NDLI: Spectroscopic and Kinetic Studies of Perturbed Trinuclear Copper Clusters: The Role of Protons in Reductive Cleavage of the O-O Bond in the Multicopper Oxidase Fet3p

Content Provider	PubMed Central
Author	Augustine, Anthony J. Quintanar, Liliana Stoj, Christopher S. Kosman, Daniel J. Solomon, Edward I.
Abstract	The multicopper oxidase Fet3p couples four 1e− oxidations of substrate to the 4e−reduction of O2 to H2O. Fet3p uses four Cu atoms to accomplish this reaction: the type 1, type 2, and coupled binuclear type 3 sites. The type 2 and type 3 sites together form a trinuclear Cu cluster (TNC) which is the site of O2 reduction. This study focuses on mutants of two residues, E487 and D94, which lie in the second coordination sphere of the TNC and defines the role that each plays in the structural integrity of the TNC, its reactivity with O2, and in the directional movement of protons during reductive cleavage of the O-O bond. The E487D, E487A, and D94E mutants have been studied in the holo and type 1 depleted (T1D) forms. Residue E487, located near the T3 center, is found to be responsible for donation of a proton during the reductive cleavage of the O-O bond in the peroxide intermediate and an inverse kinetic solvent isotope effect, which indicates that this proton is already transferred when the O-O bond is cleaved. Residue D94, near the T2 site, plays a key role in the reaction of the reduced TNC with O2, and drives electron transfer from the T2 Cu to cleave the O-O bond by deprotonating the T2 Cu water ligand. A mechanism is developed where these second sphere residues participate in the proton assisted reductive cleavage of the O-O bond at the TNC.
Related Links	http://dx.doi.org/10.1021/ja073905m
Ending Page	13126
Page Count	9
Starting Page	13118
File Format	PDF
ISSN	00027863
e-ISSN	15205126
Journal	Journal of the American Chemical Society
Issue Number	43
Volume Number	129
Language	English
Publisher Date	2007-10-01
Access Restriction	Open
Subject Keyword	Colloid and Surface Chemistry Biochemistry Chemistry(all) Catalysis Research in Higher Education
Content Type	Text
Resource Type	Article
Subject	Chemistry Colloid and Surface Chemistry Biochemistry Catalysis

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