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Electron Transfer Reactivity of Mutants of the Blue Copper Protein Plastocyanin

  • Chapter
Bioinorganic Chemistry of Copper

Abstract

This contribution focuses on the electron-transfer (ET) reactivity of plastocyanin in the PCu(l) state with the oxidants [Fe(CN)6]3- and [Co(phen)3]3+. A programme of study involving five mutant forms obtained by site directed mutagenesis has been commenced in which effects of mutations at the adjacent and remote reaction sites are considered. For two of the mutants Tyr83His and Leu12Glu the variation of rate constants (25°C; I = 0.100M NaCl) with pH is explored. Protonation at the imidazole of His83 (pKa 8.4) influences the reduction potential and hence reactivity. The results for Leu12Glu at high pH when the 1- glutamate form is present (pKa ~ 7.0) indicate a sharp decrease in reactivity with [Fe(CN)6]3~, whereas the converse applies with [Co(phen)3]3+. The very striking electrostatic influence of the 1- charge is noted. Effects observed for Tyr83Phe are low key, but the reaction of this mutant and Scenedesmus obliquus plastocyanin (which has a Tyr82Phe83 sequence) with cytochrome f suggest that the Tyr62 in S. obliquus plastocyanin (and similar 57 and 58 depleted forms) may have a significant role to play in ET at the remote site. The mutation Leu12Asn benefits [Fe(CN)6]3- (~ 5-fold), but surprisingly no change in reactivity is obtained for the Asp42Asn mutant with [Co(phen)3]3+.

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Author information

Authors and Affiliations

  1. Department of Chemistry, The University, Newcastle upon Tyne, NE1 7RU, England, UK

    A G Sykes & P Kyritsis

  2. Department of Biochemistry and Biophysics, Chalmers University of Technology and University of Göteborg, S-4129, Göteborg, Sweden

    M Nordling & S Young

Authors
  1. A G Sykes
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  2. P Kyritsis
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  3. M Nordling
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  4. S Young
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Editor information

Editors and Affiliations

  1. The Johns Hopkins University, USA

    Kenneth D. Karlin  & Zoltán Tyeklár  & 

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© 1993 Chapman & Hall, Inc.

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Sykes, A.G., Kyritsis, P., Nordling, M., Young, S. (1993). Electron Transfer Reactivity of Mutants of the Blue Copper Protein Plastocyanin. In: Karlin, K.D., Tyeklár, Z. (eds) Bioinorganic Chemistry of Copper. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-6875-5_6

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  • DOI: https://doi.org/10.1007/978-94-011-6875-5_6

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-011-6877-9

  • Online ISBN: 978-94-011-6875-5

  • eBook Packages: Springer Book Archive

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