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The melting point of sucrose esters is between 40 °C and 60 °C depending on the type of fatty acids and the degree of substitution. Sucrose esters can be heated to 185 °C without losing their functionality. However, the color of the product might change due to caramelization of sucrose.
0
Organic Chemistry
The effect of electroreflectence was first written of in a review letter from 1965 by B. O. Seraphin and R. B. Hess from Michelson Laboratory, China Lake, California where they were studying the Franz-Keldysh effect above the fundamental edge in germanium. They found that it was not only possible for the material to absorb the electrons, but also re-emit them. Following this discovery Seraphin has written numerous articles on the new found phenomenon.
7
Physical Chemistry
SU-8 is a commonly used epoxy-based negative photoresist. Negative refers to a photoresist whereby the parts exposed to UV become cross-linked, while the remainder of the film remains soluble and can be washed away during development. As shown in the structural diagram, SU-8 derives its name from the presence of 8 epoxy groups. This is a statistical average per moiety. It is these epoxies that cross-link to give the final structure. It can be made into a viscous polymer that can be spun or spread over a thickness ranging from below 1 micrometer up to above 300 micrometers, or Thick Film Dry Sheets (TFDS) for lamination up to above 1 millimetre thick. Up to 500 µm, the resist can be processed with standard contact lithography. Above 500 µm, absorption leads to increasing sidewall undercuts and poor curing at the substrate interface. It can be used to pattern high aspect ratio structures. An aspect ratio of (> 20) has been achieved with the solution formulation and (> 40) has been demonstrated from the dry resist. Its maximum absorption is for ultraviolet light with a wavelength of the i-line: 365 nm (it is not practical to expose SU-8 with g-line ultraviolet light). When exposed, SU-8's long molecular chains cross-link, causing the polymerisation of the material. SU-8 series photoresists use gamma-butyrolactone or cyclopentanone as the primary solvent. SU-8 was originally developed as a photoresist for the microelectronics industry, to provide a high-resolution mask for fabrication of semiconductor devices. It is now mainly used in the fabrication of microfluidics (mainly via soft lithography, but also with other imprinting techniques such as nanoimprint lithography) and microelectromechanical systems parts. It is also one of the most biocompatible materials known and is often used in bio-MEMS for life science applications.
7
Physical Chemistry
A stabilized liquid membrane device or SLMD is a type of passive sampling device which allows for the in situ, integrative collection of waterborne, labile ionic metal contaminants. By capturing and sequestering metal ions onto its surface continuously over a period of days to weeks, an SLMD can provide an integrative measurement of bioavailable toxic metal ions present in the aqueous environment. As such, they have been used in conjunction with other passive samplers in ecological field studies.
3
Analytical Chemistry
Arginine fingers are also present in Ras GTPases, where they help cleave GTP to turn Ras off. Ras is a GTPase which functions in signal transduction to regulate cell growth and division. In addition to being positively charged, which helps arginine fingers function as a catalyst, the arginine finger in Ras displaces solvent molecules and creates an optional charge distribution. Like those of dUPTases, the arginine fingers of Ras GTPases are assisted by a magnesium ion. Furthermore, multiple arginine finger residues can all point towards the same point, thus focusing their effect. Mutations affecting the arginine fingers of Ras lead to trouble catalyzing GTP by factors of around two to five orders of magnitude. Thus, as Ras is an oncogene and is activated and deactivated by the hydrolysis of GTP, mutations in Rass arginine finger residues can lead to cancer. Glutamate also plays a role near arginine fingers and is stabilized by the arginines backbone chain carboxyl groups, which are known as knuckles.
1
Biochemistry
HER2 is overexpressed in 20-30% of breast cancers and is commonly associated with poor prognosis. It is therefore an oncogene whose differently spliced variants have been shown to have different functions. Knocking down hnRNP H1 was shown to increase the amount of an oncogenic variant Δ16HER2. HER2 is an upstream regulator of cyclin D1 and p27, and its overexpression leads to the deregulation of the G1/S checkpoint.
1
Biochemistry
In October 2019, a French-Spanish team of scientists published an article in Nature Ecology and Evolution that concludes that while the salt plains are teeming with halophilic microorganisms, there is no life in Dallol's multi-extreme ponds due to the combination of hyperacidic and hypersaline environments, and the abundance of magnesium (which catalyzes the denaturation of biomolecules). However another team reported for the first time evidence of life existing with these hot springs using a combination of morphological and molecular analyses. Ultra-small structures are shown to be entombed within mineral deposits, which are identified as members of the Order Nanohaloarchaea.
9
Geochemistry
Inversion of tetrahedra occurs widely in organic and main group chemistry. The Walden inversion illustrates the stereochemical consequences of inversion at carbon. Nitrogen inversion in ammonia also entails transient formation of planar .
4
Stereochemistry
To back up their suggestion of the non-classical nature of the 2-norbornyl cation, Winstein and Trifan first used kinetic evidence of the increased reaction rate for formation of the 2-exo-norbornyl cation over the 2-endo-norbornyl cation. Other researchers investigated the reaction rate of compounds that could feature anchimeric assistance but could not undergo rearrangements as the norbornyl system could show similar trends in rate enhancement. This has been claimed by some to be definitive evidence for the non-classical picture. But not all agree. Other researchers found that cyclopentane derivatives that were structurally similar to the norbornyl system still featured enhanced reaction rates, leading them to claim that the classical norbornyl cation describes the system much better.
7
Physical Chemistry
Quaternary muscle relaxants bind to the nicotinic acetylcholine receptor and inhibit or interfere with the binding and effect of ACh to the receptor. Each ACh-receptor has two receptive sites and activation of the receptor requires binding to both of them. Each receptor site is located at one of the two α-subunits of the receptor. Each receptive site has two subsites, an anionic site that binds to the cationic ammonium head and a site that binds to the blocking agent by donating a hydrogen bond. Non-depolarizing agents A decrease in binding of acetylcholine leads to a decrease in its effect and neuron transmission to the muscle is less likely to occur. It is generally accepted that non-depolarizing agents block by acting as reversible competitive inhibitors. That is, they bind to the receptor as antagonists and that leaves fewer receptors available for acetylcholine to bind. Depolarizing agents Depolarizing agents produce their block by binding to and activating the ACh receptor, at first causing muscle contraction, then paralysis. They bind to the receptor and cause depolarization by opening channels just like acetylcholine does. This causes repetitive excitation that lasts longer than a normal acetylcholine excitation and is most likely explained by the resistance of depolarizing agents to the enzyme acetylcholinesterase. The constant depolarization and triggering of the receptors keeps the endplate resistant to activation by acetylcholine. Therefore, a normal neuron transmission to muscle cannot cause contraction of the muscle because the endplate is depolarized and thereby the muscle paralysed. Binding to the nicotinic receptor Shorter molecules like acetylcholine need two molecules to activate the receptor, one at each receptive site. Decamethonium congeners, which prefer straight line conformations (their lowest energy state), usually span the two receptive sites with one molecule (binding inter-site). Longer congeners must bend when fitting receptive sites. The greater energy a molecule needs to bend and fit usually results in lower potency.
1
Biochemistry
The carbonate pump, sometimes called the carbonate counter pump, starts with marine organisms at the ocean's surface producing particulate inorganic carbon (PIC) in the form of calcium carbonate (calcite or aragonite, CaCO). This CaCO is what forms hard body parts like shells. The formation of these shells increases atmospheric CO due to the production of CaCO in the following reaction with simplified stoichiometry:Coccolithophores, a nearly ubiquitous group of phytoplankton that produce shells of calcium carbonate, are the dominant contributors to the carbonate pump. Due to their abundance, coccolithophores have significant implications on carbonate chemistry, in the surface waters they inhabit and in the ocean below: they provide a large mechanism for the downward transport of CaCO. The air-sea CO flux induced by a marine biological community can be determined by the rain ratio - the proportion of carbon from calcium carbonate compared to that from organic carbon in particulate matter sinking to the ocean floor, (PIC/POC). The carbonate pump acts as a negative feedback on CO taken into the ocean by the solubility pump. It occurs with lesser magnitude than the solubility pump. The carbonate pump is sometimes referred to as the "hard tissue" component of the biological pump. Some surface marine organisms, like coccolithophores, produce hard structures out of calcium carbonate, a form of particulate inorganic carbon, by fixing bicarbonate. This fixation of DIC is an important part of the oceanic carbon cycle. :Ca + 2 HCO → CaCO + CO + HO While the biological carbon pump fixes inorganic carbon (CO) into particulate organic carbon in the form of sugar (CHO), the carbonate pump fixes inorganic bicarbonate and causes a net release of CO. In this way, the carbonate pump could be termed the carbonate counter pump. It works counter to the biological pump by counteracting the CO flux from the biological pump.
9
Geochemistry
Family-based, adoption, and twin studies have indicated that there is a strong (50%) heritable component to vulnerability to substance abuse addiction. Especially among genetically vulnerable individuals, repeated exposure to a drug of abuse in adolescence or adulthood causes addiction by inducing stable downregulation or upregulation in expression of specific genes and microRNAs through epigenetic alterations. Such downregulation or upregulation has been shown to occur in the brain's reward regions, such as the nucleus accumbens. (See, for example, Epigenetics of cocaine addiction.)
1
Biochemistry
2,2-Dimethoxypropane (DMP) is an organic compound with the formula (CH)C(OCH). A colorless liquid, it is the product of the condensation of acetone and methanol. DMP is used as a water scavenger in water-sensitive reactions. Upon acid-catalyzed reaction, DMP reacts quantitatively with water to form acetone and methanol. This property can be used to accurately determine the amount of water in a sample, alternatively to the Karl Fischer method. DMP is specifically used to prepare acetonides: :RCHOHCHOHCH + (MeO)CMe → RCHCHCHOCMe + 2 MeOH Dimethoxypropane is an intermediate for the synthesis of 2-methoxypropene. In histology, DMP is used for the dehydration of animal tissue.
0
Organic Chemistry
Ocean acidification threatens coral reproduction throughout almost all aspects of the process. Gametogenesis may be indirectly affected by coral bleaching. Additionally, the stress that acidification puts on coral can potentially harm the viability of the sperm released. Larvae can also be affected by this process; metabolism and settlement cues could be altered, changing the size of the population or viability of reproduction. Other species of calcifying larvae have shown reduced growth rates under ocean acidification scenarios. Biofilm, a bioindicator for oceanic conditions, underwent a reduced growth rate and altered composition in acidification, possibly affecting larval settlement on the biofilm itself.
