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The Hydrogen bond is relevant to drug design. According to Lipinski's rule of five the majority of orally active drugs have no more than five hydrogen bond donors and fewer than ten hydrogen bond acceptors. These interactions exist between nitrogen–hydrogen and oxygen–hydrogen centers. Many drugs do not, however, obey these "rules". | 0 | Theoretical and Fundamental Chemistry |
As a meal containing carbohydrates or protein is eaten and digested, blood glucose levels rise, and the pancreas secretes insulin. Blood glucose from the portal vein enters liver cells (hepatocytes). Insulin acts on the hepatocytes to stimulate the action of several enzymes, including glycogen synthase. Glucose molecules are added to the chains of glycogen as long as both insulin and glucose remain plentiful. In this postprandial or "fed" state, the liver takes in more glucose from the blood than it releases.
After a meal has been digested and glucose levels begin to fall, insulin secretion is reduced, and glycogen synthesis stops. When it is needed for energy, glycogen is broken down and converted again to glucose. Glycogen phosphorylase is the primary enzyme of glycogen breakdown. For the next 8–12 hours, glucose derived from liver glycogen is the primary source of blood glucose used by the rest of the body for fuel.
Glucagon, another hormone produced by the pancreas, in many respects serves as a countersignal to insulin. In response to insulin levels being below normal (when blood levels of glucose begin to fall below the normal range), glucagon is secreted in increasing amounts and stimulates both glycogenolysis (the breakdown of glycogen) and gluconeogenesis (the production of glucose from other sources). | 1 | Applied and Interdisciplinary Chemistry |
Alexander Zaytsev first published his observations regarding the products of elimination reactions in Justus Liebigs Annalen der Chemie in 1875. Although the paper contained some original research done by Zaytsevs students, it was largely a literature review and drew heavily upon previously published work. In it, Zaytsev proposed a purely empirical rule for predicting the favored regiochemistry in the dehydrohalogenation of alkyl iodides, though it turns out that the rule is applicable to a variety of other elimination reactions as well. While Zaytsevs paper was well referenced throughout the 20th century, it was not until the 1960s that textbooks began using the term "Zaytsev's rule".
Zaytsev was not the first chemist to publish the rule that now bears his name. Aleksandr Nikolaevich Popov published an empirical rule similar to Zaytsevs in 1872, and presented his findings at the University of Kazan in 1873. Zaytsev had cited Popovs 1872 paper in previous work and worked at the University of Kazan, and was thus probably aware of Popovs proposed rule. In spite of this, Zaytsevs 1875 Liebigs Annalen paper makes no mention of Popov's work.
Any discussion of Zaytsevs rule would be incomplete without mentioning Vladimir Vasilyevich Markovnikov. Zaytsev and Markovnikov both studied under Alexander Butlerov, taught at the University of Kazan during the same period, and were bitter rivals. Markovnikov, who published in 1870 what is now known as Markovnikovs rule, and Zaytsev held conflicting views regarding elimination reactions: the former believed that the least substituted alkene would be favored, whereas the latter felt the most substituted alkene would be the major product. Perhaps one of the main reasons Zaytsev began investigating elimination reactions was to disprove his rival. Zaytsev published his rule for elimination reactions just after Markovnikov published the first article in a three-part series in Comptes Rendus detailing his rule for addition reactions. | 0 | Theoretical and Fundamental Chemistry |
Rhodium-catalyzed C-C bondactivation of strained spiropentanes leads to a cyclopentenones. In terms of mechanism, the reaction proceeds by apparent oxidative addition of the 4-5 carbon-carbon bond, leading to a rhodacyclobutane intermediate. In the presence of carbon monoxide, migratory insertion of CO into one of the carbon-rhodium bonds gives a rhodacyclopentanone intermediate. Beta-carbon elimination to form an alkene from the other carbon-rhodium bond leads to a rhodacyclohexanone intermediate with an exocyclic double bond. Reductive elimination of the two carbon-rhodium bonds followed by isomerization of the exocyclic double bond leads to the desired beta-substituted cyclopentenone product. This reaction was applied to the total synthesis of (±)-β-cuparenone.
Using the same rhodium(I) catalyst and C-C bond activation strategy one can access compounds with fused rings. Once again the reaction involves oxidative addition to give a rhodacyclobutane eventually affording a rhodacycloheptene intermediate. Insertion of carbon monoxide into one of the carbon-rhodium bonds form a rhodacyclooctenone intermediate that can reductively eliminate to yield a 6,7-fused ring system. The authors propose that the regioselectivity of the initial oxidative addition is controlled by coordination of the endocyclic double bond to the rhodium catalyst. | 0 | Theoretical and Fundamental Chemistry |
PKA is also commonly known as cAMP-dependent protein kinase, because it has traditionally been thought to be activated through release of the catalytic subunits when levels of the second messenger called cyclic adenosine monophosphate, or cAMP, rise in response to a variety of signals. However, recent studies evaluating the intact holoenzyme complexes, including regulatory AKAP-bound signalling complexes, have suggested that the local sub cellular activation of the catalytic activity of PKA might proceed without physical separation of the regulatory and catalytic components, especially at physiological concentrations of cAMP. In contrast, experimentally induced supra physiological concentrations of cAMP, meaning higher than normally observed in cells, are able to cause separation of the holoenzymes, and release of the catalytic subunits.
Extracellular hormones, such as glucagon and epinephrine, begin an intracellular signalling cascade that triggers protein kinase A activation by first binding to a G protein–coupled receptor (GPCR) on the target cell. When a GPCR is activated by its extracellular ligand, a conformational change is induced in the receptor that is transmitted to an attached intracellular heterotrimeric G protein complex by protein domain dynamics. The Gs alpha subunit of the stimulated G protein complex exchanges GDP for GTP in a reaction catalyzed by the GPCR and is released from the complex. The activated Gs alpha subunit binds to and activates an enzyme called adenylyl cyclase, which, in turn, catalyzes the conversion of ATP into cAMP, directly increasing the cAMP level. Four cAMP molecules are able to bind to the two regulatory subunits. This is done by two cAMP molecules binding to each of the two cAMP binding sites (CNB-B and CNB-A) which induces a conformational change in the regulatory subunits of PKA, causing the subunits to detach and unleash the two, now activated, catalytic subunits.
Once released from inhibitory regulatory subunit, the catalytic subunits can go on to phosphorylate a number of other proteins in the minimal substrate context Arg-Arg-X-Ser/Thr., although they are still subject to other layers of regulation, including modulation by the heat stable pseudosubstrate inhibitor of PKA, termed PKI.
Below is a list of the steps involved in PKA activation:
# Cytosolic cAMP increases
# Two cAMP molecules bind to each PKA regulatory subunit
# The regulatory subunits move out of the active sites of the catalytic subunits and the R2C2 complex dissociates
# The free catalytic subunits interact with proteins to phosphorylate Ser or Thr residues. | 1 | Applied and Interdisciplinary Chemistry |
A mercury barometer is one of the classic uses of static pressure head. Such barometers are an enclosed column of mercury standing vertically with gradations on the tube. The lower end of the tube is bathed in a pool of mercury open to the ambient to measure the local atmospheric pressure. The reading of a mercury barometer (in mm of Hg, for example) can be converted into an absolute pressure using the above equations.
If we had a column of mercury 767 mm high, we could calculate the atmospheric pressure as (767 mm)•(133 kN/m) = 102 kPa. See the torr, millimeter of mercury, and pascal (unit) articles for barometric pressure measurements at standard conditions. | 1 | Applied and Interdisciplinary Chemistry |
Analytical thermal desorption, known within the analytical chemistry community simply as "thermal desorption" (TD), is a technique that concentrates volatile organic compounds (VOCs) in gas streams prior to injection into a gas chromatograph (GC). It can be used to lower the detection limits of GC methods, and can improve chromatographic performance by reducing peak widths. | 0 | Theoretical and Fundamental Chemistry |
Cholesterol uptake by cells instigates inflammation, affecting both the central nervous system and the peripheral systems. This phenomenon involves the aggregation of inflammatory proteins. For instance, in the context of TLR4, cholesterol prompts receptor dimerization. Similarly, with TNF alpha, the substrate facilitates the enzyme's binding. Subsequent hydrolysis yields soluble cytokines, contributing to the inflammatory response.
During an inflammatory response cholesterol is loaded into immune cells including macrophages. The cholesterol is a signal that activates cytokine production and other inflammatory responses. Cholesterol's role in inflammation is central to many diseases. | 1 | Applied and Interdisciplinary Chemistry |
Source: [https://www.iom3archive.org.uk/awards-archive IOM3 archive website] and [https://www.iom3.org/events-awards/awards/iom3-awards-winners.html current IOM3 website] | 1 | Applied and Interdisciplinary Chemistry |
One standard increasingly used (e.g. in the United States) is J-STD-004. It is very similar to DIN EN 61190-1-1.
Four characters (two letters, then one letter, and last a number) represent flux composition, flux activity, and whether activators include halides:
* First two letters: Base
** RO: rosin
** RE: resin
** OR: organic
** IN: inorganic
* Third letter: Activity
** L: low
** M: moderate
** H: high
* Number: Halide content
** 0: less than 0.05% in weight (“halide-free”)
** 1: halide content depends on activity:
*** less than 0.5% for low activity
*** 0.5% to 2.0% for moderate activity
*** greater than 2.0% for high activity
Any combination is possible, e.g. ROL0, REM1 or ORH0.
J-STD-004 characterizes the flux by reliability of residue from a surface insulation resistance (SIR) and electromigration standpoint. It includes tests for electromigration and surface insulation resistance (which must be greater than 100 MΩ after 168 hours at elevated temperature and humidity with a DC bias applied). | 1 | Applied and Interdisciplinary Chemistry |
The same triad geometries been converged upon by serine proteases such as the chymotrypsin and subtilisin superfamilies. Similar convergent evolution has occurred with cysteine proteases such as viral C3 protease and papain superfamilies. These triads have converged to almost the same arrangement due to the mechanistic similarities in cysteine and serine proteolysis mechanisms.
Families of cysteine proteases
Families of serine proteases | 1 | Applied and Interdisciplinary Chemistry |
Thioketenes can be stabilized by either steric protection or by electronic effects. Thus, di-tert-butylthioketene is easily isolated and air-stable. Several examples have been characterized by X-ray crystallography. The C=S distance is 157 pm and the C=C distance is 124 pm, both bonds being suitable for the C=C=S assignment. The violet color characteristic of thioketenes indicates the small HOMO-LUMO gap. These compound are prepared by treatment of the acid chloride with phosphorus pentasulfide as described by the following idealized equation:
Bis(trifluoromethyl)thioketene () is an example of an electronically stabilized thioketene. | 0 | Theoretical and Fundamental Chemistry |
The continental shelf pump is proposed as operating in the shallow waters of the continental shelves as a mechanism transporting carbon (dissolved or particulate) from the continental waters to the interior of the adjacent deep ocean. As originally formulated, the pump is thought to occur where the solubility pump interacts with cooler, and therefore denser water from the shelf floor which feeds down the continental slope into the neighbouring deep ocean. The shallowness of the continental shelf restricts the convection of cooling water, so the cooling can be greater for continental shelf waters than for neighbouring open ocean waters. These cooler waters promote the solubility pump and lead to an increased storage of dissolved inorganic carbon. This extra carbon storage is further augmented by the increased biological production characteristic of shelves. The dense, carbon-rich shelf waters then sink to the shelf floor and enter the sub-surface layer of the open ocean via isopycnal mixing. As the sea level rises in response to global warming, the surface area of the shelf seas will grow and in consequence the strength of the shelf sea pump should increase. | 0 | Theoretical and Fundamental Chemistry |
The PI curve can be applied to terrestrial and marine reactions but is most commonly used to explain ocean-dwelling phytoplankton's photosynthetic response to changes in light intensity. Using this tool to approximate biological productivity is important because phytoplankton contribute ~50% of total global carbon fixation and are important suppliers to the marine food web.
