title: The molecular basis of polysaccharide cleavage by lytic polysaccharide monooxygenases.
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.
authors.affiliation: Department of Chemistry, University of Copenhagen, Copenhagen, Denmark.
authors.forename: Kristian E H
authors.initials: KE
authors.lastname: Frandsen
authors.affiliation: Department of Biochemistry, University of Cambridge, Cambridge, UK.
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Simmons
authors.affiliation: Department of Biochemistry, University of Cambridge, Cambridge, UK.
authors.forename: Paul
authors.identifier: http://orcid.org/0000-0001-9270-6286
authors.initials: P
authors.lastname: Dupree
authors.affiliation: Department of Chemistry, University of Copenhagen, Copenhagen, Denmark.
authors.forename: Jens-Christian N
authors.initials: JC
authors.lastname: Poulsen
authors.affiliation: Department of Chemistry, University of York, York, UK.
authors.forename: Glyn R
authors.identifier: http://orcid.org/0000-0002-8226-1380
authors.initials: GR
authors.lastname: Hemsworth
authors.affiliation: Department of Chemistry, University of York, York, UK.
authors.forename: Luisa
authors.identifier: http://orcid.org/0000-0002-1667-0856
authors.initials: L
authors.lastname: Ciano
authors.affiliation: Department of Chemistry, University of York, York, UK.
authors.forename: Esther M
authors.initials: EM
authors.lastname: Johnston
authors.affiliation: Novozymes A/S, Bagsvaerd, Denmark.
authors.forename: Morten
authors.initials: M
authors.lastname: Tovborg
authors.affiliation: Novozymes A/S, Bagsvaerd, Denmark.
authors.forename: Katja S
authors.initials: KS
authors.lastname: Johansen
authors.affiliation: Novozymes A/S, Bagsvaerd, Denmark.
authors.forename: Pernille
authors.initials: P
authors.lastname: von Freiesleben
authors.affiliation: Centre de Recherches sur les Macromolecules Végétales (CERMAV), Université de Grenoble Alpes, Centre National de la Recherche Scientifique (CNRS), Grenoble, France.
authors.forename: Laurence
authors.initials: L
authors.lastname: Marmuse
authors.affiliation: Centre de Recherches sur les Macromolecules Végétales (CERMAV), Université de Grenoble Alpes, Centre National de la Recherche Scientifique (CNRS), Grenoble, France.
authors.forename: Sébastien
authors.initials: S
authors.lastname: Fort
authors.affiliation: Centre de Recherches sur les Macromolecules Végétales (CERMAV), Université de Grenoble Alpes, Centre National de la Recherche Scientifique (CNRS), Grenoble, France.
authors.forename: Sylvain
authors.initials: S
authors.lastname: Cottaz
authors.affiliation: Centre de Recherches sur les Macromolecules Végétales (CERMAV), Université de Grenoble Alpes, Centre National de la Recherche Scientifique (CNRS), Grenoble, France.
authors.forename: Hugues
authors.initials: H
authors.lastname: Driguez
authors.affiliation: Architecture et Fonction des Macromolécules Biologiques (AFMB), CNRS, Aix-Marseille Université, Marseille, France.|Institut National de la Recherche Agronomique (INRA), AFMB, Marseille, France.|Department of Biological Sciences, King Abdulaziz University, Jeddah, Saudi Arabia.
authors.forename: Bernard
authors.initials: B
authors.lastname: Henrissat
authors.affiliation: Architecture et Fonction des Macromolécules Biologiques (AFMB), CNRS, Aix-Marseille Université, Marseille, France.|Institut National de la Recherche Agronomique (INRA), AFMB, Marseille, France.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Lenfant
authors.affiliation: Engineering and Physical Sciences Research Council (EPSRC) National EPR Facility, School of Chemistry and Photon Science Institute, University of Manchester, Manchester, UK.
authors.forename: Floriana
authors.initials: F
authors.lastname: Tuna
authors.affiliation: Engineering and Physical Sciences Research Council (EPSRC) National EPR Facility, School of Chemistry and Photon Science Institute, University of Manchester, Manchester, UK.
authors.forename: Amgalanbaatar
authors.identifier: http://orcid.org/0000-0001-8767-3731
authors.initials: A
authors.lastname: Baldansuren
authors.affiliation: Department of Chemistry, University of York, York, UK.
authors.forename: Gideon J
authors.identifier: http://orcid.org/0000-0002-7343-776X
authors.initials: GJ
authors.lastname: Davies
authors.affiliation: Department of Chemistry, University of Copenhagen, Copenhagen, Denmark.
authors.forename: Leila
authors.identifier: http://orcid.org/0000-0002-5135-0882
authors.initials: L
authors.lastname: Lo Leggio
authors.affiliation: Department of Chemistry, University of York, York, UK.
authors.forename: Paul H
authors.identifier: http://orcid.org/0000-0002-1152-1480
authors.initials: PH
authors.lastname: Walton
mesh_terms: D000595:Amino Acid Sequence; D001236:Aspergillus oryzae / Q000201:enzymology / Q000235:genetics; D001665:Binding Sites; D020134:Catalytic Domain; D002482:Cellulose / Q000378:metabolism*; D002686:Chitin / Q000378:metabolism*; D003300:Copper / Q000378:metabolism; D018360:Crystallography, X-Ray; D031541:Fluorescence Resonance Energy Transfer; D020074:Lentinula / Q000201:enzymology / Q000235:genetics; D006899:Mixed Function Oxygenases / Q000737:chemistry / Q000235:genetics / Q000378:metabolism*; D008958:Models, Molecular; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000737:chemistry; D010084:Oxidation-Reduction; D013379:Substrate Specificity
chemical_list: D009844:Oligosaccharides; D002686:Chitin; D003300:Copper; D002482:Cellulose; D006899:Mixed Function Oxygenases