Selenenic Acid
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Selenenic Acid
A selenenic acid is an organoselenium compound and an oxoacid with the general formula RSeOH, where R ≠ H. It is the first member of the family of organoselenium oxoacids, which also include seleninic acids and selenonic acids, which are RSeO2H and RSeO3H, respectively. Selenenic acids derived from selenoenzymes are thought to be responsible for the antioxidant activity of these enzymes. This functional group is sometimes called SeO-selenoperoxol. Properties In contrast to selenonic and seleninic acids, selenenic acids are unstable with respect to a self-condensation reaction to form the corresponding selenoseleninates or disproportionation into corresponding seleninic acids and diselenides: :2 RSeOH → RSe(O)SeR + H2O :2 RSeOH → RSeO2H + 1/2 RSeSeR Even the very bulky 2,4,6-tri-''tert''-butylbenzeneselenenic acid disproportionates readily. A stable selenenic acid was synthesized by burying the SeOH functional group within the cavity of a ''p''-''tert''-butyl alix[6r ...
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Selenenic Acid
A selenenic acid is an organoselenium compound and an oxoacid with the general formula RSeOH, where R ≠ H. It is the first member of the family of organoselenium oxoacids, which also include seleninic acids and selenonic acids, which are RSeO2H and RSeO3H, respectively. Selenenic acids derived from selenoenzymes are thought to be responsible for the antioxidant activity of these enzymes. This functional group is sometimes called SeO-selenoperoxol. Properties In contrast to selenonic and seleninic acids, selenenic acids are unstable with respect to a self-condensation reaction to form the corresponding selenoseleninates or disproportionation into corresponding seleninic acids and diselenides: :2 RSeOH → RSe(O)SeR + H2O :2 RSeOH → RSeO2H + 1/2 RSeSeR Even the very bulky 2,4,6-tri-''tert''-butylbenzeneselenenic acid disproportionates readily. A stable selenenic acid was synthesized by burying the SeOH functional group within the cavity of a ''p''-''tert''-butyl alix[6r ...
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Calixarene
A calixarene is a macrocycle or cyclic oligomer based on a methylene-linked phenols. With hydrophobic cavities that can hold smaller molecules or ions, calixarenes belong to the class of cavitands known in host–guest chemistry. Nomenclature Calixarene nomenclature is straightforward and involves counting the number of repeating units in the ring and including it in the name. A calix rene has 4 units in the ring and a calix rene has 6. A substituent in the meso position Rb is added to the name with a prefix C- as in C-methylcalix rene The word calixarene is derived from the Greek calix or chalice because this type of molecule resembles a vase (or cup) and from the word arene that refers to the aromatic building block. Synthesis Calixarenes are generally produced by condensation of two components: an electron-rich aromatic compound, classically a 4-substituted phenol, and an aldehyde, classically formaldehyde. *The scope for the aromatic component is broad diverse. The key at ...
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Hydroperoxide
Hydroperoxides or peroxols are Chemical compound, compounds containing the hydroperoxide functional group (ROOH). If the R is organic, the compounds are called organic hydroperoxides. Such compounds are a subset of organic peroxides, which have the formula ROOR. Organic hydroperoxides can either intentionally or unintentionally initiate explosive polymerisation in materials with Unsaturated bond, unsaturated chemical bonds. Properties The O−O bond length in peroxides is about 1.45 Ångström, Å, and the R−O−O angles (R = H, C) are about 110° (water-like). Characteristically, the C−O−O−H dihedral angles are about 120°. The O−O bond is relatively weak, with a bond dissociation energy of , less than half the strengths of C−C, C−H, and C−O bonds. Hydroperoxides are typically more volatile than the corresponding alcohols: * tert-Butyl hydroperoxide, ''tert''-BuOOH (b.p. 36°C) vs tert-Butyl alcohol, ''tert''-BuOH (b.p. 82-83°C) * Methyl hydroperoxide, CH3O ...