9
Geochemistry
The Dalitz plot is a two-dimensional plot often used in particle physics to represent the relative frequency of various (kinematically distinct) manners in which the products of certain (otherwise similar) three-body decays may move apart. The phase-space of a decay of a pseudoscalar into three spin-0 particles can be completely described using two variables. In a traditional Dalitz plot, the axes of the plot are the squares of the invariant masses of two pairs of the decay products. (For example, if particle A decays to particles 1, 2, and 3, a Dalitz plot for this decay could plot m on the x-axis and m on the y-axis.) If there are no angular correlations between the decay products then the distribution of these variables is flat. However symmetries may impose certain restrictions on the distribution. Furthermore, three-body decays are often dominated by resonant processes, in which the particle decays into two decay products, with one of those decay products immediately decaying into two additional decay products. In this case, the Dalitz plot will show a non-uniform distribution, with a peak around the mass of the resonant decay. In this way, the Dalitz plot provides an excellent tool for studying the dynamics of three-body decays. Dalitz plots play a central role in the discovery of new particles in current high-energy physics experiments, including Higgs boson research, and are tools in exploratory efforts that might open avenues beyond the Standard Model. R.H. Dalitz introduced this technique in 1953 to study decays of K mesons (which at that time were still referred to as "tau-mesons"). It can be adapted to the analysis of four-body decays as well. A specific form of a four-particle Dalitz plot (for non-relativistic kinematics), which is based on a tetrahedral coordinate system, was first applied to study the few-body dynamics in atomic four-body fragmentation processes.
7
Physical Chemistry
Professor Harald Christian Pederson founded the A/S Ila and Lilleby smelteverk melting facilities in the 1920s. He worked with a chemical process which later has been called the Pederson-2 process. It consists of melting ironmalm which gives ferrosilicon as a by-product.
8
Metallurgy
Polyionic polymers are polymers with an ionic functional group. The ionic charges prevent the formation of tightly coiled polymer chains. This allows them to contribute more to viscosity in their stretched state, because the stretched-out polymer takes up more space. This is also the reason gel hardens. See polyelectrolyte for more information.
7
Physical Chemistry
The enhanced resonance parameter, , is a measure of the influence of resonance on a new reaction. When , the resonance effects for a particular reaction are no different from those for reaction of the unsubstituted reference compound. However, when , the reaction in question is more sensitive to resonance effects than the standard, and when , the reaction is less sensitive to such effects. The enhanced resonance parameter is determined by first establishing the Hammett Reaction constant from data collected from meta-substituted compounds, and subsequently correlating the remaining data to fit the modified equation described above.
7
Physical Chemistry
False brinelling is a bearing damage caused by fretting, with or without corrosion, that causes imprints that look similar to brinelling, but are caused by a different mechanism. False brinelling may occur in bearings which act under small oscillations or vibrations. The basic cause of false brinelling is that the design of the bearing does not have a method for redistribution of lubricant without large rotational movement of all bearing surfaces in the raceway. Lubricant is pushed out of a loaded region during small oscillatory movements and vibration where the bearings surfaces repeatedly do not move very far. Without lubricant, wear is increased when the small oscillatory movements occur again. It is possible for the resulting wear debris to oxidize and form an abrasive compound which further accelerates wear.
8
Metallurgy
There was no fundamental change in the technology of iron production in Europe for many centuries. European metal workers continued to produce iron in bloomeries. However, the Medieval period brought two developments—the use of water power in the bloomery process in various places (outlined above), and the first European production in cast iron.
8
Metallurgy
Bracken fern increases the oncogenic risk in humans. Epidemiological survey revealed that bracken fern consumption was positively correlated with esophageal cancer and with gastric cancer in many geographical areas of the world. In 1989, Natori and co-workers showed that ptaquiloside had clastogenic effect and caused chromosomal aberration in mammalian cells. In 2003, Santos group reported significantly increased levels of chromosomal abnormalities, such as chromatid breaks in cultured peripheral lymphocytes.
0
Organic Chemistry
Separation systems are coupled with a detector, that allows the detection and identification of VOCs based on their molecular weight and chemical properties. The most used system for the analysis of floral scent samples is GC-MS (gas chromatography coupled with mass spectrometry).
1
Biochemistry
The geochemistry of carbon is the study of the transformations involving the element carbon within the systems of the Earth. To a large extent this study is organic geochemistry, but it also includes the very important carbon dioxide. Carbon is transformed by life, and moves between the major phases of the Earth, including the water bodies, atmosphere, and the rocky parts. Carbon is important in the formation of organic mineral deposits, such as coal, petroleum or natural gas. Most carbon is cycled through the atmosphere into living organisms and then respirated back into the atmosphere. However an important part of the carbon cycle involves the trapping of living matter into sediments. The carbon then becomes part of a sedimentary rock when lithification happens. Human technology or natural processes such as weathering, or underground life or water can return the carbon from sedimentary rocks to the atmosphere. From that point it can be transformed in the rock cycle into metamorphic rocks, or melted into igneous rocks. Carbon can return to the surface of the Earth by volcanoes or via uplift in tectonic processes. Carbon is returned to the atmosphere via volcanic gases. Carbon undergoes transformation in the mantle under pressure to diamond and other minerals, and also exists in the Earth's outer core in solution with iron, and may also be present in the inner core. Carbon can form a huge variety stable compounds. It is an essential component of living matter. Living organisms can live in a limited range of conditions on the Earth that are limited by temperature and the existence of liquid water. The potential habitability of other planets or moons can also be assessed by the existence of liquid water. Carbon makes up only 0.08% of the combination of the lithosphere, hydrosphere, and atmosphere. Yet it is the twelfth most common element there. In the rock of the lithosphere, carbon commonly occurs as carbonate minerals containing calcium or magnesium. It is also found as fossil fuels in coal and petroleum and gas. Native forms of carbon are much rarer, requiring pressure to form. Pure carbon exists as graphite or diamond. The deeper parts of Earth such as the mantle are very hard to discover. Few samples are known, in the form of uplifted rocks, or xenoliths. Even fewer remain in the same state they were in where the pressure and temperature is much higher. Some diamonds retain inclusions held at pressures they were formed at, but the temperature is much lower at the surface. Iron meteorites may represent samples of the core of an asteroid, but it would have formed under different conditions to the Earth's core. Therefore, experimental studies are conducted in which minerals or substances are compressed and heated to determine what happens in similar conditions to the planetary interior. The two common isotopes of carbon are stable. On Earth, carbon 12, C is by far the most common at 98.894%. Carbon 13 is much rarer averaging 1.106%. This percentage can vary slightly and its value is important in isotope geochemistry whereby the origin of the carbon is suggested.
9
Geochemistry
The reaction between tricarbonylchromium complexes Cr(CO)L and electron-rich or electron-neutral aromatic rings produces tricarbonyl(arene)chromium complexes (arene)Cr(CO). Complexation to chromium(0) activates the side chain of the arene, facilitating dissociation of a benzylic proton, leaving group, or nucleophilic addition to the homobenzylic position of styrenes. Further transformations of the resulting conformationally restricted, benzylic anion or cation involve the approach of reagents exo to the chromium fragment. Thus, benzylic functionalization reactions of planar chiral chromium arene complexes are highly diastereoselective. Additionally, the chromium tri(carbonyl) fragment can be used as a blocking element in addition reactions to ortho-substituted aromatic aldehydes and alkenes. An ortho substituent is necessary in these reactions to restrict conformations available to the aldehyde or alkene. Removal of the chromium fragment to afford the metal-free functionalized aromatic compound is possible photolytically or with an oxidant.
0
Organic Chemistry
Esomeprazole capsules, as well as Losec/Prilosec tablets, are formulated as a "multiple-unit pellet system" (MUPS). Essentially, the capsule consists of extremely small enteric-coated granules (pellets) of the esomeprazole formulation inside an outer shell. When the capsule is immersed in an aqueous solution, as happens when the capsule reaches the stomach, water enters the capsule by osmosis. The contents swell from water absorption, causing the shell to burst, and releasing the enteric-coated granules. For most patients, the multiple-unit pellet system is of no advantage over conventional enteric-coated preparations. Patients for whom the formulation is of benefit include those requiring nasogastric tube feeding and those with difficulty swallowing (dysphagia).
4
Stereochemistry
The oldest inscription on the pillar is that of a king named Chandra (IAST: ), generally identified as the Gupta emperor Chandragupta II.
8
Metallurgy
Senapathy discovered that stop codons occur as key parts in every genetic element in eukaryotic genes. The table and figure show that the key parts of the core promoter elements, the lariat signal, the donor and acceptor splice signals, and the poly-A addition signal consist of one or more stop codons. This finding corroborates the split gene theory's claim that the underlying reason for the complete split gene paradigm is the origin of split genes from random DNA sequences, wherein random distribution of an extremely high frequency of stop codons were used by nature to define these genetic elements.
1
Biochemistry
Fluorene, the repeat unit in polyfluorene derivatives, was isolated from coal tar and discovered by Marcellin Berthelot prior to 1883. Its name originates from its interesting fluorescence (and not to fluorine, which is not one of its elements). Fluorene became the subject of chemical-structure related color variation (visible rather than luminescent), among other things, throughout the early to mid-20th century. Since it was an interesting chromophore researchers wanted to understand which parts of the molecule were chemically reactive, and how substituting these sites influenced the color. For instance, by adding various electron donating or electron accepting moieties to fluorene, and by reacting with bases, researchers were able to change the color of the molecule. The physical properties of the fluorene molecule were recognizably desirable for polymers; as early as the 1970s researchers began incorporating this moiety into polymers. For instance, because of fluorene’s rigid, planar shape a polymer containing fluorene was shown to exhibit enhanced thermo-mechanical stability. However, more promising was integrating the optoelectronic properties of fluorene into a polymer. Reports of the oxidative polymerization of fluorene (into a fully conjugated form) exist from at least 1972. However, it was not until after the highly publicized high conductivity of doped polyacetylene, presented in 1977 by Heeger, MacDiarmid and Shirakawa, that substantial interest in the electronic properties of conjugated polymers took off. As interest in conducting plastics grew, fluorene again found application. The aromatic nature of fluorene makes it an excellent candidate component of a conducting polymer because it can stabilize and conduct a charge; in the early 1980s fluorene was electropolymerized into conjugated polymer films with conductivities of 10 S cm. The optical properties (such as variable luminescence and visible light spectrum absorption) that accompany the extended conjugation in polymers of fluorene have become increasingly attractive for device applications. Throughout the 1990s and into the 2000s, many devices such as organic light-emitting diodes (OLEDs), organic solar cells., organic thin film transistors, and biosensors have all taken advantage of the luminescent, electronic and absorptive properties of polyfluorenes.
