Chemical evolution of dehydrogenases: Amino acid pentacyanoferrate (II) as possible intermediates

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Dehydrogenation of ascorbic acid and reduced nicotinamide adenine dinucleotide (NADH) with methylene blue using complexes of the type [Fe(II)(CN)5 (L)] n- (wheren=3 or 4; L=glycine, histidine, imidazole, and triglycine) as catalyst have been studied at pH 9.18. Similar kinetic behavior was observed for the dehydrogenation of ascorbic acid as well as for NADH; both reactions showed first order dependency on the substrates. First order dependence was observed only at lower concentrations of methylene blue; at higher concentrations of methylene blue, the reactions were independent of methylene blue. The order with respect to catalyst varied between 0.3 0.5. A tentative mechanism which conforms to the observed kinetics has been proposed. It is believed that on the primitive earth when the reducing potential of the atmosphere was not high enough, lower oxidation state iron complexes like [Fe(II)(CN)5(L)] n- might have been involved in dehydrogenase-type activity.

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