Bioinorganic Chemistry - download pdf or read online

By Williams R.J.P.

ISBN-10: 3540635483

ISBN-13: 9783540635482

Content material: organic nickel / J.C. Fontecilla-Camps -- Nickel in F₄₃₀ / J. Tesler -- Hemeproteins in anaerobes / I.A.C. Pereira, M. Teixeira, A.V. Xavier -- Evolutionary elements of copper binding facilities in copper proteins / B. Abolmaali, H.V. Taylor, U. Weser

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55] and extensively studied by Keltjens et al. [50] native F430 (C12, S; C13, S) can be thermally converted to 13-epimer-F43 o (C12, S; C13, R) and then to 12,13-diepimer-F430 (C12, R; C13, R). An equilibrium mixture contains 4% native, 8% 13-epimer, and 88% 12,13-diepimer-F43o [55]. Oxidation yields a red compound, F560,which is 12,13-didehydro-F430. 6. Isomers of F430. For clarity, only ring C is shown. Heat treatment of F430 leads to the thermodynamically more stable 12,13-diepimer; oxidation leads to the 12,13-didehydroform (F560) Nickelin F43o 43 be performed on a single compound; only native F430 is considered to have biological relevance.

Their argument goes as follows: if, as previously assumed, for methylation to occur the diamagnetic Aox has to be reduced to the paramagnetic Area S = 1/2 state (in CO-mediated reduction this would be the species giving rise to the NiFeC EPR signal), the resulting methylated adduct should also be paramagnetic since the reaction involves a diamagnetic methyl cation. However, the methylated A-cluster is EPR silent. As an alternative to the reduction of the A-cluster, these authors postulate that a different redox center has to be reduced prior to methylation.

Creased MCRrea2 at the expense o f MCRredl [34, 77]. In further contrast to MCRox 1, both MCRre d signals were q u e n c h e d by oxygen and by chloroform. All of this evidence indicated that the MCRreal,2 signals represented intermediates active in the catalytic cycle of MCR [77]. Their EPR parameters (see Table 2) indicated that these signals arose from a metal-centered p a r a m a g n e t i c species, for which F430was the only candidate in MCR. The MCRred2 signal was observed in b o t h isoenzymes of MCR (MCR I and MCR II) [38].

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Bioinorganic Chemistry by Williams R.J.P.

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