular ketonization is the conversion of adipic acid to cyclopentanone with barium hydroxide.
The synthesis of 4-heptanone illustrates the production of the metal carboxylate in situ. Iron powder and butyric acid are converted to iron butyrate. Pyrolysis of that salt gives the ketone. | 0 | Organic Chemistry |
A Langmuir monolayer can be compressed or expanded by modifying its area with a moving barrier in a Langmuir film balance. If the surface tension of the interface is measured during the compression, a compression isotherm is obtained. This isotherm shows the variation of surface pressure (, where is the surface tension of the interface before the monolayer is formed) with the area (the inverse of surface concentration ). It is analogous with a 3D process in which pressure varies with volume.
A variety of bidimensional phases can be detected, each separated by a phase transition. During the phase transition, the surface pressure doesnt change, but the area does, just like during normal phase transitions volume changes but pressure doesnt.
The 2D phases, in increasing pressure order:
* Bidimensional gas: there are few molecules per area unit, and they have few interactions, therefore, analogous of the equations of state for 3D gases can be used: ideal gas law , where is the area per mole. As the surface pressure increases, more complex equations are needed (Van der Waals, virial...)
* Expanded liquid
* Compressed liquid
* Solid
If the area is further reduced once the solid phase has been reached, collapse occurs, the monolayer breaks and soluble aggregates and multilayers are formed
Gibbs monolayers also follow equations of state, which can be deduced from Gibbs isotherm.
* For very dilute solutions , through Gibbs isotherm another analogous of ideal gas law is reached
* For more concentrated solutions and applying Langmuir isotherm , thus | 7 | Physical Chemistry |
These cells leave G1 and enter G0, a resting stage. A cell in G0 is doing its job without actively preparing to divide. | 1 | Biochemistry |
Some publications use a simpler form of this equation that doesn't correct for the reference range of free T4. It is calculated with
The disadvantage of this uncorrected version is that its numeric results are highly dependent on the used assays and their units of measurement. | 1 | Biochemistry |
Early TPV work focused on the use of silicon. Silicon's commercial availability, low cost, scalability and ease of manufacture makes this material an appealing candidate. However, the relatively wide bandgap of Si (1.1eV) is not ideal for use with a black body emitter at lower operating temperatures. Calculations indicate that Si PVs are only feasible at temperatures much higher than 2000 K. No emitter has been demonstrated that can operate at these temperatures. These engineering difficulties led to the pursuit of lower-bandgap semiconductor PVs.
Using selective radiators with Si PVs is still a possibility. Selective radiators would eliminate high and low energy photons, reducing heat generated. Ideally, selective radiators would emit no radiation beyond the band edge of the PV converter, increasing conversion efficiency significantly. No efficient TPVs have been realized using Si PVs. | 7 | Physical Chemistry |
eIF2 is the main protein complex responsible for delivering the initiator tRNA to the P-site of the preinitiation complex, as a ternary complex containing Met-tRNA and GTP (the eIF2-TC). eIF2 has specificity for the methionine-charged initiator tRNA, which is distinct from other methionine-charged tRNAs used for elongation of the polypeptide chain. The eIF2 ternary complex remains bound to the P-site while the mRNA attaches to the 40s ribosome and the complex begins to scan the mRNA. Once the AUG start codon is recognized and located in the P-site, eIF5 stimulates the hydrolysis of eIF2-GTP, effectively switching it to the GDP-bound form via gated phosphate release. The hydrolysis of eIF2-GTP provides the conformational change to change the scanning complex into the 48S Initiation complex with the initiator tRNA-Met anticodon base paired to the AUG. After the initiation complex is formed the 60s subunit joins and eIF2 along with most of the initiation factors dissociate from the complex allowing the 60S subunit to bind. eIF1A and eIF5B-GTP remain bound to one another in the A site and must be hydrolyzed to be released and properly initiate elongation.
eIF2 has three subunits, eIF2-α, β, and γ. The former α-subunit is a target of regulatory phosphorylation and is of particular importance for cells that may need to turn off protein synthesis globally as a response to cell signaling events. When phosphorylated, it sequesters eIF2B (not to be confused with eIF2β), a GEF. Without this GEF, GDP cannot be exchanged for GTP, and translation is repressed. One example of this is the eIF2α-induced translation repression that occurs in reticulocytes when starved for iron. In the case of viral infection, protein kinase R (PKR) phosphorylates eIF2α when dsRNA is detected in many multicellular organisms, leading to cell death.
