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Kinetic insights into the peroxygenase activity of cellulose-active lytic polysaccharide monooxygenases (LPMOs)

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  • Riin Kont

    (University of Tartu)

  • Bastien Bissaro

    (NMBU—Norwegian University of Life Sciences
    INRAE, Aix Marseille University, UMR1163 Biodiversité et Biotechnologie Fongiques)

  • Vincent G. H. Eijsink

    (NMBU—Norwegian University of Life Sciences)

  • Priit Väljamäe

    (University of Tartu)

Abstract

Lytic polysaccharide monooxygenases (LPMOs) are widely distributed in Nature, where they catalyze the hydroxylation of glycosidic bonds in polysaccharides. Despite the importance of LPMOs in the global carbon cycle and in industrial biomass conversion, the catalytic properties of these monocopper enzymes remain enigmatic. Strikingly, there is a remarkable lack of kinetic data, likely due to a multitude of experimental challenges related to the insoluble nature of LPMO substrates, like cellulose and chitin, and to the occurrence of multiple side reactions. Here, we employed competition between well characterized reference enzymes and LPMOs for the H2O2 co-substrate to kinetically characterize LPMO-catalyzed cellulose oxidation. LPMOs of both bacterial and fungal origin showed high peroxygenase efficiencies, with kcat/KmH2O2 values in the order of 105–106 M−1 s−1. Besides providing crucial insight into the cellulolytic peroxygenase reaction, these results show that LPMOs belonging to multiple families and active on multiple substrates are true peroxygenases.

Suggested Citation

  • Riin Kont & Bastien Bissaro & Vincent G. H. Eijsink & Priit Väljamäe, 2020. "Kinetic insights into the peroxygenase activity of cellulose-active lytic polysaccharide monooxygenases (LPMOs)," Nature Communications, Nature, vol. 11(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:11:y:2020:i:1:d:10.1038_s41467-020-19561-8
    DOI: 10.1038/s41467-020-19561-8
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    Cited by:

    1. Hucheng Chang & Neus Gacias Amengual & Alexander Botz & Lorenz Schwaiger & Daniel Kracher & Stefan Scheiblbrandner & Florian Csarman & Roland Ludwig, 2022. "Investigating lytic polysaccharide monooxygenase-assisted wood cell wall degradation with microsensors," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    2. Iván Ayuso-Fernández & Tom Z. Emrich-Mills & Julia Haak & Ole Golten & Kelsi R. Hall & Lorenz Schwaiger & Trond S. Moe & Anton A. Stepnov & Roland Ludwig & George E. Cutsail III & Morten Sørlie & Åsmu, 2024. "Mutational dissection of a hole hopping route in a lytic polysaccharide monooxygenase (LPMO)," Nature Communications, Nature, vol. 15(1), pages 1-15, December.

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