Pressure-Induced Deformation of the Cytochrome P450cam Active Site

Autor: Richard A. Tschirret-Guth, Paul R. Ortiz de Montellano, Gaston Hui Bon Hoa,§ and
Rok vydání: 1998
Předmět:
Zdroj: Journal of the American Chemical Society. 120:3590-3596
ISSN: 1520-5126
0002-7863
DOI: 10.1021/ja973909z
Popis: The reaction of cytochrome P450cam with aryldiazenes (ArNNH) yields σ-bonded iron−aryl (Fe−aryl) complexes. Oxidation of the complexes causes regioselective migration of the aryl group from the iron to the porphyrin nitrogens. The influence of high pressure on the formation and rearrangement of the Fe−aryl complexes is reported here. The natural logarithm of the rate of formation of the Fe−phenyl complex decreases linearly with pressure with a volume of activation of 38.2 mL mol-1. The Fe−phenyl, Fe−(2-naphthyl), and Fe−(p-biphenyl) complexes are stable at atmospheric pressure but decompose in a pressure-dependent manner at pressures above 1500 (Fe−phenyl) or 2500 bar (Fe−(2-naphthyl) or Fe−(p-biphenyl)). This pressure-induced decomposition results in formation of the N-arylprotoporphyrin IX adducts. The N-aryl porphyrin regioisomer patterns obtained by pressure-induced migration of the aryl groups (NB:NA:NC:ND, Ph, 10:14:33:43; 2-naphthyl, 12:13:37:38; p-biphenyl, 15:15:33:37) differ from those obtained ...
Databáze: OpenAIRE