Within the scientific community, the curve can be referred to as the PI, PE or Light Response Curve. While individual researchers may have their own preferences, all are readily acceptable for use in the literature. Regardless of nomenclature, the photosynthetic rate in question can be described in terms of carbon (C) fixed per unit per time. Since individuals vary in size, it is also useful to normalise C concentration to Chlorophyll a (an important photosynthetic pigment) to account for specific biomass. | 0 | Theoretical and Fundamental Chemistry |
Assume that a beam of light enters a material sample. Define as an axis parallel to the direction of the beam. Divide the material sample into thin slices, perpendicular to the beam of light, with thickness sufficiently small that one particle in a slice cannot obscure another particle in the same slice when viewed along the direction. The radiant flux of the light that emerges from a slice is reduced, compared to that of the light that entered, by where is the (Napierian) attenuation coefficient, which yields the following first-order linear, ordinary differential equation:
The attenuation is caused by the photons that did not make it to the other side of the slice because of scattering or absorption. The solution to this differential equation is obtained by multiplying the integrating factorthroughout to obtainwhich simplifies due to the product rule (applied backwards) to
Integrating both sides and solving for for a material of real thickness , with the incident radiant flux upon the slice and the transmitted radiant flux givesand finally
Since the decadic attenuation coefficient is related to the (Napierian) attenuation coefficient by we also have
To describe the attenuation coefficient in a way independent of the number densities of the attenuating species of the material sample, one introduces the attenuation cross section has the dimension of an area; it expresses the likelihood of interaction between the particles of the beam and the particles of the species in the material sample:
One can also use the molar attenuation coefficients where is the Avogadro constant, to describe the attenuation coefficient in a way independent of the amount concentrations of the attenuating species of the material sample: | 0 | Theoretical and Fundamental Chemistry |
The growth-differentiation balance hypothesis states that plant defenses are a result of a tradeoff between "growth-related processes" and "differentiation-related processes" in different environments. Differentiation-related processes are defined as "processes that enhance the structure or function of existing cells (i.e. maturation and specialization)." A plant will produce chemical defenses only when energy is available from photosynthesis, and plants with the highest concentrations of secondary metabolites are the ones with an intermediate level of available resources.
The GDBH also accounts for tradeoffs between growth and defense over a resource availability gradient. In situations where resources (e.g. water and nutrients) limit photosynthesis, carbon supply is predicted to limit both growth and defense. As resource availability increases, the requirements needed to support photosynthesis are met, allowing for accumulation of carbohydrate in tissues. As resources are not sufficient to meet the large demands of growth, these carbon compounds can instead be partitioned into the synthesis of carbon based secondary metabolites (phenolics, tannins, etc.). In environments where the resource demands for growth are met, carbon is allocated to rapidly dividing meristems (high sink strength) at the expense of secondary metabolism. Thus rapidly growing plants are predicted to contain lower levels of secondary metabolites and vice versa. In addition, the tradeoff predicted by the GDBH may change over time, as evidenced by a recent study on Salix spp. Much support for this hypothesis is present in the literature, and some scientists consider the GDBH the most mature of the plant defense hypotheses. | 1 | Applied and Interdisciplinary Chemistry |
Most artificial plasmas are generated by the application of electric and/or magnetic fields through a gas. Plasma generated in a laboratory setting and for industrial use can be generally categorized by:
*The type of power source used to generate the plasma—DC, AC (typically with radio frequency (RF)) and microwave
*The pressure they operate at—vacuum pressure (< 10 mTorr or 1 Pa), moderate pressure (≈1 Torr or 100 Pa), atmospheric pressure (760 Torr or 100 kPa)
*The degree of ionization within the plasma—fully, partially, or weakly ionized
*The temperature relationships within the plasma—thermal plasma (), non-thermal or "cold" plasma ()
*The electrode configuration used to generate the plasma
*The magnetization of the particles within the plasma—magnetized (both ion and electrons are trapped in Larmor orbits by the magnetic field), partially magnetized (the electrons but not the ions are trapped by the magnetic field), non-magnetized (the magnetic field is too weak to trap the particles in orbits but may generate Lorentz forces) | 0 | Theoretical and Fundamental Chemistry |
Transition metal carboxylate complexes are coordination complexes with carboxylate (RCO) ligands. Reflecting the diversity of carboxylic acids, the inventory of metal carboxylates is large. Many are useful commercially, and many have attracted intense scholarly scrutiny. Carboxylates exhibit a variety of coordination modes, most common are κ- (O-monodentate), κ (O,O-bidentate), and bridging. | 0 | Theoretical and Fundamental Chemistry |
NCAs are prone to hydrolysis to the parent amino acid:
:RCHNHC(O)OC(O) + HO → HNCH(R)COH + CO
Some derivatives however tolerate water briefly.
NCAs convert to homopolypeptides ( [N(H)CH(R)CO)]) through ring-opening polymerization:
:nRCHNHC(O)OC(O) → [N(H)CH(R)CO)] + nCO
Poly--lysine has been prepared from N-carbobenzyloxy-α-N-carboxy--lysine anhydride, followed by deprotection with phosphonium iodide. Peptide synthesis from NCAs does not require protection of the amino acid functional groups. N-Substituted NCAs, such as sulfenamide derivatives have also been examined. The ring-opening polymerization of NCAs is catalyzed by metal catalysts.
The polymerization of NCA’s have been considered as a prebiotic route to polypeptides. | 0 | Theoretical and Fundamental Chemistry |
[http://regulondb.ccg.unam.mx/menu/using_regulondb/tutorials/project_glossary/index.jsp Check the glossary for all definitions]. | 1 | Applied and Interdisciplinary Chemistry |
Small RNAs are noncoding RNA molecules between 20 and 200 nucleotide in length. The item "small RNA" is a rather arbitrary term, which is vaguely defined based on its length comparing with regular RNA such as messenger RNA (mRNA). Previously bacterial short regulatory RNAs have been referred to as small RNAs, but they are not related to eukaryotic small RNAs.
Small RNAs include several different classes of noncoding RNAs, depending on their sizes and functions: snRNA, snoRNA, scRNA, piRNA, miRNA, YRNA, tsRNA, rsRNA, and siRNA. Their functions go from RNAi (specific for endogenously expressed miRNA and exogenously derived siRNA), RNA processing and modification, gene silencing (i.g. X chromosome inactivation by Xist RNA), epigenetics modifications, protein stability and transport. | 1 | Applied and Interdisciplinary Chemistry |
Microcapsules termed protocells prepared by polymer-protein hybrids are the hotspot of the research area recently, enabling various functions such as bioreactors, cascade system and multiresponsive membranes, etc. | 1 | Applied and Interdisciplinary Chemistry |
There are numerous classes of natural products for which total synthesis is applied to. These include (but are not limited to): terpenes, alkaloids, polyketides and polyethers. Total synthesis targets are sometimes referred to by their organismal origin such as plant, marine, and fungal. The term total synthesis is less frequently but still accurately applied to the synthesis of natural polypeptides and polynucleotides. The peptide hormones oxytocin and vasopressin were isolated and their total syntheses first reported in 1954. It is not uncommon for natural product targets to feature multiple structural components of several natural product classes. | 0 | Theoretical and Fundamental Chemistry |
Recent excavations in Middle Ganges Valley show iron working in India may have begun as early as 1800 BCE. In the 5th century BCE, the Greek historian Herodotus observed that "Indian and the Persian army used arrows tipped with iron." Ancient Romans used armour and cutlery made of Indian iron. Pliny the Elder also mentioned Indian iron. Muhammad al-Idrisi wrote the Hindus excelled in the manufacture of iron, and that it would be impossible to find anything to surpass the edge from Hindwani steel. Quintus Curtius wrote about an Indian present of steel to Alexander. Ferrum indicum appeared in the list of articles subject to duty under Marcus Aurelius and Commodus. Indian Wootz steel was held in high regard in Europe, and Indian iron was often considered to be the best. | 1 | Applied and Interdisciplinary Chemistry |
The simplest spin system exhibiting the SE DNP mechanism is an electron-nucleus spin pair. The Hamiltonian of the system can be written as:
These terms are referring respectively to the electron and nucleus Zeeman interaction with the external magnetic field, and the hyperfine interaction. S and I are the electron and nuclear spin operators in the Zeeman basis (spin considered for simplicity), ω and ω are the electron and nuclear Larmor frequencies, and A and B are the secular and pseudo-secular parts of the hyperfine interaction. For simplicity we will only consider the case of |A|,|B||. In such a case A has little effect on the evolution of the spin system. During DNP a MW irradiation is applied at a frequency ω and intensity ω, resulting in a rotating frame Hamiltonian given by
:where
The MW irradiation can excite the electron single quantum transitions ("allowed transitions") when ω is close to ω, resulting in a loss of the electron polarization. In addition, due to the small state mixing caused by the B term of the hyperfine interaction, it is possible to irradiate on the electron-nucleus zero quantum or double quantum ("forbidden") transitions around ω = ω ± ω, resulting in polarization transfer between the electrons and the nuclei. The effective MW irradiation on these transitions is approximately given by Bω/2ω. | 0 | Theoretical and Fundamental Chemistry |
The Zisman theory is the simplest commonly used theory, as it is a one-component theory, and is best used for non-polar surfaces. This means that polymer surfaces that have been subjected to heat treatment, corona treatment, plasma cleaning, or polymers that contain heteroatoms do not lend themselves to this particular theory, as they tend to be at least somewhat polar. The Zisman theory also tends to be more useful in practice for surfaces with lower energies.
The Zisman theory simply defines the surface energy as being equal to the surface energy of the highest surface energy liquid that wets the solid completely. That is to say, the droplet will disperse as much as possible, i.e. completely wetting the surface, for this liquid and any liquids with lower surface energies, but not for liquids with higher surface energies. Since this probe liquid could hypothetically be any liquid, including an imaginary liquid, the best way to determine the surface energy by the Zisman method is to acquire data points of contact angles for several probe liquids on the solid surface in question, and then plot the cosine of that angle against the known surface energy of the probe liquid. By constructing the Zisman plot, one can extrapolate the highest liquid surface energy, real or hypothetical, that would result in complete wetting of the sample with a contact angle of zero degrees. | 0 | Theoretical and Fundamental Chemistry |
The development of resistance to chemotherapies such as paclitaxel and cisplatin in non-small-cell lung cancer (NSCLC) is strongly associated with overexpression of beta III tubulin. Investigations by the Children's Cancer Institute Australia (University of NSW, Lowy Cancer Research Centre) demonstrated that beta III-tubulin knockdown by DDRNAI delayed tumor growth and increased chemosensitivity in mouse models.
Tributarna is a triple DNA cassette expressing three shRNA molecules each of which separately targets beta III tubulin and strongly inhibits its expression. Studies in an orthotopic-mouse model, where the construct is delivered by a modified polyethylenimine vector, jetPEI, that targets lung tissue are in progress. | 1 | Applied and Interdisciplinary Chemistry |
The brush type, or Pirkle type chiral stationary phases are also called π-π Donnor-Acceptor columns. According to some theoretical models separation on these CSPs is based on a three-point attachment between the solute and the bonded chiral ligand on the surface of the stationary phase. These interactions may be attractive or repulsive in nature, depending on the mutual properties. Pirkle columns discriminate enantiomers by binding of one enantiomer with the chiral stationary phase, thereby forming a diastereomeric complex through π-π bonding, hydrogen bonding, steric interactions, and/or dipole stacking. Pirkle CSP can be categorized into three classes:
(i) π-electron acceptor
(ii) π-electron donor
(iii) π-electron donor-π-electron acceptor. | 0 | Theoretical and Fundamental Chemistry |
One strategy to provide full 360° rotation of THz polarization of equal electric field magnitude at the sample is to generate a circular state of polarization, then select particular linear polarization states from the circularly polarized beam with a THz polarizer.