7
Physical Chemistry
In parallel kinetic resolution (PKR), a racemic mixture reacts to form two non-enantiomeric products, often through completely different reaction pathways. With PKR, there is no tradeoff between conversion and ee, as the formed products are not enantiomers. One strategy for PKR is to remove the less reactive enantiomer (towards the desired chiral catalyst) from the reaction mixture by subjecting it to a second set of reaction conditions that preferentially react with it, ideally with an approximately equal reaction rate. Thus, both enantiomers are consumed in different pathways at equal rates. PKR experiments can be stereodivergent, regiodivergent, or structurally divergent. One of the most highly efficient PKR's reported to date was accomplished by Yoshito Kishi in 1998; CBS reduction of a racemic steroidal ketone resulted in stereoselective reduction, producing two diastereomers of >99% ee, as shown below. PKR have also been accomplished with the use of enzyme catalysts. Using the fungus Mortierella isabellina NRRL 1757, reduction of racemic β-ketonitriles affords two diastereomers, which can be separated and re-oxidized to give highly enantiopure β-ketonitriles. Highly synthetically useful parallel kinetic resolutions have truly yet to be discovered, however. A number of procedures have been discovered that give acceptable ees and yields, but there are very few examples which give highly selective parallel kinetic resolution and not simply somewhat selective reactions. For example, Fus parallel kinetic resolution of 4-alkynals yields very enantioenriched cyclobutanone in low yield and slightly enantioenriched cyclopentenone, as shown below. In theory, parallel kinetic resolution can give the highest ee's of products, since only one enantiomer gives each desired product. For example, for two complementary reactions both with s=49, 100% conversion would give products in 50% yield and 96% ee. These same values would require s=200 for a simple kinetic resolution. As such, the promise of PKR continues to attract much attention. The Kishi CBS reduction remains one of the few examples to fulfill this promise.
4
Stereochemistry
After graduation, Ekimov moved to the Vavilov State Optical Institute to conduct research. He began studying semiconductor-activated glasses, known as Schott glasses, and developing theories to explain their color. When the glasses were heated and then cooled, copper chloride crystals formed, as revealed by X-rays, creating blue colors. Smaller crystals produced bluer glass. In 1981, Ekimov, along with Alexei A. Onushchenko, reported the discovery of quantum size effects in copper chloride nanocrystals in glass, a phenomenon known now known as quantum dots. During his time at the institute he further investigated these system and developed the theory of quantum confinement with Alexander Efros. Since 1999, Ekimov has been living and working in the United States as a scientist for Nanocrystals Technology, a company based in New York State.
7
Physical Chemistry
The RNA world hypothesis assumes that very early in evolution, prior to the emergence of DNA as a genetic material and prior to the emergence of protein enzymes, RNA was the key player in the emergence of life. A central idea in this hypothesis is an RNA replicase (ribozyme) that is capable of copying its own genome. A holopolymerase ribozyme has been engineered that uses a sigma factor-like specificity primer to recognize an RNA promoter sequence. This ribozyme can then, in a second step rearrange to a processive form that can polymerize from certain RNA promoters and not others.
1
Biochemistry
1,3-Propanedithiol is the chemical compound with the formula HSCHCHCHSH. This dithiol is a useful reagent in organic synthesis. This liquid, which is readily available commercially, has an intense stench.
0
Organic Chemistry
Enamines act as nucleophiles that require less acid/base activation for reactivity than their enolate counterparts. They have also been shown to offer a greater selectivity with less side reactions. There is a gradient of reactivity among different enamine types, with a greater reactivity offered by ketone enamines than their aldehyde counterparts. Cyclic ketone enamines follow a reactivity trend where the five membered ring is the most reactive due to its maximally planar conformation at the nitrogen, following the trend 5>8>6>7 (the seven membered ring being the least reactive). This trend has been attributed to the amount of p-character on the nitrogen lone pair orbital - the higher p character corresponding to a greater nucleophilicity because the p-orbital would allow for donation into the alkene π- orbital. Analogously, if the N lone pair participates in stereoelectronic interactions on the amine moiety, the lone pair will pop out of the plane (will pyramidalize) and compromise donation into the adjacent π C-C bond. There are many ways to modulate enamine reactivity in addition to altering the steric/electronics at the nitrogen center including changing temperature, solvent, amounts of other reagents, and type of electrophile. Tuning these parameters allows for the preferential formation of E/Z enamines and also affects the formation of the more/less substituted enamine from the ketone starting material.
0
Organic Chemistry
Dr. R.U. Lemieux received numerous awards and honours for his work in chemistry: * Induction into the Royal Society of Canada (1954) * C.S. Hudson Award of the American Chemical Society (1966) * Became the first western Canadian to be elected a fellow of the Royal Society (England) (1967) * Appointed Officer of the Order of Canada (1968) * Haworth Award and Medal (1983) * The Tishler Award, Harvard University (1983) * Gairdner Foundation International Award (1985) * Made Honorary Doctor of Philosophy from the University of Stockholm (1988) * Induction into the Alberta Order of Excellence (1990) * King Faisal International Prize for Science (first Canadian) (1990) * NSERC Gold Medal in Science (1991) * Albert Einstein World Award of Science (1992) * Made Companion of the Order of Canada (1994) * Wolf Prize in Chemistry (1999)
0
Organic Chemistry
Soderholm was awarded her PhD in 1982 by McMaster University under the direction of Prof John Greedan. Her dissertation focused on characterizing the structural and magnetic properties of a series of ternary f-ion oxides. After graduating, she was awarded a NATO postdoctoral fellow at the Centre national de la recherche scientifique in France from 1982 until 1985. After a short postdoctoral appointment as an Argonne postdoctoral fellow she was promoted to staff scientist the same year. Over several years, she moved up the ranks, becoming a senior chemist in 2001. She was also an adjunct professor at the University of Notre Dame from 2003 until 2007. In 2021, Soderholm was appointed interim Division Director for the Chemical Sciences and Engineering Division.
7
Physical Chemistry
As a base, pyridine can be used as the Karl Fischer reagent, but it is usually replaced by alternatives with a more pleasant odor, such as imidazole. Pyridinium chlorochromate, pyridinium dichromate, and the Collins reagent (the complex of chromium(VI) oxide) are used for the oxidation of alcohols.
0
Organic Chemistry
Carboxypeptidase E (CPE), also known as carboxypeptidase H (CPH) and enkephalin convertase, is an enzyme that in humans is encoded by the CPE gene. This enzyme catalyzes the release of C-terminal arginine or lysine residues from polypeptides. CPE is involved in the biosynthesis of most neuropeptides and peptide hormones. The production of neuropeptides and peptide hormones typically requires two sets of enzymes that cleave the peptide precursors, which are small proteins. First, proprotein convertases cut the precursor at specific sites to generate intermediates containing C-terminal basic residues (lysine and/or arginine). These intermediates are then cleaved by CPE to remove the basic residues. For some peptides, additional processing steps, such as C-terminal amidation, are subsequently required to generate the bioactive peptide, although for many peptides the action of the proprotein convertases and CPE is sufficient to produce the bioactive peptide.
1
Biochemistry
Generally this topic is discussed when covering mass spectrometry and occurs generally by the same mechanisms. To neutralize the positive charge on the ionization site a single two-electron transfer must be made. Neutralization of the positive charge at the ionization site is performed at the expense of the atom adjacent to the ionization site, transferring the positive charge to this atom as a result of the bond cleavage.
0
Organic Chemistry
During periods of high blood sugar, glucose 6-phosphate from glycolysis is diverted to the glycogen-storing pathway. It is changed to glucose-1-phosphate by phosphoglucomutase and then to UDP-glucose by UTP--glucose-1-phosphate uridylyltransferase. Glycogen synthase adds this UDP-glucose to a glycogen chain.
1
Biochemistry
Willauer et al. (2012) estimated that jet fuel could be synthesized from seawater in quantities up to per day, at a cost of three to six U.S. dollars per gallon. Willauer et al. (2014) showed that the Fischer-Tropsch catalyst could be modified to synthesize various fuels such as methanol and natural gas, as well as the olefins that can be used as the building blocks for jet fuel. Willauer et al. calculated that about of seawater must be driven through the process to obtain the quantities of hydrogen and CO necessary to synthesize one gallon of jet fuel. Seawater was chosen because it contains 140 times more CO by volume than the atmosphere, and conventional water electrolysis also yields H. The equipment for processing seawater is much smaller than that for processing air. Willauer considered that seawater was the "best option" for a source of synthetic jet fuel. By April 2014, the Willauer's team had not yet made fuel to the quality standard required for military jets, but they were able in September 2013 to use the fuel to fly a radio-controlled model airplane powered by a common two-stroke internal combustion engine. Because the process requires a considerable input of electrical energy (~ 250 MW electricity mainly for the H production by water electrolysis and also to a lesser extent for the CO recovery from seawater), it cannot be performed on a large ship, even on a nuclear aircraft-carrier. The installations processing seawater to obtain H and CO (in fact CO), the two essential ingredients necessary for the Fischer–Tropsch process, must be constructed on-shore, close to the sea, on islands in strategic remote locations (e.g., Hawai, Guam, Diego-Garcia) and powered by a nuclear reactor, or by ocean thermal energy conversion (OTEC).
3
Analytical Chemistry
In organic chemistry and biochemistry, a side chain is a chemical group that is attached to a core part of the molecule called the "main chain" or backbone. The side chain is a hydrocarbon branching element of a molecule that is attached to a larger hydrocarbon backbone. It is one factor in determining a molecule's properties and reactivity. A side chain is also known as a pendant chain, but a pendant group (side group) has a different definition.
0
Organic Chemistry
Oral exemestane 25 mg/day for 2–3 years of adjuvant therapy was generally more effective than 5 years of continuous adjuvant tamoxifen in the treatment of postmenopausal women with early-stage estrogen receptor-positive/unknown receptor status breast in a large well-designed trial. Preliminary data from the open-label TEAM trial comparing exemestane with tamoxifen indicated in 2009 that exemestane 25 mg/day is also effective in the primary adjuvant treatment of early-stage breast cancer in postmenopausal women. Interim phase III trial results in 2011 showed that adding everolimus to exemestane therapy against advanced breast cancer can significantly improve progression-free survival compared with exemestane therapy alone. A Phase III trial was reported in 2011, concluding that the use of exemestane in postmenopausal women at an increased risk for breast cancer reduced the incidence of invasive breast cancer. In 4,560 women, after 35 months, the administration of exemestane at a dose of 25 mg/day resulted in a 65% reduction in the risk of breast cancer compared with placebo; annual incidence rates were 0.19% and 0.55%, respectively (hazard ratio: 0.35; 95% CI [0.18-0.70]; p = 0.002).
