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Further information: Health and environmental impact of the coal industry
In conjunction with enhanced oil recovery and other applications, commercial-scale CCS is currently being tested in the U.S. and other countries. Proposed CCS sites are subjected to extensive investigation and monitoring to avoid potential hazards, which could include leakage of sequestered CO2 to the atmosphere, induced geological instability, or contamination of water sources such as oceans and aquifers used for drinking water supplies. As of 2021, the only demonstrator for CCS on a coal plant that stores the gas underground is part of the Boundary Dam Power Station.
The Great Plains Synfuels plant supports the technical feasibility of carbon dioxide sequestration. Carbon dioxide from the coal gasification is shipped to Canada, where it is injected into the ground to aid in oil recovery. A drawback of the carbon sequestration process is that it is expensive compared to traditional processes. | 1 | Applied and Interdisciplinary Chemistry |
A Pythagorean cup looks like a normal drinking cup, except that the bowl has a central column in it, giving it a shape like a Bundt pan. The central column of the bowl is positioned directly over the stem of the cup and over a hole at the bottom of the stem. A small open pipe runs from this hole almost to the top of the central column, where there is an open chamber. The chamber is connected by a second pipe to the bottom of the central column, where a hole in the column exposes the pipe to (the contents of) the bowl of the cup.
When the cup is filled, liquid rises through the second pipe up to the chamber at the top of the central column, following Pascal's principle of communicating vessels. As long as the level of the liquid does not rise beyond the level of the chamber, the cup functions as normal. If the level rises further, however, the liquid spills through the chamber into the first pipe and out of the bottom. Gravity then creates a siphon through the central column, causing the entire contents of the cup to be emptied through the hole at the bottom of the stem. | 1 | Applied and Interdisciplinary Chemistry |
The pK of DMSO is 35, which leads NaDMSO to be a powerful Brønsted base. NaDMSO is used in the generation of phosphorus and sulfur ylides. NaDMSO in DMSO is especially convenient in the generation of dimethyloxosulfonium methylide and dimethylsulfonium methylide. | 0 | Theoretical and Fundamental Chemistry |
Tectin is an organic substance secreted by certain ciliates. Tectin may form an adhesive stalk, disc or other sticky secretion. Tectin may also form a gelatinous envelope or membrane enclosing some ciliates as a protective capsule or lorica. Tectin is also called pseudochitin. Granules or rods (called protrichocysts) in the pellicle of some ciliates are also thought to be involved in tectin secretion. | 1 | Applied and Interdisciplinary Chemistry |
It has also been discovered that GLD2 has medical uses.
For example, such enzyme is overexpressed in patients who suffer from cancer; that's why it can be used as a prognostic factor for early appearance in breast cancer patients. Moreover, PAP activity is used to measure the effect of anticancer drugs as etoposide and cordycepin in two carcinoma cell lines: HeLa, which is the human epithelioid cervix carcinoma, and MCF-7 (human breast cancer).
However, in spite its utilities it can also be involved in the expression of several common diseases such as: leukemia, liver cirrhosis, brain injuries, hepatitis and in some cases infertility in male patients. | 1 | Applied and Interdisciplinary Chemistry |
Two-dimensional maps of elemental compositions can be generated by scanning the microPIXE beam across the target. | 0 | Theoretical and Fundamental Chemistry |
Calcareous sinter is characterised by laminations of prismatic crystals growing perpendicular to the substrate; laminations are separated by thin layers of microcrystalline carbonate. Calcareous sinter is porous due to the calcareous crystals enclosing many small cavities. Macrophytes are absent, consequently porosity is very low. Exclusion of species is due either to high temperature (travertine), high pH/ionic strength (tufa) or absence of light (speleothems).
Pedley (1990) suggests the term be abandoned in favour of tufa for ambient temperature deposits. This avoids any potential confusion with siliceous sinter and prevents deposits formed in different environmental conditions (hot spring deposits, cold spring deposits and speleothems are all lumped together under the term sinter) from being amalgamated into one group. | 0 | Theoretical and Fundamental Chemistry |
Feed ingredients are normally first hammered to reduce the particle size of the ingredients. Ingredients are then batched, and then combined and mixed thoroughly by a feed mixer. Once the feed has been prepared to this stage the feed is ready to be pelletized. | 1 | Applied and Interdisciplinary Chemistry |
Some early evidence for nuclear fission was the formation of a short-lived radioisotope of barium which was isolated from neutron irradiated uranium (Ba, with a half-life of 83 minutes and Ba, with a half-life of 12.8 days, are major fission products of uranium). At the time, it was thought that this was a new radium isotope, as it was then standard radiochemical practice to use a barium sulfate carrier precipitate to assist in the isolation of radium. | 0 | Theoretical and Fundamental Chemistry |
Nickel has a wide utility of application in manufactured metals because it is both strong and malleable, leading to ubiquitous presence and the potential for consumers to be in contact with it daily. However, for those who have the rash of allergic contact dermatitis (ACD) due to a nickel allergy, it can be a challenge to avoid. Foods, common kitchen utensils, cell phones, jewelry, and many other items may contain nickel and be a source of irritation due to the allergic reaction caused by the absorption of free released nickel through direct and prolonged contact. The most appropriate measure for nickel-allergic persons is to prevent contact with the allergen.
In 2011, researchers showed that applying a thin layer of glycerine emollient containing nanoparticles of either calcium carbonate or calcium phosphate on an isolated piece of pig skin (in vitro) and on the skin of mice (in vivo) prevents the penetration of nickel ions into the skin. The nanoparticles capture nickel ions by cation exchange, and remain on the surface of the skin, allowing them to be removed by simple washing with water. Approximately 11-fold fewer nanoparticles by mass are required to achieve the same efficacy as the chelating agent ethylenediamine tetraacetic acid. Using nanoparticles with diameters smaller than 500 nm in topical creams may be an effective way to limit the exposure to metal ions that can cause skin irritation'.
Pre-emptive avoidance strategies (PEAS) might ultimately lower the sensitization rates of children who would develop ACD It is theorized that prevention of exposure to nickel early on could reduce the number of those that are sensitive to nickel by one-quarter to one-third. Identification of the many sources of nickel is vital to understanding the nickel sensitization story, food like chocolate and fish, zippers, buttons, cell phones and even orthodontic braces and eyeglass frames might contain nickel. Items that contain sentimental value (heirlooms, wedding rings) could be treated with an enamel or rhodium plating.
The Dermatitis Academy has created an educational website to provide more information about nickel, including information about prevention, exposure, sources, and general information about nickel allergy. These resources provide guidance in a prevention initiative for children worldwide.
Prevention of SNAS includes modifying dietary choices to avoid certain foods that are higher in nickel than others. | 1 | Applied and Interdisciplinary Chemistry |
While SERS can be performed in colloidal solutions, today the most common method for performing SERS measurements is by depositing a liquid sample onto a silicon or glass surface with a nanostructured noble metal surface. While the first experiments were performed on electrochemically roughened silver, now surfaces are often prepared using a distribution of metal nanoparticles on the surface as well as using lithography or porous silicon as a support. Two dimensional silicon nanopillars decorated with silver have also been used to create SERS active substrates. The most common metals used for plasmonic surfaces in visible light SERS are silver and gold; however, aluminium has recently been explored as an alternative plasmonic material, because its plasmon band is in the UV region, contrary to silver and gold. Hence, there is great interest in using aluminium for UV SERS. It has, however, surprisingly also been shown to have a large enhancement in the infrared, which is not fully understood. In the current decade, it has been recognized that the cost of SERS substrates must be reduced in order to become a commonly used analytical chemistry measurement technique. To meet this need, plasmonic paper has experienced widespread attention in the field, with highly sensitive SERS substrates being formed through approaches such as soaking, in-situ synthesis, screen printing and inkjet printing.
The shape and size of the metal nanoparticles strongly affect the strength of the enhancement because these factors influence the ratio of absorption and scattering events. There is an ideal size for these particles, and an ideal surface thickness for each experiment. If concentration and particle size can be tuned better for each experiment this will go a long way in the cost reduction of substrates. Particles that are too large allow the excitation of multipoles, which are nonradiative. As only the dipole transition leads to Raman scattering, the higher-order transitions will cause a decrease in the overall efficiency of the enhancement. Particles that are too small lose their electrical conductance and cannot enhance the field. When the particle size approaches a few atoms, the definition of a plasmon does not hold, as there must be a large collection of electrons to oscillate together.
An ideal SERS substrate must possess high uniformity and high field enhancement. Such substrates can be fabricated on a wafer scale and label-free superresolution microscopy has also been demonstrated using the fluctuations of surface enhanced Raman scattering signal on such highly uniform, high-performance plasmonic metasurfaces.
Due to their unique physical and chemical properties, two-dimensional (2D) materials have gained significant attention as alternative substrates for surface-enhanced Raman spectroscopy (SERS). The use of 2D materials as SERS substrates offers several advantages over traditional metal substrates, including high sensitivity, reproducibility, and chemical stability.
Graphene is one of the most widely studied 2D materials for SERS applications. Graphene has a high surface area, high electron mobility, and excellent chemical stability, making it an attractive substrate for SERS. Graphene-based SERS sensors have also been shown to be highly reproducible and stable, making them attractive for real-world applications. In addition to graphene, other 2D materials, especially MXenes, have also been investigated for SERS applications. MXenes have a high surface area, good electrical conductivity, and chemical stability, making them attractive for SERS applications. As a result, MXene-based SERS sensors have been used to detect various analytes, including organic molecules, drugs and their metabolites.
As research and development continue, 2D materials-based SERS sensors will likely be more widely used in various industries, including environmental monitoring, healthcare, and food safety. | 0 | Theoretical and Fundamental Chemistry |
Omega Chi Epsilon (or , sometimes simplified to OXE) is an International honor society for chemical engineering students. | 1 | Applied and Interdisciplinary Chemistry |
In 2010, NIF researchers conducted a series of "tuning" shots to determine the optimal target design and laser parameters for high-energy ignition experiments with fusion fuel. Net fuel energy gain was achieved in September 2013.
In April 2014, LLNL ended the Laser Inertial Fusion Energy (LIFE) program and directed their efforts towards NIF.
A 2012 paper demonstrated that a dense plasma focus had achieved temperatures of 1.8 billion degrees Celsius, sufficient for boron fusion, and that fusion reactions were occurring primarily within the contained plasmoid, necessary for net power.
In August 2014, MIT announced a tokamak it named the ARC fusion reactor, using rare-earth barium-copper oxide (REBCO) superconducting tapes to construct high-magnetic field coils that it claimed produced comparable magnetic field strength in a smaller configuration than other designs.
In October 2015, researchers at the Max Planck Institute of Plasma Physics completed building the largest stellarator to date, the Wendelstein 7-X. In December they produced the first helium plasma, and in February 2016 produced hydrogen plasma. In 2015, with plasma discharges lasting up to 30 minutes, Wendelstein 7-X attempted to demonstrate the essential stellarator attribute: continuous operation of a high-temperature plasma.
In 2014 EAST achieved a record confinement time of 30 seconds for plasma in the high-confinement mode (H-mode), thanks to improved heat dispersal. This was an order of magnitude improvement vs other reactors. In 2017 the reactor achieved a stable 101.2-second steady-state high confinement plasma, setting a world record in long-pulse H-mode operation.
In 2018 MIT scientists formulated a theoretical means to remove the excess heat from compact nuclear fusion reactors via larger and longer divertors.