A circular polarization state may be generated by a quarter waveplate, however, common optical waveplates are typically designed for visible, near- and mid-infrared regions of the electromagnetic spectrum. A quarter waveplate designed for use in the THz frequency range consists of a right-angle silicon prism together with metal-coated planar mirrors as input/output. In particular, the silicon prism acts analogously to a Fresnel rhomb with a single total internal reflection on the longer face of the prism and is a passive broadband component that permits a wide frequency sweep during measurements. | 0 | Theoretical and Fundamental Chemistry |
As sketched above, the ARM domain of β-catenin acts as a platform to which specific linear motifs may bind. Located in structurally diverse partners, the β-catenin binding motifs are typically disordered on their own, and typically adopt a rigid structure upon ARM domain engagement – as seen for short linear motifs. However, β-catenin interacting motifs also have a number of peculiar characteristics. First, they might reach or even surpass the length of 30 amino acids in length, and contact the ARM domain on an excessively large surface area. Another unusual feature of these motifs is their frequently high degree of phosphorylation. Such Ser/Thr phosphorylation events greatly enhance the binding of many β-catenin associating motifs to the ARM domain.
The structure of β-catenin in complex with the catenin binding domain of the transcriptional transactivation partner TCF provided the initial structural roadmap of how many binding partners of β-catenin may form interactions. This structure demonstrated how the otherwise disordered N-terminus of TCF adapted what appeared to be a rigid conformation, with the binding motif spanning many beta-catenin repeats. Relatively strong charged interaction "hot spots" were defined (predicted, and later verified, to be conserved for the β-catenin/E-cadherin interaction), as well as hydrophobic regions deemed important in the overall mode of binding and as potential therapeutic small molecule inhibitor targets against certain cancer forms. Furthermore, following studies demonstrated another peculiar characteristic, plasticity in the binding of the TCF N-terminus to beta-catenin.
Similarly, we find the familiar E-cadherin, whose cytoplasmatic tail contacts the ARM domain in the same canonical fashion. The scaffold protein axin (two closely related paralogs, axin 1 and axin 2) contains a similar interaction motif on its long, disordered middle segment. Although one molecule of axin only contains a single β-catenin recruitment motif, its partner the adenomatous polyposis coli (APC) protein contains 11 such motifs in tandem arrangement per protomer, thus capable to interact with several β-catenin molecules at once. Since the surface of the ARM domain can typically accommodate only one peptide motif at any given time, all these proteins compete for the same cellular pool of β-catenin molecules. This competition is the key to understand how the Wnt signaling pathway works.
However, this "main" binding site on the ARM domain β-catenin is by no means the only one. The first helices of the ARM domain form an additional, special protein-protein interaction pocket: This can accommodate a helix-forming linear motif found in the coactivator BCL9 (or the closely related BCL9L) – an important protein involved in Wnt signaling. Although the precise details are much less clear, it appears that the same site is used by alpha-catenin when β-catenin is localized to the adherens junctions. Because this pocket is distinct from the ARM domain's "main" binding site, there is no competition between alpha-catenin and E-cadherin or between TCF1 and BCL9, respectively. On the other hand, BCL9 and BCL9L must compete with α-catenin to access β-catenin molecules. | 1 | Applied and Interdisciplinary Chemistry |
The sticking probability is the probability that molecules are trapped on surfaces and adsorb chemically. From Langmuir's adsorption isotherm, molecules cannot adsorb on surfaces when the adsorption sites are already occupied by other molecules, so the sticking probability can be expressed as follows:
where is the initial sticking probability and is the surface coverage fraction ranging from 0 to 1.
Similarly, when molecules adsorb on surfaces dissociatively, the sticking probability is
The square is owing to the fact that a disassociation of 1 molecule into 2 parts requires 2 adsorption sites. These equations are simple and can be easily understood but cannot explain experimental results.
In 1958, P. Kisliuk presented an equation for the sticking probability that can explain experimental results. In his theory, molecules are trapped in precursor states of physisorption before chemisorption. Then the molecules meet adsorption sites that molecules can adsorb to chemically, so the molecules behave as follows.
If these sites are not occupied, molecules do the following (with probability in parentheses):
# adsorb on the surface chemically ()
# desorb from the surface ()
# move to the next precursor state ()
and if these sites are occupied, they
# desorb from the surface ()
# move to the next precursor state ()
Note that an occupied site is defined as one where there is a chemically bonded adsorbate so by definition it would be . Then the sticking probability is, according to equation (6) of the reference,
When , this equation is identical in result to Langmuir's adsorption isotherm. | 0 | Theoretical and Fundamental Chemistry |
Cornforth was named the Australian of the Year in 1975, jointly with Maj. Gen. Alan Stretton. In 1977, Cornforth was recognised by his alma mater, the University of Sydney, with the award of an honorary Doctor of Science. Cornforth's other awards and recognitions follow:
* Davy Medal (1968)
* Elected a Fellow of the Royal Society (FRS) in 1953
* Commander of the Order of the British Empire (CBE; 1972)
* Nobel Prize in Chemistry (1975)
* Royal Medal (1976)
* Knight Bachelor (1977)
* Corresponding Fellow of the Australian Academy of Science (1977)
* Foreign member of the Royal Netherlands Academy of Arts and Sciences (since 1978)
* Copley Medal (1982)
* Companion of the Order of Australia (AC; 1991)
* Centenary Medal (2001)
Cornforth's certificate of election for the Royal Society reads: | 0 | Theoretical and Fundamental Chemistry |
Nitrogen removal in the A-stage can reach 30–40%, as nitrogen of organic compounds is incorporated in upflow anaerobic sludge blanket (UASB) reactor sludge.
The sludge age of the B-stage is typically between 8 and 20 days promoting the growth of nitrifiers. Therefore, complete nitrification is usually achieved in the B-stage. Complete denitrification is difficult to achieve, because of the low C:N ratio in the influent of the B-stage. Insufficient carbon supply of carbon source to the B-stage occurs due to the high efficiency of organic matter removal in the A-stage. The problem can be solved by decreasing organic matter removal in the A-stage, external carbon source supply, intermittent aeration or decreased HRT of the A-stage and/or on-line control of certain operational parameters. To achieve biological nitrogen and phosphorus removal anaerobic and anoxic compartments are introduced before the aerated zone of the B-stage.
Phosphorus removal from the secondary effluent of the B-stage can be achieved by coagulation with ferric and aluminium salts, e.g. FeCl or Al(SO). | 1 | Applied and Interdisciplinary Chemistry |
The reciprocating steam engine has been used to produce mechanical power since the 18th century, with notable improvements being made by James Watt. When the first commercially developed central electrical power stations were established in 1882 at Pearl Street Station in New York and Holborn Viaduct power station in London, reciprocating steam engines were used. The development of the steam turbine in 1884 provided larger and more efficient machine designs for central generating stations. By 1892 the turbine was considered a better alternative to reciprocating engines; turbines offered higher speeds, more compact machinery, and stable speed regulation allowing for parallel synchronous operation of generators on a common bus. After about 1905, turbines entirely replaced reciprocating engines in almost all large central power stations.
The largest reciprocating engine-generator sets ever built were completed in 1901 for the Manhattan Elevated Railway. Each of seventeen units weighed about 500 tons and was rated 6000 kilowatts; a contemporary turbine set of similar rating would have weighed about 20% as much. | 1 | Applied and Interdisciplinary Chemistry |
Most solid materials undergo plastic deformations when subjected to strong shocks. The point on the shock Hugoniot at which a material transitions from a purely elastic state to an elastic-plastic state is called the Hugoniot elastic limit (HEL) and the pressure at which this transition takes place is denoted p. Values of p can range from 0.2 GPa to 20 GPa. Above the HEL, the material loses much of its shear strength and starts behaving like a fluid. | 1 | Applied and Interdisciplinary Chemistry |
Pathway building has been performed by individual groups studying a network of interest (e.g., immune signaling pathway) as well as by large bioinformatics consortia (e.g., the Reactome Project) and commercial entities (e.g., Ingenuity Systems). Pathway building is the process of identifying and integrating the entities, interactions, and associated annotations, and populating the knowledge base. Pathway construction can have either a data-driven objective (DDO) or a knowledge-driven objective (KDO). Data-driven pathway construction is used to generate relationship information of genes or proteins identified in a specific experiment such as a microarray study. Knowledge-driven pathway construction entails development of a detailed pathway knowledge base for particular domains of interest, such as a cell type, disease, or system. The curation process of a biological pathway entails identifying and structuring content, mining information manually and/or computationally, and assembling a knowledgebase using appropriate software tools. A schematic illustrating the major steps involved in the data-driven and knowledge-driven construction processes.
For either DDO or KDO pathway construction, the first step is to mine pertinent information from relevant information sources about the entities and interactions. The information retrieved is assembled using appropriate formats, information standards, and pathway building tools to obtain a pathway prototype. The pathway is further refined to include context-specific annotations such as species, cell/tissue type, or disease type. The pathway can then be verified by the domain experts and updated by the curators based on appropriate feedback. Recent attempts to improve knowledge integration have led to refined classifications of cellular entities, such as GO, and to the assembly of structured knowledge repositories. Data repositories, which contain information regarding sequence data, metabolism, signaling, reactions, and interactions are a major source of information for pathway building. A few useful databases are described in the following table.
Legend: Y – Yes, N – No; BIND – Biomolecular Interaction Network Database, DIP – Database of Interacting Proteins, GNPV – Genome Network Platform Viewer, HPRD = Human Protein Reference Database, MINT – Molecular Interaction database, MIPS – Munich Information center for Protein Sequences, UNIHI – Unified Human Interactome, OPHID – Online Predicted Human Interaction Database, EcoCyc – Encyclopaedia of E. Coli Genes and Metabolism, MetaCyc – aMetabolic Pathway database, KEGG – Kyoto Encyclopedia of Genes and Genomes, PANTHER – Protein Analysis Through Evolutionary Relationship database, STKE – Signal Transduction Knowledge Environment, PID – The Pathway Interaction Database, BioPP – Biological Pathway Publisher. A comprehensive list of resources can be found at http://www.pathguide.org. | 0 | Theoretical and Fundamental Chemistry |
Robert Brill is an American archaeologist, best known for his work on the chemical analysis of ancient glass. Born in the US in 1929, Brill attended West Side High School in Newark, New Jersey, before going on to study for his B.S. degree at Upsala College (Brill 1993a, Brill 2006, Getty Conservation Institute 2009). Having completed his Ph.D. in physical chemistry at Rutgers University in 1954, Brill returned to Upsala College to teach chemistry. In 1960, he joined the staff of the Corning Museum of Glass as their second research scientist.
Throughout his career at Corning, where a four-year directorship punctuated his time as a research scientist, Brill was a forerunner in the scientific investigation of glass, glazes and colorants, developing and challenging the usefulness of emerging techniques. His pioneering work with the application of lead and oxygen isotope analysis in archaeology led him occasionally to add the investigation of metal objects to his portfolio so that, together, his published works number more than 160 (Brill and Wampler 1967). Perhaps the most famous of these is his Chemical Analyses of Early Glass, a sum of his 39 years of work and now a seminal reference guide in the field (Brill 1999).