4
Stereochemistry
Assuming that the concentration of fermions does not change with temperature, then the total chemical potential µ (Fermi level) of the three-dimensional ideal Fermi gas is related to the zero temperature Fermi energy E by a Sommerfeld expansion (assuming ): where T is the temperature. Hence, the internal chemical potential, µ-E, is approximately equal to the Fermi energy at temperatures that are much lower than the characteristic Fermi temperature T. This characteristic temperature is on the order of 10 K for a metal, hence at room temperature (300 K), the Fermi energy and internal chemical potential are essentially equivalent.
7
Physical Chemistry
Mixtures are another common issue faced by forensic scientists when they are analyzing unknown or questionable DNA samples. A mixture is defined as a DNA sample that contains two or more individual contributors. That can often occur when a DNA sample is swabbed from an item that is handled by more than one person or when a sample contains both the victims and the assailants DNA. The presence of more than one individual in a DNA sample can make it challenging to detect individual profiles, and interpretation of mixtures should be performed only by highly trained individuals. Mixtures that contain two or three individuals can be interpreted with difficulty. Mixtures that contain four or more individuals are much too convoluted to get individual profiles. One common scenario in which a mixture is often obtained is in the case of sexual assault. A sample may be collected that contains material from the victim, the victim's consensual sexual partners, and the perpetrator(s). Mixtures can generally be sorted into three categories: Type A, Type B, and Type C. Type A mixtures have alleles with similar peak-heights all around, so the contributors cannot be distinguished from each other. Type B mixtures can be deconvoluted by comparing peak-height ratios to determine which alleles were donated together. Type C mixtures cannot be safely interpreted with current technology because the samples were affected by DNA degradation or having too small a quantity of DNA present. When looking at an electropherogram, it is possible to determine the number of contributors in less complex mixtures based on the number of peaks located in each locus. In comparison to a single source profile, which will only have one or two peaks at each locus, a mixture is when there are three or more peaks at two or more loci. If there are three peaks at only a single locus, then it is possible to have a single contributor who is tri-allelic at that locus. Two person mixtures will have between two and four peaks at each locus, and three person mixtures will have between three and six peaks at each locus. Mixtures become increasingly difficult to deconvolute as the number of contributors increases. As detection methods in DNA profiling advance, forensic scientists are seeing more DNA samples that contain mixtures, as even the smallest contributor can now be detected by modern tests. The ease in which forensic scientists have in interpenetrating DNA mixtures largely depends on the ratio of DNA present from each individual, the genotype combinations, and the total amount of DNA amplified. The DNA ratio is often the most important aspect to look at in determining whether a mixture can be interpreted. For example, if a DNA sample had two contributors, it would be easy to interpret individual profiles if the ratio of DNA contributed by one person was much higher than the second person. When a sample has three or more contributors, it becomes extremely difficult to determine individual profiles. Fortunately, advancements in probabilistic genotyping may make that sort of determination possible in the future. Probabilistic genotyping uses complex computer software to run through thousands of mathematical computations to produce statistical likelihoods of individual genotypes found in a mixture. Plant DNA profiling (fingerprinting) is a method for identifying cultivars that uses molecular marker techniques. This method is gaining attention due to Trade Related Intellectual property rights (TRIPs) and the Convention on Biological Diversity (CBD). Identification, authentication, specific distinction, detecting adulteration and identifying phytoconstituents are all possible with DNA fingerprinting in medical plants. DNA based markers are critical for these applications, determining the future of scientific study in pharmacognosy. It also helps with determining the traits (such as seed size and leaf color) are likely to improve the offspring or not.
1
Biochemistry
Various methods exist to introduce this functionality. Carboxylic acids can be converted to trifluoromethyl groups by treatment with sulfur tetrafluoride and trihalomethyl compounds, particularly trifluoromethyl ethers and trifluoromethyl aromatics, are converted into trifluoromethyl compounds by treatment with antimony trifluoride/antimony pentachloride (the Swarts reaction). Another route to trifluoromethyl aromatics is the reaction of aryl iodides with trifluoromethyl copper. Finally, trifluoromethyl carbonyls can be prepared by reaction of aldehydes and esters with Ruppert's reagent.
0
Organic Chemistry
The starting materials for the Kröhnke synthesis are often trivial to prepare, lending to the convenience and broad scope of the method. Preparation of the α-pyridinium methyl ketone salts can be easily achieved by treatment of the corresponding bromomethyl ketone with pyridine. The α,β-unsaturated ketones are often available commercially or can be prepared using a number of known methods. Additionally, Mannich bases can also be utilized as the Michael acceptor for the scheme, further diversifying the scope of starting materials that can be incorporated into the Kröhnke scheme. The reaction conditions for the Kröhnke synthesis are generally facile and the reactions often proceed in high yields with reaction temperatures generally not exceeding 140 °C. The Kröhnke synthesis is generally performed in either glacial acetic acid or methanol, but it can also be done under aqueous conditions, and more recently under solvent-free conditions. 1,3-dicarbonyl compounds have also been shown to be viable starting materials in place of the α-pyridinium methyl ketone salts. For example, treatment of 1,3-diketone 14 with base in ethanol followed by ammonium acetate, acetic acid, the corresponding enone and a Lewis acid yields 3-acyltriarylpyridines of the form 15. These acyl pyridine are attractive intermediates because they have an electrophilic handle that allows for additional functionality to be incorporated into the molecule. This allows for straightforward construction of complex polyaryl systems, an attractive method for library synthesis of drug targets containing functionalized pyridine moieties.
0
Organic Chemistry
The most common NMR techniques used when discriminating chiral compounds are H-NMR, F-NMR and C-NMR. H-NMR is the primary technique used to assign absolute configuration. F-NMR is almost exclusive applied to optical purity studies, and C-NMR is primarily used to characterize substrates that do not have protons that are directly bonded to an asymmetrical carbon atom.
4
Stereochemistry
The enteric nervous system consists of some one hundred million neurons that are embedded in the peritoneum, the lining of the gastrointestinal tract extending from the esophagus to the anus. These neurons are collected into two plexuses – the myenteric (or Auerbachs) plexus that lies between the longitudinal and the smooth muscle layers, and the submucosal (or Meissners) plexus that lies between the circular smooth muscle layer and the mucosa. Parasympathetic innervation to the ascending colon is supplied by the vagus nerve. Sympathetic innervation is supplied by the splanchnic nerves that join the celiac ganglia. Most of the digestive tract is innervated by the two large celiac ganglia, with the upper part of each ganglion joined by the greater splanchnic nerve and the lower parts joined by the lesser splanchnic nerve. It is from these ganglia that many of the gastric plexuses arise.
1
Biochemistry
Allylic strain, or A strain is closely associated to syn-pentane strain. An example of allylic strain can be seen in the compound 2-pentene. It's possible for the ethyl substituent of the olefin to rotate such that the terminal methyl group is brought near to the vicinal methyl group of the olefin. These types of compounds usually take a more linear conformation to avoid the steric strain between the substituents.
4
Stereochemistry
Another beneficial cell modification is the adjustment of substrate and growth requirements of a cell. By changing cell needs, the raw material cost, equipment expenses, and skill required to grow and maintain cell cultures can be significantly reduced. For example, scientists have used foreign enzymes to engineer a common industrial yeast strain which allows the cells to grow on substrate cheaper than the traditional glucose. Because of the biological engineering focus on improving scale-up costs, research in this area is largely focused on the ability of various enzymes to metabolize low-cost substrates.
1
Biochemistry
Dissimilatory nitrate reduction to ammonium is a two step process, reducing NO to NO then NO to NH, though the reaction may begin with NO directly. Each step is mediated by a different enzyme, the first step of dissimilatory nitrate reduction to ammonium is usually mediated by a periplasmic nitrate reductase. The second step (respiratory NO reduction to NH) is mediated by cytochrome c nitrite reductase, occurring at the periplasmic membrane surface. Despite DNRA not producing nitrous oxide (NO) as an intermediate during nitrate reduction (as denitrification does), NO may still be released as a byproduct, thus DNRA may also act as a sink of fixed, bioavailable nitrogen. DNRA's production of NO may be enhanced at higher pH levels.
1
Biochemistry
Forgione, P., Bilodeau, F. et al. reported that heteroatoms containing a carboxylic acid also are tolerated by palladium monometallic systems and undergo decarboxylative cross coupling with aryl halides. In the proposed mechanism the initial step is oxidative addition of the aryl halide forming an aryl–palladium intermediate. Electrophilic palladation then occurs at carbon-3 of the heteroatom. From this intermediate there are two possible pathways for the cycle to continue on. The first is palladium migration from carbon-3 to carbon-2 along with the expulsion of carbon dioxide. This forms the aryl–palladium–heteroatom intermediate, which undergoes reductive elimination to form the final heteroaromatic compound. The second pathway only occurs when R is a proton. If this is the case, deprotonation occurs to regain aromaticity of the heteroatom. This intermediate then undergoes reductive elimination, coupling the aryl to the carbon-3 position of the heteroatom. As this compound still contains the carboxylic acid it is then free to re enter the catalytic cycle where it undergoes coupling at the carbon 2 position, along with the expulsion of carbon dioxide to form a biaryl heteroatom. As this pathway competes with the decarboxylation step, two products are formed making this reaction less selective. As a result, heteroatoms, which are substituted at the carbon 3 position and are more favored due to the higher level of control they provide.
0
Organic Chemistry
Methanogenesis, the process that generates methane from CO, involves a series of methylation reactions. These reactions are caused by a set of enzymes harbored by a family of anaerobic microbes. In reverse methanogenesis, methane is the methylating agent.
0
Organic Chemistry
GOSAT was launched along with seven other piggyback probes using the H-IIA, Japan's primary large-scale expendable launch system, at 3:54 am on 23 January 2009 UTC on Tanegashima, a small island in southern Japan, after a two-day delay due to unfavourable weather. At approximately 16 minutes after liftoff, the separation of Ibuki from the launch rocket was confirmed.
2
Environmental Chemistry
Temporary tattoo-based sweat diagnostic tools have been demonstrated by Dr. Joseph Wang's group from University of California, San Diego. Their work includes sweat diagnostics for sodium, lactate, ammonium, pH and biofuel opportunities.
