Neutron and Atomic Resolution X-ray Structures of a Lytic Polysaccharide Monooxygenase Reveal Copper-Mediated Dioxygen Binding and Evidence for N-Terminal Deprotonation

Bacik, John-Paul; Mekasha, Sophanit; Forsberg, Zarah; Kovalevsky, Andrey Y.; Vaaje-Kolstad, Gustav; Eijsink, Vincent G.  H.; Nix, Jay C.; Coates, Leighton; Cuneo, Matthew J.; Unkefer, Clifford J.; Chen, Julian C. -H.

doi:10.1021/acs.biochem.7b00019

Title: Neutron and Atomic Resolution X-ray Structures of a Lytic Polysaccharide Monooxygenase Reveal Copper-Mediated Dioxygen Binding and Evidence for N-Terminal Deprotonation

Journal Article · Mon May 08 00:00:00 EDT 2017 · Biochemistry

DOI: https://doi.org/10.1021/acs.biochem.7b00019 · OSTI ID:1376613

Bacik, John-Paul ^[1]; Mekasha, Sophanit ^[2]; Forsberg, Zarah ^[2];

^[3]; Vaaje-Kolstad, Gustav ^[2]; Eijsink, Vincent G. H. ^[2]; Nix, Jay C. ^[4]; Coates, Leighton ^[3];

^[3]; Unkefer, Clifford J. ^[1];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Norwegian Univ., of Life Sciences (NMBU), As (Norway). Faculty of Chemistry, Biotechnology and Food Science
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biology and Soft Matter Division
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

A 1.1 Å resolution, room-temperature X-ray structure and a 2.1 Å resolution neutron structure of a chitin-degrading lytic polysaccharide monooxygenase domain from the bacterium Jonesia denitrificans (JdLPMO10A) show a putative dioxygen species equatorially bound to the active site copper. We found that both structures show an elongated density for the dioxygen, most consistent with a Cu(II)-bound peroxide. The coordination environment is consistent with Cu(II). Furthermore, in the neutron and X-ray structures, difference maps reveal the N-terminal amino group, involved in copper coordination, is present as a mixed ND₂ and ND^–, suggesting a role for the copper ion in shifting the pK_a of the amino terminus.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231; AC52-06NA25396

OSTI ID:: 1376613

Report Number(s):: LA-UR--16-29648; 101148

Journal Information:: Biochemistry, Journal Name: Biochemistry Journal Issue: 20 Vol. 56; ISSN 0006-2960

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Molecular mechanism of lytic polysaccharide monooxygenases Hedegård, Erik Donovan; Ryde, Ulf Chemical Science, Vol. 9, Issue 15 https://doi.org/10.1039/c8sc00426a	journal	January 2018
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Title: Neutron and Atomic Resolution X-ray Structures of a Lytic Polysaccharide Monooxygenase Reveal Copper-Mediated Dioxygen Binding and Evidence for N-Terminal Deprotonation

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