TY - JOUR
T1 - Electron transfer activation of chromopyrrolic acid by cytochrome P450 en route to the formation of an antitumor indolocarbazole derivative
T2 - Theory supports experiment
AU - Wang, Yong
AU - Hirao, Hajime
AU - Chen, Hui
AU - Onaka, Hiroyasu
AU - Nagano, Shingo
AU - Shaik, Sason
PY - 2008/6/11
Y1 - 2008/6/11
N2 - QM/MM calculations support experiment and show that StaP is a P450 that functions like a peroxidase: its active species is the one-electron-reduced Cpd II species with a radical on CPA, by analogy to cytochrome c peroxidase (CcP), and its reaction with the substrate proceeds by overall proton-coupled electron transfer (PCET), in analogy to the corresponding mechanism in horseradish peroxidase (HRP). The electron transfer is enabled by His250, the presence of carboxylate groups in CPA, and by the H-bonding network that tunes the energetic of the process. Theory supports experiment but reveals some novel aspects of this unusual P450.
AB - QM/MM calculations support experiment and show that StaP is a P450 that functions like a peroxidase: its active species is the one-electron-reduced Cpd II species with a radical on CPA, by analogy to cytochrome c peroxidase (CcP), and its reaction with the substrate proceeds by overall proton-coupled electron transfer (PCET), in analogy to the corresponding mechanism in horseradish peroxidase (HRP). The electron transfer is enabled by His250, the presence of carboxylate groups in CPA, and by the H-bonding network that tunes the energetic of the process. Theory supports experiment but reveals some novel aspects of this unusual P450.
UR - http://www.scopus.com/inward/record.url?scp=44949255484&partnerID=8YFLogxK
U2 - 10.1021/ja711426y
DO - 10.1021/ja711426y
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C2 - 18481854
AN - SCOPUS:44949255484
SN - 0002-7863
VL - 130
SP - 7170
EP - 7171
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 23
ER -