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Gewählte Publikation:

Sun, PC; Laurent, CVFP; Boerkamp, VJP; van Erven, G; Ludwig, R; van Berkel, WJH; Kabel, MA.
(2022): Regioselective C4 and C6 Double Oxidation of Cellulose by Lytic Polysaccharide Monooxygenases
CHEMSUSCHEM. 2022; 15(2): FullText FullText_BOKU

Lytic polysaccharide monooxygenases (LPMOs) play a key role in enzymatic degradation of hard-to-convert polysaccharides, such as chitin and cellulose. It is widely accepted that LPMOs catalyze a single regioselective oxidation of the C1 or C4 carbon of a glycosidic linkage, after which the destabilized linkage breaks. Here, a series of novel C4/C6 double oxidized cello-oligosaccharides was discovered. Products were characterized, aided by sodium borodeuteride reduction and hydrophilic interaction chromatography coupled to mass spectrometric analysis. The C4/C6 double oxidized products were generated by C4 and C1/C4 oxidizing LPMOs, but not by C1 oxidizing ones. By performing incubation and reduction in (H2O)-O-18, it was confirmed that the C6 gem-diol structure resulted from oxygenation, although oxidation to a C6 aldehyde, followed by hydration to the C6 gem-diol, could not be excluded. These findings can be extended to how the reactive LPMO-cosubstrate complex is positioned towards the substrate.
Autor*innen der BOKU Wien:
Laurent Christophe Victor
Ludwig Roland
BOKU Gendermonitor:

Find related publications in this database (Keywords)
isotopic labeling
lytic polysaccharide monooxygenase
mass spectrometry

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