Since 1982, Brill has served on the International Commission on Glass. Within this, he founded TC17, the technical committee for the Archaeometry of Glass, which lists among its aims the ‘promotion of collaboration among glass specialists in widely separated countries’ and the stimulation and encouragement of glass scientists ‘in developing countries’ (Archaeometry of Glass 2005). His internationalism is aptly demonstrated by his study of glasses from around the world, with his attentions most recently being focused on those from the Silk Road. It seems he was attracted by the lack of previous study and the need for further development in the field. Seeing a disparity between contemporary knowledge of glasses from the western world and those from East Asia, Brill was keen to add insight to a hitherto unexploited field and, as such, has gone on to contribute a great deal to Silk Road studies (Brill 1993b). | 0 | Theoretical and Fundamental Chemistry |
Myristoylation is a lipidation modification where a myristoyl group, derived from myristic acid, is covalently attached by an amide bond to the alpha-amino group of an N-terminal glycine residue. Myristic acid is a 14-carbon saturated fatty acid (14:0) with the systematic name of n-tetradecanoic acid. This modification can be added either co-translationally or post-translationally. N-myristoyltransferase (NMT) catalyzes the myristic acid addition reaction in the cytoplasm of cells. This lipidation event is the most common type of fatty acylation and is present in many organisms, including animals, plants, fungi, protozoans and viruses. Myristoylation allows for weak protein–protein and protein–lipid interactions and plays an essential role in membrane targeting, protein–protein interactions and functions widely in a variety of signal transduction pathways. | 1 | Applied and Interdisciplinary Chemistry |
A wide variety of divinylcyclopropanes undergo the titular reaction. These precursors have been generated by a variety of methods, including the addition of cyclopropyl nucleophiles (salts of lithium, or copper) to activated double or triple bonds, elimination of bis(2-haloethyl)cyclopropanes and cyclopropanation.
In the example below, cuprate addition-elimination generates the transient enone 1, which rearranges to spirocycle 2.
Organolithiums can be employed in a similar role, but add in a direct fashion to carbonyls. Products with fused topology result.
Rearrangement after elimination of ditosylates has been observed; the chlorinated cycloheptadiene thus produced isomerizes to conjugated heptadiene 3 during the reaction.
Cyclopropanation with conjugated diazo compounds produces divinylcyclopropanes that then undergo rearrangement. When cyclic starting materials are used, bridged products result.
Substrates containing three-membered heterocyclic rings can also undergo the reaction. cis-Divinylepoxides give oxepines at elevated temperatures (100 °C). trans Isomers undergo an interesting competitive rearrangement to dihydrofurans through the intermediacy of a carbonyl ylide and the same ylide intermediate has been proposed as the direct precursor to the oxepine product 4. Conjugated dienyl epoxides form similar products, lending support to the existence of an ylide intermediate.
Divinyl aziridines undergo a similar suite of reactions providing azepines or vinyl pyrrolines depending on the relative configuration of the aziridine starting material. Divinyl thiiranes can provide thiepines or dihydrothiophenes, although these reactions are slower than those of the corresponding nitrogen- and oxygen-containing compounds. | 0 | Theoretical and Fundamental Chemistry |
The use of highly reactive metals in chemical synthesis was popularized in the 1960s. One development in this theme is the use of metal vapor synthesis, as described by Skell, Timms, Ozin, and others. All of these methods relied on elaborate instrumentation to vaporize the metals, releasing an atomic form of these reactants.
In 1972, Reuben D. Rieke, a professor of chemistry at the University of North Carolina, published the method that now bears his name. In contrast to previous methods, it did not require special equipment, and the main challenges were only the handling of pyrophoric reagents and/or products, and the need for anhydrous reagents and air-free techniques. Thus his discovery gained much attention because of its simplicity and the reactivity of the activated metals.
Rieke continued this work at the University of Nebraska-Lincoln. He and his wife Loretta founded Rieke Metals LLC in 1991, based on these materials. | 0 | Theoretical and Fundamental Chemistry |
The tetratricopeptide repeat domain provides the concave surface necessitated for SIP recognition. RopB-CTD houses 5 stacked TPR motifs, each having sets of paired antiparallel helices that aid in the formation of a concave inner pathway and a convex exterior. The base of the recognition site is constructed by α6 and α8 helices [See Also: alpha helix], while the supporting walls are constructed from helices α2, and α12. The exterior portion of the recognition site is flanked by asparagines N152 and N192 thus providing a ridge of support for the peptide-protein complex. | 1 | Applied and Interdisciplinary Chemistry |
Waste heat is heat that is produced by a machine, or other process that uses energy, as a byproduct of doing work. All such processes give off some waste heat as a fundamental result of the laws of thermodynamics. Waste heat has lower utility (or in thermodynamics lexicon a lower exergy or higher entropy) than the original energy source. Sources of waste heat include all manner of human activities, natural systems, and all organisms, for example, incandescent light bulbs get hot, a refrigerator warms the room air, a building gets hot during peak hours, an internal combustion engine generates high-temperature exhaust gases, and electronic components get warm when in operation.
Instead of being "wasted" by release into the ambient environment, sometimes waste heat (or cold) can be used by another process (such as using hot engine coolant to heat a vehicle), or a portion of heat that would otherwise be wasted can be reused in the same process if make-up heat is added to the system (as with heat recovery ventilation in a building).
Thermal energy storage, which includes technologies both for short- and long-term retention of heat or cold, can create or improve the utility of waste heat (or cold). One example is waste heat from air conditioning machinery stored in a buffer tank to aid in night time heating. Another is seasonal thermal energy storage (STES) at a foundry in Sweden. The heat is stored in the bedrock surrounding a cluster of heat exchanger equipped boreholes, and is used for space heating in an adjacent factory as needed, even months later. An example of using STES to use natural waste heat is the Drake Landing Solar Community in Alberta, Canada, which, by using a cluster of boreholes in bedrock for interseasonal heat storage, obtains 97 percent of its year-round heat from solar thermal collectors on the garage roofs. Another STES application is storing winter cold underground, for summer air conditioning.
On a biological scale, all organisms reject waste heat as part of their metabolic processes, and will die if the ambient temperature is too high to allow this.
Anthropogenic waste heat can contribute to the urban heat island effect. The biggest point sources of waste heat originate from machines (such as electrical generators or industrial processes, such as steel or glass production) and heat loss through building envelopes. The burning of transport fuels is a major contribution to waste heat. | 0 | Theoretical and Fundamental Chemistry |
Molecular gyroscopes are chemical compounds or supramolecular complexes containing a rotor that moves freely relative to a stator, and therefore act as gyroscopes. Though any single bond or triple bond permits a chemical group to freely rotate, the compounds described as gyroscopes may protect the rotor from interactions, such as in a crystal structure with low packing density or by physically surrounding the rotor avoiding steric contact. A qualitative distinction can be made based on whether the activation energy needed to overcome rotational barriers is higher than the available thermal energy. If the activation energy required is higher than the available thermal energy, the rotor undergoes "site exchange", jumping in discrete steps between local energy minima on the potential energy surface. If there is thermal energy sufficiently higher than that needed to overcome the barrier to rotation, the molecular rotor can behave more like a macroscopic freely rotating inertial mass.
For example, several studies in 2002 with a p-phenylene rotor found that some structures using variable-temperature (VT) solid-state C CPMAS and quadrupolar echo H NMR were able to detect a two-site exchange rate of 1.6 MHz (over 10/second at 65 °C), described as "remarkably fast for a phenylene group in a crystalline solid", with steric barriers of 12–14 kcal/mol. However, tert-butyl modification of the rotor increased the exchange rate to over 10 per second at room temperature, and the rate for inertially rotating p-phenylene without barriers is estimated to be approximately 2.4 x 10 revolutions per second. | 0 | Theoretical and Fundamental Chemistry |
Acetoacetic ester synthesis is a chemical reaction where ethyl acetoacetate is alkylated at the α-carbon to both carbonyl groups and then converted into a ketone, or more specifically an α-substituted acetone. This is very similar to malonic ester synthesis. | 0 | Theoretical and Fundamental Chemistry |
Beryllium can coordinate with an N-hetereocyclic carbene (NHC). NHCs are defined as heterocyclic species containing a carbene carbon and at least one nitrogen atom within the ring structure. NHCs have found numerous applications in some of the most important catalytic transformations in chemical industry, but their reactivity in coordinating with main group elements especially with beryllium’s potential as a reactive organocatalyst has opened new areas of research. | 0 | Theoretical and Fundamental Chemistry |
Bachrach is an organic chemist specialising in computational organic chemistry and began his career at Northern Illinois University, where he earned a Professorship. He spent 17 years at Trinity University, holding positions including the Dr. D. R. Semmes Distinguished Professor of Chemistry, Chair of the Department of Chemistry, and Assistant Vice-President for Special Projects. He took up the position of Dean of Science in 2016 at Monmouth University. | 0 | Theoretical and Fundamental Chemistry |
The self-ionization of water was first proposed in 1884 by Svante Arrhenius as part of the theory of ionic dissociation which he proposed to explain the conductivity of electrolytes including water. Arrhenius wrote the self-ionization as . At that time, nothing was yet known of atomic structure or subatomic particles, so he had no reason to consider the formation of an ion from a hydrogen atom on electrolysis as any less likely than, say, the formation of a ion from a sodium atom.
In 1923 Johannes Nicolaus Brønsted and Martin Lowry proposed that the self-ionization of water actually involves two water molecules: . By this time the electron and the nucleus had been discovered and Rutherford had shown that a nucleus is very much smaller than an atom. This would include a bare ion which would correspond to a proton with zero electrons. Brønsted and Lowry proposed that this ion does not exist free in solution, but always attaches itself to a water (or other solvent) molecule to form the hydronium ion (or other protonated solvent).
Later spectroscopic evidence has shown that many protons are actually hydrated by more than one water molecule. The most descriptive notation for the hydrated ion is , where aq (for aqueous) indicates an indefinite or variable number of water molecules. However the notations and are still also used extensively because of their historical importance. This article mostly represents the hydrated proton as , corresponding to hydration by a single water molecule. | 0 | Theoretical and Fundamental Chemistry |
The treatment of industrial wastewater may involve specialized trickling filters which use plastic media and high flow rates. Wastewaters from a variety of industrial processes have been treated in trickling filters. Such industrial wastewater trickling filters consist of two types:
* Large tanks or concrete enclosures filled with plastic packing or other media.
* Vertical towers filled with plastic packing or other media.
The availability of inexpensive plastic tower packings has led to their use as trickling filter beds in tall towers, some as high as 20 meters. As early as the 1960s, such towers were in use at: the Great Northern Oil's Pine Bend Refinery in Minnesota; the Cities Service Oil Company Trafalgar Refinery in Oakville, Ontario and at a kraft paper mill.
The treated water effluent from industrial wastewater trickling filters is typically processed in a clarifier to remove the sludge that sloughs off the microbial slime layer attached to the trickling filter media as for other trickling filter applications.
Some of the latest trickle filter technology involves aerated biofilters of plastic media in vessels using blowers to inject air at the bottom of the vessels, with either downflow or upflow of the wastewater. | 1 | Applied and Interdisciplinary Chemistry |
A symmetric linear molecule ABA can perform:
* Antisymmetric longitudinal vibrations with frequency
* Symmetric longitudinal vibrations with frequency
* Symmetric transversal vibrations with frequency
In the previous formulas, M is the total mass of the molecule, m and m are the masses of the elements A and B, k and k are the spring constants of the molecule along its axis and perpendicular to it. | 0 | Theoretical and Fundamental Chemistry |
In organic chemistry, a hemiacetal or a hemiketal has the general formula , where is hydrogen or an organic substituent. They generally result from the addition of an alcohol (a compound with at least one group) to an aldehyde () or a ketone (), although the latter are sometimes called hemiketals. Most sugars are hemiacetals. | 0 | Theoretical and Fundamental Chemistry |
If there is an electropositive substituent (e.g. –SiR, –SnR, –HgR, etc.) at the β-position of carbocation, the positive charge could be stabilized which is also due largely to the stereoelectronic effect (illustrated below using –SiR3 as an example). The orientation of the two interacting orbitals can have a significant effect on the stabilization effect (σ(C–Si) → empty p orbital), where antiperiplanar (180°) > perpendicular (90°) > syn (0°). | 0 | Theoretical and Fundamental Chemistry |
Many methods of transfection and transformation – two ways of expressing a foreign or modified gene in an organism – are effective in only a small percentage of a population subjected to the techniques. Thus, a method for identifying those few successful gene uptake events is necessary. Reporter genes used in this way are normally expressed under their own promoter (DNA regions that initiates gene transcription) independent from that of the introduced gene of interest; the reporter gene can be expressed constitutively (that is, it is "always on") or inducibly with an external intervention such as the introduction of Isopropyl β-D-1-thiogalactopyranoside (IPTG) in the β-galactosidase system. As a result, the reporter genes expression is independent of the gene of interests expression, which is an advantage when the gene of interest is only expressed under certain specific conditions or in tissues that are difficult to access.
