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Spectral features associated with per oxide reactivity of the coupled bi nuclear copper active site in type 2 depleted and native rhus vernicifera laccase/

, : Spectral features associated with per oxide reactivity of the coupled bi nuclear copper active site in type 2 depleted and native rhus vernicifera laccase/. Biochemical & Biophysical Research Communications 119(2): 567-574

An X-ray absorption spectroscopic (XAS) determination was reported of the oxidation state of the Cu sites in T2D and native Rhus laccase. The increase in intensity of the 330 nm absorption feature which results from peroxide titration of T2D laccase (T3:[Cu(I)Cu(I)],T1:[Cu(II)]) correlates linearly with the percent of oxidation of the binuclear Cu site (determined by XAS analysis). Apparently, peroxide oxidizes but does not bind to the T3 site. This correlation was used to determine that native laccase, as isolated, contains .apprx. 25% reduced T3 sites and that all spectral changes observed upon peroxide addition to native laccase can be accounted for by oxidation of these reduced sites. The importance of this result to previous reports of peroxide binding at the laccase active site is discussed.

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