In 2019 the United Kingdom announced a planned £200-million (US$248-million) investment to produce a design for a fusion facility named the Spherical Tokamak for Energy Production (STEP), by the early 2040s. | 0 | Theoretical and Fundamental Chemistry |
When the B cells get activated, class switching can occur. The class switching involves switch regions that made up of multiple copies of short repeats (GAGCT and TGGGG). These switches occur at the level of rearrangements of the DNA because there is a looping event that chops off the constant regions for IgM and IgD and form the IgG mRNAs. Any continuous looping occurrence will produce IgE or IgA mRNAs. In addition, cytokines are factors that have great effects on class switching of different classes of antibodies. Their interaction with B cells provides the appropriates signals needed for B cells differentiation and eventual class switching occurrence. For example, interleukin-4 induces the rearrangements of heavy chain immunoglobulin genes. That is IL- 4 induces the switching of Cμ to Cγ to Cκ | 1 | Applied and Interdisciplinary Chemistry |
The effect has mainly been observed on alkaline atoms which have nuclear properties particularly suitable for working with traps. As of 2012, using ultra-low temperatures of or below, Bose–Einstein condensates had been obtained for a multitude of isotopes, mainly of alkali metal, alkaline earth metal,
and lanthanide atoms (, , , , , , , , , , , , , , and ). Research was finally successful in hydrogen with the aid of the newly developed method of evaporative cooling. In contrast, the superfluid state of below is not a good example, because the interaction between the atoms is too strong. Only 8% of atoms are in the ground state of the trap near absolute zero, rather than the 100% of a true condensate.
The bosonic behavior of some of these alkaline gases appears odd at first sight, because their nuclei have half-integer total spin. It arises from a subtle interplay of electronic and nuclear spins: at ultra-low temperatures and corresponding excitation energies, the half-integer total spin of the electronic shell and half-integer total spin of the nucleus are coupled by a very weak hyperfine interaction. The total spin of the atom, arising from this coupling, is an integer lower value. The chemistry of systems at room temperature is determined by the electronic properties, which is essentially fermionic, since room temperature thermal excitations have typical energies much higher than the hyperfine values. | 0 | Theoretical and Fundamental Chemistry |
An electrical conductivity meter (EC meter) measures the electrical conductivity in a solution. It has multiple applications in research and engineering, with common usage in hydroponics, aquaculture, aquaponics, and freshwater systems to monitor the amount of nutrients, salts or impurities in the water. | 0 | Theoretical and Fundamental Chemistry |
Biorheology is the study of flow properties (rheology) of biological fluids. The term was first proposed by Alfred L. Copley, a German-American medical scientist, at the first International Congress on Rheology in 1948. | 1 | Applied and Interdisciplinary Chemistry |
During the 1930s and 1940s, the DuPont company commercialized organofluorine compounds at large scales. Following trials of chlorofluorocarbons as refrigerants by researchers at General Motors, DuPont developed large-scale production of Freon-12. The work was carried out by DuPont scientist Dr. Thomas Midgley Jr. DuPont and GM formed a joint venture in 1930 to market the new product; in 1949 DuPont took over the business. Freon proved to be a marketplace hit, rapidly replacing earlier, more toxic, refrigerants and growing the overall market for kitchen refrigerators.
In 1938, polytetrafluoroethylene (Teflon) was discovered by accident by a recently hired DuPont PhD, Roy J. Plunkett. While working with a cylinder of tetrafluoroethylene, he was unable to release the gas, although the weight had not changed. Scraping down the container, he found white flakes of a polymer new to the world. Tests showed the substance was resistant to corrosion from most substances and had better high temperature stability than any other plastic. By early 1941, a crash program was making commercial quantities.
Large-scale productions of elemental fluorine began during World War II. Germany used high-temperature electrolysis to produce tons of chlorine trifluoride, a compound planned to be used as an incendiary. The Manhattan project in the United States produced even more fluorine for use in uranium separation. Gaseous uranium hexafluoride was used to separate uranium-235, an important nuclear explosive, from the heavier uranium-238 in diffusion plants. Because uranium hexafluoride releases small quantities of corrosive fluorine, the separation plants were built with special materials. All pipes were coated with nickel; joints and flexible parts were fabricated from Teflon.
In 1958, a DuPont research manager in the Teflon business, Bill Gore, left the company because of its unwillingness to develop Teflon as wire-coating insulation. Gore's son Robert found a method for solving the wire-coating problem and the company W. L. Gore and Associates was born. In 1969, Robert Gore developed an expanded polytetrafluoroethylene (ePTFE) membrane which led to the large Gore-Tex business in breathable rainwear. The company developed many other uses of PTFE.
In the 1970s and 1980s, concerns developed over the role chlorofluorocarbons play in damaging the ozone layer. By 1996, almost all nations had banned chlorofluorocarbon refrigerants and commercial production ceased. Fluorine continued to play a role in refrigeration though: hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) were developed as replacement refrigerants. | 1 | Applied and Interdisciplinary Chemistry |
With the increase in computational power, depth-resolved models have become a powerful tool to study gravity and turbidity currents. These models, in general, are mainly focused on the solution of the Navier-Stokes equations for the fluid phase.
With dilute suspension of particles, a Eulerian approach proved to be accurate to describe the evolution of particles in terms of a continuum particle concentration field. Under these models, no such assumptions as shallow-water models are needed and, therefore, accurate calculations and measurements are performed to study these currents. Measurements such as, pressure field, energy budgets, vertical particle concentration and accurate deposit heights are a few to mention. Both Direct numerical simulation (DNS) and Turbulence modeling are used to model these currents. | 1 | Applied and Interdisciplinary Chemistry |
Nitrification inhibitors are also of interest from an environmental standpoint because of the production of nitrates and nitrous oxide from the process of nitrification. Nitrous oxide (NO), although its atmospheric concentration is much lower than that of CO has a global warming potential of about 300 times greater than carbon dioxide and contributes 6% of planetary warming due to greenhouse gases. This compound is also notable for catalyzing the breakup of ozone in the stratosphere. Nitrates, a toxic compound for wildlife and livestock and a product of nitrification, are also of concern.
Soil, consisting of polyanionic clays and silicates, generally has a net anionic charge. Consequently, ammonium (NH) binds tightly to the soil but nitrate ions (NO) do not. Because nitrate is more mobile, it leaches into groundwater supplies through agricultural runoff. Nitrates in groundwater can affect surface water concentrations, either through direct groundwater-surface water interactions (e.g., gaining stream reaches, springs), or from when it is extracted for surface use. As an example, much of the drinking water in the United States comes from groundwater, but most wastewater treatment plants discharge to surface water.
Wildlife such as amphibians, freshwater fish, and insects are sensitive to nitrate levels, and have been known to cause death and developmental anomalies in affected species. Nitrate levels also contribute to eutrophication, a process in which large algal blooms reduce oxygen levels in bodies of water and lead to death in oxygen-consuming creatures due to anoxia. Nitrification is also thought to contribute to the formation of photochemical smog, ground level ozone, acid rain, changes in species diversity, and other undesirable processes. In addition, nitrification inhibitors have also been shown to suppress the oxidation of methane (CH), a potent greenhouse gas, to CO. Both nitrapyrin and acetylene are shown to be especially strong suppressors of both processes, although the modes of action distinguishing them are unclear. | 1 | Applied and Interdisciplinary Chemistry |
More O’Ferrall–Jencks plots are two-dimensional representations of multiple reaction coordinate potential energy surfaces for chemical reactions that involve simultaneous changes in two bonds. As such, they are a useful tool to explain or predict how changes in the reactants or reaction conditions can affect the position and geometry of the transition state of a reaction for which there are possible competing pathways. | 0 | Theoretical and Fundamental Chemistry |
Activated by calcium, the enzyme digests proteins preferentially after hydrophobic amino acids (aliphatic, aromatic and other hydrophobic amino acids). Although calcium ions do not affect the enzyme activity, they do contribute to its stability.
Proteins will be completely digested if the incubation time is long and the protease concentration high enough. Upon removal of the calcium ions, the stability of the enzyme is reduced, but the proteolytic activity remains. Proteinase K has two binding sites for Ca, which are located close to the active center, but are not directly involved in the catalytic mechanism. The residual activity is sufficient to digest proteins, which usually contaminate nucleic acid preparations. Therefore, the digestion with Proteinase K for the purification of nucleic acids is usually performed in the presence of EDTA (inhibition of metal-ion dependent enzymes such as nucleases).
Proteinase K is also stable over a wide pH range (4–12), with a pH optimum of pH 8.0.
An elevation of the reaction temperature from 37 °C to 50–60 °C may increase the activity several times, like the addition of 0.5–1% sodium dodecyl sulfate (SDS) or Guanidinium chloride (3 M), Guanidinium thiocyanate (1 M) and urea (4 M) . The above-mentioned conditions enhance proteinase K activity by making its substrate cleavage sites more accessible. Temperatures above 65 °C, trichloroacetic acid (TCA) or the serine protease-inhibitors AEBSF, PMSF or DFP inhibit the activity.
Proteinase K will not be inhibited by Guanidinium chloride, Guanidinium thiocyanate, urea, Sarkosyl, Triton X-100, Tween 20, SDS, citrate, iodoacetic acid, EDTA or by other serine protease inhibitors like Nα-Tosyl-Lys Chloromethyl Ketone (TLCK) and Nα-Tosyl-Phe Chloromethyl Ketone (TPCK).
Protease K activity in commonly used buffers | 1 | Applied and Interdisciplinary Chemistry |
The first time that A15 structure was observed was in 1931 when an electrolytically deposited layer of tungsten was examined. Discussion of whether the β-tungsten structure is an allotrope of tungsten or the structure of a tungsten suboxide was long-standing, but since the 1950s there has been many publications showing that the material is a true allotrope of tungsten.
The first intermetallic compound discovered with typical AB composition was chromium silicide CrSi, discovered in 1933. Several other compounds with A15 structure were discovered in following years. No large interest existed in research on those compounds. This changed with the discovery that vanadium silicide VSi showed superconductivity at around 17 K in 1953. In following years, several other AB superconductors were found. Niobium-germanium held the record for the highest temperature of 23.2 K from 1973 until the discovery of the cuprate superconductors in 1986. It took time for the method to produce wires from the very brittle A15 phase materials to be established. This method is still complicated. Though some A15 phase materials can withstand higher magnetic field intensity and have higher critical temperatures than the NbZr and NbTi alloys, NbTi is still used for most applications due to easier manufacturing.
NbSn is used for some high field applications, for example high-end MRI scanners and NMR spectrometers.
A relaxed form of the Voronoi diagram of the A15 phase seems to have the least surface area among all the possible partitions of three-dimensional Euclidean space in regions of equal volume. This partition, also known as the Weaire–Phelan structure, is often present in clathrate hydrates. | 1 | Applied and Interdisciplinary Chemistry |
*4-Nitrophenol is an intermediate in the synthesis of paracetamol. It is reduced to 4-aminophenol, then acetylated with acetic anhydride.
* 4-Nitrophenol is used as the precursor for the preparation of phenetidine and acetophenetidine, indicators, and raw materials for fungicides. Bioaccumulation of this compound rarely occurs.
* In peptide synthesis, carboxylate ester derivatives of 4-nitrophenol may serve as activated components for construction of amide moieties. | 0 | Theoretical and Fundamental Chemistry |
Diffusion-controlled (or diffusion-limited) reactions are reactions in which the reaction rate is equal to the rate of transport of the reactants through the reaction medium (usually a solution). The process of chemical reaction can be considered as involving the diffusion of reactants until they encounter each other in the right stoichiometry and form an activated complex which can form the product species. The observed rate of chemical reactions is, generally speaking, the rate of the slowest or "rate determining" step. In diffusion controlled reactions the formation of products from the activated complex is much faster than the diffusion of reactants and thus the rate is governed by collision frequency.
