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Intracomplex electron transfer between ruthenium-65-cytochrome b5 and position-82 variants of yeast iso-1-cytochrome c
Journal article   Peer reviewed

Intracomplex electron transfer between ruthenium-65-cytochrome b5 and position-82 variants of yeast iso-1-cytochrome c

Anne Willie, Mark McLean, Rui Qin Liu, Sharon Hilgen-Willis, Aleister J Saunders, Gary J Pielak, Stephen G Sligar, Bill Durham and Francis Millett
Biochemistry (Easton), v 32(29), pp 7519-7525
27 Jul 1993
PMID: 8393343

Abstract

We tested the idea that the aromatic ring on the invariant residue Phe-82 in cytochrome c acts as an electron-transfer bridge between cytochrome c and cytochrome bs. Ru-65-cyt bs was prepared by labeling the single sulfhydryl group on T65C cytochrome bs with [4-(bromomethyl)-4'-methylbipy-ridine] [bis(bipyridine)] ruthenium2"1" as previously described [Willie, A., Stayton, P. S., Sligar, S. G., Durham,B., & Millett, F. (1992) Biochemistry 31, 7237-7242], Laser excitation of the complex formed betweenRu-65-cyt bs and Saccharomyces cerevisiae iso-1 -cytochrome c at low ionic strength results in rapid electron transfer from the excited-state Ru(II*) to the heme group of Ru-65-cyt bs followed by biphasic electron transfer to the heme group of cytochrome c with rate constants of (1.0 ± 0.2) X 105 s™1 and (2.0 ± 0.4)X 104 s_1. Variants of iso-1 -cytochrome c substituted at Phe-82 with Tyr, Gly, Leu, and lie have fast-phase rate constants of 0.4, 1.9, 2.1, and 2.0 X 105 s_1 and slow-phase rate constants of 5.3, 3.5, 2.4, and 2.0 X103 s_1, respectively. Increasing the ionic strength to 50 mM results in single-phase intracomplex electron transfer with rate constants of 3.8, 3.1, 3.0, 5.0, and 4.5 X 104 s_1 for the wild-type, Tyr, Gly, Leu, and He variants, respectively. These results demonstrate that an aromatic side chain at residue 82 is not needed for rapid electron transfer with cytochrome bs. Furthermore, two conformational forms of the complex are present at low ionic strength with fast and slow electron-transfer rates. When the ionic strength is increased to 50 mM, interconversion between the two forms of the complex becomes rapid, resulting in a single phase for electron transfer with a rate constant that is intermediate between the slow and fast rates. At still higher ionic strength the complex dissociates, and second-order kinetics are observed

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Collaboration types
Domestic collaboration
Web of Science research areas
Biochemistry & Molecular Biology
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