title: ThePodospora anserinalytic polysaccharide monooxygenasePaLPMO9H catalyzes oxidative cleavage of diverse plant cell wall matrix glycans.
abstract: BACKGROUND
  The enzymatic conversion of plant biomass has been recently revolutionized by the discovery of lytic polysaccharide monooxygenases (LPMO) that catalyze oxidative cleavage of polysaccharides. These powerful enzymes are secreted by a large number of fungal saprotrophs and are important components of commercial enzyme cocktails used for industrial biomass conversion. Among the 33 AA9 LPMOs encoded by the genome ofPodospora anserina, thePaLPMO9H enzyme catalyzes mixed C1/C4 oxidative cleavage of cellulose and cello-oligosaccharides. Activity ofPaLPMO9H on several hemicelluloses has been suggested, but the regioselectivity of the cleavage remained to be determined.
  
  
  RESULTS
  In this study, we investigated the activity ofPaLPMO9H on mixed-linkage glucans, xyloglucan and glucomannan using tandem mass spectrometry and ion mobility-mass spectrometry. Structural analysis of the released products revealed thatPaLPMO9H catalyzes C4 oxidative cleavage of mixed-linkage glucans and mixed C1/C4 oxidative cleavage of glucomannan and xyloglucan. Gem-diols and ketones were produced at the non-reducing end, while aldonic acids were produced at the reducing extremity of the products.
  
  
  CONCLUSIONS
  The ability ofPaLPMO9H to target polysaccharides, differing from cellulose by their linkages, glycosidic composition and/or presence of sidechains, could be advantageous for this coprophilous fungus when catabolizing highly variable polysaccharides and for the development of optimized enzyme cocktails in biorefineries.
authors.affiliation: Unité de Recherche Biopolymères, Interactions, Assemblages, INRA, 44316 Nantes, France.
authors.forename: Mathieu
authors.initials: M
authors.lastname: Fanuel
authors.affiliation: Polytech Marseille, UMR1163 Biodiversité et Biotechnologie Fongiques, INRA, Aix-Marseille Université, Avenue de Luminy, 13288 Marseille, France.
authors.forename: Sona
authors.initials: S
authors.lastname: Garajova
authors.affiliation: Unité de Recherche Biopolymères, Interactions, Assemblages, INRA, 44316 Nantes, France.
authors.forename: David
authors.initials: D
authors.lastname: Ropartz
authors.affiliation: Michael Smith Laboratories, University of British Columbia, 2185 East Mall, Vancouver, BC V6T 1Z4 Canada.|Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 Canada.
authors.forename: Nicholas
authors.initials: N
authors.lastname: McGregor
authors.affiliation: Michael Smith Laboratories, University of British Columbia, 2185 East Mall, Vancouver, BC V6T 1Z4 Canada.|Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 Canada.|Department of Biochemistry, University of British Columbia, 2350 Health Sciences Mall, Vancouver, BC V6T 1Z3 Canada.|Department of Botany, University of British Columbia, 6270 University Boulevard, Vancouver, BC V6T 1Z4 Canada.
authors.forename: Harry
authors.initials: H
authors.lastname: Brumer
authors.affiliation: Unité de Recherche Biopolymères, Interactions, Assemblages, INRA, 44316 Nantes, France.
authors.forename: Hélène
authors.initials: H
authors.lastname: Rogniaux
authors.affiliation: Polytech Marseille, UMR1163 Biodiversité et Biotechnologie Fongiques, INRA, Aix-Marseille Université, Avenue de Luminy, 13288 Marseille, France.
authors.forename: Jean-Guy
authors.identifier: 0000-0001-7570-3745
authors.initials: JG
authors.lastname: Berrin
keywords: AA9; Biomass; Biorefinery; LPMO; Lignocellulose; Mass spectrometry; Polysaccharides