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Methanogenesis Cycle
Methanogenesis or biomethanation is the formation of methane coupled to energy conservation by microbes known as methanogens. Organisms capable of producing methane for energy conservation have been identified only from the domain Archaea, a group phylogenetically distinct from both eukaryotes and bacteria, although many live in close association with anaerobic bacteria. Other forms of methane production that are not coupled to ATP synthesis exist within all three domains of life. The production of methane is an important and widespread form of microbial metabolism. In anoxic environments, it is the final step in the decomposition of biomass. Methanogenesis is responsible for significant amounts of natural gas accumulations, the remainder being thermogenic. Biochemistry Methanogenesis in microbes is a form of anaerobic respiration. Methanogens do not use oxygen to respire; in fact, oxygen inhibits the growth of methanogens. The terminal electron acceptor in methanogenesis is ...
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Methane
Methane ( , ) is a chemical compound with the chemical formula (one carbon atom bonded to four hydrogen atoms). It is a group-14 hydride, the simplest alkane, and the main constituent of natural gas. The relative abundance of methane on Earth makes it an economically attractive fuel, although capturing and storing it poses technical challenges due to its gaseous state under normal conditions for temperature and pressure. Naturally occurring methane is found both below ground and under the seafloor and is formed by both geological and biological processes. The largest reservoir of methane is under the seafloor in the form of methane clathrates. When methane reaches the surface and the atmosphere, it is known as atmospheric methane. The Earth's atmospheric methane concentration has increased by about 150% since 1750, and it accounts for 20% of the total radiative forcing from all of the long-lived and globally mixed greenhouse gases. It has also been detected on other plane ...
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Methane
Methane ( , ) is a chemical compound with the chemical formula (one carbon atom bonded to four hydrogen atoms). It is a group-14 hydride, the simplest alkane, and the main constituent of natural gas. The relative abundance of methane on Earth makes it an economically attractive fuel, although capturing and storing it poses technical challenges due to its gaseous state under normal conditions for temperature and pressure. Naturally occurring methane is found both below ground and under the seafloor and is formed by both geological and biological processes. The largest reservoir of methane is under the seafloor in the form of methane clathrates. When methane reaches the surface and the atmosphere, it is known as atmospheric methane. The Earth's atmospheric methane concentration has increased by about 150% since 1750, and it accounts for 20% of the total radiative forcing from all of the long-lived and globally mixed greenhouse gases. It has also been detected on other plane ...
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Thiyl Radical
In chemistry, a thiyl radical has the formula RS, sometimes written RS• to emphasize that they are free radicals. R is typically an alkyl or aryl substituent. Because S–H bonds are about 20% weaker than C–H bonds, thiyl radicals are relatively easily generated from thiols RSH. Thiyl radicals are intermediates in the thiol-ene reaction In organosulfur chemistry, the thiol-ene reaction (also alkene hydrothiolation) is an organic reaction between a thiol () and an alkene () to form a thioether (). This reaction was first reported in 1905, but it gained prominence in the late 1990s ..., which is the basis of some polymeric coatings and adhesives. They are generated by hydrogen-atom abstraction from thiols using initiators such as AIBN: : RN=NR → 2 R• + N2 :R• + R′SH → R′S• + RH Thiyl radicals are also invoked as intermediates in some biochemical reactions. References Free radicals Organosulfur compounds {{organic-chemistry-stub ...
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Methanopterin
Tetrahydromethanopterin (THMPT, ) is a coenzyme in methanogenesis. It is the carrier of the C1 group as it is reduced to the methyl level, before transferring to the coenzyme M. Tetrahydrosarcinapterin (THSPT, ) is a modified form of THMPT, wherein a glutamyl group linked to the 2-hydroxyglutaric acid terminus. THMPT is the main platform for C1 transformations N-Formylmethanofuran donates the C1 group to the N5 site of the pterin to give the formyl- THMPT. The formyl group subsequently condenses intramolecularly to give methenyl- , which is then reduced to methylene- THMPT. Methylene- MPT is subsequently converted, using coenzyme F420 as the electron source, to methyl- THMPT, catalyzed by F420-dependent methylene-THMPT reductase. Methyl- THMPT is the methyl donor to coenzyme M, a conversion mediated by methyl-THMPT:coenzyme M methyltransferase. Comparison with tetrahydrofolic acid THMPT is related to the better known tetrahydrofolic acid (THFA, ). The most important d ...