Diffusion control is rare in the gas phase, where rates of diffusion of molecules are generally very high. Diffusion control is more likely in solution where diffusion of reactants is slower due to the greater number of collisions with solvent molecules. Reactions where the activated complex forms easily and the products form rapidly are most likely to be limited by diffusion control. Examples are those involving catalysis and enzymatic reactions. Heterogeneous reactions where reactants are in different phases are also candidates for diffusion control.
One classical test for diffusion control of a heterogeneous reaction is to observe whether the rate of reaction is affected by stirring or agitation; if so then the reaction is almost certainly diffusion controlled under those conditions. | 0 | Theoretical and Fundamental Chemistry |
In 2006 the group of E.J. Corey published a novel route bypassing shikimic acid starting from butadiene and acrylic acid. The inventors chose not to patent this procedure which is described below.
Butadiene 1 reacts in an asymmetric Diels-Alder reaction with the esterification product of acrylic acid and 2,2,2-trifluoroethanol 2 catalysed by the CBS catalyst. The ester 3 is converted into an amide in 4 by reaction with ammonia and the next step to lactam 5 is an iodolactamization with iodine initiated by trimethylsilyltriflate. The amide group is fitted with a BOC protecting group by reaction with Boc anhydride in 6 and the iodine substituent is removed in an elimination reaction with DBU to the alkene 7. Bromine is introduced in 8 by an allylic bromination with NBS and the amide group is cleaved with ethanol and caesium carbonate accompanied by elimination of bromide to the diene ethyl ester 9. The newly formed double bond is functionalized with N-bromoacetamide 10 catalyzed with
tin(IV) bromide with complete control of stereochemistry. In the next step the bromine atom in 11 is displaced by the nitrogen atom in the amide group with the strong base KHMDS to the aziridine 12 which in turn is opened by reaction with 3-pentanol 13 to the ether 14. In the final step the BOC group is removed with phosphoric acid and the oseltamivir phosphate 15 is formed. | 0 | Theoretical and Fundamental Chemistry |
The metabolism of an animal is estimated by determining rates of carbon dioxide production (VCO) and oxygen consumption (VO) of individual animals, either in a closed or an open-circuit respirometry system. Two measures are typically obtained: standard (SMR) or basal metabolic rate (BMR) and maximal rate (VO2max). SMR is measured while the animal is at rest (but not asleep) under specific laboratory (temperature, hydration) and subject-specific conditions (e.g., size or allometry), age, reproduction status, post-absorptive to avoid thermic effect of food). VOmax is typically determined during aerobic exercise at or near physiological limits. In contrast, field metabolic rate (FMR) refers to the metabolic rate of an unrestrained, active animal in nature. Whole-animal metabolic rates refer to these measures without correction for body mass. If SMR or BMR values are divided by the body mass value for the animal, then the rate is termed mass-specific. It is this mass-specific value that one typically hears in comparisons among species. | 1 | Applied and Interdisciplinary Chemistry |
The Cornforth reagent is prepared by slow addition of a concentrated aqueous solution of chromium trioxide to pyridine. The reaction may cause explosion, which is avoided by thoroughly dissolving the trioxide in water and cooling the solution by ice. The product is filtered, washed with acetone and dried, yielding an orange powder. The powder is stable in air, not particularly hygroscopic and has an almost neutral pH that facilitates its handling; it is only slightly acidic owing to the presence of pyridinium cations. The Cornforth reagent is readily soluble in water, dimethylformamide and dimethyl sulfoxide (DMSO). It is poorly soluble in acetone and chlorinated organic solvents, such as dichloromethane, and forms suspensions. | 0 | Theoretical and Fundamental Chemistry |
Diastereoselective conjugate addition reactions of chiral organocuprates provide β-functionalized ketones in high yield and diastereoselectivity. A disadvantage of these reactions is the requirement of a full equivalent of enantiopure starting material.
More recently, catalytic enantioselective methods have been developed based on the copper(I)-catalyzed conjugate addition of Grignard reactions to enones. The proposed mechanism involves transmetalation from the Grignard reagent to copper, conjugate addition, and rate-determining reductive elimination (see the analogous upper pathway in equation (2)). | 0 | Theoretical and Fundamental Chemistry |
These processes are the physicochemical phenomena and reactions caused by movement of hydrothermal water within the crust, often as a consequence of magmatic intrusion or tectonic upheavals. The foundations of hydrothermal processes are the source-transport-trap mechanism.
Sources of hydrothermal solutions include seawater and meteoric water circulating through fractured rock, formational brines (water trapped within sediments at deposition), and metamorphic fluids created by dehydration of hydrous minerals during metamorphism.
Metal sources may include a plethora of rocks. However most metals of economic importance are carried as trace elements within rock-forming minerals, and so may be liberated by hydrothermal processes. This happens because of:
*incompatibility of the metal with its host mineral, for example zinc in calcite, which favours aqueous fluids in contact with the host mineral during diagenesis.
*solubility of the host mineral within nascent hydrothermal solutions in the source rocks, for example mineral salts (halite), carbonates (cerussite), phosphates (monazite and thorianite), and sulfates (barite)
*elevated temperatures causing decomposition reactions of minerals
Transport by hydrothermal solutions usually requires a salt or other soluble species which can form a metal-bearing complex. These metal-bearing complexes facilitate transport of metals within aqueous solutions, generally as hydroxides, but also by processes similar to chelation.
This process is especially well understood in gold metallogeny where various thiosulfate, chloride, and other gold-carrying chemical complexes (notably tellurium-chloride/sulfate or antimony-chloride/sulfate). The majority of metal deposits formed by hydrothermal processes include sulfide minerals, indicating sulfur is an important metal-carrying complex. | 0 | Theoretical and Fundamental Chemistry |
Ro-vibrational spectra are usually measured at high spectral resolution. In the past, this was achieved by using an echelle grating as the spectral dispersion element in a grating spectrometer. This is a type of diffraction grating optimized to use higher diffraction orders. Today at all resolutions the preferred method is FTIR. The primary reason for this is that infrared detectors are inherently noisy, and FTIR detects summed signals at multiple wavelengths simultaneously achieving a higher signal to noise by virtue of Fellgett's advantage for multiplexed methods. The resolving power of an FTIR spectrometer depends on the maximum retardation of the moving mirror. For example, to achieve a resolution of 0.1 cm, the moving mirror must have a maximum displacement of 10 cm from its position at zero path difference. Connes measured the vibration-rotation spectrum of Venusian CO at this resolution. A spectrometer with 0.001 cm resolution is now available commercially. The throughput advantage of FTIR is important for high-resolution spectroscopy as the monochromator in a dispersive instrument with the same resolution would have very narrow entrance and exit slits.
When measuring the spectra of gases it is relatively easy to obtain very long path-lengths by using a multiple reflection cell. This is important because it allows the pressure to be reduced so as to minimize pressure broadening of the spectral lines, which may degrade resolution. Path lengths up to 20m are commercially available. | 0 | Theoretical and Fundamental Chemistry |
The above formula can be used to determine the 99% confidence level that all sequences in a genome are represented by using a vector with an insert size of twenty thousand basepairs (such as the phage lambda vector). The genome size of the organism is three billion basepairs in this example.
clones
Thus, approximately 688,060 clones are required to ensure a 99% probability that a given DNA sequence from this three billion basepair genome will be present in a library using a vector with an insert size of twenty thousand basepairs. | 1 | Applied and Interdisciplinary Chemistry |
Given 3 faces of a polyhedron which meet at a common vertex P and have edges AP, BP and CP, the cosine of the dihedral angle between the faces containing APC and BPC is:
This can be deduced from Spherical law of cosines | 0 | Theoretical and Fundamental Chemistry |
A molecule in the gas phase is free to rotate relative to a set of mutually orthogonal axes of fixed orientation in space, centered on the center of mass of the molecule. Free rotation is not possible for molecules in liquid or solid phases due to the presence of intermolecular forces. Rotation about each unique axis is associated with a set of quantized energy levels dependent on the moment of inertia about that axis and a quantum number. Thus, for linear molecules the energy levels are described by a single moment of inertia and a single quantum number, , which defines the magnitude of the rotational angular momentum.
For nonlinear molecules which are symmetric rotors (or symmetric tops - see next section), there are two moments of inertia and the energy also depends on a second rotational quantum number, , which defines the vector component of rotational angular momentum along the principal symmetry axis. Analysis of spectroscopic data with the expressions detailed below results in quantitative determination of the value(s) of the moment(s) of inertia. From these precise values of the molecular structure and dimensions may be obtained.
For a linear molecule, analysis of the rotational spectrum provides values for the rotational constant and the moment of inertia of the molecule, and, knowing the atomic masses, can be used to determine the bond length directly. For diatomic molecules this process is straightforward. For linear molecules with more than two atoms it is necessary to measure the spectra of two or more isotopologues, such as OCS and OCS. This allows a set of simultaneous equations to be set up and solved for the bond lengths). A bond length obtained in this way is slightly different from the equilibrium bond length. This is because there is zero-point energy in the vibrational ground state, to which the rotational states refer, whereas the equilibrium bond length is at the minimum in the potential energy curve. The relation between the rotational constants is given by
where v is a vibrational quantum number and α is a vibration-rotation interaction constant which can be calculated if the B values for two different vibrational states can be found.
For other molecules, if the spectra can be resolved and individual transitions assigned both bond lengths and bond angles can be deduced. When this is not possible, as with most asymmetric tops, all that can be done is to fit the spectra to three moments of inertia calculated from an assumed molecular structure. By varying the molecular structure the fit can be improved, giving a qualitative estimate of the structure. Isotopic substitution is invaluable when using this approach to the determination of molecular structure. | 0 | Theoretical and Fundamental Chemistry |
Under atmospheric pressure mercuric oxide has two crystalline forms: one is called montroydite (orthorhombic, 2/m 2/m 2/m, Pnma), and the second is analogous to the sulfide mineral cinnabar (hexagonal,
hP6, P3221); both are characterized by Hg-O chains. At pressures above 10 GPa both structures convert to a tetragonal form. | 0 | Theoretical and Fundamental Chemistry |
The luciferases of fireflies – of which there are over 2000 species – and of the other Elateroidea (click beetles and relatives in general) are diverse enough to be useful in molecular phylogeny. In fireflies, the oxygen required is supplied through a tube in the abdomen called the abdominal trachea. One well-studied luciferase is that of the Photinini firefly Photinus pyralis, which has an optimum pH of 7.8. | 1 | Applied and Interdisciplinary Chemistry |
In 1833, Adam August Krantz (who studied pharmacy and later "Geognosie" at the Bergakademie Freiberg) founded the Krantz company in Bonn. Four years later, Krantz moved to Berlin and sold minerals, fossils, rocks and basically acquired a monopoly in the production of crystal models made of pear wood or walnut. Ever since its foundation, the firm was always in contact with renowned scientists and important collectors. Hence in 1880, Krantz proposed a series of 743 pear wood models compiled for teaching purposes by the crystallographer Paul Groth. Seven years later, a supplementary collection of 213 models was available.
At the onset of the 20th century, Friedrich Krantz (a nephew of August Krantz, with a degree in mineralogy) supported by his teacher the crystallographer Carl Hintze, offered a collection of 928 models including most of the Groth models. Later, and along with many other productions, a Dana collection of 282 models was manufactured. Krantz offered a choice of collections of wooden models in different sizes (5, 10, 15–25 cm). In addition, he sold a variety of glass models having the crystallographic axes illustrated by colored silk threads or with the holohedral form made of cardboard inside. Also available were models in massive cut and polished glass (colored and uncolored), cardboard models, wire crystal models, crystal lattice models, models with rotating parts, etc.
