Proton-coupled electron transfer from tyrosine in a tyrosine-ruthenium- tris-bipyridine complex: Comparison with tyrosinez oxidation in photosystem II

Martin Sjödin, Stenbjörn Styring, Björn Åkermark, Licheng Sun, Leif Hammarström*

*この研究の対応する著者

研究成果: Article査読

242 被引用数 (Scopus)

抄録

The pH- and the temperature dependence of the rate constant for electron transfer from tyrosine to ruthenium in Ru(II)(bpy)2(4-Me-4'CONH-L-tyrosine etyl ester-2,2'-bpy) 2PF6 was investigated using flash photolysis. At a pH below the tyrosine pK(a) ≃ 10 the rate constant increased monotonically with pH. This increase was consistent with a concerted electron transfer/deprotonation mechanism. Also indicative of a concerted reaction was the unusually high reorganization energy, 2 eV, extracted from temperature- dependent measurements. Deprotonation of the tyrosine group, at pH > pK(a), resulted in a 100-fold increase in rate constant due to a decreased reorganization energy, λ = 0.9 eV. Also, the rate constant became independent of pH. In Mn-depleted photosystem II a similar pH dependence has been found for electron transfer from tyrosine(z) (Tyr(z)) to the oxidized primary donor P680+. On the basis of the kinetic similarities we propose that the mechanisms in the two systems are the same, that is, the electron transfer occurs as a concerted protoncoupled electron-transfer reaction, and at pH < 7 the Tyr(z) proton is released directly to the bulk water.

本文言語English
ページ(範囲)3932-3936
ページ数5
ジャーナルJournal of the American Chemical Society
122
16
DOI
出版ステータスPublished - 2000 4月 26
外部発表はい

ASJC Scopus subject areas

  • 触媒
  • 化学 (全般)
  • 生化学
  • コロイド化学および表面化学

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