In the case of selectable-marker reporters such as CAT, the transfected population of bacteria can be grown on a substrate that contains chloramphenicol. Only those cells that have successfully taken up the construct containing the CAT gene will survive and multiply under these conditions. | 1 | Applied and Interdisciplinary Chemistry |
Praseodymium(IV) fluoride (also praseodymium tetrafluoride) is a binary inorganic compound, a highly oxidised metal salt of praseodymium and fluoride with the chemical formula PrF. | 0 | Theoretical and Fundamental Chemistry |
Many approaches can potentially quantify radiation absorption, with key examples following.
* The absorption coefficient along with some closely related derived quantities
* The attenuation coefficient (NB used infrequently with meaning synonymous with "absorption coefficient")
* The Molar attenuation coefficient (also called "molar absorptivity"), which is the absorption coefficient divided by molarity (see also Beer–Lambert law)
* The mass attenuation coefficient (also called "mass extinction coefficient"), which is the absorption coefficient divided by density
* The absorption cross section and scattering cross-section, related closely to the absorption and attenuation coefficients, respectively
* "Extinction" in astronomy, which is equivalent to the attenuation coefficient
* Other measures of radiation absorption, including penetration depth and skin effect, propagation constant, attenuation constant, phase constant, and complex wavenumber, complex refractive index and extinction coefficient, complex dielectric constant, electrical resistivity and conductivity.
* Related measures, including absorbance (also called "optical density") and optical depth (also called "optical thickness")
All these quantities measure, at least to some extent, how well a medium absorbs radiation. Which among them practitioners use varies by field and technique, often due simply to the convention. | 0 | Theoretical and Fundamental Chemistry |
* Glucose (), ribose (), Acetic acid (), and formaldehyde () all have different molecular formulas but the same empirical formula: . This is the actual molecular formula for formaldehyde, but acetic acid has double the number of atoms, ribose has five times the number of atoms, and glucose has six times the number of atoms. | 0 | Theoretical and Fundamental Chemistry |
Chlorprothixene was the first of the thioxanthene antipsychotics to be synthesized. It was introduced in 1959 by Lundbeck.
Lometraline, tametraline, and sertraline were reportedly derived via structural modification of chlorprothixene. | 0 | Theoretical and Fundamental Chemistry |
Fast spin echo (RARE, FAISE or FSE), also called turbo spin echo (TSE) is an MRI sequence that results in fast scan times. In this sequence, several 180 refocusing radio-frequency pulses are delivered during each echo time (TR) interval, and the phase-encoding gradient is briefly switched on between echoes.
The FSE/TSE pulse sequence superficially resembles a conventional spin-echo (CSE) sequence in that it uses a series of 180º-refocusing pulses after a single 90º-pulse to generate a train of echoes. The FSE/TSE technique, however, changes the phase-encoding gradient for each of these echoes (a conventional multi-echo sequence collects all echoes in a train with the same phase encoding). As a result of changing the phase-encoding gradient between echoes, multiple lines of k-space (i.e., phase-encoding steps) can be acquired within a given repetition time (TR). As multiple phase-encoding lines are acquired during each TR interval, FSE/TSE techniques may significantly reduce imaging time. | 0 | Theoretical and Fundamental Chemistry |
An indicator may be used to obtain quite precise measurements of pH by measuring absorbance quantitatively at two or more wavelengths. The principle can be illustrated by taking the indicator to be a simple acid, HA, which dissociates into H and A.
:HA H + A
The value of the acid dissociation constant, pK, must be known. The molar absorbances, ε and ε at wavelengths λ and λ must also have been determined by previous experiment. Assuming Beers law to be obeyed, the measured absorbances A and A' at the two wavelengths are simply the sum of the absorbances due to each species.
These are two equations in the two concentrations [HA] and [A]. Once solved, the pH is obtained as
If measurements are made at more than two wavelengths, the concentrations [HA] and [A] can be calculated by linear least squares. In fact, a whole spectrum may be used for this purpose. The process is illustrated for the indicator bromocresol green. The observed spectrum (green) is the sum of the spectra of HA (gold) and of A (blue), weighted for the concentration of the two species.
When a single indicator is used, this method is limited to measurements in the pH range pK ± 1, but this range can be extended by using mixtures of two or more indicators. Because indicators have intense absorption spectra, the indicator concentration is relatively low, and the indicator itself is assumed to have a negligible effect on pH. | 0 | Theoretical and Fundamental Chemistry |
Victor Meyer suggested a method for determining the types of alcohol i.e. (primary, secondary or tertiary). In this method the sample alcohol is treated with PI to get the iodoalkane which is again treated with AgNO to get the nitroalkane. The nitroalkane is then treated with nitrous acid which is obtained by NaNO and HCl. The resulting solution is treated with KOH and the colour is observed. The red, blue and no colour indicates the primary, secondary and tertiary alcohol respectively. | 0 | Theoretical and Fundamental Chemistry |
Antitermination is the prokaryotic cell's aid to fix premature termination of RNA synthesis during the transcription of RNA. It occurs when the RNA polymerase ignores the termination signal and continues elongating its transcript until a second signal is reached. Antitermination provides a mechanism whereby one or more genes at the end of an operon can be switched either on or off, depending on the polymerase either recognizing or not recognizing the termination signal.
Antitermination is used by some phages to regulate progression from one stage of gene expression to the next. The lambda gene N, codes for an antitermination protein (pN) that is necessary to allow RNA polymerase to read through the terminators located at the ends of the immediate early genes. Another antitermination protein, pQ, is required later in phage infection. pN and pQ act on RNA polymerase as it passes specific sites. These sites are located at different relative positions in their respective transcription units. | 1 | Applied and Interdisciplinary Chemistry |
This jumping library uses adaptors containing markers for fragment selection in combination with barcodes for multiplexing. The protocol was developed by Talkowski et al. and based on mate-pair library preparation for SOLiD sequencing. The selected DNA fragment size is 3.5 – 4.5 kb. Two adaptors were involved: one containing an EcoP15I recognition site and an AC overhang; the other containing a GT overhang, a biotinylated thymine, and an oligo barcode. The circularized DNA was digested and the fragments with biotynylated adaptors were selected for (see Figure 3). The EcoP15I recognition site and barcode help to distinguish junction fragments from nonjump fragments. These targeted fragments should contain 25 to 27bp of genomic DNA, the EcoP15I recognition site, the overhang, and the barcode. | 1 | Applied and Interdisciplinary Chemistry |
Before the discovery of ribozymes, enzymes—which are defined as catalytic proteins—were the only known biological catalysts. In 1967, Carl Woese, Francis Crick, and Leslie Orgel were the first to suggest that RNA could act as a catalyst. This idea was based upon the discovery that RNA can form complex secondary structures. These ribozymes were found in the intron of an RNA transcript, which removed itself from the transcript, as well as in the RNA component of the RNase P complex, which is involved in the maturation of pre-tRNAs. In 1989, Thomas R. Cech and Sidney Altman shared the Nobel Prize in chemistry for their "discovery of catalytic properties of RNA". The term ribozyme was first introduced by Kelly Kruger et al. in a paper published in Cell in 1982.
It had been a firmly established belief in biology that catalysis was reserved for proteins. However, the idea of RNA catalysis is motivated in part by the old question regarding the origin of life: Which comes first, enzymes that do the work of the cell or nucleic acids that carry the information required to produce the enzymes? The concept of "ribonucleic acids as catalysts" circumvents this problem. RNA, in essence, can be both the chicken and the egg.
In the 1980s, Thomas Cech, at the University of Colorado Boulder, was studying the excision of introns in a ribosomal RNA gene in Tetrahymena thermophila. While trying to purify the enzyme responsible for the splicing reaction, he found that the intron could be spliced out in the absence of any added cell extract. As much as they tried, Cech and his colleagues could not identify any protein associated with the splicing reaction. After much work, Cech proposed that the intron sequence portion of the RNA could break and reform phosphodiester bonds. At about the same time, Sidney Altman, a professor at Yale University, was studying the way tRNA molecules are processed in the cell when he and his colleagues isolated an enzyme called RNase-P, which is responsible for conversion of a precursor tRNA into the active tRNA. Much to their surprise, they found that RNase-P contained RNA in addition to protein and that RNA was an essential component of the active enzyme. This was such a foreign idea that they had difficulty publishing their findings. The following year, Altman demonstrated that RNA can act as a catalyst by showing that the RNase-P RNA subunit could catalyze the cleavage of precursor tRNA into active tRNA in the absence of any protein component.
Since Cechs and Altmans discovery, other investigators have discovered other examples of self-cleaving RNA or catalytic RNA molecules. Many ribozymes have either a hairpin – or hammerhead – shaped active center and a unique secondary structure that allows them to cleave other RNA molecules at specific sequences. It is now possible to make ribozymes that will specifically cleave any RNA molecule. These RNA catalysts may have pharmaceutical applications. For example, a ribozyme has been designed to cleave the RNA of HIV. If such a ribozyme were made by a cell, all incoming virus particles would have their RNA genome cleaved by the ribozyme, which would prevent infection. | 0 | Theoretical and Fundamental Chemistry |
Tetrafluoromethane is the product when any carbon compound, including carbon itself, is burned in an atmosphere of fluorine. With hydrocarbons, hydrogen fluoride is a coproduct. It was first reported in 1926. It can also be prepared by the fluorination of carbon dioxide, carbon monoxide or phosgene with sulfur tetrafluoride. Commercially it is manufactured by the reaction of hydrogen fluoride with dichlorodifluoromethane or chlorotrifluoromethane; it is also produced during the electrolysis of metal fluorides MF, MF using a carbon electrode.
Although it can be made from a myriad of precursors and fluorine, elemental fluorine is expensive and difficult to handle. Consequently, is prepared on an industrial scale using hydrogen fluoride:
:CClF + 2 HF → CF + 2 HCl | 1 | Applied and Interdisciplinary Chemistry |
Transporting chemicals out of a cell against a gradient is often associated with ATP hydrolysis. Transport is mediated by ATP binding cassette transporters. The human genome encodes 48 ABC transporters, that are used for exporting drugs, lipids, and other compounds. | 1 | Applied and Interdisciplinary Chemistry |
Recognition of stop codons in bacteria have been associated with the so-called tripeptide anticodon, a highly conserved amino acid motif in RF1 (PxT) and RF2 (SPF). Even though this is supported by structural studies, it was shown that the tripeptide anticodon hypothesis is an oversimplification. | 1 | Applied and Interdisciplinary Chemistry |
Non-metallic inclusions, the presence of which defines purity of steel, are classified by chemical and mineralogical content, by stability and by origin. By chemical content non-metallic inclusions are divided into the following groups:
#sulfides (simple — FeS, MnS, AlS, CaS, MgS, ZrS and others; compound — FeS·FeO, MnS·MnO and others);
#nitrides (simple — ZrN, TiN, AlN, CeN and others; compound — Nb(C, N), V(c, N) and others), which can be found in alloyed steel and has strong nitride-generative elements in its content: titanium, aluminium, vanadium, cerium and others;
#silicates
#oxides (simple — FeO, MnO, CrO, SiO, AlO, TiO and others; compound — FeO·FeO, FeO·AlO, FeO·CrO, MgO·AlO, 2FeO·SiO and others;
The majority of inclusions in metals are oxides and sulfides since the content of phosphorus is very small.