The proteins eIF2A and eIF2D are both technically named eIF2 but neither are part of the eIF2 heterotrimer and they seem to play unique functions in translation. Instead, they appear to be involved in specialized pathways, such as eIF2-independent translation initiation or re-initiation, respectively. | 1 | Biochemistry |
Transition metal sulfates form a variety of hydrates, each of which crystallizes in only one form. The sulfate group often binds to the metal, especially for those salts with fewer than six aquo ligands. The heptahydrates, which are often the most common salts, crystallize as monoclinic and the less common orthorhombic forms. In the heptahydrates, one water is in the lattice and the other six are coordinated to the ferrous center. Many of the metal sulfates occur in nature, being the result of weathering of mineral sulfides. Many monohydrates are known. | 3 | Analytical Chemistry |
Addition of CO to a solution in contact with a solid can (over time) affect the alkalinity, especially for carbonate minerals in contact with groundwater or seawater. The dissolution (or precipitation) of carbonate rock has a strong influence on the alkalinity. This is because carbonate rock is composed of CaCO and its dissociation will add Ca and into solution. Ca will not influence alkalinity, but will increase alkalinity by 2 units. Increased dissolution of carbonate rock by acidification from acid rain and mining has contributed to increased alkalinity concentrations in some major rivers throughout the eastern U.S. The following reaction shows how acid rain, containing sulfuric acid, can have the effect of increasing river alkalinity by increasing the amount of bicarbonate ion:
:2 CaCO + HSO → 2 Ca + 2 +
Another way of writing this is:
:CaCO + H ⇌ Ca +
The lower the pH, the higher the concentration of bicarbonate will be. This shows how a lower pH can lead to higher alkalinity if the amount of bicarbonate produced is greater than the amount of H remaining after the reaction. This is the case since the amount of acid in the rainwater is low. If this alkaline groundwater later comes into contact with the atmosphere, it can lose CO, precipitate carbonate, and thereby become less alkaline again. When carbonate minerals, water, and the atmosphere are all in equilibrium, the reversible reaction
:CaCO + 2 H ⇌ Ca + CO + HO
shows that pH will be related to calcium ion concentration, with lower pH going with higher calcium ion concentration. In this case, the higher the pH, the more bicarbonate and carbonate ion there will be, in contrast to the paradoxical situation described above, where one does not have equilibrium with the atmosphere. | 9 | Geochemistry |
Pack cementation is a widely used CVD technique that consists of immersing the components to be coated in a metal powder mixture and ammonium halide activators and sealing them in a retort. The entire apparatus is placed inside a furnace and heated in a protective atmosphere to a lower than normal temperature that allows diffusion, due to the halide salts chemical reaction that causes a eutectic bond between the two metals. The surface alloy that is formed due to thermal-diffused ion migration has a metallurgical bond to the substrate and an intermetallic layer found in the gamma layer of the surface alloys.
The traditional pack consists of four components at temperatures below (750 °C):
* Substrate or parts
* Ferrous and non-ferrous powdered alloy: (Ti and/or Al, Si and/or Zn, B and/ or Cr)
* Halide salt activator: Ammonium halide salts
* Relatively inert filler powder (Al2O3, SiO2, or SiC)
This process includes:
* Aluminizing
* Chromizing
* Siliconizing
* Sherardizing
* Boronizing
* Titaniumizing
Pack cementation has reemerged when combined with other chemical processes to lower the temperatures of metal combinations and give intermetallic properties to different alloy combinations for surface treatments. | 8 | Metallurgy |
Gold, copper and tumbaga objects started being produced in Panama and Costa Rica between 300–500 CE. Open-molded casting with oxidation gilding and cast filigrees were in use. By 700–800 CE, small metal sculptures were common and an extensive range of gold and tumbaga ornaments constituted the usual regalia of persons of high status in Panama and Costa Rica.