1
Biochemistry
Ribulose-1,5-bisphosphate carboxylase/oxygenase, commonly known by the abbreviations RuBisCo, rubisco, RuBPCase, or RuBPco, is an enzyme () involved in light-independent (or "dark") part of photosynthesis, including the carbon fixation by which atmospheric carbon dioxide is converted by plants and other photosynthetic organisms to energy-rich molecules such as glucose. It emerged approximately four billion years ago in primordial metabolism prior to the presence of oxygen on Earth. It is probably the most abundant enzyme on Earth. In chemical terms, it catalyzes the carboxylation of ribulose-1,5-bisphosphate (also known as RuBP).
5
Photochemistry
Optical depth of a material, denoted , is given by:where * is the radiant flux received by that material; * is the radiant flux transmitted by that material; * is the transmittance of that material. The absorbance is related to optical depth by:
7
Physical Chemistry
1-Arseno-3-phosphoglycerate can be derived from the glycolytic pathway via the bonding of Arsenate and glyceraldehyde-3-phosphate, which is catalyzed by glyceraldehyde phosphate dehydrogenase (GAPDH). The net production of ATP is zero as a result of the formation of the intermediate, 1-arseno-3-phosphoglycerate, as opposed to the conventional pathway, which produces a net result of two ATP molecules.
1
Biochemistry
Lee's group combines experimental and computational methods to understand mechanisms of reactions important for chemistry and biology. Specifically, Lee has pioneered the use of traditionally physical methods, primarily mass spectrometry and computational chemistry, to tackle problems at the chemistry/biology interface, focusing on catalysis.
0
Organic Chemistry
Immediate manifestations of caustic substance ingestions include erosions of mucosal surfaces of the gastrointestinal tract or airway (which can cause bleeding if the erosions extend to a blood vessel), mouth and tongue swelling, drooling or hypersalivation, nausea, vomiting, dyspnea, dysphonia/aphonia irritation of the eyes and skin. Perforation of the esophagus can lead to mediastinitis or perforation of the stomach or bowel can lead to peritonitis Swelling of the airway or laryngospasm can occur leading to compromised breathing. Injuries affecting the respiratory system include aspiration pneumonia and laryngeal sores. Signs of respiratory compromise include stridor and a change in a person's voice. Later manifestations of caustic substance ingestions include esophageal strictures or stenosis; which can result in chronic pain and malnutrition. Esophageal strictures more commonly occur after more severe mucosal injury, occurring in to 71% and 100% of grade 2b and 3 mucosal lesions respectively. Remote manifestations of caustic ingestions include esophageal cancer. People who have a history of caustic substance ingestion are 1000-3000 times more likely to develop esophageal cancer with most cases occurring 10–30 years after the ingestion.
8
Metallurgy
The existence of two A-to-I modifications in relatively close proximity, which is common in Alu elements, means the downstream mod is less likely to be detected since the cDNA synthesis will be truncated at a prior nucleotide. The throughput is low, and the initial method required specific primers; the protocol is complicated and labour-intensive.
1
Biochemistry
Smelting or the reduction of an ore to its metallic state is the primary source of experimentation in archaeometallurgy. In its simplest form smelting can be accomplished by placing an ore sample between two pieces of combusting charcoal in an oxygen reducing atmosphere with a compressed air source to feed the combustion and result in temperatures high enough to smelt metal. But to reach this final metallic state several things need to be done first including the processing of the ore to remove waste or gangue material, the possible roasting of the ore, the smelting of the ore, and then there is the possibility of refining the metal through a series of remelts. Then, through chemical or microscopic analysis, the products of the smelt are analyzed and compared with the findings of archaeological excavation in order to examine the likelihood of various manufacturing processes.
8
Metallurgy
The Puckorius scaling index (PSI) uses slightly different parameters to quantify the relationship between the saturation state of the water and the amount of limescale deposited.
3
Analytical Chemistry
Glycosyltransferases can be segregated into "retaining" or "inverting" enzymes according to whether the stereochemistry of the donor's anomeric bond is retained (α→α) or inverted (α→β) during the transfer. The inverting mechanism is straightforward, requiring a single nucleophilic attack from the accepting atom to invert stereochemistry. The retaining mechanism has been a matter of debate, but there exists strong evidence against a double displacement mechanism (which would cause two inversions about the anomeric carbon for a net retention of stereochemistry) or a dissociative mechanism (a prevalent variant of which was known as SNi). An "orthogonal associative" mechanism has been proposed which, akin to the inverting enzymes, requires only a single nucleophilic attack from an acceptor from a non-linear angle (as observed in many crystal structures) to achieve anomer retention.
0
Organic Chemistry
1,1,1,2-Tetrafluoroethane is a non-flammable gas used primarily as a "high-temperature" refrigerant for domestic refrigeration and automobile air conditioners. These devices began using 1,1,1,2-tetrafluoroethane in the early 1990s as a replacement for the more environmentally harmful R-12. Retrofit kits are available to convert units that were originally R-12-equipped. Other common uses include plastic foam blowing, as a cleaning solvent, a propellant for the delivery of pharmaceuticals (e.g. bronchodilators), wine cork removers, gas dusters ("canned air"), and in air driers for removing the moisture from compressed air. 1,1,1,2-Tetrafluoroethane has also been used to cool computers in some overclocking attempts. It is the refrigerant used in plumbing pipe freeze kits. It is also commonly used as a propellant for airsoft airguns. The gas is often mixed with a silicone-based lubricant.
2
Environmental Chemistry
Polycationic complexes tend to form ion pairs with anions and these ion pairs often undergo reactions via the I pathway. The electrostatically held nucleophile can exchange positions with a ligand in the first coordination sphere, resulting in net substitution. An illustrative process comes from the "anation" (reaction with an anion) of chromium(III) hexaaquo complex: ::[Cr(HO)] + SCN {[Cr(HO)], NCS} ::{[Cr(HO)], NCS} [Cr(HO)NCS] + HO
0
Organic Chemistry
Superconductors are promising candidate materials for devising fundamental circuit elements of electronic, spintronic, and quantum technologies. One such example is a superconducting diode, in which supercurrent flows along one direction only, that promise dissipationless superconducting and semiconducting-superconducting hybrid technologies. Superconducting magnets are some of the most powerful electromagnets known. They are used in MRI/NMR machines, mass spectrometers, the beam-steering magnets used in particle accelerators and plasma confining magnets in some tokamaks. They can also be used for magnetic separation, where weakly magnetic particles are extracted from a background of less or non-magnetic particles, as in the pigment industries. They can also be used in large wind turbines to overcome the restrictions imposed by high electrical currents, with an industrial grade 3.6 megawatt superconducting windmill generator having been tested successfully in Denmark. In the 1950s and 1960s, superconductors were used to build experimental digital computers using cryotron switches. More recently, superconductors have been used to make digital circuits based on rapid single flux quantum technology and RF and microwave filters for mobile phone base stations. Superconductors are used to build Josephson junctions which are the building blocks of SQUIDs (superconducting quantum interference devices), the most sensitive magnetometers known. SQUIDs are used in scanning SQUID microscopes and magnetoencephalography. Series of Josephson devices are used to realize the SI volt. Superconducting photon detectors can be realised in a variety of device configurations. Depending on the particular mode of operation, a superconductor–insulator–superconductor Josephson junction can be used as a photon detector or as a mixer. The large resistance change at the transition from the normal to the superconducting state is used to build thermometers in cryogenic micro-calorimeter photon detectors. The same effect is used in ultrasensitive bolometers made from superconducting materials. Superconducting nanowire single-photon detectors offer high speed, low noise single-photon detection and have been employed widely in advanced photon-counting applications. Other early markets are arising where the relative efficiency, size and weight advantages of devices based on high-temperature superconductivity outweigh the additional costs involved. For example, in wind turbines the lower weight and volume of superconducting generators could lead to savings in construction and tower costs, offsetting the higher costs for the generator and lowering the total levelized cost of electricity (LCOE). Promising future applications include high-performance smart grid, electric power transmission, transformers, power storage devices, compact fusion power devices, electric motors (e.g. for vehicle propulsion, as in vactrains or maglev trains), magnetic levitation devices, fault current limiters, enhancing spintronic devices with superconducting materials, and superconducting magnetic refrigeration. However, superconductivity is sensitive to moving magnetic fields, so applications that use alternating current (e.g. transformers) will be more difficult to develop than those that rely upon direct current. Compared to traditional power lines, superconducting transmission lines are more efficient and require only a fraction of the space, which would not only lead to a better environmental performance but could also improve public acceptance for expansion of the electric grid. Another attractive industrial aspect is the ability for high power transmission at lower voltages. Advancements in the efficiency of cooling systems and use of cheap coolants such as liquid nitrogen have also significantly decreased cooling costs needed for superconductivity.
7
Physical Chemistry
The cDNA library derived from RNA biotypes is then sequenced into a computer-readable format. There are many high-throughput sequencing technologies for cDNA sequencing including platforms developed by Illumina, Thermo Fisher, BGI/MGI, PacBio, and Oxford Nanopore Technologies. For Illumina short-read sequencing, a common technology for cDNA sequencing, adapters are ligated to the cDNA, DNA is attached to a flow cell, clusters are generated through cycles of bridge amplification and denaturing, and sequence-by-synthesis is performed in cycles of complementary strand synthesis and laser excitation of bases with reversible terminators. Sequencing platform choice and parameters are guided by experimental design and cost. Common experimental design considerations include deciding on the sequencing length, sequencing depth, use of single versus paired-end sequencing, number of replicates, multiplexing, randomization, and spike-ins.
1
Biochemistry
Blood feeding organisms digest hemoglobin and release high quantities of free toxic heme. To avoid destruction by this molecule, the parasite biocrystallizes heme to form hemozoin. To date, the only definitively characterized product of hematin disposal is the pigment hemozoin. Hemozoin is per definitionem not a mineral and therefore not formed by biomineralization. Heme biocrystallization has been found in blood feeding organisms of great medical importance including Plasmodium, Rhodnius and Schistosoma. Heme biocrystallization is inhibited by quinoline antimalarials such as chloroquine. Targeting heme biocrystallization remains one of the most promising avenues for antimalarial drug development because the drug target is highly specific to the malarial parasite, and outside the genetic control of the parasite.