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Methanofuran
Methanofurans are a family of chemical compounds found in methanogenic archaea. These species feature a 2-aminomethylfuran linked to phenoxy group. At least three different end groups are recognized: R = tricarboxyheptanoyl (methanofuran), glutamyl-glutamyl (methanofuran b), tricarboxy-2-hydroxyheptanoyl (methanofuran c, see picture). Formylation of MFR Methanofuran converts to formylmethanofuran in an early stage of methanogenesis. The enzyme formylmethanofuran dehydrogenase ( EC: 1.2.99.5) formylates methanofuran using , the primary C1 source in methanogenesis. Deformylation of MFR The enzyme formylmethanofuran:tetrahydromethanopterin formyltransferase catalyzes the transfer of the formyl group from formylmethanofuran to N5 on tetrahydromethanopterin, . This enzyme has been crystallized; it contains no prosthetic group A prosthetic group is the non-amino acid component that is part of the structure of the heteroproteins or conjugated proteins, being tightly linked to t ...
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Coenzyme M
Coenzyme M is a coenzyme required for methyl-transfer reactions in the metabolism of archaeal methanogens, and in the metabolism of other substrates in bacteria. It is also a necessary cofactor in the metabolic pathway of alkene-oxidizing bacteria. CoM helps eliminate the toxic epoxides formed from the oxidation of alkenes such as propylene. The structure of this coenzyme was discovered by CD Taylor and RS Wolfe in 1974 while they were studying methanogenesis, the process by which carbon dioxide is transformed into methane in some anaerobic bacteria. The coenzyme is an anion with the formula . It is named 2-mercaptoethanesulfonate and abbreviated HS–CoM. The cation is unimportant, but the sodium salt is most available. Mercaptoethanesulfonate contains both a thiol, which is the main site of reactivity, and a sulfonate group, which confers solubility in aqueous media. Biochemical role Methanogenesis The coenzyme is the C1 donor in methanogenesis. It is converted to methyl-c ...
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Coenzyme B
Coenzyme B is a coenzyme required for redox reactions in methanogens. The full chemical name of coenzyme B is 7-mercaptoheptanoylthreoninephosphate. The molecule contains a thiol, which is its principal site of reaction. Coenzyme B reacts with 2-methylthioethanesulfonate (methyl-Coenzyme M, abbreviated ), to release methane in methanogenesis: : + HS–CoB → + CoB–S–S–CoM This conversion is catalyzed by the enzyme methyl coenzyme M reductase, which contains cofactor F430 as the prosthetic group. A related conversion that utilizes both HS-CoB and HS-CoM is the reduction of fumarate to succinate, catalyzed by fumarate reductase Fumarate reductase is the enzyme that converts fumarate to succinate, and is important in microbial metabolism as a part of anaerobic respiration. Succinate + acceptor fumarate + reduced acceptor Fumarate reductases can be divided into two classe ...: :HS–CoM + HS–CoB + − → − + CoB–S–S–CoM Importance of Coenzyme B in Metha ...
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Coenzyme F420
Coenzyme F420 or 8-hydroxy-5-deazaflavin is a coenzyme (sometimes called a cofactor) involved in redox reactions in methanogens, in many Actinomycetota, and sporadically in other bacterial lineages. It is a flavin derivative. The coenzyme is a substrate for coenzyme F420 hydrogenase, 5,10-methylenetetrahydromethanopterin reductase and methylenetetrahydromethanopterin dehydrogenase. A particularly rich natural source of F420 is ''Mycobacterium smegmatis'', in which several dozen enzymes use F420 instead of the related cofactor FMN used by homologous enzymes in most other species. Eukaryotes including the fruit fly ''Drosophila melanogaster'' and the algae ''Ostreococcus tauri'' also use a precursor to this cofactor. Biosynthesis Coenzyme F420 is synthesized via a multi-step pathway: * 7,8-didemethyl-8-hydroxy-5-deazariboflavin synthase produces Coenzyme FO (also written F0), itself a cofactor of DNA photolyase (antenna). This is the head portion of the molecule. * 2-phos ...