The earliest specimen of metalwork from the Caribbean is a gold-alloy sheet carbon dated to 70–374 CE. Most Caribbean metallurgy has been dated to between 1200 and 1500 CE and consists of simple, small pieces such as sheets, pendants, beads and bells. These are mostly gold or a gold alloy (with copper or silver) and have been found to be largely cold hammered and sand-polished alluvial nuggets, although a few items seem to have been produced by lost wax casting. It is presumed that at least some of these items were acquired by trade from Colombia. | 8 | Metallurgy |
In plants, the first step in the light-independent reactions of photosynthesis is the fixation of by the enzyme RuBisCO to form 3-phosphoglycerate. However, RuBisCo has a dual carboxylase and oxygenase activity. Oxygenation results in part of the substrate being oxidized rather than carboxylated, resulting in loss of substrate and consumption of energy, in what is known as photorespiration. Oxygenation and carboxylation are competitive, meaning that the rate of the reactions depends on the relative concentration of oxygen and .
In order to reduce the rate of photorespiration, plants increase the concentration of around RuBisCO. To do so two partially isolated compartments differentiate within leaves, the mesophyll and the bundle sheath. Instead of direct fixation by RuBisCO, is initially incorporated into a four-carbon organic acid (either malate or aspartate) in the mesophyll. The organic acids then diffuse through plasmodesmata into the bundle sheath cells. There, they are decarboxylated creating a -rich environment. The chloroplasts of the bundle sheath cells convert this into carbohydrates by the conventional pathway.
There is large variability in the biochemical features of C4 assimilation, and it is generally grouped in three subtypes, differentiated by the main enzyme used for decarboxylation ( NADP-malic enzyme, NADP-ME; NAD-malic enzyme, NAD-ME; and PEP carboxykinase, PEPCK). Since PEPCK is often recruited atop NADP-ME or NAD-ME it was proposed to classify the biochemical variability in two subtypes. For instance, maize and sugarcane use a combination of NADP-ME and PEPCK, millet uses preferentially NAD-ME and Megathyrsus maximus, uses preferentially PEPCK. | 5 | Photochemistry |
For the hexagonal close-packed structure the derivation is similar. Here the unit cell (equivalent to 3 primitive unit cells) is a hexagonal prism containing six atoms (if the particles in the crystal are atoms). Indeed, three are the atoms in the middle layer (inside the prism); in addition, for the top and bottom layers (on the bases of the prism), the central atom is shared with the adjacent cell, and each of the six atoms at the vertices is shared with other six adjacent cells. So the total number of atoms in the cell is 3 + (1/2)×2 + (1/6)×6×2 = 6. Each atom touches other twelve atoms. Now let be the side length of the base of the prism and be its height. The latter is twice the distance between adjacent layers, i. e., twice the height of the regular tetrahedron whose vertices are occupied by (say) the central atom of the lower layer, two adjacent non-central atoms of the same layer, and one atom of the middle layer "resting" on the previous three. Obviously, the edge of this tetrahedron is . If , then its height can be easily calculated to be , and, therefore, . So the volume of the hcp unit cell turns out to be (3/2) , that is 24 .
