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

Biochemistry. 2017 May 23;56(20):2529-2532. doi: 10.1021/acs.biochem.7b00019. Epub 2017 May 11.

Abstract

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. 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). 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 pKa of the amino terminus.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalytic Domain
  • Copper / chemistry*
  • Crystallography, X-Ray
  • Mixed Function Oxygenases / chemistry*
  • Oxygen / chemistry*
  • Polysaccharides / chemistry*
  • Protein Conformation
  • Protons

Substances

  • Polysaccharides
  • Protons
  • Copper
  • Mixed Function Oxygenases
  • Oxygen