Structural and electronic snapshots during the transition from a Cu(II) to Cu(I) metal center of a lytic polysaccharide onooxygenase by x-ray photoreduction

Abstract

Background: Lytic polysaccharide monooxygenases (LPMOs) exhibit a copper center that binds dioxygen for catalysis. Results: We present LPMO structures from Cu(II) to Cu(I) and analyze the transition with quantum mechanical calculations. Conclusion: Reduction changes the copper coordination state but requires only minor structural and electronic changes. Significance: These structures provide insight into LPMO catalytic activation for further mechanistic studies. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.