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Methanethiol
Methanethiol (also known as methyl mercaptan) is an organosulfur compound with the chemical formula . It is a colorless gas with a distinctive putrid smell. It is a natural substance found in the blood, brain and feces of animals (including humans), as well as in plant tissues. It also occurs naturally in certain foods, such as some nuts and cheese. It is one of the chemical compounds responsible for bad breath and the smell of flatus. Methanethiol is the simplest thiol and is sometimes abbreviated as MeSH. It is very flammable. Structure and reactions The molecule is tetrahedral at the carbon atom, like methanol. It is a weak acid, with a p''K''a of ~10.4, but is about a hundred thousand times more acidic than methanol. The colorless salt can be obtained in this way: :CH3SH + CH3ONa → CH3SNa + CH3OH The resulting thiolate anion is a strong nucleophile. It can be oxidized to dimethyl disulfide: :2CH3SH + → CH3SSCH3 + H2O Further oxidation takes the disulfide to two mol ...
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Dimethyl Sulfide
Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula (CH3)2S. Dimethyl sulfide is a flammable liquid that boils at and has a characteristic disagreeable odor. It is a component of the smell produced from cooking of certain vegetables, notably maize, cabbage, beetroot, and seafoods. It is also an indication of bacterial contamination in malt production and brewing. It is a breakdown product of dimethylsulfoniopropionate (DMSP), and is also produced by the bacterial metabolism of methanethiol. Occurrence and production DMS originates primarily from DMSP, a major secondary metabolite in some marine algae. DMS is the most abundant biological sulfur compound emitted to the atmosphere. Emission occurs over the oceans by phytoplankton. DMS is also produced naturally by bacterial transformation of dimethyl sulfoxide (DMSO) waste that is disposed of into sewers, where it can cause environmental odor problems. DMS is oxidized in the marine atmos ...
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Tetramethylammonium
Tetramethylammonium (TMA) or (Me4N+) is the simplest quaternary ammonium cation, consisting of four methyl groups attached to a central nitrogen atom, and is isoelectronic with neopentane. It is positively charged and can only be isolated in association with a counter-ion. Common salts include tetramethylammonium chloride and tetramethylammonium hydroxide. Tetramethylammonium salts are commonly used in chemical synthesis and are widely employed in pharmacological research. Common nomenclature In the toxicological literature, ''naturally occurring'' tetramethylammonium (anion unspecified) is often referred to by the name "tetramine". Unfortunately, this non-systematic or "trivial" name is also used for other chemical entities, including a toxic rodenticide (Tetramethylenedisulfotetramine). Similarly, the acronym "TMA", which is frequently used for tetramethylammonium in the pharmacological literature, may also refer to the investigational drug 3,4,5-trimethoxyamphetamine, which, ...
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Methylamines
Methylamine is an organic compound with a formula of . This colorless gas is a derivative of ammonia, but with one hydrogen atom being replaced by a methyl group. It is the simplest primary amine. Methylamine is sold as a solution in methanol, ethanol, tetrahydrofuran, or water, or as the anhydrous gas in pressurized metal containers. Industrially, methylamine is transported in its anhydrous form in pressurized railcars and tank trailers. It has a strong odor similar to rotten fish. Methylamine is used as a building block for the synthesis of numerous other commercially available compounds. Industrial production Methylamine is prepared commercially by the reaction of ammonia with methanol in the presence of an aluminosilicate catalyst. Dimethylamine and trimethylamine are co-produced; the reaction kinetics and reactant ratios determine the ratio of the three products. The product most favored by the reaction kinetics is trimethylamine. : In this way, an estimated 115,000 tons ...
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