Over the years, Krantz published numerous detailed catalogues of the collections he offered; they constitute a precious documentation. | 0 | Theoretical and Fundamental Chemistry |
The introduction of a mechanical bond alters the chemistry of the sub components of rotaxanes and catenanes. Steric hindrance of reactive functionalities is increased and the strength of non-covalent interactions between the components are altered. | 0 | Theoretical and Fundamental Chemistry |
Ruderfer et al. analyzed the ancestry of natural S. cerevisiae strains and concluded that matings involving out-crossing occur only about once every 50,000 cell divisions. Thus it appears that, in nature, mating is most often between closely related yeast cells. Mating occurs when haploid cells of opposite mating type MATa and MATα come into contact. Ruderfer et al. pointed out that such contacts are frequent between closely related yeast cells for two reasons. The first is that cells of opposite mating type are present together in the same ascus, the sac that contains the cells directly produced by a single meiosis, and these cells can mate with each other. The second reason is that haploid cells of one mating type, upon cell division, often produce cells of the opposite mating type with which they can mate (see section "Mating type switching", above). The relative rarity in nature of meiotic events that result from out-crossing appears to be inconsistent with the idea that production of genetic variation is the primary selective force maintaining mating capability in this organism. However this finding is consistent with the alternative idea that the primary selective force maintaining mating capability is enhanced recombinational repair of DNA damage during meiosis, since this benefit is realized during each meiosis subsequent to a mating, whether or not out-crossing occurs. | 1 | Applied and Interdisciplinary Chemistry |
The history of sewage treatment had the following developments: It began with land application (sewage farms) in the 1840s in England, followed by chemical treatment and sedimentation of sewage in tanks, then biological treatment the late 19th century, which led to the development of the activated sludge process starting in 1912. | 1 | Applied and Interdisciplinary Chemistry |
* According to the Big Bang theory, in the early universe at high temperatures when the universe was only a few tens of microseconds old, the phase of matter took the form of a hot phase of quark matter called the quark–gluon plasma (QGP).
* Compact stars (neutron stars). A neutron star is much cooler than 10 K, but gravitational collapse has compressed it to such high densities, that it is reasonable to surmise that quark matter may exist in the core. Compact stars composed mostly or entirely of quark matter are called quark stars or strange stars.
* QCD matter may exist within the collapsar of a gamma-ray burst, where temperatures as high as 6.7 × 10 K may be generated.
At this time no star with properties expected of these objects has been observed, although some evidence has been provided for quark matter in the cores of large neutron stars.
* Strangelets. These are theoretically postulated (but as yet unobserved) lumps of strange matter comprising nearly equal amounts of up, down and strange quarks. Strangelets are supposed to be present in the galactic flux of high energy particles and should therefore theoretically be detectable in cosmic rays here on Earth, but no strangelet has been detected with certainty.
* Cosmic ray impacts. Cosmic rays comprise a lot of different particles, including highly accelerated atomic nuclei, particularly that of iron.
Laboratory experiments suggests that the inevitable interaction with heavy noble gas nuclei in the upper atmosphere would lead to quark–gluon plasma formation.
* Quark matter with baryon number over about 300 may be more stable than nuclear matter. This form of baryonic matter could possibly form a continent of stability. | 0 | Theoretical and Fundamental Chemistry |
Favipiravir, sold under the brand name Avigan among others, is an antiviral medication used to treat influenza in Japan. It is also being studied to treat a number of other viral infections, including SARS-CoV-2. Like the experimental antiviral drugs T-1105 and T-1106, it is a pyrazinecarboxamide derivative.
It is being developed and manufactured by Toyama Chemical (a subsidiary of Fujifilm) and was approved for medical use in Japan in 2014. In 2016, Fujifilm licensed it to Zhejiang Hisun Pharmaceutical Co. It became a generic drug in 2019. | 0 | Theoretical and Fundamental Chemistry |
Indirect immunoperoxidase assay (IPA) is a laboratory technique used to detect and titrate viruses that do not cause measurable cytopathic effects and cannot be measured by classical plaque assays. These viruses include human coronavirus 229E and OC43. | 1 | Applied and Interdisciplinary Chemistry |
Solid-phase extraction (SPE) is a solid-liquid extractive technique, by which compounds that are dissolved or suspended in a liquid mixture are separated, isolated or purified, from other compounds in this mixture, according to their physical and chemical properties. Analytical laboratories use solid phase extraction to concentrate and purify samples for analysis. Solid phase extraction can be used to isolate analytes of interest from a wide variety of matrices, including urine, blood, water, beverages, soil, and animal tissue.
SPE uses the affinity of solutes, dissolved or suspended in a liquid (known as the mobile phase), to a solid packing inside a small column, through which the sample is passed (known as the stationary phase), to separate a mixture into desired and undesired components. The result is that either the desired analytes of interest or undesired impurities in the sample are retained on the stationary phase. The portion that passes through the stationary phase is collected or discarded, depending on whether it contains the desired analytes or undesired impurities. If the portion retained on the stationary phase includes the desired analytes, they can then be removed from the stationary phase for collection in an additional step, in which the stationary phase is rinsed with an appropriate eluent.
It is possible to have an incomplete recovery of the analytes by SPE caused by incomplete extraction or elution. In the case of an incomplete extraction, the analytes do not have enough affinity for the stationary phase and part of them will remain in the permeate. In an incomplete elution, part of the analytes remain in the sorbent because the eluent used does not have a strong enough affinity.
Many of the adsorbents/materials are the same as in chromatographic methods, but SPE is distinctive, with aims separate from chromatography, and so has a unique niche in modern chemical science. | 0 | Theoretical and Fundamental Chemistry |
Susceptibility-weighted imaging (SWI) is a new type of contrast in MRI different from spin density, T, or T imaging. This method exploits the susceptibility differences between tissues and uses a fully velocity-compensated, three-dimensional, RF-spoiled, high-resolution, 3D-gradient echo scan. This special data acquisition and image processing produces an enhanced contrast magnitude image very sensitive to venous blood, hemorrhage and iron storage. It is used to enhance the detection and diagnosis of tumors, vascular and neurovascular diseases (stroke and hemorrhage), multiple sclerosis, Alzheimer's, and also detects traumatic brain injuries that may not be diagnosed using other methods. | 0 | Theoretical and Fundamental Chemistry |
*Axiom of Maria
*Alchemical Studies (Carl Jung)
*Aurora consurgens
*Buch der heiligen Dreifaltigkeit
*Cantong qi
*Chymical Wedding of Christian Rosenkreutz
*Hermetica
**Emerald Tablet
**Sirr al-khalīqa ("The Secret of Creation")
*The Hermetical Triumph
*Fasciculus Chemicus
*Musaeum Hermeticum
*Mutus Liber
*Rosary of the Philosophers
*Splendor Solis
*Theatrum Chemicum
*Theatrum Chemicum Britannicum
*The Mirror of Alchimy
*Turba Philosophorum | 1 | Applied and Interdisciplinary Chemistry |
Potassium sulfide is an inorganic compound with the formula KS. The colourless solid is rarely encountered, because it reacts readily with water, a reaction that affords potassium hydrosulfide (KSH) and potassium hydroxide (KOH). Most commonly, the term potassium sulfide refers loosely to this mixture, not the anhydrous solid. | 0 | Theoretical and Fundamental Chemistry |
* 2004 – Pearse Prize, Royal Microscopical Society
* 2005 – Emile Chamot Award
* 2006 – Asahi Prize
* 2008 – Nobel Prize in Chemistry
* 2008 – Order of Culture
* 2008 – Person of Cultural Merit
* 2012 – Golden Goose Award
* 2013 – Member of the United States National Academy of Sciences
* 2018 – Junior third rank (posthumous) | 0 | Theoretical and Fundamental Chemistry |
There are three main categories for triggering the release of sigmas factors from anti-sigma factors: partner switching, direct signaling, and a mechanism regulated by proteolysis.
The partner-switching mechanism is commonly found in Gram-positive bacteria. It consists of four key players: a sigma factor, an anti-sigma factor, an anti-anti-sigma factor, and an input phosphatase complex. A cell that is not under stress has an anti-sigma factor that is bound to the sigma factor on the gene and keeps it inactive. In times of stress, a phosphatase complex dephosphorylates the anti-sigma factor, allowing the anti-sigma factor to switch partners and bind to the anti-anti-sigma factor. This frees the sigma factors to activate the gene. Environmental stressors, such as heat, often activate this mechanism.
The direct signaling mechanism is as it sounds: the anti-sigma factor binds to a signal, which causes conformation changes in the structure of the anti-sigma factors, resulting in the release of the sigma factors.
The regulated intramembrane proteolysis (RIP) mechanism allows signal transduction across membranes. This mechanism is often used to regulate ECF sigma factors. The mechanism involves two sequential cleavages, the first being an external cleavage of membrane-traversing anti-sigma factor and the second cleavage of the anti-sigma factors in the membrane's plane, resulting in a free cytoplasmic domain. | 1 | Applied and Interdisciplinary Chemistry |
The typical workflow of metabolomics studies is shown in the figure. First, samples are collected from tissue, plasma, urine, saliva, cells, etc. Next, metabolites extracted often with the addition of internal standards and derivatization. During sample analysis, metabolites are quantified (liquid chromatography or gas chromatography coupled with MS and/or NMR spectroscopy). The raw output data can be used for metabolite feature extraction and further processed before statistical analysis (such as principal component analysis, PCA). Many bioinformatic tools and software are available to identify associations with disease states and outcomes, determine significant correlations, and characterize metabolic signatures with existing biological knowledge. | 1 | Applied and Interdisciplinary Chemistry |
The regulation of gene expression in eukaryotes is achieved through the interaction of several levels of control that acts both locally to turn on or off individual genes in response to a specific cellular need and globally to maintain a chromatin-wide gene expression pattern that shapes cell identity. Because eukaryotic genome is wrapped around histones to form nucleosomes and higher-order chromatin structures, the substrates for transcriptional machinery are in general partially concealed. Without regulatory proteins, many genes are expressed at low level or not expressed at all. Transcription requires displacement of the positioned nucleosomes to enable the transcriptional machinery to gain access of the DNA.
All steps in the transcription are subject to some degree of regulation. Transcription initiation in particular is the primary level at which gene expression is regulated. Targeting the rate-limiting initial step is the most efficient in terms of energy costs for the cell. Transcription initiation is regulated by cis-acting elements (enhancers, silencers, isolators) within the regulatory regions of the DNA, and sequence-specific trans-acting factors that act as activators or repressors. Gene transcription can also be regulated post-initiation by targeting the movement of the elongating polymerase. | 1 | Applied and Interdisciplinary Chemistry |
A number of other unexpected applications have been identified in the last few years, mostly in multiferroic bismuth ferrite, that do not seem to be directly related to the coupled magnetism and ferroelectricity. These include a photovoltaic effect, photocatalysis, and gas sensing behaviour. It is likely that the combination of ferroelectric polarisation, with the small band gap composed partially of transition-metal d states are responsible for these favourable properties.
Multiferroic films with appropriate band gap structure into solar cells was developed which results in high energy conversion efficiency due to efficient ferroelectric polarization driven carrier separation and overband spacing generation photo-voltage. Various films have been researched, and there is also a new approach to effectively adjust the band gap of the double perovskite multilayer oxide by engineering the cation order for Bi2FeCrO6. | 0 | Theoretical and Fundamental Chemistry |
The first certified subunit vaccine by clinical trials on humans is the hepatitis B vaccine, containing the surface antigens of the hepatitis B virus itself from infected patients and adjusted by newly developed technology aiming to enhance the vaccine safety and eliminate possible contamination through individuals plasma. | 1 | Applied and Interdisciplinary Chemistry |
In biochemistry, the conformation–activity relationship is the relationship between the biological activity and the chemical structure or conformational changes of a biomolecule. This terminology emphasizes the importance of dynamic conformational changes for the biological function, rather than the importance of static three-dimensional structure used in the analysis of structure–activity relationships.