Silicates are very detrimental to steels, especially if it has to undergo heat treatment at a later stage.
Usually nitrides are present in special steels that contain an element with a high affinity to nitrogen.
By mineralogical content, oxygen inclusions divide into the following main groups:
* Free oxides — FeO, MnO, CrO, SiO (quartz), AlO (corundum) and others
* Spinels — compound oxides formed by bi and trivalent elements
Ferrites, chromites and aluminates are in this group.
*silicates, which are present in steel like a glass or SiO with admixture of iron, manganese, chromium, aluminium and tungsten oxides and also crystalline silicates. Silicates are the biggest group among non-metallic inclusions. In liquid steel non-metallic inclusions are in solid or liquid condition. It depends on the melting temperature.
By stability, non-metallic inclusions are either stable or unstable. Unstable inclusions are those that dissolve in dilute acids (less than 10%concentration). Unstable inclusions are iron and manganese sulfides and also some free oxides.
Present-day levels of steel production allow to move off from the metal different inclusions. However, in general the content of inclusions in different steels varies within wide limits and has a big influence on the metal properties. | 1 | Applied and Interdisciplinary Chemistry |
The parent phosphonium is as found in the iodide salt, phosphonium iodide. Salts of the parent are rarely encountered, but this ion is an intermediate in the preparation of the industrially useful tetrakis(hydroxymethyl)phosphonium chloride:
:PH + HCl + 4 CHO →
Many organophosphonium salts are produced by protonation of primary, secondary, and tertiary phosphines:
:PR + H →
The basicity of phosphines follows the usual trends, with R = alkyl being more basic than R = aryl. | 0 | Theoretical and Fundamental Chemistry |
Expressed in metric units, the "specific speed" is n = 0.2626 n /h
* where n is the wheel speed in rpm
* P is the power in kilowatts
* h is the water head in meters
The factor 0.2626 is only required when the specific speed is to be adjusted to English units. In countries which use the metric system, the factor is omitted, and quoted specific speeds are correspondingly larger. | 1 | Applied and Interdisciplinary Chemistry |
Much of the SIMIBI class of GTPases is activated by dimerization. Named after the signal recognition particle (SRP), MinD, and BioD, the class is involved in protein localization, chromosome partitioning, and membrane transport. Several members of this class, including MinD and Get3, has shifted in substrate specificity to become ATPases. | 1 | Applied and Interdisciplinary Chemistry |
Schymanski's first research publications were from her undergraduate work when she worked on developing new metal-containing polymers which resulted in three lead author publications.
As a graduate student, Schymanski started using information on the fragmentation pattern of organic compounds as a means to expand the identification of unknown compounds. Schymanski applied these novel methods to the identification of unknown organic compounds found in wastewater, and used data collectively gathered by the NORMAN Association to define barriers to the identification of unknown organic compounds in water. Identifying and tracking unknown organic compounds continues to be an avenue of research pursued by Schymanski and she is a co-author on a 2014 textbook describing these methods.
In 2012, Schymanski and Steffen Neumann started the Critical Assessment of Small Molecule Identification (CASMI) contest that provided researchers with information about unknown organic compounds and challenged them to use automated computational tools identify the unknown compounds. The Metabolomics Society highlighted the 2012 contest in their newsletter. There have been multiple iterations of the contest, and Schymanski examined the results of the 2016 contest.
Schymanski's research focuses on characterizing organic compounds found in wastewater and exposomics, or the science of compounds that people are exposed to over their lifetimes. Schymanski has developed a subset of PubChem for exposomics, PubChemLite, which can be annotated to increase ability of researchers to identify unknown environmental compounds. Within this field, Schymanski is working to automate the identification of a group of fluorinated compounds called ‘per- and poly-fluoroalkyl substances’ (PFASs) in order to increase the ability of researchers to find unknown PFAS in the environment.
Schymanski is an advocate for open science and data sharing. Within the NORMAN network, a collaborative activity across Europe, North America, and Asia, Schymanski worked in 2011 with the team that established NORMAN MassBank, which was a community-driven project to gather information about small molecules. In 2015, Schymanski expanded this type of data with the NORMAN Suspect List Exchange. Schymanski has also worked to develop computational tools that allow the processing of complex high resolution mass spectrometry data and sought to establish standards to consider the quality of the mass spectrometry data. Schymanskis 2014 publication in Environmental Science & Technology' establishes a means to estimate confidence in the quality of unknown organic compound identifications and, as of 2021, has over 1000 citations. In 2018, Schymanski considered this paper her greatest achievement because it established the standard for compound identification in metabolomics and encouraged community conversation about future of these tools. | 0 | Theoretical and Fundamental Chemistry |
The halides of low-valent early metals often are clusters with extensive M-M bonding. The situation contrasts with the higher halides of these metals and virtually all halides of the late transition metals, where metal-halide bonding is replete.
Transition metal halide clusters are prevalent for the heavier metals: Zr, Hf, Nb, Ta, Mo, W, and Re. For the earliest metals Zr and Hf, interstitial carbide ligands are also common. One example is ZrCCl. One structure type features six terminal halides and 12 edge-bridging halides. This motif is exemplified by tungsten(III) chloride, [TaCl], Another common structure has six terminal halides and 8 bridging halides, e.g. MoCl.
Many of the early metal clusters can only be prepared when they incorporate interstitial atoms.
In terms of history, Linus Pauling showed that "MoCl" consisted of Mo octahedra. F. Albert Cotton established that "ReCl" in fact features subunits of the cluster ReCl, which could be converted to a host of adducts without breaking the Re-Re bonds. Because this compound is diamagnetic and not paramagnetic the rhenium bonds are double bonds and not single bonds. In the solid state further bridging occurs between neighbours and when this compound is dissolved in hydrochloric acid a ReCl complex forms. An example of a tetranuclear complex is hexadecamethoxytetratungsten W(OCH) with tungsten single bonds. A related group of clusters with the general formula MMoX such as PbMoS. These sulfido clusters are called Chevrel phases. | 0 | Theoretical and Fundamental Chemistry |
One of the most commonly used self-cleaning products, titanium dioxide, utilizes a unique self-cleaning mechanism that combines an initial photocatalytic step and subsequent superhydrophilicity. A titanium dioxide coating, typically on glass windows, when exposed to UV light, will generate free electrons that will interact with oxygen and water in the air to create free radicals. These free radicals will in turn breakdown any fouling organic matter deposited on the surface of the glass. Titanium dioxide also changes the normally hydrophobic glass to a superhydrophilic surface. Thus, when rainfall occurs, instead of water beading up on the window surface and instantly falling down the glass, rain drops will rapidly spread out on the hydrophilic surface. The water will then move down the surface of the window, as a film rather than a droplet, essentially acting like a squeegee to remove surface debris. | 0 | Theoretical and Fundamental Chemistry |
In the spring of 1774, Lavoisier carried out experiments on the calcination of tin and lead in sealed vessels, the results of which conclusively confirmed that the increase in weight of metals in combustion was due to combination with air. But the question remained about whether it was in combination with common atmospheric air or with only a part of atmospheric air. In October the English chemist Joseph Priestley visited Paris, where he met Lavoisier and told him of the air which he had produced by heating the red calx of mercury with a burning glass and which had supported combustion with extreme vigor. Priestley at this time was unsure of the nature of this gas, but he felt that it was an especially pure form of common air. Lavoisier carried out his own research on this peculiar substance. The result was his memoir On the Nature of the Principle Which Combines with Metals during Their Calcination and Increases Their Weight, read to the Academy on 26 April 1775 (commonly referred to as the Easter Memoir). In the original memoir, Lavoisier showed that the mercury calx was a true metallic calx in that it could be reduced with charcoal, giving off Black's fixed air in the process. When reduced without charcoal, it gave off an air which supported respiration and combustion in an enhanced way. He concluded that this was just a pure form of common air and that it was the air itself "undivided, without alteration, without decomposition" which combined with metals on calcination.
After returning from Paris, Priestley took up once again his investigation of the air from mercury calx. His results now showed that this air was not just an especially pure form of common air but was "five or six times better than common air, for the purpose of respiration, inflammation, and ... every other use of common air". He called the air dephlogisticated air, as he thought it was common air deprived of its phlogiston. Since it was therefore in a state to absorb a much greater quantity of phlogiston given off by burning bodies and respiring animals, the greatly enhanced combustion of substances and the greater ease of breathing in this air were explained. | 1 | Applied and Interdisciplinary Chemistry |
In a one-dimensional system at a given mode the vibration will have nodes, or places where the displacement is always zero. These nodes correspond to points in the mode shape where the mode shape is zero. Since the vibration of a system is given by the mode shape multiplied by a time function, the displacement of the node points remain zero at all times.
When expanded to a two dimensional system, these nodes become lines where the displacement is always zero. If you watch the animation above you will see two circles (one about halfway between the edge and center, and the other on the edge itself) and a straight line bisecting the disk, where the displacement is close to zero. In an idealized system these lines equal zero exactly, as shown to the right. | 0 | Theoretical and Fundamental Chemistry |
The Soviet Alfa-class submarines used LBE as a coolant for their nuclear reactors throughout the Cold War.
OKB Gidropress (the Russian developers of the VVER-type Light-water reactors) has expertise in LBE reactors. The SVBR-75/100, a modern design of this type, is one example of the extensive Russian experience with this technology.
Gen4 Energy (formerly Hyperion Power Generation), a United States firm connected with Los Alamos National Laboratory, announced plans in 2008 to design and deploy a uranium nitride fueled small modular reactor cooled by lead-bismuth eutectic for commercial power generation, district heating, and desalinization. The proposed reactor, called the Gen4 Module, is planned as a 70 MW reactor of the sealed modular type, factory assembled and transported to site for installation, and transported back to factory for refueling. | 1 | Applied and Interdisciplinary Chemistry |
A common form of crevice failure occurs due to stress corrosion cracking, where a crack or cracks develop from the base of the crevice where the stress concentration is greatest. This was the root cause of the fall of the Silver Bridge over the Ohio River, in 1967 in West Virginia, where a single critical crack only about 3 mm long suddenly grew and fractured a tie bar joint. The rest of the bridge fell in less than a minute. The disaster was caused by one single point of failure (SPOF).
The eyebars in the Silver Bridge were not redundant, as links were composed of only two bars each, of high strength steel (more than twice as strong as common mild steel), rather than a thick stack of thinner bars of modest material strength "combed" together as is usual for redundancy. With only two bars, the failure of one could impose excessive loading on the second, causing total failure—unlikely if more bars are used. While a low-redundancy chain can be engineered to the design requirements, the safety is completely dependent upon correct, high quality manufacturing and assembly. | 1 | Applied and Interdisciplinary Chemistry |
Flexibility
Your DNA sequence of interest can be moved across any expression system in just one recombination step when you create the entry clone with it.
Speed
Instead of taking two or more days with conventional restriction and ligation cloning, the Gateway approach allows for the creation of the expression construct in just one day. The attB-PCR products can also be immediately cloned into the target vectors by performing the BP and LR reactions in the same tube. There are no procedures for restriction, ligation, or gel purification during the cloning process.
Multiple fragment cloning
Gateway cloning can be used to simultaneously insert several DNA pieces into numerous vectors in a single tube. To create the necessary expression clone, up to four DNA segments can be cloned into a single Gateway vector in a precise order and orientation in a single tube. The design of the Gateway vectors makes this possible.
High efficiency
The Gateway Cloning Method uses positive and negative selection markers to increase the chance of successfully cloning a gene. This means that the process is more efficient, meaning it is more likely to produce successful results.
Universality
All types of DNA fragments can be cloned using PCR techniques. Cloning is available for many different kinds of organisms, from mammals to bacteria. | 1 | Applied and Interdisciplinary Chemistry |
Gamma rays provide information about some of the most energetic phenomena in the universe; however, they are largely absorbed by the Earth's atmosphere. Instruments aboard high-altitude balloons and satellites missions, such as the Fermi Gamma-ray Space Telescope, provide our only view of the universe in gamma rays.
