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Substrates for Rapid Delivery of Electrons and Holes to Buried Active Sites in Proteins
Author(s) -
Wilker Jonathan J.,
Dmochowski Ivan J.,
Dawson John H.,
Winkler Jay R.,
Gray Harry B.
Publication year - 1999
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/(sici)1521-3773(19990115)38:1/2<89::aid-anie89>3.0.co;2-r
Subject(s) - photosensitizer , photochemistry , heme , chemistry , electron , electron transfer , bipyridine , active site , porphyrin , cytochrome , hydrocarbon , crystallography , stereochemistry , catalysis , organic chemistry , crystal structure , physics , enzyme , quantum mechanics
New reduced and oxidized states of cytochrome P450 cam have been generated by electron transfer to and from the heme group of the buried active site. This is achieved with the photosensitizer [Ru(bpy) 3 ] 2+ (bpy=2,2′‐bipyridine), which is linked through a hydrocarbon chain to a species with high affinity for the heme cavity (see picture). The direction of photoinduced charge transfer is controlled with a suitable quencher; the new oxidation states are formed in about 0.1 ms and persist for approximately 100 ms.