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Glutathione
Glutathione (GSH, ) is an antioxidant in plants, animals, fungi, and some bacteria and archaea. Glutathione is capable of preventing damage to important cellular components caused by sources such as reactive oxygen species, free radicals, peroxides, lipid peroxides, and heavy metals. It is a tripeptide with a gamma peptide linkage between the carboxyl group of the glutamate side chain and cysteine. The carboxyl group of the cysteine residue is attached by normal peptide linkage to glycine. Biosynthesis and occurrence Glutathione biosynthesis involves two adenosine triphosphate-dependent steps: *First, γ-glutamylcysteine is synthesized from L- glutamate and cysteine. This conversion requires the enzyme glutamate–cysteine ligase (GCL, glutamate cysteine synthase). This reaction is the rate-limiting step in glutathione synthesis. *Second, glycine is added to the C-terminal of γ-glutamylcysteine. This condensation is catalyzed by glutathione synthetase. While all animal ...
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Glutathione Peroxidase
Glutathione peroxidase (GPx) () is the general name of an enzyme family with peroxidase activity whose main biological role is to protect the organism from oxidative damage. The biochemical function of glutathione peroxidase is to reduce lipid hydroperoxides to their corresponding alcohols and to reduce free hydrogen peroxide to water. Isozymes Several isozymes are encoded by different genes, which vary in cellular location and substrate specificity. Glutathione peroxidase 1 (GPx1) is the most abundant version, found in the cytoplasm of nearly all mammalian tissues, whose preferred substrate is hydrogen peroxide. Glutathione peroxidase 4 (GPx4) has a high preference for lipid hydroperoxides; it is expressed in nearly every mammalian cell, though at much lower levels. Glutathione peroxidase 2 is an intestinal and extracellular enzyme, while glutathione peroxidase 3 is extracellular, especially abundant in plasma. So far, eight different isoforms of glutathione peroxidase ( ...
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Cell Signaling
In biology, cell signaling (cell signalling in British English) or cell communication is the ability of a cell to receive, process, and transmit signals with its environment and with itself. Cell signaling is a fundamental property of all cellular life in prokaryotes and eukaryotes. Signals that originate from outside a cell (or extracellular signals) can be physical agents like mechanical pressure, voltage, temperature, light, or chemical signals (e.g., small molecules, peptides, or gas). Cell signaling can occur over short or long distances, and as a result can be classified as autocrine, juxtacrine, intracrine, paracrine, or endocrine. Signaling molecules can be synthesized from various biosynthetic pathways and released through passive or active transports, or even from cell damage. Receptors play a key role in cell signaling as they are able to detect chemical signals or physical stimuli. Receptors are generally proteins located on the cell surface or within the interio ...
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Selenocysteine
Selenocysteine (symbol Sec or U, in older publications also as Se-Cys) is the 21st proteinogenic amino acid. Selenoproteins contain selenocysteine residues. Selenocysteine is an analogue of the more common cysteine with selenium in place of the sulfur. Selenocysteine is present in several enzymes (for example glutathione peroxidases, tetraiodothyronine 5′ deiodinases, thioredoxin reductases, formate dehydrogenases, glycine reductases, selenophosphate synthetase 2, methionine-''R''-sulfoxide reductase B1 (SEPX1), and some hydrogenases). It occurs in all three domains of life, including important enzymes (listed above) present in humans. Selenocysteine was discovered by biochemist Thressa Stadtman at the National Institutes of Health. Chemistry Selenocysteine is the Se-analogue of cysteine. It is rarely encountered outside of living tissue (and is not available commercially) because it is very susceptible to air-oxidation. More common is the oxidized derivative selenocystine ...