Gamma-induced molecular changes can also be used to alter the properties of semi-precious stones, and is often used to change white topaz into blue topaz.
Non-contact industrial sensors commonly use sources of gamma radiation in refining, mining, chemicals, food, soaps and detergents, and pulp and paper industries, for the measurement of levels, density, and thicknesses. Gamma-ray sensors are also used for measuring the fluid levels in water and oil industries. Typically, these use Co-60 or Cs-137 isotopes as the radiation source.
In the US, gamma ray detectors are beginning to be used as part of the Container Security Initiative (CSI). These machines are advertised to be able to scan 30 containers per hour.
Gamma radiation is often used to kill living organisms, in a process called irradiation. Applications of this include the sterilization of medical equipment (as an alternative to autoclaves or chemical means), the removal of decay-causing bacteria from many foods and the prevention of the sprouting of fruit and vegetables to maintain freshness and flavor.
Despite their cancer-causing properties, gamma rays are also used to treat some types of cancer, since the rays also kill cancer cells. In the procedure called gamma-knife surgery, multiple concentrated beams of gamma rays are directed to the growth in order to kill the cancerous cells. The beams are aimed from different angles to concentrate the radiation on the growth while minimizing damage to surrounding tissues.
Gamma rays are also used for diagnostic purposes in nuclear medicine in imaging techniques. A number of different gamma-emitting radioisotopes are used. For example, in a PET scan a radiolabeled sugar called fluorodeoxyglucose emits positrons that are annihilated by electrons, producing pairs of gamma rays that highlight cancer as the cancer often has a higher metabolic rate than the surrounding tissues. The most common gamma emitter used in medical applications is the nuclear isomer technetium-99m which emits gamma rays in the same energy range as diagnostic X-rays. When this radionuclide tracer is administered to a patient, a gamma camera can be used to form an image of the radioisotope's distribution by detecting the gamma radiation emitted (see also SPECT). Depending on which molecule has been labeled with the tracer, such techniques can be employed to diagnose a wide range of conditions (for example, the spread of cancer to the bones via bone scan). | 0 | Theoretical and Fundamental Chemistry |
Soap is known to have been used as a surfactant for washing clothes since the Sumerian time in 2,500 B.C. In ancient Egypt, soda was used as a wash additive. In the 19th century, synthetic surfactants began to be created, for example from olive oil. Sodium silicate (water glass) was used in soap-making in the United States in the 1860s, and in 1876, Henkel sold a sodium silicate-based product that can be used with soap and marketed as a "universal detergent" (Universalwaschmittel) in Germany. Soda was then mixed with sodium silicate to produce Germanys first brand name detergent Bleichsoda. In 1907, Henkel also added a bleaching agent sodium perborate to launch the first self-acting' laundry detergent Persil to eliminate the laborious rubbing of laundry by hand.
During the First World War, there was a shortage of oils and fats needed to make soap. In order find alternatives for soap, synthetic detergents were made in Germany by chemists using raw material derived from coal tar. These early products, however, did not provide sufficient detergency. In 1928, effective detergent was made through the sulfation of fatty alcohol, but large-scale production was not feasible until low-cost fatty alcohols become available in the early 1930s. The synthetic detergent created was more effective and less likely to form scum than soap in hard water, and can also eliminate acid and alkaline reactions and decompose dirt. Commercial detergent products with fatty alcohol sulphates began to be sold, initially in 1932 in Germany by Henkel. In the United States, detergents were sold in 1933 by Procter & Gamble (Dreft) primarily in areas with hard water. However, sales in the US grew slowly until the introduction of built detergents with the addition of effective phosphate builder developed in the early 1940s. The builder improves the performance of the surfactants by softening the water through the chelation of calcium and magnesium ions, helping to maintain an alkaline pH, as well as dispersing and keeping the soiling particles in solution. The development of the petrochemical industry after the Second World War also yielded material for the production of a range of synthetic surfactants, and alkylbenzene sulfonates became the most important detergent surfactants used. By the 1950s, laundry detergents had become widespread, and largely replaced soap for cleaning clothes in developed countries.
Over the years, many types of detergents have been developed for a variety of purposes, for example, low-sudsing detergents for use in front-loading washing machines, heavy-duty detergents effective in removing grease and dirt, all-purpose detergents and specialty detergents. They become incorporated in various products outside of laundry use, for example in dishwasher detergents, shampoo, toothpaste, industrial cleaners, and in lubricants and fuels to reduce or prevent the formation of sludge or deposits. The formulation of detergent products may include bleach, fragrances, dyes and other additives. The use of phosphates in detergent, however, led to concerns over nutrient pollution and demand for changes to the formulation of the detergents. Concerns were also raised over the use of surfactants such as branched alkylbenzene sulfonate (tetrapropylenebenzene sulfonate) that lingers in the environment, which led to their replacement by surfactants that are more biodegradable, such as linear alkylbenzene sulfonate. Developments over the years have included the use of enzymes, substitutes for phosphates such as zeolite A and NTA, TAED as bleach activator, sugar-based surfactants which are biodegradable and milder to skin, and other green friendly products, as well as changes to the form of delivery such as tablets, gels and pods. | 0 | Theoretical and Fundamental Chemistry |
Photocatalytic water splitting separates water into hydrogen and oxygen:
The most prevalently investigated material, , is inefficient. Mixtures of and nickel oxide (NiO) are more active. NiO allows a significant explоitation of the visible spectrum. One efficient photocatalyst in the UV range is based on sodium tantalite (NaTaO) doped with lanthanum and loaded with a nickel oxide cocatalyst. The surface is grooved with nanosteps from doping with lanthanum (3–15 nm range, see nanotechnology). The NiO particles are present on the edges, with the oxygen evolving from the grooves. | 0 | Theoretical and Fundamental Chemistry |
In the early 1990s, Hammarby Sjöstad had a reputation for being a run-down, polluted and unsafe industrial and residential area. Now, it is a new district in Stockholm where the City has imposed tough environmental requirements on buildings, technical installations and the traffic environment.
An ‘eco-cycle’ solution named the Hammarby Model, developed by Fortum, Stockholm Water Company and the Stockholm Waste Management Administration, is an integral energy, waste and water system for both housing and offices. The goal is to create a residential environment based on sustainable resource usage. Examples include waste heat from the treated wastewater being used for heating up the water in the district heating system, rainwater runoff is returned to the natural cycle through infiltration in green roofs and treatment pools, sludge from the local wastewater treatment is recycled as fertiliser for farming and forestry.
This sustainable model has been a source of inspiration to many urban development projects including the Toronto (Canada) Waterfront, London's New Wembley, and a number of cities/city areas in China. | 1 | Applied and Interdisciplinary Chemistry |
During the process of DNA replication, errors occasionally occur in the polymerization of the second strand. These errors, mutations, can affect an organism's phenotype, especially if they occur within the protein coding sequence of a gene. Error rates are typically 1 error in every 10–100 million bases—due to the "proofreading" ability of DNA polymerases.
Missense mutations and nonsense mutations are examples of point mutations that can cause genetic diseases such as sickle-cell disease and thalassemia respectively. Clinically important missense mutations generally change the properties of the coded amino acid residue among basic, acidic, polar or non-polar states, whereas nonsense mutations result in a stop codon.
Mutations that disrupt the reading frame sequence by indels (insertions or deletions) of a non-multiple of 3 nucleotide bases are known as frameshift mutations. These mutations usually result in a completely different translation from the original, and likely cause a stop codon to be read, which truncates the protein. These mutations may impair the proteins function and are thus rare in in vivo' protein-coding sequences. One reason inheritance of frameshift mutations is rare is that, if the protein being translated is essential for growth under the selective pressures the organism faces, absence of a functional protein may cause death before the organism becomes viable. Frameshift mutations may result in severe genetic diseases such as Tay–Sachs disease.
Although most mutations that change protein sequences are harmful or neutral, some mutations have benefits. These mutations may enable the mutant organism to withstand particular environmental stresses better than wild type organisms, or reproduce more quickly. In these cases a mutation will tend to become more common in a population through natural selection. Viruses that use RNA as their genetic material have rapid mutation rates, which can be an advantage, since these viruses thereby evolve rapidly, and thus evade the immune system defensive responses. In large populations of asexually reproducing organisms, for example, E. coli, multiple beneficial mutations may co-occur. This phenomenon is called clonal interference and causes competition among the mutations. | 1 | Applied and Interdisciplinary Chemistry |
Technetium-99m's short half-life of 6 hours makes long-term storage impossible. Transport of Tc from the limited number of production sites to radiopharmacies (for manufacture of specific radiopharmaceuticals) and other end users would be complicated by the need to significantly overproduce to have sufficient remaining activity after long journeys. Instead, the longer-lived parent nuclide Mo can be supplied to radiophamacies in a generator, after its extraction from the neutron-irradiated uranium targets and its purification in dedicated processing facilities. Radiopharmacies may be hospital-based or stand-alone facilities, and in many cases will subsequently distribute Tc radiopharmaceuticals to regional nuclear medicine departments. Development in direct production of Tc, without first producing the parent Mo, precludes the use of generators; however, this is uncommon and relies on suitable production facilities close to radiopharmacies. | 0 | Theoretical and Fundamental Chemistry |
Under normal conditions, ATP and ADP cannot cross the inner mitochondrial membrane due to their high negative charges, but ADP/ATP translocase, an antiporter, couples the transport of the two molecules. The depression in ADP/ATP translocase alternatively faces the matrix and the cytoplasmic sides of the membrane. ADP in the intermembrane space, coming from the cytoplasm, binds the translocase and induces its eversion, resulting in the release of ADP into the matrix. Binding of ATP from the matrix induces eversion and results in the release of ATP into the intermembrane space, subsequently diffusing to the cytoplasm, and concomitantly brings the translocase back to its original conformation. ATP and ADP are the only natural nucleotides recognized by the translocase.
The net process is denoted by:
:ADP + ATP → ADP + ATP
ADP/ATP exchange is energetically expensive: about 25% of the energy yielded from electron transfer by aerobic respiration, or one hydrogen ion, is consumed to regenerate the membrane potential that is tapped by ADP/ATP translocase.
The translocator cycles between two states, called the cytoplasmic and matrix state, opening up to these compartments in an alternating way. There are structures available that show the translocator locked in a cytoplasmic state by the inhibitor carboxyatractyloside, or in the matrix state by the inhibitor bongkrekic acid. | 1 | Applied and Interdisciplinary Chemistry |
Finely ground agricultural lime is often applied to acid soils to increase soil pH (liming). The amount of limestone or chalk needed to change pH is determined by the mesh size of the lime (how finely it is ground) and the buffering capacity of the soil. A high mesh size (60 mesh = 0.25 mm; 100 mesh = 0.149 mm) indicates a finely ground lime that will react quickly with soil acidity. The buffering capacity of a soil depends on the clay content of the soil, the type of clay, and the amount of organic matter present, and may be related to the soil cation exchange capacity. Soils with high clay content will have a higher buffering capacity than soils with little clay, and soils with high organic matter will have a higher buffering capacity than those with low organic matter. Soils with higher buffering capacity require a greater amount of lime to achieve an equivalent change in pH. The buffering of soil pH is often directly related to the quantity of aluminium in soil solution and taking up exchange sites as part of the cation exchange capacity. This aluminium can be measured in a soil test in which it is extracted from the soil with a salt solution, and then is quantified with a laboratory analysis. Then, using the initial soil pH and the aluminium content, the amount of lime needed to raise the pH to a desired level can be calculated.