The conformational changes usually take place during intermolecular association, such as protein–protein interaction or protein–ligand binding. A binding partner changes the conformation of a biomolecule (e.g. a protein) to enable or disable its biochemical activity.
Methods for analysis of conformation activity relationship vary from in silico or using experimental methods such as X-ray crystallography and NMR where the conformation before and after activity can be compared statically or using dynamic methods such as multi-parametric surface plasmon resonance, dual-polarisation interferometry or circular dichroism where the kinetics as well as degree of conformational change can be quantified. | 1 | Applied and Interdisciplinary Chemistry |
After ingestion, is converted to following dissociation of the calcium moiety in the gut. When the HMB-Ca dosage form is ingested, the magnitude and time at which the peak plasma concentration of HMB occurs depends on the dose and concurrent food intake. Higher HMB-Ca doses increase the rate of absorption, resulting in a peak plasma HMB level (C) that is disproportionately greater than expected of a linear dose-response relationship and which occurs sooner relative to lower doses. Consumption of HMB-Ca with sugary substances slows the rate of HMB absorption, resulting in a lower peak plasma HMB level that occurs later. | 1 | Applied and Interdisciplinary Chemistry |
Trifluoromethanesulfonyl chloride (or triflyl chloride, CF3SO2Cl) can be used in a highly efficient method to introduce a trifluoromethyl group to aromatic and heteroaromatic systems, including known pharmaceuticals such as Lipitor. The chemistry is general and mild, and uses a photoredox catalyst and a light source at room temperature. | 0 | Theoretical and Fundamental Chemistry |
Biomethylation is the pathway for converting some heavy elements into more mobile or more lethal derivatives that can enter the food chain. The biomethylation of arsenic compounds starts with the formation of methanearsonates. Thus, trivalent inorganic arsenic compounds are methylated to give methanearsonate. S-adenosylmethionine is the methyl donor. The methanearsonates are the precursors to dimethylarsonates, again by the cycle of reduction (to methylarsonous acid) followed by a second methylation. Related pathways are found in the microbial methylation of mercury to methylmercury. | 0 | Theoretical and Fundamental Chemistry |
The level of beryllium-7 in the air is related to the Sun spot cycle, as radiation from the Sun forms this radioisotope in the atmosphere. The rate at which it is transferred from the air to the ground is controlled in part by the weather. | 0 | Theoretical and Fundamental Chemistry |
A relatively recent analytical tool that has been used for the separation of UCMs is comprehensive two-dimensional GC (GCxGC). This powerful technique, introduced by Liu and Phillips combines two GC columns with different separation mechanisms: typically a primary column that separates compounds based on volatility coupled to a second short column that separates by polarity. The two columns are connected by a modulator, a device that traps, focuses and re-injects the peaks that elute from the first column into the second column. Each peak eluting from the first column (which may be a number of co-eluting peaks) is further separated on the second column. The second separation is rapid, allowing the introduction of subsequent fractions from the first column without mutual interference. Dallüge et al. reviewed the principles, advantages and main characteristics of this technique. One of the main advantages is the very high separation power, making the technique ideal for unravelling the composition of complex mixtures. Another important feature of GC×GC is that chemically related compounds show up as ordered structures within the chromatograms, i.e. isomers appear as distinct groups in the chromatogram as a result of their similar interaction with the second dimension column phase. The use of GC×GC for the characterization of complex petrochemical mixtures has been extensively reviewed. Most research into petrochemical hydrocarbons using GC×GC has utilised flame ionisation detection (FID) but mass spectrometry (MS) is necessary to obtain the structural information necessary to identify unknown compounds. Currently, only time-of-flight MS (ToF-MS) can deliver the high acquisition rates required to analyse GC×GC. | 0 | Theoretical and Fundamental Chemistry |
In organic chemistry, carbonyl allylation describes methods for adding an allyl anion to an aldehyde or ketone to produce a homoallylic alcohol. The carbonyl allylation was first reported in 1876 by Alexander Zaitsev and employed an allylzinc reagent. | 0 | Theoretical and Fundamental Chemistry |
Since Yaghi and coworkers’ seminal work in 2005, COF synthesis has expanded to include a wide range of organic connectivity such as boron-, nitrogen-, other atom-containing linkages. The linkages in the figures shown are not comprehensive as other COF linkages exist in the literature, especially for the formation of 3D COFs. | 0 | Theoretical and Fundamental Chemistry |
An abbreviated form of the Hermann–Mauguin notation commonly used for space groups also serves to describe crystallographic point groups. Group names are | 0 | Theoretical and Fundamental Chemistry |
In the lin⊥lin configuration cooling is achieved via a Sisyphus effect. Consider two counterpropagating electromagnetic waves with equal amplitude and orthogonal linear polarizations and , where k is the wavenumber . The superposition of and is given as:
Introducing a new pair of coordinates and the field can be written as:
The polarization of the total field changes with z. For example: we see that at the field is linearly polarized along , at the field has left circular polarization, at the field is linearly polarized along , at the field has right circular polarization, and at the field is again linearly polarized along .
Consider an atom interacting with the field detuned below the transition from atomic states and (). The variation of the polarization along z results in a variation in the light shifts of the atomic Zeeman sublevels with z. The Clebsch-Gordan coefficient connecting the state to the state is 3 times larger than connecting the state to the state. Thus for polarization the light shift is three times larger for the state than for the state. The situation is reversed for polarization, with the light shift being three times larger for the state than the state. When the polarization is linear, there is no difference in the light shifts between the two states. Thus the energies of the states will oscillate in z with period .
As an atom moves along z, it will be optically pumped to the state with the largest negative light shift. However, the optical pumping process takes some finite time . For field wavenumber k and atomic velocity v such that , the atom will travel mostly uphill as it moves along z before being pumped back down to the lowest state. In this velocity range, the atom travels more uphill than downhill and gradually loses kinetic energy, lowering its temperature. This is called the Sisyphus effect after the mythological Greek character. Note that this initial condition for velocity requires the atom to be cooled already, for example through Doppler cooling. | 0 | Theoretical and Fundamental Chemistry |
Biological cell membranes and cell walls are polyanionic surfaces. This has important implications for the transport of ions, in particular because it has been shown that different membranes preferentially bind different ions. Both Mg and Ca regularly stabilize membranes by the cross-linking of carboxylated and phosphorylated head groups of lipids. However, the envelope membrane of E. coli has also been shown to bind Na, K, Mn and Fe. The transport of ions is dependent on both the concentration gradient of the ion and the electric potential (ΔΨ) across the membrane, which will be affected by the charge on the membrane surface. For example, the specific binding of Mg to the chloroplast envelope has been implicated in a loss of photosynthetic efficiency by the blockage of K uptake and the subsequent acidification of the chloroplast stroma. | 1 | Applied and Interdisciplinary Chemistry |
Discovery of the novel antioxidant function of coenzyme A highlights its protective role during cellular stress. Mammalian and Bacterial cells subjected to oxidative and metabolic stress show significant increase in the covalent modification of protein cysteine residues by coenzyme A. This reversible modification is termed protein CoAlation (Protein-S-SCoA), which plays a similar role to protein S-glutathionylation by preventing the irreversible oxidation of the thiol group of cysteine residues.
Using anti-coenzyme A antibody and liquid chromatography tandem mass spectrometry (LC-MS/MS) methodologies, more than 2,000 CoAlated proteins were identified from stressed mammalian and bacterial cells. The majority of these proteins are involved in cellular metabolism and stress response. Different research studies have focused on deciphering the coenzyme A-mediated regulation of proteins. Upon protein CoAlation, inhibition of the catalytic activity of different proteins (e.g. metastasis suppressor NME1, peroxiredoxin 5, GAPDH, among others) is reported. To restore the protein's activity, antioxidant enzymes that reduce the disulfide bond between coenzyme A and the protein cysteine residue play an important role. This process is termed protein deCoAlation. So far, two bacterial proteins, Thioredoxin A and Thioredoxin-like protein (YtpP), are shown to deCoAlate proteins. | 1 | Applied and Interdisciplinary Chemistry |
The software is used primarily by component and system engineers in the automotive, hydraulic, and aerospace industry as a virtual test-bed to study efficiency, cavitation, pressure ripple, and noise for hydrodynamic pumps, and fluid power equipment. | 1 | Applied and Interdisciplinary Chemistry |
Native populations are often characterized by substantial genotype diversity and dispersed populations (growth in a mixture with many other plant species). They also have undergone of plant-pathogen coevolution. Hence as long as novel pathogens are not introduced/do not evolve, such populations generally exhibit only a low incidence of severe disease epidemics.
Monocrop agricultural systems provide an ideal environment for pathogen evolution, because they offer a high density of target specimens with similar/identical genotypes. The rise in mobility stemming from modern transportation systems provides pathogens with access to more potential targets. Climate change can alter the viable geographic range of pathogen species and cause some diseases to become a problem in areas where the disease was previously less important.
These factors make modern agriculture more prone to disease epidemics. Common solutions include constant breeding for disease resistance, use of pesticides, use of border inspections and plant import restrictions, maintenance of significant genetic diversity within the crop gene pool (see crop diversity), and constant surveillance to accelerate initiation of appropriate responses. Some pathogen species have much greater capacity to overcome plant disease resistance than others, often because of their ability to evolve rapidly and to disperse broadly. | 1 | Applied and Interdisciplinary Chemistry |
*SK1
*PDE4A1
*Raf1
*mTOR
*PP1
*SHP1
*Spo20p
*p47phox
*PKCε
*PLCβ
*PIP5K
*[https://www.yeastgenome.org/locus/S000001012 Opi1]
*TREK-1
*K
*K2.2 | 1 | Applied and Interdisciplinary Chemistry |
Hydrodynamic delivery involves rapid injection of a high volume of a solution into vasculature (such as into the inferior vena cava, bile duct, or tail vein). The solution contains molecules that are to be inserted into cells, such as DNA plasmids or siRNA, and transfer of these molecules into cells is assisted by the elevated hydrostatic pressure caused by the high volume of injected solution. | 1 | Applied and Interdisciplinary Chemistry |
The Science History Institute is particularly interested in the origins of early science and chemistry. Its varied holdings have considerable depth both in alchemical books and fine-art depictions of early modern alchemists. The institution's collection of alchemy-related artwork, one of the largest in the world, builds upon two significant collections. Chester Garfield Fisher, founder of Fisher Scientific, started collecting alchemical art in the 1920s. In 2000, his collection of alchemical paintings was donated by Fisher Scientific International to the Chemical Heritage Foundation. In 2002, the institution received another gift from Roy Eddleman, founder of Spectrum Laboratories, whose collection contained paintings from the 17th, 18th, and 19th centuries. Together, the two collections contain more than 90 paintings and 200 works on paper illustrating the work of alchemists and their influence on the development of chemistry as a science. | 1 | Applied and Interdisciplinary Chemistry |
Early investigations into low bandgap semiconductors focused on germanium (Ge). Ge has a bandgap of 0.66 eV, allowing for conversion of a much higher fraction of incoming radiation. However, poor performance was observed due to the high effective electron mass of Ge. Compared to III-V semiconductors, Ge's high electron effective mass leads to a high density of states in the conduction band and therefore a high intrinsic carrier concentration. As a result, Ge diodes have fast decaying "dark" current and therefore, a low open-circuit voltage. In addition, surface passivation of germanium has proven difficult. | 0 | Theoretical and Fundamental Chemistry |
The metabolism of progesterone is rapid and extensive and occurs mainly in the liver, though enzymes that metabolize progesterone are also expressed widely in the brain, skin, and various other extrahepatic tissues. Progesterone has an elimination half-life of only approximately 5 minutes in circulation. The metabolism of progesterone is complex, and it may form as many as 35 different unconjugated metabolites when it is ingested orally. Progesterone is highly susceptible to enzymatic reduction via reductases and hydroxysteroid dehydrogenases due to its double bond (between the C4 and C5 positions) and its two ketones (at the C3 and C20 positions).
