Effects of single and double mutations in plastocyanin on the rate constant and activation parameters for the rearrangement gating the electron-transfer reaction between the triplet state of zinc cytochrome c and cupriplastocyanin

Biochemistry
M M Ivković-JensenN M Kostić

Abstract

The unimolecular rate constant for the photoinduced electron-transfer reaction 3Zncyt/pc(II) --> Zncyt+/pc(I) within the electrostatic complex of zinc cytochrome c and spinach cupriplastocyanin is kF. We report the effects on kF of the following factors, all at pH 7.0: 12 single mutations on the plastocyanin surface (Leu12Asn, Leu12Glu, Leu12Lys, Asp42Asn, Asp42Lys, Glu43Asn, Glu59Gln, Glu59Lys, Glu60Gln, Glu60Lys, Gln88Glu, and Gln88Lys), the double mutation Glu59Lys/Glu60Gln, temperature (in the range 273.3-302.9 K), and solution viscosity (in the range 1. 00-116.0 cP) at 283.2 and 293.2 K. We also report the effects of the plastocyanin mutations on the association constant (Ka) and the corresponding free energy of association (DeltaGa) with zinc cytochrome c at 298.2 K. Dependence of kF on temperature yielded the activation parameters DeltaH, DeltaS, and DeltaG. Dependence of kF on solution viscosity yielded the protein friction and confirmed the DeltaG values determined from the temperature dependence. The aforementioned intracomplex reaction is not a simple electron-transfer reaction because donor-acceptor electronic coupling (HAB) and reorganizational energy (lambda), obtained by fitting of the temperature dependence of k...Continue Reading

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Citations

Jul 12, 2001·Chemistry : a European Journal·I M van AmsterdamG W Canters
May 15, 2008·Photosynthesis Research·G Matthias UllmannElisa Bombarda
Apr 16, 2010·Journal of the American Chemical Society·Judith M NocekBrian M Hoffman
Nov 3, 2010·Journal of the American Chemical Society·Katarzyna I JankowskaPiotr Piotrowiak
Aug 28, 2004·BMC Bioinformatics·Zhaoyang FengWilliam R Schafer
Feb 9, 2005·BMC Genetics·Christopher J CroninPaul W Sternberg
Mar 19, 2009·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Shin-ichi J TakayamaYasuhiko Yamamoto
Jan 8, 2004·Journal of the American Chemical Society·Liu LiuMichael Y Ogawa

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