1
Biochemistry
Lactonase (EC 3.1.1.81, acyl-homoserine lactonase; systematic name N-acyl--homoserine-lactone lactonohydrolase) is a metalloenzyme, produced by certain species of bacteria, which targets and inactivates acylated homoserine lactones (AHLs). It catalyzes the reaction : an N-acyl--homoserine lactone + HO an N-acyl--homoserine Many species of α-, β-, and γ-proteobacteria produce acylated homoserine lactones, small hormone-like molecules commonly used as communication signals between bacterial cells in a population to regulate certain gene expression and phenotypic behaviours. This type of gene regulation is known as quorum sensing. Other names for these types of enzymes are Quorum-quenching N-acyl-homoserine lactonase, acyl homoserine degrading enzyme, acyl-homoserine lactone acylase, AHL lactonase, AHL-degrading enzyme, AHL-inactivating enzyme, AHLase, AhlD, AhlK, AiiA, AiiA lactonase, AiiA-like protein, AiiB, AiiC, AttM, delactonase, lactonase-like enzyme, N-acyl homoserine lactonase, N-acyl homoserine lactone hydrolase, N-acyl-homoserine lactone lactonase, N-acyl--homoserine lactone hydrolase, quorum-quenching lactonase, quorum-quenching N-acyl homoserine lactone hydrolase.
1
Biochemistry
In biology, glycosylation is the process by which a carbohydrate is covalently attached to an organic molecule, creating structures such as glycoproteins and glycolipids.
0
Organic Chemistry
Capillary electrophoresis may be used for the simultaneous determination of the ions NH, Na, K, Mg and Ca in saliva. One of the main applications of CE in forensic science is the development of methods for amplification and detection of DNA fragments using polymerase chain reaction (PCR), which has led to rapid and dramatic advances in forensic DNA analysis. DNA separations are carried out using thin CE 50-mm fused silica capillaries filled with a sieving buffer. These capillaries have excellent capabilities to dissipate heat, permitting much higher electric field strengths to be used than slab gel electrophoresis. Therefore separations in capillaries are rapid and efficient. Additionally, the capillaries can be easily refilled and changed for efficient and automated injections. Detection occurs via fluorescence through a window etched in the capillary. Both single-capillary and capillary-array instruments are available with array systems capable of running 16 or more samples simultaneously for increased throughput. A major use of CE by forensic biologists is typing of STR from biological samples to generate a profile from highly polymorphic genetic markers which differ between individuals. Other emerging uses for CE include the detection of specific mRNA fragments to help identify the biological fluid or tissue origin of a forensic sample. Another application of CE in forensics is ink analysis, where the analysis of inkjet printing inks is becoming more necessary due to increasingly frequent counterfeiting of documents printed by inkjet printers. The chemical composition of inks provides very important information in cases of fraudulent documents and counterfeit banknotes. Micellar electrophoretic capillary chromatography (MECC) has been developed and applied to the analysis of inks extracted from paper. Due to its high resolving power relative to inks containing several chemically similar substances, differences between inks from the same manufacturer can also be distinguished. This makes it suitable for evaluating the origin of documents based on the chemical composition of inks. It is worth noting that because of the possible compatibility of the same cartridge with different printer models, the differentiation of inks on the basis of their MECC electrophoretic profiles is a more reliable method for the determination of the ink cartridge of origin (its producer and cartridge number) rather than the printer model of origin. A specialized type of CE, affinity capillary electrophoresis (ACE), utilizes intermolecular binding interactions to understand protein-ligand interactions. Pharmaceutical companies use ACE for a multitude of reasons, with one of the main ones being the association/binding constants for drugs and ligands or drugs and certain vehicle systems like micelles. It is a widely used technique because of its simplicity, rapid results, and low analyte usage. The use of ACE can provide specific details in binding, separation, and detection of analytes and is proven to be highly practical for studies in life sciences. Aptamer-based affinity capillary electrophoresis is utilized for the analysis and modifications of specific affinity reagents. Modified aptamers ideally exhibit and high binding affinity, specificity, and nuclease resistance. Ren et al. incorporated modified nucleotides in aptamers to introduce new confrontational features and high affinity interactions from the hydrophobic and polar interactions between IL-1α and the aptamer. Huang et al. uses ACE to investigate protein-protein interactions using aptamers. A α-thrombin binding aptamer was labeled with 6-carboxyfluorescein for use as a selective fluorescent probe and was studied to elucidate information on binding sites for protein-protein and protein-DNA interactions. Capillary electrophoresis (CE) has become an important, cost-effective approach to do DNA sequencing that provides high throughput and high accuracy sequencing information. Woolley and Mathies used a CE chip to sequence DNA fragments with 97% accuracy and a speed of 150 bases in 540 seconds. They used a 4-color labeling and detection format to collect fluorescent data. Fluorescence is used to view the concentrations of each part of the nucleic acid sequence, A, T, C and G, and these concentration peaks that are graphed from the detection are used to determine the sequence of the DNA.
3
Analytical Chemistry
There are two major classes of devices: single-beam and double-beam. A double-beam spectrophotometer compares the light intensity between two light paths, one path containing a reference sample and the other the test sample. A single-beam spectrophotometer measures the relative light intensity of the beam before and after a test sample is inserted. Although comparison measurements from double-beam instruments are easier and more stable, single-beam instruments can have a larger dynamic range and are optically simpler and more compact. Additionally, some specialized instruments, such as spectrophotometers built onto microscopes or telescopes, are single-beam instruments due to practicality. Historically, spectrophotometers use a monochromator containing a diffraction grating to produce the analytical spectrum. The grating can either be movable or fixed. If a single detector, such as a photomultiplier tube or photodiode is used, the grating can be scanned stepwise (scanning spectrophotometer) so that the detector can measure the light intensity at each wavelength (which will correspond to each "step"). Arrays of detectors (array spectrophotometer), such as charge coupled devices (CCD) or photodiode arrays (PDA) can also be used. In such systems, the grating is fixed and the intensity of each wavelength of light is measured by a different detector in the array. Additionally, most modern mid-infrared spectrophotometers use a Fourier transform technique to acquire the spectral information. This technique is called Fourier transform infrared spectroscopy. When making transmission measurements, the spectrophotometer quantitatively compares the fraction of light that passes through a reference solution and a test solution, then electronically compares the intensities of the two signals and computes the percentage of transmission of the sample compared to the reference standard. For reflectance measurements, the spectrophotometer quantitatively compares the fraction of light that reflects from the reference and test samples. Light from the source lamp is passed through a monochromator, which diffracts the light into a "rainbow" of wavelengths through a rotating prism and outputs narrow bandwidths of this diffracted spectrum through a mechanical slit on the output side of the monochromator. These bandwidths are transmitted through the test sample. Then the photon flux density (watts per meter squared usually) of the transmitted or reflected light is measured with a photodiode, charge coupled device or other light sensor. The transmittance or reflectance value for each wavelength of the test sample is then compared with the transmission or reflectance values from the reference sample. Most instruments will apply a logarithmic function to the linear transmittance ratio to calculate the absorbency of the sample, a value which is proportional to the concentration of the chemical being measured. In short, the sequence of events in a scanning spectrophotometer is as follows: # The light source is shone into a monochromator, diffracted into a rainbow, and split into two beams. It is then scanned through the sample and the reference solutions. # Fractions of the incident wavelengths are transmitted through, or reflected from, the sample and the reference. # The resultant light strikes the photodetector device, which compares the relative intensity of the two beams. # Electronic circuits convert the relative currents into linear transmission percentages and/or absorbance/concentration values. In an array spectrophotometer, the sequence is as follows: # The light source is shone into the sample and focused into a slit # The transmitted light is refracted into a rainbow with the reflection grating # The resulting light strikes the photodetector device which compares the intensity of the beam # Electronic circuits convert the relative currents into linear transmission percentages and/or absorbance/concentration values Many older spectrophotometers must be calibrated by a procedure known as "zeroing", to balance the null current output of the two beams at the detector. The transmission of a reference substance is set as a baseline (datum) value, so the transmission of all other substances is recorded relative to the initial "zeroed" substance. The spectrophotometer then converts the transmission ratio into absorbency, the concentration of specific components of the test sample relative to the initial substance.
7
Physical Chemistry
Following the Peoples National Movements defeat in the 2010 general election, Rowley was appointed as Leader of the Opposition on the 1st June. He was then elected political leader of the People's National Movement as he was seen as the most capable to lead the party. As political leader he advocated implementation of the one man, one vote system within the party. Rowley has served on several parliamentary committees. In 2004, he chaired the Joint Select Committee of Parliament which examined and made recommendations for the live broadcasting of parliamentary debates. He served as the representative governor of Trinidad and Tobago for the Inter-American Development Bank and the Caribbean Development Bank.
9
Geochemistry
Inositol polyphosphate 5-phosphatase OCRL-1, also known as Lowe oculocerebrorenal syndrome protein, is an enzyme encoded by the OCRL gene located on the X chromosome in humans. This gene encodes an inositol polyphosphate 5-phosphatase. The responsible gene locus is at Xq26.1. This phosphatase enzyme is in part responsible for regulating membrane trafficking actin polymerization, and is located in several subcellular parts of the trans-Golgi network. Deficiencies in OCRL-1 may cause with oculocerebrorenal syndrome and also have been linked to Dent's disease.
1
Biochemistry
The first two steps in an oxidation reaction involving N-tert-butylbenzenesulfinimidoyl chloride are similar to a nucleophilic acyl substitution reaction. A nucleophile, such as an alkoxide (1), attacks the S=N bond in 2. The resulting intermediate (3) collapses and ejects chloride ion, which is a good leaving group. The resulting sulfimide has two resonance forms - 4a and 4b. Because of this, the nitrogen is basic, and via a five-membered ring transition state, it can abstract the hydrogen adjacent to the oxygen. This forms a new C=O bond and ejects a neutral sulfenamide (5), giving ketone 6 as the product. N-tert-Butylbenzenesulfinimidoyl chloride reacts with enolates, amides, and primary alkoxides by the same general mechanism. The Swern oxidation, which converts primary and secondary alcohols to aldehydes and ketones, respectively, also uses a sulfur-containing compound (DMSO) as the oxidant and proceeds by a similar mechanism. In the Swern oxidation, elimination also occurs via a five-membered ring transition state, but the basic species is a sulfur ylide instead of a negatively charged nitrogen. Several other oxidation reactions also make use of DMSO as the oxidant and pass through a similar transition state (see #See also).