Amendments other than agricultural lime that can be used to increase the pH of soil include wood ash, industrial calcium oxide (burnt lime), magnesium oxide, basic slag (calcium silicate), and oyster shells. These products increase the pH of soils through various acid–base reactions. Calcium silicate neutralizes active acidity in the soil by reacting with H ions to form monosilicic acid (HSiO), a neutral solute. | 0 | Theoretical and Fundamental Chemistry |
Antoine-Laurent Lavoisier was born to a wealthy family of the nobility in Paris on 26 August 1743. The son of an attorney at the Parlement of Paris, he inherited a large fortune at the age of five upon the death of his mother. Lavoisier began his schooling at the Collège des Quatre-Nations, University of Paris (also known as the Collège Mazarin) in Paris in 1754 at the age of 11. In his last two years (1760–1761) at the school, his scientific interests were aroused, and he studied chemistry, botany, astronomy, and mathematics. In the philosophy class he came under the tutelage of Abbé Nicolas Louis de Lacaille, a distinguished mathematician and observational astronomer who imbued the young Lavoisier with an interest in meteorological observation, an enthusiasm which never left him. Lavoisier entered the school of law, where he received a bachelor's degree in 1763 and a licentiate in 1764. Lavoisier received a law degree and was admitted to the bar, but never practiced as a lawyer. However, he continued his scientific education in his spare time. | 1 | Applied and Interdisciplinary Chemistry |
The National Fire Protection Association have a special labeling system in the standard for Health Care Facilities, such as hospitals and dentistry offices. This standard puts more emphasis on gases found in Medical gas supply systems, which consist of both oxidizing gases and gases that displace oxygen. | 1 | Applied and Interdisciplinary Chemistry |
Secondary sulfides—those formed by supergene secondary enrichment—are resistant (refractory) to sulfuric leaching. Secondary copper sulfides are dominated by the mineral chalcocite; a mineral formed from primary sulfides, like chalcopyrite, that undergo chemical processes such as oxidation or reduction. Typically, secondary sulfide ores are concentrated using froth flotation. Other extraction processes like leaching are effectively used for the extraction of secondary copper sulfides, but as demand for copper rises, extraction processes tailored for low-grade ores are required, due to the depletion of copper resources. Processes including in situ, dump, and heap leaching are cost-effective methods that are suitable for extracting copper from low-grade ores.
Extraction processes for secondary copper sulfides and low-grade ores includes the process of heap bioleaching. Heap bioleaching presents a cost efficient extraction method that requires a less intensive energy input resulting in a higher profit. This extraction process can be applied to large quantities of low-grade ores, at a lower capital cost with minimal environmental impact.
Generally, direct froth flotation is not used to concentrate copper oxide ores, as a result of the largely ionic and hydrophilic structure of the copper oxide mineral surface. Copper oxide ores are typically treated via chelating-reagent flotation and fatty-acid flotation, which use organic reagents to ensure adsorption onto the mineral surface through the formation of hydrophobic compounds on the mineral surface.
Some supergene sulfide deposits can be leached using a bacterial oxidation heap leach process to oxidize the sulfides to sulfuric acid, which also allows for simultaneous leaching with sulfuric acid to produce a copper sulfate solution. For oxide ores, solvent extraction and electrowinning technologies are used to recover the copper from the pregnant leach solution. To ensure the best recovery of copper, it is important to acknowledge the effect copper dissolution, acid consumption, and gangue mineral composition has on the efficacy of extraction.
Supergene sulfide ores rich in native copper are refractory to treatment with sulfuric acid leaching on all practicable time scales, and the dense metal particles do not react with froth flotation media. Typically, if native copper is a minor part of a supergene profile it will not be recovered and will report to the tailings. When rich enough, native copper ore bodies may be treated to recover the contained copper by gravity separation. Often, the nature of the gangue is important, as clay-rich native copper ores prove difficult to liberate. This is because clay minerals interact with flotation reagents used in extraction processes, that are then consumed, which results in minimal recovery of a high grade copper concentrate. | 1 | Applied and Interdisciplinary Chemistry |
CPT requires specialized chimeric probes, making CPT assays more expensive than PCR. Because CPT probes are so specific, a new probe must be designed for each unique assay, further increasing cost. Clinical implementation is hampered financially, but it is also limited by the possibility of samples containing nonspecific RNases other than RNase H. | 1 | Applied and Interdisciplinary Chemistry |
SCO was first observed in 1931 by Cambi et al. who discovered anomalous magnetic behavior for the tris(N,N-dialkyldithiocarbamatoiron(III) complexes. The spin states of these complexes were sensitive to the nature of the amine substituents. In the 1960s, the first Co SCO complex was reported. Magnetic measurements and Mössbauer spectroscopic studies established the nature of the spin transition in iron(II) SCO complexes. Building on those early studies, there is now interest in applications of SCO in electronic and optical displays. | 0 | Theoretical and Fundamental Chemistry |
Homoaromaticity can better be explained using Perturbation Molecular Orbital Theory (PMO) as described in a 1975 study by Robert C. Haddon. The homotropenylium cation can be considered as a perturbed version of the tropenylium cation due to the addition of a homoconjugate linkage interfering with the resonance of the original cation. | 0 | Theoretical and Fundamental Chemistry |
The modern bulbous bow was developed by Dr. Takao Inui at the University of Tokyo during the 1950s and 1960s, independently of Japanese naval research. Inui based his research on earlier findings by scientists made after Taylor discovered that ships fitted with a bulbous forefoot exhibited substantially lower drag characteristics than predicted. The bulbous bow concept was first definitively studied by Thomas Havelock, Cyril Wigley and Georg Weinblum, including Wigleys 1936 work "The Theory of the Bulbous Bow and its Practical Application" which examined the issues of wave production and damping. Inuis initial scientific papers on the effect of bulbous bow on wave-making resistance were collected into a report published by the University of Michigan in 1960. His work came to widespread attention with his paper "Wavemaking Resistance of Ships" published by the Society of Naval Architects and Marine Engineers in 1962. It was eventually found that drag could be reduced by about five per cent. Experimentation and refinement slowly improved the geometry of bulbous bows, but they were not widely exploited until computer modelling techniques enabled researchers at the University of British Columbia to increase their performance to a practical level in the 1980s. | 1 | Applied and Interdisciplinary Chemistry |
Maternal undernutrition has been linked with low birth weight and also a number of diseases, including Cardiovascular disease, stroke, hypertension and diabetes. When a foetus is in the womb and is not receiving sufficient nutrition, it can adapt to prioritize organ growth and increased metabolic efficiency to prepare itself for life in an energy deficient environment. Postnatally, when given the correct nutrition, babies exhibit ‘catch up growth’, potentially leading to obesity and other related complications. Studies based around restricting animals food intake throughout gestation have discovered that a reduction of just 30% of normal intake can cause low birth weight and increase sensitivity to high-fat-diet induced obesity.
In animal models, intrauterine undernutrition has been shown to be associated with hypertension later in life. This is because the formation of the kidneys is inhibited, which decreases filtration and flow rate through the nephrons, leading to increased blood pressure.
More extreme prenatal conditions such as famine have been shown to have effects on the neurodevelopment of a foetus. After the Dutch Famine of the winter of 1944–1945, it was found that the risk of schizophrenia was significantly higher in those conceived at the height of the famine, as was the prevalence of schizoid personality. | 1 | Applied and Interdisciplinary Chemistry |
Methyl red (2-(N,N-dimethyl-4-aminophenyl) azobenzenecarboxylic acid), also called C.I. Acid Red 2, is an indicator dye that turns red in acidic solutions. It is an azo dye, and is a dark red crystalline powder. Methyl red is a pH indicator; it is red in pH under 4.4, yellow in pH over 6.2, and orange in between, with a pK of 5.1. Murexide and methyl red are investigated as promising enhancers of sonochemical destruction of chlorinated hydrocarbon pollutants. Methyl red is classed by the IARC in group 3 - unclassified as to carcinogenic potential in humans. | 0 | Theoretical and Fundamental Chemistry |
Clues to the existence of a post-mortem transcriptome existed at least since the beginning of the 21st century, but the word thanatotranscriptome (from (thanatos-, Greek for "death") seems to have been first used in the scientific literature by Javan et al. in 2015, following the introduction of the concept of the human thanatomicrobiome in 2014 at the 66th Annual Meeting of the American Academy of Forensic Sciences in Seattle, Washington.
In 2016, researchers at the University of Washington confirmed that up to 2 days (48 hours) after the death of mice and zebrafish, many genes still functioned. Changes in the quantities of mRNA in the bodies of the dead animals proved that hundreds of genes with very different functions awoke just after death. The researchers detected 548 genes that awoke after death in zebrafish and 515 in laboratory mice. Among these were genes involved in development of the organism, including genes that are normally activated only in utero or in ovo (in the egg) during fetal development.
The thanatomicrobiome is characterized by a diverse assortment of microorganisms located in internal organs (brain, heart, liver, and spleen) and blood samples collected after a human dies. It is defined as the microbial community of internal body sites, created by a successional process whereby trillions of microorganisms populate, proliferate, and/or die within the dead body, resulting in temporal modifications in the community composition over time. | 1 | Applied and Interdisciplinary Chemistry |
Atmospheric chemists often define the Henry solubility as
Here is the concentration of a species in the aqueous phase, and is the partial pressure of that species in the gas phase under equilibrium conditions.
The SI unit for is mol/(m·Pa); however, often the unit M/atm is used, since is usually expressed in M (1M = 1 mol/dm) and in atm (1atm = 101325Pa). | 0 | Theoretical and Fundamental Chemistry |
Ethyltoluenes are prepared by alkylation of toluene with ethylene:
These alkylations are catalyzed by various Lewis acids, such as aluminium trichloride.
3- and 4-Ethyltoluenes are mainly of interest as precursors to methylstyrenes:
This dehydrogenation is conducted in the presence of zinc oxide catalysts. | 0 | Theoretical and Fundamental Chemistry |
Lipolysis is the metabolic pathway through which lipid triglycerides are hydrolyzed into a glycerol and free fatty acids. It is used to mobilize stored energy during fasting or exercise, and usually occurs in fat adipocytes. The most important regulatory hormone in lipolysis is insulin; lipolysis can only occur when insulin action falls to low levels, as occurs during fasting. Other hormones that affect lipolysis include leptin, glucagon, epinephrine, norepinephrine, growth hormone, atrial natriuretic peptide, brain natriuretic peptide, and cortisol. | 1 | Applied and Interdisciplinary Chemistry |
Bacterial DNA is packed with the help of polyamines and proteins called nucleoid-associated proteins. Protein-associated DNA occupies about 1/4 of the intracellular volume forming a concentrated viscous phase with liquid crystalline properties, called the nucleoid. Other research also indicated that the genome of bacteria occupies approximately 10-15% of the bacteria's volume. Similar DNA packaging exists also in chloroplasts and mitochondria. Bacterial DNA is sometimes referred to as the bacterial chromosome. Bacterial nucleoid evolutionary represents an intermediate engineering solution between the protein-free DNA packing in viruses and protein-determined packing in eukaryotes.
Sister chromosomes in the bacterium Escherichia coli are induced by stressful conditions to condense and undergo pairing. Stress-induced condensation occurs by a non-random, zipper-like convergence of sister chromosomes. This convergence appears to depend on the ability of identical double-stranded DNA molecules to specifically identify each other, a process that culminates in the proximity of homologous sites along the paired chromosomes. Diverse stress conditions appear to prime bacteria to effectively cope with severe DNA damages such as double-strand breaks. The apposition of homologous sites associated with stress-induced chromosome condensation helps explain how repair of double-strand breaks and other damages occurs. | 1 | Applied and Interdisciplinary Chemistry |
Thermochemical cycles combine solely heat sources (thermo) with chemical reactions to split water into its hydrogen and oxygen components. The term cycle is used because aside of water, hydrogen and oxygen, the chemical compounds used in these processes are continuously recycled.
If work is partially used as an input, the resulting thermochemical cycle is defined as a hybrid one. | 0 | Theoretical and Fundamental Chemistry |
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