The major metabolic pathway of progesterone is reduction by 5α-reductase and 5β-reductase into the dihydrogenated 5α-dihydroprogesterone and 5β-dihydroprogesterone, respectively. This is followed by the further reduction of these metabolites via 3α-hydroxysteroid dehydrogenase and 3β-hydroxysteroid dehydrogenase into the tetrahydrogenated allopregnanolone, pregnanolone, isopregnanolone, and epipregnanolone. Subsequently, 20α-hydroxysteroid dehydrogenase and 20β-hydroxysteroid dehydrogenase reduce these metabolites to form the corresponding hexahydrogenated pregnanediols (eight different isomers in total), which are then conjugated via glucuronidation and/or sulfation, released from the liver into circulation, and excreted by the kidneys into the urine. The major metabolite of progesterone in the urine is the 3α,5β,20α isomer of pregnanediol glucuronide, which has been found to constitute 15 to 30% of an injection of progesterone. Other metabolites of progesterone formed by the enzymes in this pathway include 3α-dihydroprogesterone, 3β-dihydroprogesterone, 20α-dihydroprogesterone, and 20β-dihydroprogesterone, as well as various combination products of the enzymes aside from those already mentioned. Progesterone can also first be hydroxylated (see below) and then reduced. Endogenous progesterone is metabolized approximately 50% into 5α-dihydroprogesterone in the corpus luteum, 35% into 3β-dihydroprogesterone in the liver, and 10% into 20α-dihydroprogesterone.
Relatively small portions of progesterone are hydroxylated via 17α-hydroxylase (CYP17A1) and 21-hydroxylase (CYP21A2) into 17α-hydroxyprogesterone and 11-deoxycorticosterone (21-hydroxyprogesterone), respectively, and pregnanetriols are formed secondarily to 17α-hydroxylation. Even smaller amounts of progesterone may be also hydroxylated via 11β-hydroxylase (CYP11B1) and to a lesser extent via aldosterone synthase (CYP11B2) into 11β-hydroxyprogesterone. In addition, progesterone can be hydroxylated in the liver by other cytochrome P450 enzymes which are not steroid-specific. 6β-Hydroxylation, which is catalyzed mainly by CYP3A4, is the major transformation, and is responsible for approximately 70% of cytochrome P450-mediated progesterone metabolism. Other routes include 6α-, 16α-, and 16β-hydroxylation. However, treatment of women with ketoconazole, a strong CYP3A4 inhibitor, had minimal effects on progesterone levels, producing only a slight and non-significant increase, and this suggests that cytochrome P450 enzymes play only a small role in progesterone metabolism. | 0 | Theoretical and Fundamental Chemistry |
In 2016 a new study showed that flat roofs in urban areas are fruitful places to extract micrometeorites. The "urban" cosmic spherules have a shorter terrestrial age and are less altered than the previous findings.
Amateur collectors may find micrometeorites in areas where dust from a large area has been concentrated, such as from a roof downspout. | 0 | Theoretical and Fundamental Chemistry |
* Ushinsky Medal
* Honored Science Worker of the RSFSR (1967)
* Latvian SSR State Prize
* Order of the Patriotic War, 2nd class
* Order of the Red Banner of Labour | 0 | Theoretical and Fundamental Chemistry |
After the first bond is synthesized, the RNA polymerase must clear the promoter. During this time, there is a tendency to release the RNA transcript and produce truncated transcripts. This is called abortive initiation and is common for both eukaryotes and prokaryotes. Abortive initiation continues to occur until the σ factor rearranges, resulting in the transcription elongation complex (which gives a 35 bp-moving footprint). The σ factor is released before 80 nucleotides of mRNA are synthesized. Once the transcript reaches approximately 23 nucleotides, it no longer slips and elongation can occur. | 1 | Applied and Interdisciplinary Chemistry |
In research, Jeannin shows an interest in the chemistry of transition metals, in the synthesis and structure of the species they form. First in solid state chemistry with the study of the non-stoichiometry of binary and ternary chalcogenides of titanium and zirconium, then he studies the iron complexes formed by solvation in non-aqueous media, the synthesis and X-ray study of organometallic polymetallic species, and finally the chemistry of polyoxotungstates. In the latter case, it is essentially the compounds containing the XW9 brick that have attracted his attention. The laboratory has made a major contribution to the development of their synthesis and structural study by X-ray and NMR of tungsten, holding the record for the largest known polytungstate. In organometallic chemistry, study of the action of aminoalkynes and thioalkynes on iron carbonyl and ruthenium carbonyl; cluster compounds of up to five iron atoms have been isolated. He has also been interested in the coordination chemistry of copper and molybdenum. In order to carry out this research on the creation of a centre for structure determination by X-ray diffraction, he was made available to French and foreign chemists and to external laboratories.
This research has resulted in more than 300 publications. | 0 | Theoretical and Fundamental Chemistry |
Sodium-bonded fuel consists of fuel that has liquid sodium in the gap between the fuel slug (or pellet) and the cladding. This fuel type is often used for sodium-cooled liquid metal fast reactors. It has been used in EBR-I, EBR-II, and the FFTF. The fuel slug may be metallic or ceramic. The sodium bonding is used to reduce the temperature of the fuel. | 0 | Theoretical and Fundamental Chemistry |
The polymerase chain reaction (PCR) uses a pair of custom primers to direct DNA elongation toward each other at opposite ends of the sequence being amplified. These primers are typically between 18 and 24 bases in length and must code for only the specific upstream and downstream sites of the sequence being amplified. A primer that can bind to multiple regions along the DNA will amplify them all, eliminating the purpose of PCR.
A few criteria must be brought into consideration when designing a pair of PCR primers. Pairs of primers should have similar melting temperatures since annealing during PCR occurs for both strands simultaneously, and this shared melting temperature must not be either too much higher or lower than the reactions annealing temperature. A primer with a T (melting temperature) too much higher than the reactions annealing temperature may mishybridize and extend at an incorrect location along the DNA sequence. A T significantly lower than the annealing temperature may fail to anneal and extend at all.
Additionally, primer sequences need to be chosen to uniquely select for a region of DNA, avoiding the possibility of hybridization to a similar sequence nearby. A commonly used method for selecting a primer site is BLAST search, whereby all the possible regions to which a primer may bind can be seen. Both the nucleotide sequence as well as the primer itself can be BLAST searched. The free NCBI tool Primer-BLAST integrates primer design and BLAST search into one application, as do commercial software products such as ePrime and Beacon Designer. Computer simulations of theoretical PCR results (Electronic PCR) may be performed to assist in primer design by giving melting and annealing temperatures, etc.
As of 2014, many online tools are freely available for primer design, some of which focus on specific applications of PCR. Primers with high specificity for a subset of DNA templates in the presence of many similar variants can be designed using by some software (e.g. DECIPHER) or be developed independently for a specific group of animals.
Selecting a specific region of DNA for primer binding requires some additional considerations. Regions high in mononucleotide and dinucleotide repeats should be avoided, as loop formation can occur and contribute to mishybridization. Primers should not easily anneal with other primers in the mixture; this phenomenon can lead to the production of primer dimer products contaminating the end solution. Primers should also not anneal strongly to themselves, as internal hairpins and loops could hinder the annealing with the template DNA.
When designing primers, additional nucleotide bases can be added to the back ends of each primer, resulting in a customized cap sequence on each end of the amplified region. One application for this practice is for use in TA cloning, a special subcloning technique similar to PCR, where efficiency can be increased by adding AG tails to the 5′ and the 3′ ends. | 1 | Applied and Interdisciplinary Chemistry |
Cannon's initial publications, alongside Stanley Prusiner, definitively showed that thermogenesis was primarily driven by mitochondrial uncoupling, likely induced by the presence of free fatty acids. She subsequently showcased important elements in controlling the immediate function of the uncoupling protein, involving fatty acids, possibly their CoA derivatives, and reactive oxygen species (ROS) products. Her articles on regulating ATP synthase levels in mitochondria relative to electron transport chain density, demonstrated in brown adipose tissue, suggest that this concept applies universally, with the P1 isoform of subunit c governing fully assembled enzyme levels in the membrane.
Cannon pioneered primary cell culture systems that underpin knowledge of brown adipocyte development and recruitment. Using these cultures, she identified adrenergic signal transduction pathways responsible for both acute thermogenesis and chronic actions like cell proliferation and differentiation triggered by noradrenaline. She further clarified that the development paths of brown and white adipocytes are separate, with brown adipocytes showing characteristics of skeletal muscle early in their differentiation process. In her later research, she found that cultured adipocytes from different white adipose depots contained precursor cells capable of adopting a brown-like or "brite" phenotype, also known as beige fat. Although these findings have sparked significant interest, she has advised caution regarding the belief that these cells alone will solve obesity problems.
Focusing on integrative physiology, Cannon's research on mice lacking the UCP1 gene revealed that there are no alternative mechanisms for adrenergically induced adaptive thermogenesis apart from UCP1 in brown adipose tissue. This finding challenges the notion of adaptive adrenergic muscular thermogenesis and suggests that UCP1-deficient mice tend to develop modest obesity spontaneously. Moreover, she advocated for humanizing mice by providing them with appealing diets and maintaining their housing conditions at thermoneutral temperatures to mimic the metabolism of adult humans at its lowest point. Furthermore, her review on active brown adipose tissue in adult humans has prompted numerous follow-up experiments and offered promising avenues for pharmacological interventions in obesity management. | 1 | Applied and Interdisciplinary Chemistry |
One probe for testing whether or not the 2-norbornyl cation is non-classical is investigating the inherent symmetry of the cation. Many spectroscopic tools, such as nuclear magnetic resonance spectroscopy (NMR spectroscopy) and Raman spectroscopy, give hints about the reflectional and rotational symmetry present in a molecule or ion. Each of the three proposed structures of the 2-norbornyl cation illustrates a different molecular symmetry. The non-classical form contains a reflection plane through carbons 4, 5, 6, and the midpoint of carbons 1 and 2. The classical form contains neither reflectional nor rotational symmetry. The protonated nortricyclene structure contains a C-symmetric rotation axis through carbon 4.
Each peak in an NMR spectrum corresponds to a set of a particular element's atoms that are in similar chemical environments. The NMR spectrum of the antimony chloropentafluoride salt of the 2-norbornyl cation is not helpful at room temperature because hydride shifts occur faster than the timescale of an NMR experiment; most of the hydrogens are thus seen as equivalent and are accounted for in the same absorption peak. By lowering the temperature of the NMR experiment to −60 °C, hydride shifts are "frozen out" and more structural information can be gleaned from the spectrum. Researchers found that at these low temperatures, the H NMR spectrum matched what would be expected for the non-classical structure of the ion.
