The molecular basis of polysaccharide cleavage by lytic polysaccharide monooxygenases

Kristian E H Frandsen; Thomas J Simmons; Paul Dupree; Jens-Christian N Poulsen; Glyn R Hemsworth; Luisa Ciano; Esther M Johnston; Morten Tovborg; Katja S Johansen; Pernille von Freiesleben; Laurence Marmuse; Sébastien Fort; Sylvain Cottaz; Hugues Driguez; Bernard Henrissat; Nicolas Lenfant; Floriana Tuna; Amgalanbaatar Baldansuren; Gideon J Davies; Leila Lo Leggio; Paul H Walton

doi:10.1038/nchembio.2029

The molecular basis of polysaccharide cleavage by lytic polysaccharide monooxygenases

Nat Chem Biol. 2016 Apr;12(4):298-303. doi: 10.1038/nchembio.2029. Epub 2016 Feb 29.

Authors

Kristian E H Frandsen¹, Thomas J Simmons², Paul Dupree², Jens-Christian N Poulsen¹, Glyn R Hemsworth³, Luisa Ciano³, Esther M Johnston³, Morten Tovborg⁴, Katja S Johansen⁴, Pernille von Freiesleben⁴, Laurence Marmuse⁵, Sébastien Fort⁵, Sylvain Cottaz⁵, Hugues Driguez⁵, Bernard Henrissat^{6

7

8}, Nicolas Lenfant^{6

7}, Floriana Tuna⁹, Amgalanbaatar Baldansuren⁹, Gideon J Davies³, Leila Lo Leggio¹, Paul H Walton³

Affiliations

¹ Department of Chemistry, University of Copenhagen, Copenhagen, Denmark.
² Department of Biochemistry, University of Cambridge, Cambridge, UK.
³ Department of Chemistry, University of York, York, UK.
⁴ Novozymes A/S, Bagsvaerd, Denmark.
⁵ Centre de Recherches sur les Macromolecules Végétales (CERMAV), Université de Grenoble Alpes, Centre National de la Recherche Scientifique (CNRS), Grenoble, France.
⁶ Architecture et Fonction des Macromolécules Biologiques (AFMB), CNRS, Aix-Marseille Université, Marseille, France.
⁷ Institut National de la Recherche Agronomique (INRA), AFMB, Marseille, France.
⁸ Department of Biological Sciences, King Abdulaziz University, Jeddah, Saudi Arabia.
⁹ Engineering and Physical Sciences Research Council (EPSRC) National EPR Facility, School of Chemistry and Photon Science Institute, University of Manchester, Manchester, UK.

Abstract

Lytic polysaccharide monooxygenases (LPMOs) are copper-containing enzymes that oxidatively break down recalcitrant polysaccharides such as cellulose and chitin. Since their discovery, LPMOs have become integral factors in the industrial utilization of biomass, especially in the sustainable generation of cellulosic bioethanol. We report here a structural determination of an LPMO-oligosaccharide complex, yielding detailed insights into the mechanism of action of these enzymes. Using a combination of structure and electron paramagnetic resonance spectroscopy, we reveal the means by which LPMOs interact with saccharide substrates. We further uncover electronic and structural features of the enzyme active site, showing how LPMOs orchestrate the reaction of oxygen with polysaccharide chains.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Amino Acid Sequence
Aspergillus oryzae / enzymology
Aspergillus oryzae / genetics
Binding Sites
Catalytic Domain
Cellulose / metabolism*
Chitin / metabolism*
Copper / metabolism
Crystallography, X-Ray
Fluorescence Resonance Energy Transfer
Lentinula / enzymology
Lentinula / genetics
Mixed Function Oxygenases / chemistry
Mixed Function Oxygenases / genetics
Mixed Function Oxygenases / metabolism*
Models, Molecular
Molecular Sequence Data
Oligosaccharides / chemistry
Oxidation-Reduction
Substrate Specificity

Substances

Oligosaccharides
Chitin
Copper
Cellulose
Mixed Function Oxygenases

Associated data

PubChem-Substance/310264795
PubChem-Substance/310264796
PubChem-Substance/310264797
PubChem-Substance/310264798
PubChem-Substance/310264799
PubChem-Substance/310264800
PubChem-Substance/310264801
PubChem-Substance/310264802

Abstract

Publication types

MeSH terms

Substances

Associated data

Grants and funding