Abstract

The absorption spectra of oxidized P-450-isocyanide complexes were the same in difference spectra irrespective of the isocyanide derivative tested. However, with these reduced P-450-isocyanide complexes, absorption at 455 mμ increased, and that at 430 mμ decreased, with increasing carbon atom number of the isocyanide derivative at a definite pH. The same changes were seen with individual complexes with increasing pH. The dissociation constants of oxidized P-450-isocyanide complexes decreased with increase in carbon atom number of the isocyanide. These results were confirmed by electron spin resonance (ESR) spectroscopy. However, the dissociation constants of reduced P-450-isocyanide complexes were essentially identical and the dissociation constants of the oxidized and reduced P-450-isocyanide complexes were little affected by pH. The oxidized P-450-isocyanide complexes gave magnetically specific ESR signals. The orbital energy differences of d ε orbitals of the heme iron of the complexes increased with increase in the carbon atom number of the isocyanide. Purified P-450 and its isocyanide complexes were rapidly reduced by a ferredoxin-NADP + reductase system.

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