H and C NMR studies were able to confirm that any proposed Wagner-Meerwein rearrangements occurred faster than the timescale of the NMR experiment, even at low temperatures. For molecules in static equilibrium with respect to rearrangements, NMR reveals how many sets of symmetry-related nuclei are in the molecule and how many nuclei each of these sets accounts for via spectrum integration. For molecules in dynamic equilibrium such as the 2-norbornyl cation, nuclei within each set can also be transformed to one another through rearrangements with fast reaction rates. Since the proposed dynamic equilibrium of the classical ion proponents had very fast rates of rearrangement, the first NMR studies did not favor nor invalidate any of the three proposed structures. But by using solid-state NMR analysis, one can lower the temperature of the NMR experiment to and thus significantly slow down any rearrangement phenomena. Solid-state C NMR spectra of the 2-norbornyl cation shows that carbons 1 and 2 are in identical chemical environments, which is consistent only with the non-classical picture of the 2-norbornyl cation.
Raman spectra of the 2-norbornyl cation show a more symmetric species than would be expected for a pair of rapidly equilibrating classical ions. Since the proposed reaction rates for the classical ion rearrangements are slower than the Raman timescale, one would expect the Raman spectra to indicate a less symmetric species if the classical picture were correct.
Some studies of the C NMR in particular favored interpretation via the protonated nortricyclene structure. In addition, Raman spectra of the 2-norbornyl cation in some acidic solvents show an absorption band at 3110 cm indicative of an electron-depleted cyclopropane ring. Since that absorption band would be expected in the C-symmetric protonated nortricyclene, some scientists claimed this as convincing evidence for this interpretation. Other chemists have postulated that the properties of the 2-norbornyl cation are very dependent on the solvent environment. Though the high acidity and low nucleophilicity of the solvents used in aforementioned experiments may cause the protonated nortricylconium geometry to be the most stable, this geometry need not be the most energetically favorable in other solvents. | 0 | Theoretical and Fundamental Chemistry |
Diaconescu was born in Romania and received a Bachelor of Science degree from the University of Bucharest in 1998 conducting research on transition metal complexes and f-block metals. In 2003, Diaconescu received a PhD in chemistry from the Massachusetts Institute of Technology working with Christopher C. Cummins on uranium chemistry. Before joining the faculty at UCLA in 2005, she spent two years as a postdoctoral fellow at the California Institute of Technology with Robert Grubbs. | 0 | Theoretical and Fundamental Chemistry |
DNA sequencing is the process of determining the nucleotide sequence of a given DNA fragment. The sequence of the DNA of a living thing encodes the necessary information for that living thing to survive and reproduce. Therefore, determining the sequence is useful in fundamental research into why and how organisms live, as well as in applied subjects. Because of the importance of DNA to living things, knowledge of a DNA sequence may be useful in practically any biological research. For example, in medicine it can be used to identify, diagnose and potentially develop treatments for genetic diseases. Similarly, research into pathogens may lead to treatments for contagious diseases. Biotechnology is a burgeoning discipline, with the potential for many useful products and services.
RNA is not sequenced directly. Instead, it is copied to a DNA by reverse transcriptase, and this DNA is then sequenced.
Current sequencing methods rely on the discriminatory ability of DNA polymerases, and therefore can only distinguish four bases. An inosine (created from adenosine during RNA editing) is read as a G, and 5-methyl-cytosine (created from cytosine by DNA methylation) is read as a C. With current technology, it is difficult to sequence small amounts of DNA, as the signal is too weak to measure. This is overcome by polymerase chain reaction (PCR) amplification. | 1 | Applied and Interdisciplinary Chemistry |
Virtually every molecule and every ion can serve as a ligand for (or "coordinate to") metals. Monodentate ligands include virtually all anions and all simple Lewis bases. Thus, the halides and pseudohalides are important anionic ligands whereas ammonia, carbon monoxide, and water are particularly common charge-neutral ligands. Simple organic species are also very common, be they anionic (RO and Carboxylate|) or neutral (RO, RS, RNH, and RP). The steric properties of some ligands are evaluated in terms of their cone angles.
Beyond the classical Lewis bases and anions, all unsaturated molecules are also ligands, utilizing their pi electrons in forming the coordinate bond. Also, metals can bind to the σ bonds in for example silanes, hydrocarbons, and dihydrogen (see also: Agostic interaction).
In complexes of non-innocent ligands, the ligand is bonded to metals via conventional bonds, but the ligand is also redox-active. | 0 | Theoretical and Fundamental Chemistry |
Two-component systems are rare in eukaryotes. They appear in yeasts, filamentous fungi, and slime molds, and are relatively common in plants, but have been described as "conspicuously absent" from animals. Two-component systems in eukaryotes likely originate from lateral gene transfer, often from endosymbiotic organelles, and are typically of the hybrid kinase phosphorelay type. For example, in the yeast Candida albicans, genes found in the nuclear genome likely originated from endosymbiosis and remain targeted to the mitochondria. Two-component systems are well-integrated into developmental signaling pathways in plants, but the genes probably originated from lateral gene transfer from chloroplasts. An example is the chloroplast sensor kinase (CSK) gene in Arabidopsis thaliana, derived from chloroplasts but now integrated into the nuclear genome. CSK function provides a redox-based regulatory system that couples photosynthesis to chloroplast gene expression; this observation has been described as a key prediction of the CoRR hypothesis, which aims to explain the retention of genes encoded by endosymbiotic organelles.
It is unclear why canonical two-component systems are rare in eukaryotes, with many similar functions having been taken over by signaling systems based on serine, threonine, or tyrosine kinases; it has been speculated that the chemical instability of phosphoaspartate is responsible, and that increased stability is needed to transduce signals in the more complex eukaryotic cell. Notably, cross-talk between signaling mechanisms is very common in eukaryotic signaling systems but rare in bacterial two-component systems. | 1 | Applied and Interdisciplinary Chemistry |
The peridinin-chlorophyll-protein complex (PCP or PerCP) is a soluble molecular complex consisting of the peridinin-chlorophyll a-protein bound to peridinin, chlorophyll, and lipids. The peridinin molecules absorb light in the blue-green wavelengths (470 to 550 nm) and transfer energy to the chlorophyll molecules with extremely high efficiency. PCP complexes are found in many photosynthetic dinoflagellates, in which they may be the primary light-harvesting complexes. | 0 | Theoretical and Fundamental Chemistry |
Cyclic AMP is synthesized from ATP by adenylate cyclase located on the inner side of the plasma membrane and anchored at various locations in the interior of the cell. Adenylate cyclase is activated by a range of signaling molecules through the activation of adenylate cyclase stimulatory G (G)-protein-coupled receptors. Adenylate cyclase is inhibited by agonists of adenylate cyclase inhibitory G (G)-protein-coupled receptors. Liver adenylate cyclase responds more strongly to glucagon, and muscle adenylate cyclase responds more strongly to adrenaline.
cAMP decomposition into AMP is catalyzed by the enzyme phosphodiesterase. | 1 | Applied and Interdisciplinary Chemistry |
AdoMet is a methyl donor for transmethylation. It gives away its methyl group and is also the propylamino donor in polyamine biosynthesis. S-adenosylmethionine synthesis can be considered the rate-limiting step of the methionine cycle.
As a methyl donor SAM allows DNA methylation. Once DNA is methylated, it switches the genes off and therefore, S-adenosylmethionine can be considered to control gene expression.
SAM is also involved in gene transcription, cell proliferation, and production of secondary metabolites. Hence SAM synthetase is fast becoming a drug target, in particular for the following diseases: depression, dementia, vacuolar myelopathy, liver injury, migraine, osteoarthritis, and as a potential cancer chemopreventive agent.
This article discusses the protein domains that make up the SAM synthetase enzyme and how these domains contribute to its function. More specifically, this article explores the shared pseudo-3-fold symmetry that makes the domains well-adapted to their functions.
This enzyme catalyses the following chemical reaction
: ATP + L-methionine + HO phosphate + diphosphate + S-adenosyl-L-methionine | 1 | Applied and Interdisciplinary Chemistry |
Because of the strength of the carbon–fluorine bond, organofluorines endure in the environment. Perfluorinated compounds (PFCs) have attracted particular attention as persistent global contaminants. These compounds can enter the environment from their direct uses in waterproofing treatments and firefighting foams or indirectly from leaks from fluoropolymer production plants (where they are intermediates). Because of the acid group, PFCs are water-soluble in low concentrations. While there are other PFAAs, the lion's share of environmental research has been done on the two most well-known: perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). The U.S. Environmental Protection Agency classifies these materials as "emerging contaminants" based on the growing but still incomplete understanding of their environmental impact.
Trace quantities of PFCs have been detected worldwide, in organisms from polar bears in the Arctic to the global human population. Both PFOS and PFOA have been detected in breast milk and the blood of newborns. A 2013 review showed widely varying amounts of PFOS and PFOA in different soils and groundwater, with no clear pattern of one chemical dominating. PFC concentrations were generally higher in areas with more human population or industrial activity, and areas with more PFOS generally also had more PFOA. the two chemicals have been found at different concentrations in different populations; for example, one study showed more PFOS than PFOA in Germans, while another study showed the reverse for Americans. PFCs may be starting to decrease in the biosphere: one study indicated that PFOS levels in wildlife in Minnesota were decreasing, presumably because 3M discontinued its production.
In the body, PFCs bind to proteins such as serum albumin. Their tissue distribution in humans is unknown, but studies in rats suggest it is present mostly in the liver, kidney, and blood. They are not metabolized by the body but are excreted by the kidneys. Dwell time in the body varies greatly by species. Rodents have half-lives of days, while in humans they remain for years. Many animals show sex differences in the ability to rid the body of PFAAs, but without a clear pattern. Gender differences of half lives vary by animal species.
The potential health impact of PFCs is unclear. Unlike chlorinated hydrocarbons, PFCs are not lipophilic (stored in fat), nor genotoxic (damaging genes). Both PFOA and PFOS in high doses cause cancer and the death of newborns in rodents. Studies on humans have not been able to prove an impact at current exposures. Bottlenose dolphins have some of the highest PFOS concentrations of any wildlife studied; one study suggests an impact on their immune systems.
The biochemical causes of toxicity are also unclear and may differ by molecule, health effect, and even animal. PPAR-alpha is a protein that interacts with PFAAs and is commonly implicated in contaminant-caused rodent cancers.
Less fluorinated chemicals (i.e. not perfluorinated compounds) can also be detected in the environment. Because biological systems do not metabolize fluorinated molecules easily, fluorinated pharmaceuticals like antibiotics and antidepressants can be found in treated city sewage and wastewater. Fluorine-containing agrichemicals are measurable in farmland runoff and nearby rivers. | 1 | Applied and Interdisciplinary Chemistry |
Papakostas et al. observed in 2003 that planar chirality affects the polarization of light diffracted by arrays of planar chiral microstructures, where large polarization changes of opposite sign were detected in light diffracted from planar structures of opposite handedness. | 0 | Theoretical and Fundamental Chemistry |
Superconductivity in UPdAl has a critical temperature of 2.0K and a critical field around 3T. The critical field does not show anisotropy despite the hexagonal crystal structure.
For heavy-fermion superconductors it is generally believed that the coupling mechanism cannot be phononic in nature. In contrast to many other unconventional superconductors, for UPdAl there actually exists strong experimental evidence (namely from neutron scattering and tunneling spectroscopy ) that superconductivity is magnetically mediated.
In the first years after the discovery of UPdAl it was actively discussed whether its superconducting state can support a Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) phase, but this suggestion was later refuted. | 1 | Applied and Interdisciplinary Chemistry |
Hobart Hurd Willard (June 3, 1881 – May 7, 1974) was an analytical chemist and inorganic chemist who spent most of his career at the University of Michigan. He was known for his teaching skill and his authorship of widely used textbooks. His research interests were wide-ranging and involved the characterization of perchloric acid and periodic acid salts. | 0 | Theoretical and Fundamental Chemistry |
Drug development and pre-clinical trials focus on non-human subjects and work on animals such as rats. This is the most inexpensive phase of testing.