It is then possible to calculate the APF as follows: | 3 | Analytical Chemistry |
Chiral ligands work by asymmetric induction somewhere along the reaction coordinate. The image to the right illustrates how a chiral ligand may induce an enantioselective reaction. The ligand (in green) has C symmetry with its nitrogen, oxygen or phosphorus atoms hugging a central metal atom (in red). In this particular ligand the right side is sticking out and its left side points away. The substrate in this reduction is acetophenone and the reagent (in blue) a hydride ion. In absence of the metal and the ligand the Re face approach of the hydride ion gives the (S)-enantiomer and the Si face approach the (R)-enantiomer in equal amounts (a racemic mixture like expected). The ligand and metal presence changes all that. The carbonyl group will coordinate with the metal and due to the steric bulk of the phenyl group it will only be able to do so with its Si face exposed to the hydride ion with in the ideal situation exclusive formation of the (R) enantiomer. The re face will simply hit the chiral fence. Note that when the ligand is replaced by its mirror image the other enantiomer will form and that a racemic mixture of ligand will once again yield a racemic product. Also note that if the steric bulk of both carbonyl substituents is very similar the strategy will fail. | 4 | Stereochemistry |
A single conductive wire is used as feedstock for the system. A supersonic plasma jet—formed by a transferred arc between a non-consumable cathode and the wire—melts and atomizes the wire. A stream of air transports the atomized metal onto the substrate. The particles flatten upon striking the surface of the substrate due to their high kinetic energy. The particles rapidly solidify upon contact and can assume both crystalline and amorphous phases. There is also the possibility of producing multi-layer coatings via stacked layers of particles, increasing wear resistance. All conductive wires up to and including can be used as feedstock material, including "cored" wires. Refractory metals, as well as low melt materials, are easily deposited. | 8 | Metallurgy |
Force spectroscopy is a set of techniques for the study of the interactions and the binding forces between individual molecules. These methods can be used to measure the mechanical properties of single polymer molecules or proteins, or individual chemical bonds. The name "force spectroscopy", although widely used in the scientific community, is somewhat misleading, because there is no true matter-radiation interaction.
Techniques that can be used to perform force spectroscopy include atomic force microscopy, optical tweezers, magnetic tweezers, acoustic force spectroscopy, microneedles, and biomembranes.
Force spectroscopy measures the behavior of a molecule under stretching or torsional mechanical force. In this way a great deal has been learned in recent years about the mechanochemical coupling in the enzymes responsible for muscle contraction, transport in the cell, energy generation (F1-ATPase), DNA replication and transcription (polymerases), DNA unknotting and unwinding (topoisomerases and helicases).
As a single-molecule technique, as opposed to typical ensemble spectroscopies, it allows a researcher to determine properties of the particular molecule under study. In particular, rare events such as conformational change, which are masked in an ensemble, may be observed. | 7 | Physical Chemistry |
Amines are named in several ways. Typically, the compound is given the prefix "amino-" or the suffix "-amine". The prefix "N-" shows substitution on the nitrogen atom. An organic compound with multiple amino groups is called a diamine, triamine, tetraamine and so forth.
Lower amines are named with the suffix -amine.
Higher amines have the prefix amino as a functional group. IUPAC however does not recommend this convention, but prefers the alkanamine form, e.g. butan-2-amine. | 0 | Organic Chemistry |
The system of DNA profiling used today is based on polymerase chain reaction (PCR) and uses simple sequences.
From country to country, different STR-based DNA-profiling systems are in use. In North America, systems that amplify the CODIS 20 core loci are almost universal, whereas in the United Kingdom the DNA-17 loci system is in use, and Australia uses 18 core markers.
The true power of STR analysis is in its statistical power of discrimination. Because the 20 loci that are currently used for discrimination in CODIS are independently assorted (having a certain number of repeats at one locus does not change the likelihood of having any number of repeats at any other locus), the product rule for probabilities can be applied. This means that, if someone has the DNA type of ABC, where the three loci were independent, then the probability of that individual having that DNA type is the probability of having type A times the probability of having type B times the probability of having type C. This has resulted in the ability to generate match probabilities of 1 in a quintillion (1x10) or more. However, DNA database searches showed much more frequent than expected false DNA profile matches. | 1 | Biochemistry |
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