Spectroscopic and computational insight into the activation of O 2 by the mononuclear Cu center in polysaccharide monooxygenases

• DOI: 10.1073/pnas.1408115111
• Publication Date: 2014-06-03T06:56:28Z
• Authors: Christian H. Kjae...; Munzarin F. Qayyum; Shaun D. Wong; Feng Xu; Glyn R. Hemsworth; Daniel J. Walton; Nigel A. Young; Gideon J. Davies; Paul H. Walton; Katja Salomon Joh...; Keith O. Hodgson; Britt Hedman; Edward I. Solomon
• Keywords: Reactivity; Active center

Significance Activation of the O-O bond in dioxygen is difficult but fundamental biology. Nature has evolved several strategies to achieve this, often including copper as an enzyme cofactor. Copper-dependent enzymes usually use more than one metal activate O 2 by multielectron reduction, recently it was discovered that cellulose and chitin degrading polysaccharide monooxygenase only a single Cu center for catalysis, reaction great interest biofuel industries. To understand this reactivity, we have determined solution structures both reduced oxidized site, experimentally computationally how site capable facile activation thermodynamically one-electron via inner-sphere Cu-superoxide intermediate.