Oxygen Activation at the Active Site of a Fungal Lytic Polysaccharide Monooxygenase
Abstract
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.
- Authors:
-
[1];
[2];
[1]
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Dept. of Molecular and Structural Biochemistry
- 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:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF); National Institutes of Health (NIH)
- OSTI Identifier:
- 1407721
- Grant/Contract Number:
- AC05-00OR22725; MRI 09229719; IGERT 1069091; GM105978
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Volume: 129; Journal Issue: 3; Journal ID: ISSN 0044-8249
- Publisher:
- German Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; copper; oxidoreductases; oxygen activation; polysaccharide monooxygenases; protein structures
Citation Formats
O'Dell, William B., Agarwal, Pratul K., and Meilleur, Flora. Oxygen Activation at the Active Site of a Fungal Lytic Polysaccharide Monooxygenase. United States: N. p., 2016.
Web. doi:10.1002/ange.201610502.
O'Dell, William B., Agarwal, Pratul K., & Meilleur, Flora. Oxygen Activation at the Active Site of a Fungal Lytic Polysaccharide Monooxygenase. United States. https://doi.org/10.1002/ange.201610502
O'Dell, William B., Agarwal, Pratul K., and Meilleur, Flora. Thu .
"Oxygen Activation at the Active Site of a Fungal Lytic Polysaccharide Monooxygenase". United States. https://doi.org/10.1002/ange.201610502. https://www.osti.gov/servlets/purl/1407721.
@article{osti_1407721,
title = {Oxygen Activation at the Active Site of a Fungal Lytic Polysaccharide Monooxygenase},
author = {O'Dell, William B. and Agarwal, Pratul K. and Meilleur, Flora},
abstractNote = {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.},
doi = {10.1002/ange.201610502},
journal = {Angewandte Chemie},
number = 3,
volume = 129,
place = {United States},
year = {Thu Dec 22 00:00:00 EST 2016},
month = {Thu Dec 22 00:00:00 EST 2016}
}
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