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Title: Oxygen Activation at the Active Site of a Fungal Lytic Polysaccharide Monooxygenase

Lytic polysaccharide monooxygenases have attracted vast attention owing to their abilities to disrupt glycosidic bonds via oxidation instead of hydrolysis and to enhance enzymatic digestion of recalcitrant substrates including chitin and cellulose. Here, we determined the high-resolution X-ray crystal structures of an enzyme from Neurospora crassa in the resting state and of a copper(II) dioxo intermediate complex formed in the absence of substrate. X-ray crystal structures also revealed “pre-bound” molecular oxygen adjacent to the active site. An examination of protonation states enabled by neutron crystallography and density functional theory calculations identified a role for a conserved histidine in promoting oxygen activation. Our results provide a new structural description of oxygen activation by substrate free lytic polysaccharide monooxygenases and provide insights that can be extended to reactivity in the enzyme–substrate complex.
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Dept. of Molecular and Structural Biochemistry
  2. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Biochemisty, Cellular and Molecular Biology; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Knoxville and Computatinal Biology Inst., Computer Science, Mathematics Division
Publication Date:
Grant/Contract Number:
AC05-00OR22725; MRI 09229719; IGERT 1069091; GM105978
Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Volume: 129; Journal Issue: 3; Journal ID: ISSN 0044-8249
German Chemical Society
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Science Foundation (NSF); National Institutes of Health (NIH)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; copper; oxidoreductases; oxygen activation; polysaccharide monooxygenases; protein structures
OSTI Identifier: