词条 | Bioorganometallic chemistry |
释义 |
Naturally occurringVitamin B12 is the preeminent bioorganometallic species. B12 is shorthand for a collection of related enzymes which effect numerous reactions involving the making and breaking of C-C and C-H bonds. Several bioorganometallic enzymes carry out reactions involving carbon monoxide. Carbon monoxide dehydrogenase (CODH) catalyzes the water gas shift reaction which provides CO for the biosynthesis of acetylcoenzyme A. The latter step is effected by the Ni-Fe enzyme acetylCoA synthase. ACS”. CODH and ACS often occur together in a tetrameric complex, the CO being transported via a tunnel and the methyl group being provided by methyl cobalamin. Hydrogenases are bioorganometallic in the sense that their active sites feature Fe-CO functionalities, although the CO ligands are only spectators.[3] The Fe-only hydrogenases have a Fe2(μ-SR)2(μ-CO)(CO)2(CN)2 active site connected to a 4Fe4S cluster via a bridging thiolate. The active site of the [NiFe]-hydrogenases are described as (NC)2(OC)Fe(μ-SR)2Ni(SR)2 (where SR is cysteinyl).[4] The “FeS-free” hydrogenases have an undetermined active site containing an Fe(CO)2 center. Methanogenesis, the biosynthesis of methane, entails as its final step, the scission of a nickel-methyl bond in cofactor F430. The iron-molybdenum cofactor (FeMoco) of nitrogenases contains an Fe6C unit and is an example of an interstitial carbide found in biology.[5][6] Sensor proteinsSome [NiFe]-containing proteins are known to sense H2 and thus regulate transcription. Copper-containing proteins are known to sense ethylene, which is known to be a hormone relevant to the ripening of fruit. This example illustrates the essential role of organometallic chemistry in nature, as few molecules outside of low-valent transition metal complexes reversibly bind alkenes. Cyclopropenes inhibit ripening by binding to the copper(I) center. Binding to copper is also implicated in the mammalian olfaction of olefins.[7]Carbon monoxide occurs naturally and is a transcription factor via its complex with a sensor protein based on ferrous porphyrins. In medicineSeveral organometallic compounds are under study as candidates for diverse therapies. Much work was instigated by the success of cisplatin in chemotherapy, and the related compounds carboplatin and oxaliplatin. Titanocene dichloride displays anti-cancer activity, and Dichloridobis[(p-methoxybenzyl)cyclopentadienyl]titanium is a current anticancer drug candidate. Arene- and cyclopentadienyl complexes are kinetically inert platforms for the design of new radiopharmaceuticals. Furthermore, there have been made studies utilizing exogenous semi-synthetic ligands; specifically to the dopamine transporter, observing increased resultant efficacy in regard to reward facilitating behavior (incentive salience) and habituation, namely with the phenyltropane compound [η6-(2β-carbomethoxy-3β-phenyl)tropane]tricarbonylchromium. ToxicologyWithin the realm of bioorganometallic chemistry is the study of the fates of synthetic organometallic compounds. Tetraethyllead has received considerable attention in this regard as has its successors such as methylcyclopentadienyl manganese tricarbonyl. Methylmercury is a particularly infamous case, this cation is produced by the action of vitamin B12-related enzymes on mercury. References1. ^{{cite book|title=Metal-carbon bonds in enzymes and cofactors| veditors = Sigel A, Sigel H, Sigel RK |publisher=Royal Society of Chemistry|year=2009|series=Metal Ions in Life Sciences|volume=6|isbn=978-1-84755-915-9}} 2. ^{{cite book | vauthors = Linck RC, Rauchfuss TB | chapter = Synthetic Models for Bioorganometallic Reaction Centers | title = Bioorganometallics: Biomolecules, Labeling, Medicine | pages = 403–435 | veditors = Jaouen G | publisher = Wiley-VCH | location = Weinheim | year = 2005 | doi = 10.1002/3527607692.ch12 | isbn = 978-3-527-30990-0 }} 3. ^{{cite book | vauthors = Cammack R, Frey M, Robson R | title = Hydrogen as a Fuel: Learning from Nature | publisher = Taylor & Francis | location = London | year = 2001 | isbn = 978-0-415-24242-4 }} 4. ^{{cite journal | vauthors = Volbeda A, Fontecilla-Camps JC | title = The Active Site and Catalytic Mechanism of NiFe Hydrogenases | journal = Dalton Transactions | issue = 21 | year = 2003 | pages = 4030–4038 | doi = 10.1039/B304316A }} 5. ^{{cite journal | vauthors = Spatzal T, Aksoyoglu M, Zhang L, Andrade SL, Schleicher E, Weber S, Rees DC, Einsle O | title = Evidence for interstitial carbon in nitrogenase FeMo cofactor | journal = Science | volume = 334 | issue = 6058 | pages = 940 | date = November 2011 | pmid = 22096190 | pmc = 3268367 | doi = 10.1126/science.1214025 | url = http://science.sciencemag.org/content/334/6058/940 | bibcode = 2011Sci...334..940S }} 6. ^{{cite journal | vauthors = Lancaster KM, Roemelt M, Ettenhuber P, Hu Y, Ribbe MW, Neese F, Bergmann U, DeBeer S | title = X-ray emission spectroscopy evidences a central carbon in the nitrogenase iron-molybdenum cofactor | journal = Science | volume = 334 | issue = 6058 | pages = 974–7 | date = November 2011 | pmid = 22096198 | pmc = 3800678 | doi = 10.1126/science.1206445 | url = http://science.sciencemag.org/content/334/6058/974 | bibcode = 2011Sci...334..974L }} 7. ^{{cite journal | vauthors = Duan X, Block E, Li Z, Connelly T, Zhang J, Huang Z, Su X, Pan Y, Wu L, Chi Q, Thomas S, Zhang S, Ma M, Matsunami H, Chen GQ, Zhuang H | display-authors = 6 | title = Crucial role of copper in detection of metal-coordinating odorants | journal = Proceedings of the National Academy of Sciences of the United States of America | volume = 109 | issue = 9 | pages = 3492–7 | date = February 2012 | pmid = 22328155 | pmc = 3295281 | doi = 10.1073/pnas.1111297109 }} 5 : Biochemistry|Inorganic chemistry|Organometallic chemistry|Medicinal inorganic chemistry|Bioinorganic chemistry |
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