The Food and Drug Administration mandates a 3 phase clinical trial testing that tests for side effects and the effectiveness of the drug with a single phase clinical trial costing upwards of $100 million.
After a drug has passed through all three phases, the pharmaceutical company can move forward with a New Drug Application from the FDA. In 2014, the FDA charged between $1 million to $2 million for an NDA. | 1 | Applied and Interdisciplinary Chemistry |
Born on 17 September 1940 in the south Indian state of Tamil Nadu, Paramasivam Natarajan graduated in chemistry from the University of Madras in 1959. He started his career as a lecturer at the Government Arts College of the Madras University in 1959 but later moved to the NGM College, Pollachi in 1963. The next year, he joined the Banaras Hindu University (BHU) as a CSIR Junior Research fellow and during the tenure of the fellowship, obtained his master's degree in 1963. After continuing at BHU for a year more, he became a lecturer at the Jawaharlal Institute of Postgraduate Medical Education and Research (JIPMER) where he stayed till 1970. Later he went to the US as a teaching assistant at the University of Southern California, simultaneously pursuing his doctoral studies under the guidance of John F. Endicott. He secured a PhD in 1971 and did his post doctoral studies under his PhD guide, Endicott, at Wayne State University as the latter had moved to the Michigan-based university by that time.
Natarajan returned to India in 1974 and joined his alma mater, Madras University, as a reader of the department of physical chemistry. In 1977, he became a professor in charge of the Post Graduate Centre of the university in Tiruchirappalli. In 1982, he returned to the university headquarters in Chennai as the head of the department of inorganic chemistry. In 1991, he was deputed by the university as the director of Central Salt and Marine Chemicals Research Institute (CSMCRI), a post he held till 1996. After the completion of the assignment at CSMCRI, he resumed his duties at the university and became a senior professor in 1998. At time of his superannuation in 2001, he held the post of an INSA Senior Scientist at the National Centre for Ultrafast Process of the university and served as a member of the university syndicate.
Natarajan was married to Sivabagyam and the couple had two daughters, Shiva Sukanthi and Shakthi. He died on 18 March 2016, at the age of 75, survived by his wife, children and their families. | 0 | Theoretical and Fundamental Chemistry |
Whole genome sequencing has established the mutation frequency for whole human genomes. The mutation frequency in the whole genome between generations for humans (parent to child) is about 70 new mutations per generation. An even lower level of variation was found comparing whole genome sequencing in blood cells for a pair of monozygotic (identical twins) 100-year-old centenarians. Only 8 somatic differences were found, though somatic variation occurring in less than 20% of blood cells would be undetected.
In the specifically protein coding regions of the human genome, it is estimated that there are about 0.35 mutations that would change the protein sequence between parent/child generations (less than one mutated protein per generation).
In cancer, mutation frequencies are much higher, due to genome instability. This frequency can further depend on patient age, exposure to DNA damaging agents (such as UV-irradiation or components of tobacco smoke) and the activity/inactivity of DNA repair mechanisms. Furthermore, mutation frequency can vary between cancer types: in germline cells, mutation rates occur at approximately 0.023 mutations per megabase, but this number is much higher in breast cancer (1.18-1.66 somatic mutations per Mb), in lung cancer (17.7) or in melanomas (≈33). Since the haploid human genome consists of approximately 3,200 megabases, this translates into about 74 mutations (mostly in noncoding regions) in germline DNA per generation, but 3,776-5,312 somatic mutations per haploid genome in breast cancer, 56,640 in lung cancer and 105,600 in melanomas.
The distribution of somatic mutations across the human genome is very uneven, such that the gene-rich, early-replicating regions receive fewer mutations than gene-poor, late-replicating heterochromatin, likely due to differential DNA repair activity. In particular, the histone modification H3K9me3 is associated with high, and H3K36me3 with low mutation frequencies. | 1 | Applied and Interdisciplinary Chemistry |
Polysorbates are a class of emulsifiers used in some pharmaceuticals and food preparation. They are commonly used in oral and topical pharmaceutical dosage forms. They are also often used in cosmetics to solubilize essential oils into water-based products. Polysorbates are oily liquids derived from ethoxylated sorbitan (a derivative of sorbitol) esterified with fatty acids. Common brand names for polysorbates include Kolliphor, Scattics, Alkest, Canarcel, Tween, and Kotilen. | 0 | Theoretical and Fundamental Chemistry |
Equilibrium chemistry is concerned with systems in chemical equilibrium. The unifying principle is that the free energy of a system at equilibrium is the minimum possible, so that the slope of the free energy with respect to the reaction coordinate is zero. This principle, applied to mixtures at equilibrium provides a definition of an equilibrium constant. Applications include acid–base, host–guest, metal–complex, solubility, partition, chromatography and redox equilibria. | 0 | Theoretical and Fundamental Chemistry |
The compound has uses ranging from medicine to laboratory syntheses of chemically similar compounds. o-Cresophthalein has been used to derive polyamides and polyimides, colorimetrically estimate calcium in serum, and predict amount of time to wait before blood collection after a patient receives gadodiamide. | 0 | Theoretical and Fundamental Chemistry |
Dideoxynucleosides are analogues of nucleoside where the sugar ring lacks both 2´ and 3´-hydroxyl groups. Three years after the synthesis of zidovudine, Jerome Horwitz and his colleagues in Chicago prepared another dideoxynucleoside now known as zalcitabine (ddC). Zalcitabine is a synthetic pyrimidine nucleoside analogue, structurally related to deoxycytidine, in which the 3´-hydroxyl group of the ribose sugar moiety is substituted with hydrogen. Zalcitabine was approved by the FDA for the treatment
of HIV-1 in June 1992.
2´,3´-dideoxyinosine or didanosine is converted into dideoxyadenosine in vivo. Its development has a long history. In 1964 dideoxyadenosine, the corresponding adenosine analogue of zalcitabine was synthesised. Dideoxyadenosine caused kidney damage so didanosine was prepared from dideoxyadenosine by enzymatic oxidation (see table 1). It was found to be active against HIV without causing kidney damage. Didanosine was approved by the FDA for the treatment
of HIV-1 in October 1991.
Zalcitabine and didanosine are both obligate chain terminators, that have been developed for anti-HIV treatment. Unfortunately, both drugs lack selectivity and therefore cause side-effects.
Further modification of the dideoxy framework led to the development of 2´,3´-didehydro-3´-deoxythymidine (stavudine, d4T). Activity of stavudine was shown to be similar to that of zidovudine, although their phosphorylation patterns differ; the
affinity for zidovudine to thymidine kinase (the enzyme responsible for the first phosphorylation) is similar to that of thymidine, whereas the affinity<br /> for stavudine is 700-fold weaker.
2,3-dideoxy-3'-thiacytidine (lamivudine, 3TC) was discovered by Bernard Belleau. The history
of lamivudine can be traced back to the mid-1970s while Bernard Belleau was investigating sugar derivatives. Lamivudine was developed as the sulfur analogue of zalcitabine (see table 2). It was initially synthesized as a racemic mixture (BCH-189) and analysis showed that both positive and negative enantiomers of BCH-189 (2,3-dideoxy-3-thiacytidine) had in vitro activity against HIV. Lamivudine is the negative enantiomer and is a pyrimidine nucleoside analogue. The 3 carbon of the ribose ring of 2'-deoxycytidine has been replaced by a sulfur atom because it had greater anti-HIV activity and is less toxic than the positive enantiomer.
Next in line was 2,3-dideoxy-5-fluoro-3'-thiacytidine (Emtricitabine, FTC) which is
a structural homologue of lamivudine. The structural difference is the 5-fluoro-modification of the base moiety of lamivudine. It is similar in many ways to lamivudine and is active against both HIV-1 and hepatitis B virus (HBV). | 1 | Applied and Interdisciplinary Chemistry |
Hydrogen atom transfer (HAT) is distinct from PCET. In HAT, the proton and electron start in the same orbitals and move together to the final orbital. HAT is recognized as a radical pathway, although the stoichiometry is similar to that for PCET. | 0 | Theoretical and Fundamental Chemistry |
During the late 1940s, Woodward synthesized many complex natural products including quinine, cholesterol, cortisone, strychnine, lysergic acid, reserpine, chlorophyll, cephalosporin, and colchicine. With these, Woodward opened up a new era of synthesis, sometimes called the Woodwardian era in which he showed that natural products could be synthesized by careful applications of the principles of physical organic chemistry, and by meticulous planning.
Many of Woodwards syntheses were described as spectacular by his colleagues and before he did them, it was thought by some that it would be impossible to create these substances in the lab. Woodwards syntheses were also described as having an element of art in them, and since then, synthetic chemists have always looked for elegance as well as utility in synthesis. His work also involved the exhaustive use of the then newly developed techniques of infrared spectroscopy and later, nuclear magnetic resonance spectroscopy. Another important feature of Woodwards syntheses was their attention to stereochemistry or the particular configuration of molecules in three-dimensional space. Most natural products of medicinal importance are effective, for example as drugs, only when they possess a specific stereochemistry. This creates the demand for stereoselective synthesis', producing a compound with a defined stereochemistry. While today a typical synthetic route routinely involves such a procedure, Woodward was a pioneer in showing how, with exhaustive and rational planning, one could conduct reactions that were stereoselective. Many of his syntheses involved forcing a molecule into a certain configuration by installing rigid structural elements in it, another tactic that has become standard today. In this regard, especially his syntheses of reserpine and strychnine were landmarks.
During World War II, Woodward was an advisor to the War Production Board on the penicillin project. Although often given credit for proposing the beta-lactam structure of penicillin, it was actually first proposed by chemists at Merck and Edward Abraham at Oxford and then investigated by other groups, as well (e.g., Shell). Woodward at first endorsed an incorrect tricyclic (thiazolidine fused, amino bridged oxazinone) structure put forth by the penicillin group at Peoria. Subsequently, he put his imprimatur on the beta-lactam structure, all of this in opposition to the thiazolidine–oxazolone structure proposed by Robert Robinson, the then leading organic chemist of his generation. Ultimately, the beta-lactam structure was shown to be correct by Dorothy Hodgkin using X-ray crystallography in 1945.
Woodward also applied the technique of infrared spectroscopy and chemical degradation to determine the structures of complicated molecules. Notable among these structure determinations were santonic acid, strychnine, magnamycin and terramycin. In each one of these cases, Woodward again showed how rational facts and chemical principles, combined with chemical intuition, could be used to achieve the task.
In the early 1950s, Woodward, along with the British chemist Geoffrey Wilkinson, then at Harvard, postulated a novel structure for ferrocene, a compound consisting of a combination of an organic molecule with iron. This marked the beginning of the field of transition metal organometallic chemistry which grew into an industrially very significant field. Wilkinson won the Nobel Prize for this work in 1973, along with Ernst Otto Fischer. Some historians think that Woodward should have shared this prize along with Wilkinson. Remarkably, Woodward himself thought so, and voiced his thoughts in a letter sent to the Nobel Committee.
Woodward won the Nobel Prize in 1965 for his synthesis of complex organic molecules. He had been nominated a total of 111 times from 1946 to 1965. In his Nobel lecture, he described the total synthesis of the antibiotic cephalosporin, and claimed that he had pushed the synthesis schedule so that it would be completed around the time of the Nobel ceremony. | 0 | Theoretical and Fundamental Chemistry |
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