0
Organic Chemistry
The pedosphere () is the outermost layer of the Earth that is composed of soil and subject to soil formation processes. It exists at the interface of the lithosphere, atmosphere, hydrosphere and biosphere. The pedosphere is the skin of the Earth and only develops when there is a dynamic interaction between the atmosphere (air in and above the soil), biosphere (living organisms), lithosphere (unconsolidated regolith and consolidated bedrock) and the hydrosphere (water in, on and below the soil). The pedosphere is the foundation of terrestrial life on Earth. The pedosphere acts as the mediator of chemical and biogeochemical flux into and out of these respective systems and is made up of gaseous, mineralic, fluid and biologic components. The pedosphere lies within the Critical Zone, a broader interface that includes vegetation, pedosphere, aquifer systems, regolith and finally ends at some depth in the bedrock where the biosphere and hydrosphere cease to make significant changes to the chemistry at depth. As part of the larger global system, any particular environment in which soil forms is influenced solely by its geographic position on the globe as climatic, geologic, biologic and anthropogenic changes occur with changes in longitude and latitude. The pedosphere lies below the vegetative cover of the biosphere and above the hydrosphere and lithosphere. The soil forming process (pedogenesis) can begin without the aid of biology but is significantly quickened in the presence of biologic reactions, where it forms a soil carbon sponge. Soil formation begins with the chemical and/or physical breakdown of minerals to form the initial material that overlies the bedrock substrate. Biology quickens this by secreting acidic compounds that help break rock apart. Particular biologic pioneers are lichen, mosses and seed bearing plants, but many other inorganic reactions take place that diversify the chemical makeup of the early soil layer. Once weathering and decomposition products accumulate, a coherent soil body allows the migration of fluids both vertically and laterally through the soil profile, causing ion exchange between solid, fluid and gaseous phases. As time progresses, the bulk geochemistry of the soil layer will deviate away from the initial composition of the bedrock and will evolve to a chemistry that reflects the type of reactions that take place in the soil.
9
Geochemistry
Diffusional flow is a regime typically below dislocation creep and occurs at high temperatures due to the diffusion of point defects in the material. Diffusional flow can be further broken down into more specific mechanisms: Nabarro–Herring creep, Coble creep, and Harper–Dorn creep. While most materials will exhibit Nabarro-Herring creep and Coble creep, Harper-Dorn creep is quite rare, having only been reported in a select few materials at low stresses including aluminium, lead, and tin. The equation for Nabarro-Herring creep is dominated by vacancy diffusion within the lattice, whereas Coble creep is dominated by vacancy diffusion within the grain boundaries. The equation for these mechanisms is shown below where is the applied shear stress, Ω is the atomic volume, k is the Boltzmann constant ,d is the grain size, T is the temperature, and is the effective diffusion coefficient. The effective diffusion coefficient, = (the volumetric diffusion constant) for Nabarro-Herring creep which dominates at high temperatures, and (where is the grain boundary width and is the diffusion coefficient in the boundary) for Coble creep which dominates at low-temperatures. From these equations it becomes clear that the boundary between boundary diffusion and lattice diffusion is heavily dependent on grain size. For systems with larger grains, the Nabarro-Herring lattice diffusion region of the deformation mechanism map will be larger than in maps with very small grains. Additionally, the larger the grains, the less diffusional creep and thus the power-law creep region of the map will be larger for large grained materials. Grain boundary engineering is thus an effective strategy to manipulate creep rates.
8
Metallurgy
The NICE-OHMS technique combines cavity enhanced absorption spectrometry (CEAS) for prolonged interaction length with the sample with frequency modulation (fm) spectrometry FMS for reduction of 1/f noise. By choosing the fm-modulation frequency equal to the free spectral range (FSR) of the cavity, all components of the spectral fm-triplet are transmitted through the cavity in an identical manner. Therefore, the cavity does not compromise the balance of the fm-triplet, which otherwise would give rise to fm-background signals. It also does not convert any fluctuations of the laser frequency with respect to the transmission mode of the cavity to intensity modulation, which would deteriorate the detectability by the introduction of intensity noise. This is referred to as "noise immunity". All this implies that FMS can be performed as if the cavity were not present, yet fully benefiting from the prolonged interaction length.
7
Physical Chemistry
Three days after the failed February 2009 launch, the OCO science team sent NASA headquarters a proposal to build and launch an OCO copy by late 2011. On 1 February 2010, the FY 2011 NASA budget request did include $170 million for NASA to develop and fly a replacement for the Orbiting Carbon Observatory: OCO-2. NASA, in 2010, initially selected Orbital Sciences for launching the replacement in February 2013 on a Taurus XL 3110 from Vandenberg Air Force Base in California. The launch of the Glory satellite took place on 4 March 2011 and ended in failure, like OCO. Then, in February 2012 both NASA and Orbital Sciences came to an agreement to terminate the launch contract. OCO-2 was initially scheduled for launch on 1 July 2014 at 09:56 UTC aboard a Delta II rocket, though that launch was scrubbed at 46 seconds on the countdown clock due to a faulty valve on the water suppression system that is used to flow water on the launch pad to dampen the acoustic energy during launch. The rocket launched 2 July at the same time.
2
Environmental Chemistry
When a continuum radiation source is used for AAS, it is necessary to use a high-resolution monochromator, as will be discussed later. In addition, it is necessary that the lamp emits radiation of intensity at least an order of magnitude above that of a typical HCL over the entire wavelength range from 190 nm to 900 nm. A special high-pressure xenon short arc lamp, operating in a hot-spot mode has been developed to fulfill these requirements.
3
Analytical Chemistry
Pharmacodynamic (PD) biomarkers can measure the direct interaction between a drug and its receptor. Pharmacodynamic biomarkers reveal drug mechanisms, if the drug has its intended effect on the biology of the disease, ideal biological dosing concentrations, and physiologic response/resistance mechanisms. Pharmacodynamic biomarkers are particularly relevant in drug mechanisms of tumor cells, where pharmacodynamic endpoints for drug interventions can be assessed directly on tumor tissues. For example, protein phosphorylation biomarkers indicate alterations in target protein kinases and activation of downstream signaling molecules.
1
Biochemistry
As a precursor of a photosensitizer, 5ALA is also used as an add-on agent for photodynamic therapy. In contrast to larger photosensitizer molecules, it is predicted by computer simulations to be able to penetrate tumor cell membranes.
1
Biochemistry
Human health effects include excess nitrate in drinking water (blue baby syndrome); disinfection by-products in drinking water. Swimming in water affected by a harmful algal bloom can cause skin rashes and respiratory problems.
2
Environmental Chemistry
Many authors, for example Greco and Hakala, have claimed that non-linear regression is always superior to regression of the linear forms of the Michaelis–Menten equation. However, that is correct only if the appropriate weighting scheme is used, preferably on the basis of experimental investigation, something that is almost never done. As noted above, Burk carried out the appropriate investigation, and found that the error structure of his data was consistent with a uniform standard deviation in . More recent studies found that a uniform coefficient of variation (standard deviation expressed as a percentage) was closer to the truth with the techniques in use in the 1970s. However, this truth may be more complicated than any dependence on alone can represent. Uniform standard deviation of . If the rates are considered to have a uniform standard deviation the appropriate weight for every value for non-linear regression is 1. If the double-reciprocal plot is used each value of should have a weight of , whereas if the Hanes plot is used each value of should have a weight of . Uniform coefficient variation of . If the rates are considered to have a uniform coefficient variation the appropriate weight for every value for non-linear regression is . If the double-reciprocal plot is used each value of should have a weight of , whereas if the Hanes plot is used each value of should have a weight of . Ideally the in each of these cases should be the true value, but that is always unknown. However, after a preliminary estimation one can use the calculated values for refining the estimation. In practice the error structure of enzyme kinetic data is very rarely investigated experimentally, therefore almost never known, but simply assumed. It is, however, possible to form an impression of the error structure from internal evidence in the data. This is tedious to do by hand, but can readily be done in the computer.
7
Physical Chemistry
Adam17 may facilitate entry of the SARS‑CoV‑2 virus, possibly by enabling fusion of virus particles with the cytoplasmic membrane. Adam17 has similar ACE2 cleavage activity as TMPRSS2, but by forming soluble ACE2, Adam17 may actually have the protective effect of blocking circulating SARS‑CoV‑2 virus particles. Adam17 sheddase activity may contribute to COVID-19 inflammation by cleavage of TNF-α and Interleukin-6 receptor.
1
Biochemistry
In eastern Washington and northern Idaho, meadow voles are found in relative abundance in sedge (Carex sp.) fens, but not in adjacent cedar (Thuja sp.)-hemlock (Tsuga sp.), Douglas-fir (Pseudotsuga menziesii), or ponderosa pine (Pinus ponderosa) forests. Meadow voles are also absent from fescue (Festuca sp.)-snowberry (Symphoricarpos sp.) associations. Moisture may be a major factor in habitat use; possibly the presence of free water is a deciding factor. In southeastern Montana, western meadow voles were the second-most abundant small mammal (after deer mice, Peromyscus maniculatus) in riparian areas within big sagebrush (Artemisia tridentata)-buffalo grass (Bouteloua dactyloides) habitats. Western meadow voles are listed as riparian-dependent vertebrates in the Snake River drainage of Wyoming. In a compilation of 11 studies on small mammals, western meadow voles were reported in only three of 29 sites in subalpine forests of the central Rocky Mountains. Their range extensions were likely to be related to irrigation practices. They are now common in hayfields, pastures, and along ditches in the Rocky Mountain states. In Pipestone National Monument, Minnesota, western meadow voles were present in riparian shrublands, tallgrass prairie, and other habitats.
2
Environmental Chemistry
Gene targeting is relatively high efficiency in yeast, bacterial and moss (but is rare in higher eukaryotes). Hence gene targeting has been used in reverse genetics approaches to study gene function in these systems.
