Transient kinetics of redox reactions of flavodoxin: effects of chemical modification of the flavin mononucleotide prosthetic group on the dynamics of intermediate complex formation and electron transfer.

Abstract:

:The effects of structural modifications of the flavin mononucleotide (FMN) prosthetic group of Clostridium pasteurianum flavodoxin on the kinetics of electron transfer to the oxidized form (from 5-deazariboflavin semiquinone produced by laser flash photolysis) and from the semiquinone form (to horse heart cytochrome c by using stopped-flow spectrophotometry) have been investigated. The analogues used were 7,8-dichloro-FMN, 8-chloro-FMN, 7-chloro-FMN, and 5,6,7,8-tetrahydro-FMN. The ionic strength dependence of cytochrome c reduction was not affected by chlorine substitution, although the specific rate constants for complex formation and decay were appreciably smaller. On the other hand, all of the chlorine analogues had the same rate constant for deazariboflavin semiquinone oxidation. The rate constants for tetrahydro-FMN flavodoxin semiquinone reduction of cytochrome c were considerably smaller than those for the native protein. The implications of these results for the electron-transfer mechanism of flavodoxin are discussed.

journal_name

Biochemistry

journal_title

Biochemistry

authors

Simondsen RP,Tollin G

doi

10.1021/bi00281a034

subject

Has Abstract

pub_date

1983-06-07 00:00:00

pages

3008-16

issue

12

eissn

0006-2960

issn

1520-4995

journal_volume

22

pub_type

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