Electrochemical aspects of a NADH/FAD model system.
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概要
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A model system of the NADH/FAD redox couple has been studied by the use of electrochemical techniques. The system studied was composed of 1-benzyl-1,4-dihydronicotinamide (BNAH) and riboflavin (RF), which were used in place of NADH and FAD respectively, dissolved in a DMSO solution. The results obtained were as follows. RF is reduced either by BNAH or sodium borohydride, obeying a second-order rate law, presumably by the mechanism of hydride-ion transfer. The resultant product is inactive to the electrochemical reduction at a mercury-pool electrode. Entirely different products were produced when RF was reduced electrochemically. RF was reduced at a rate of 1 <I>F</I>/mol at the initial stage of controlled potential electrolysis to form, probably, a dimeric compound, but the latter product underwent further reduction and the total quantity of electricity necessary for the complete reduction exceeded 10 <I>F</I>/mol. Interestingly, the electrolytic reduction gives the same product as that obtained by BNAH when electrolysis is performed in the presence of a sufficient amount of BNAH, indicating that the initial product of electrochemical reduction receives the hydride ion rather than further electrons.<BR>2RF+2e\rightleftarrows(RF)_2^2-\overset+H^-,+H^+→2RFH^-<BR>The Zn<SUP>2+</SUP> added to the BNAH/RF system was found to act as the oxidizing agent of RFH<SUP>−</SUP> and regenerated the neutral RF. This is markedly different from the case of BNAH/organic carbonyl compounds, where the metal ions behave as catalysts to promote the reaction.
- 公益社団法人 日本化学会の論文
著者
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Kunai Atsutaka
Department Of Applied Chemistry Graduate School Of Engineering Hiroshima University
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Kitani Akira
Department Of Applied Chemistry Faculty Of Engineering Hiroshima University
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Miyake Hitoshi
Depart-ment Of Neurosurgery Juzenkai Hospital
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Sasaki Kazuo
Department Of Applied Chemistry Faculty Of Engineering Hiroshima University
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Kunai Atsutaka
Department of Applied Chemistry, Hiroshima University
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