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Sulfenic Acid
In chemistry, a sulfenic acid is an organosulfur compound and oxoacid with the general formula . It is the first member of the family of organosulfur oxoacids, which also include sulfinic acids () and sulfonic acids (), respectively. The base member of the sulfenic acid series with R = H is hydrogen thioperoxide. Properties In contrast to sulfinic and sulfonic acids, simple sulfenic acids, such as methanesulfenic acid, CH3SOH, are highly reactive and cannot be isolated in solution. In the gas phase the lifetime of methanesulfenic acid is about one minute. The gas phase structure of methanesulfenic acid was found by microwave spectroscopy (rotational spectroscopy) to be CH3–S–O–H. Sulfenic acids can be stabilized through steric effects, which prevent the sulfenic acid from condensing with itself to form thiosulfinates, RS(O)SR, such as allicin from garlic. Through the use of X-ray crystallography, the structure of such stabilized sulfenic acids were shown to be R–S– ...
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X-ray Crystallography
X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles and intensities of these diffracted beams, a crystallographer can produce a three-dimensional picture of the density of electrons within the crystal. From this electron density, the mean positions of the atoms in the crystal can be determined, as well as their chemical bonds, their crystallographic disorder, and various other information. Since many materials can form crystals—such as salts, metals, minerals, semiconductors, as well as various inorganic, organic, and biological molecules—X-ray crystallography has been fundamental in the development of many scientific fields. In its first decades of use, this method determined the size of atoms, the lengths and types of chemical bonds, and the atomic-scale differences among various mat ...
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Diselenide
Diselenide may refer to: *Diselane, H-Se-Se-H *Carbon diselenide, CSe2, a yellow-orange oily liquid with pungent odor * Any organic chemical compound with a selenium-selenium bond, R-Se-Se-R **Diphenyl diselenide, (C6H5)–Se–Se–(C6H5) *Metal dichalcogenides **Manganese diselenide (MnSe2) **Molybdenum diselenide (MoSe2) **Tungsten diselenide Tungsten diselenide is an inorganic compound with the formula WSe2. The compound adopts a hexagonal crystalline structure similar to molybdenum disulfide. Every tungsten atom is covalently bonded to six selenium ligands in a trigonal prismatic c ... (WSe2) ** Titanium diselenide (TiSe2) {{Chemistry index ...
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Organoselenium Compound
Organoselenium compounds (or seleno-organic) are chemical compounds containing carbon-to-selenium chemical bonds. Organoselenium chemistry is the corresponding science exploring their properties and reactivity. Selenium belongs with oxygen and sulfur to the group 16 elements or chalcogens, and similarities in chemistry are to be expected. Organoselenium compounds are found at trace levels in ambient waters, soils and sediments. Selenium can exist with oxidation state −2, +2, +4, +6. Se(II) is the dominant form in organoselenium chemistry. Down the group 16 column, the bond strength becomes increasingly weaker (234 kJ/ mol for the C−Se bond and 272 kJ/mol for the C−S bond) and the bond lengths longer (C−Se 198 pm, C−S 181 pm and C−O 141 pm). Selenium compounds are more nucleophilic than the corresponding sulfur compounds and also more acidic. The p''K''a values of XH2 are 16 for oxygen, 7 for sulfur and 3.8 for selenium. In contrast to sulfoxides, the corresponding sel ...
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Disproportionation
In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. More generally, the term can be applied to any desymmetrizing reaction of the following type, regardless of whether it is a redox or some other type of process: :2A -> A' + A'' Examples *Mercury(I) chloride disproportionates upon UV-irradiation: :Hg2Cl2 → Hg + HgCl2 *Phosphorous acid disproportionates upon heating to give phosphoric acid and phosphine: :4 → 3 H3PO4 + PH3 *Desymmetrizing reactions are sometimes referred to as disproportionation, as illustrated by the thermal degradation of bicarbonate: :2 → + H2CO3 :The oxidation numbers remain constant in this acid-base reaction. This process is also called autoionization. *Another variant on disproportionation is radical disproportionation, in which two radicals form an alkene and an alkane. : Reverse r ...
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