Molecular mechanism of the chitinolytic peroxygenase reaction

Bissaro, Bastien; Streit, Bennett; Isaksen, Ingvild; Eijsink, Vincent G. H.; Beckham, Gregg T.; DuBois, Jennifer L.; Røhr, Åsmund K.

doi:10.1073/pnas.1904889117

Title: Molecular mechanism of the chitinolytic peroxygenase reaction

Journal Article · 06 January 2020 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.1904889117 · OSTI ID:1581447

^[1]; Streit, Bennett ^[2]; Isaksen, Ingvild ^[1];

^[1];

^[3];

^[2];

^[1]

Faculty of Chemistry, Biotechnology and Food Science, Norwegian University of Life Sciences, N-1432 Ås, Norway,
Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT 59717,
National Bioenergy Center, National Renewable Energy Laboratory, Golden, CO 80401

Significance Biomass decomposition by microorganisms relies on a battery of enzymes, of which lytic polysaccharide monooxygenases (LPMOs) constitute a central player. LPMOs are notably able to disrupt the abundant recalcitrant carbohydrates cellulose and chitin and thus increase the overall rate of their degradation. It has recently been demonstrated that LPMOs prefer hydrogen peroxide over molecular oxygen to oxidize and cleave their substrates. Here, we explain through molecular simulations and experiments how a chitin-active LPMO activates hydrogen peroxide and catalyzes substrate hydrogen abstraction. Thereby, we reveal the molecular details of this unusual bioinorganic chemistry, which is of high relevance for the understanding of pathogenesis-defense mechanisms and biomass turnover.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1581447

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 3 Vol. 117; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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