Proton-coupled electron transfer from tyrosine in a tyrosine-ruthenium-tris-bipyridine complex: Comparison with Tyrosine(z) oxidation in photosystem II
2000 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 122, no 16, 3932-3936 p.Article in journal (Refereed) Published
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) 2PF(6) was investigated using flash photolysis. At a pH below the tyrosine pK(a) approximate to 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, lambda = 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 proton-coupled electron-transfer reaction, and at pH < 7 the Tyr(Z) proton is released directly to the bulk water.
Place, publisher, year, edition, pages
2000. Vol. 122, no 16, 3932-3936 p.
water oxidation, involvement, chemistry, dynamics
IdentifiersURN: urn:nbn:se:kth:diva-19721ISI: 000086766200016OAI: oai:DiVA.org:kth-19721DiVA: diva2:338413
QC 201005252010-08-102010-08-10Bibliographically approved