1
Biochemistry
Olefin metathesis has several industrial applications. Almost all commercial applications employ heterogeneous catalysts using catalysts developed well before the Nobel-Prize winning work on homogeneous complexes. Representative processes include: *The Phillips Triolefin and the Olefin conversion technology. This process interconverts propylene with ethylene and 2-butenes. Rhenium and molybdenum catalysts are used. Nowadays, only the reverse reaction, i.e., the conversion of ethylene and 2-butene to propylene is industrially practiced, however. *Shell higher olefin process (SHOP) produces (alpha-olefins) for conversion to detergents. The process recycles certain olefin fractions using metathesis. *Neohexene production, which involves ethenolysis of isobutene dimers. The catalyst is derived from tungsten trioxide supported on silica and MgO. *1,5-Hexadiene and 1,9-decadiene, useful crosslinking agents and synthetic intermediates, are produced commercially by ethenolysis of 1,5-cyclooctadiene and cyclooctene. The catalyst is derived from ReO on alumina. *Synthesis of pharmaceutical drugs,
0
Organic Chemistry
The Journal of Physical Chemistry A is a scientific journal which reports research on the chemistry of molecules - including their dynamics, spectroscopy, kinetics, structure, bonding, and quantum chemistry. It is published weekly by the American Chemical Society. Before 1997 the title was simply Journal of Physical Chemistry. Owing to the ever-growing amount of research in the area, in 1997 the journal was split into Journal of Physical Chemistry A (molecular theoretical and experimental physical chemistry) and The Journal of Physical Chemistry B (solid state, soft matter, liquids, etc.). Beginning in 2007, the latter underwent a further split, with The Journal of Physical Chemistry C now being dedicated to nanotechnology, molecular electronics, and related subjects. According to the Journal Citation Reports, the journal had an impact factor of 2.944 for 2021.
7
Physical Chemistry
The precipitation method is the one used for the determination of the amount of calcium in water. Using this method, an excess of oxalic acid, HCO, is added to a measured, known volume of water. By adding a reagent, here ammonium oxalate, the calcium will precipitate as calcium oxalate. The proper reagent, when added to aqueous solution, will produce highly insoluble precipitates from the positive and negative ions that would otherwise be soluble with their counterparts (equation 1). The reaction is: Formation of calcium oxalate: Ca + CO → CaCO The precipitate is collected, dried and ignited to high (red) heat which converts it entirely to calcium oxide. The reaction is pure calcium oxide formed CaCO → CaO + CO+ CO The pure precipitate is cooled, then measured by weighing, and the difference in weights before and after reveals the mass of analyte lost, in this case calcium oxide. That number can then be used to calculate the amount, or the percent concentration, of it in the original mix.
3
Analytical Chemistry
The Smoluchowski factor, also known as von Smoluchowski's f-factor is related to inter-particle interactions. It is named after Marian Smoluchowski.
7
Physical Chemistry
According to structural and functional similarity, many local hormones fall into either the gastrin or the secretin family.
1
Biochemistry
The color of blue eyes is due to the Tyndall scattering of light by a translucent layer of turbid media in the iris containing numerous small particles of about 0.6 micrometers in diameter. These particles are finely suspended within the fibrovascular structure of the stroma or front layer of the iris. Some brown irises have the same layer, except with more melanin in it. Moderate amounts of melanin make hazel, dark blue and green eyes. In eyes that contain both particles and melanin, melanin absorbs light. In the absence of melanin, the layer is translucent (i.e. the light passing through is randomly and diffusely scattered by the particles) and a noticeable portion of the light that enters this translucent layer re-emerges via a radial scattered path. That is, there is backscatter, the redirection of the light waves back out to the open air. Scattering takes place to a greater extent at shorter wavelengths. The longer wavelengths tend to pass straight through the translucent layer with unaltered paths of yellow light, and then encounter the next layer further back in the iris, which is a light absorber called the epithelium or uvea that is colored brownish-black. The brightness or intensity of scattered blue light that is scattered by the particles is due to this layer along with the turbid medium of particles within the stroma. Thus, the longer wavelengths are not reflected (by scattering) back to the open air as much as the shorter wavelengths. Because the shorter wavelengths are the blue wavelengths, this gives rise to a blue hue in the light that comes out of the eye. The blue iris is an example of a structural color because it relies only on the interference of light through the turbid medium to generate the color. Blue eyes and brown eyes, therefore, are anatomically different from each other in a genetically non-variable way because of the difference between turbid media and melanin. Both kinds of eye color can remain functionally separate despite being "mixed" together.
7
Physical Chemistry
The method of slipping is one which exploits the thermodynamic stability of the rotaxane. If the end groups of the dumbbell are an appropriate size it will be able to reversibly thread through the macrocycle at higher temperatures. By cooling the dynamic complex, it becomes kinetically trapped as a rotaxane at the lower temperature.
6
Supramolecular Chemistry
Transporting chemicals out of a cell against a gradient is often associated with ATP hydrolysis. Transport is mediated by ATP binding cassette transporters. The human genome encodes 48 ABC transporters, that are used for exporting drugs, lipids, and other compounds.
1
Biochemistry
ZMapp was first used during the 2014 West Africa Ebola Virus outbreak, having not previously undergone any human clinical trials to determine its efficacy or potential risks. By October 2014, the United States Food and Drug Administration had approved the use of several experimental drugs, including ZMapp, to be used on patients infected with Ebola virus. The use of such drugs during the epidemic was also deemed ethical by the World Health Organization. In 2014, a limited supply of ZMapp was used to treat 7 individuals infected with the Ebola virus; of these 2 died. The outcome is not considered to be statistically significant. Mapp announced in August 2014, that supplies of ZMapp had been exhausted.
1
Biochemistry
Thermal additions of stannanes are limited (because of the high temperatures and pressures required) to only simple aldehyde substrates. Lewis acid promoted and transmetalation reactions are much milder and have achieved synthetic utility. Intramolecular addition gives five- or six-membered rings under Lewis acidic or thermal conditions. The possibility of incorporating oxygen-containing substituents into allyl- and allenylstannanes expands their scope and utility substantially over methods relying on more reactive organometallics. These compounds are usually prepared by enantioselective reduction with a chiral reducing agent such as BINAL-H. In the presence of a Lewis acid, isomerization of α-alkoxy allylstannanes to the corresponding γ-alkoxy isomers takes place. The use of chiral electrophiles is common and can provide "double diastereoselection" if the stannane is also chiral. Chelation control using Lewis acids such as magnesium bromide can lead to high stereoselectivities for reactions of α-alkoxy aldehydes. Nucleophilic addition to propargyl mesylates or tosylates is used to form allenylstannanes. These compounds react similarly to allylstannanes to afford homopropargyl alcohols, and any of the three reaction modes described above can be used with this class of reagents as well. Imines are less reactive than the corresponding aldehydes, but palladium catalysis can be used to facilitate addition into imines. The use of iminium ions as electrophiles has also been reported.
0
Organic Chemistry
Ortho-substitution of the aromatic units results in a stabilization against oxidation, but the closed-ring form still has a low thermodynamic stability in most cases (e.g. 2,3-dimesityl-2-butene has a half-life of 90 seconds at 20°C). This problem can be addressed by lowering the aromaticity of the system. The most commonly used example are the dithienylethenes, i.e. alkenes with a thiophene ring on either side. Dithienylethene derivatives have shown different types of photochemical side reactions, e.g., oxidation or elimination reactions of the ring-closed isomer and formation of an annulated ring isomer as a byproduct of the photochromic reaction. In order to overcome the first, the 2-position of the thiophenes is substituted with a methyl group, preventing oxidation of the ring closed form. Also often the two free α-positions on the double bond are connected in a 5 or 6-membered ring in order to lock the double bond into the cis-form. This makes the dithienylethene undergo only open-closed ring isomerization, unconfused by E-Z isomerization. More recently, based on recent findings showing that by-product formation most likely occurs exclusively from the lowest singlet excited state, a superior fatigue resistance of dithienylethenes upon visible-light excitation has been achieved by attaching small triplet-sensitizing moieties to the diarylethene core via a -conjugated linkage. The dithienylethenes are also of interest for the fact that their isomerization requires very little change of shape. This means that their isomerization in a solid matrix can take place much more quickly than with most other photochromic molecules. In the case of some analogs, photochromic behavior can even be carried out in single crystals without disrupting the crystal structure.
5
Photochemistry
On the news of Lulu and Nana having been born, the Peoples Daily announced the experimental result as "a historical breakthrough in the application of gene editing technology for disease prevention." But scientists at the Second International Summit on Human Genome Editing immediately developed serious concerns. Robin Lovell-Badge, head of the Laboratory of Stem Cell Biology and Developmental Genetics at the Francis Crick Institute, who moderated the session on 28 November, recalled that He Jiankui did not mention human embryos in the draft summary of the presentation. He received an urgent message on 25 November through Jennifer Doudna of the University of California, Berkeley, a pioneer of the CRISPR/Cas9 technology, to whom he had confided the news earlier that morning. As the news already broke out before the day of the presentation, he had to be brought in by the University of Hong Kong security from his hotel. Nobel laureate David Baltimore, the chair of the organizing committee of the summit, was the first to react after Hes speech, and declared his horror and dismay at his work. He did not disclose the parents names (other than their pseudonyms Mark and Grace) and they did not make themselves available to be interviewed, so their reaction to this experiment and the ensuing controversy is not known. There was widespread criticism in the media and scientific community over the conduct of the clinical project and its secrecy, and concerns raised for the long term well-being of Lulu and Nana. Bioethicist Henry T. Greely of Stanford Law School declared, "I unequivocally condemn the experiment," and later, "He Jiankui’s experiment was, amazingly, even worse than I first thought." Kiran Musunuru, one of the experts called on to review Hes manuscript and who later wrote a book on the scandal, called it a "historic ethical fiasco, a deeply flawed experiment". On the night of 26 November 122 Chinese scientists issued a statement criticizing his research. They declared that the experiment was unethical, "crazy" and "a huge blow to the global reputation and development of Chinese science". The Chinese Academy of Medical Sciences made a condemnation statement on 5 January 2019 saying that: A series of investigations was opened by Hes university, local authorities, and the Chinese government. On 26 November 2018, SUSTech released a public notification on its website condemning Hes conduct, mentioning the key points as: * The research work was conducted off-campus by Associate Professor He Jiankui without reporting to the university and the Department of Biology, and the university and the Department of Biology were unaware of it. * The Academic Committee of the Department of Biology considers that Associate Professor He Jiankui's use of gene editing technology for human embryo research is a serious violation of academic ethics and academic standards. * SUSTech strictly requires scientific research to comply with national laws and regulations and to respect and abide by international academic ethics and academic norms. The university will immediately hire authoritative experts to set up an independent committee to conduct an in-depth investigation, and will publish relevant information after the investigation. On 28 November 2018, the organising committee of the Second International Summit on Human Genome Editing, led by Baltimore, issued a statement, declaring:On 29 January 2019, it was learned that a U.S. Nobel laureate Craig Mello interviewed He about his experiment with gene-edited babies. In February 2019, He's claims were reported to have been confirmed by Chinese investigators, according to NPR News. Around that time, news reported that the Chinese government may have helped fund the CRISPR babies experiment, at least in part, based on newly uncovered documents.
1
Biochemistry