Mass spectrometric fragmentation patterns discriminate C1- and C4-oxidised cello-oligosaccharides from their non-oxidised and reduced forms
Autor: | Mirjam A. Kabel, Edwin J. Bakx, Maloe Kleine Haar, Willem J. H. van Berkel, Matthias Frommhagen, Gijs van Erven, Peicheng Sun |
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Jazyk: | angličtina |
Rok vydání: | 2020 |
Předmět: |
Polymers and Plastics
Collision-induced dissociation Stereochemistry Oligosaccharides 02 engineering and technology 010402 general chemistry Polysaccharide Mass spectrometry HILIC-ESI-CID-MS/MS 01 natural sciences Mass Spectrometry Mixed Function Oxygenases chemistry.chemical_compound Fragmentation (mass spectrometry) Cello-oligosaccharides Polysaccharides Oxidation Levensmiddelenchemie Materials Chemistry Cellulose VLAG Reduction chemistry.chemical_classification Molecular Structure Food Chemistry Biomass conversion Hydrophilic interaction chromatography Organic Chemistry LPMOs Glycosidic bond Monooxygenase 021001 nanoscience & nanotechnology 0104 chemical sciences chemistry Mass spectrometric fragmentation 0210 nano-technology Oxidation-Reduction Lignocellulose |
Zdroj: | Carbohydrate Polymers 234 (2020) Carbohydrate Polymers, 234 |
ISSN: | 0144-8617 |
DOI: | 10.1016/j.carbpol.2020.115917 |
Popis: | Lytic polysaccharide monooxygenases (LPMOs) are powerful enzymes that degrade recalcitrant polysaccharides, such as cellulose. However, the identification of LPMO-generated C1- and/or C4-oxidised oligosaccharides is far from straightforward. In particular, their fragmentation patterns have not been well established when using mass spectrometry. Hence, we studied the fragmentation behaviours of non-, C1- and C4-oxidised cello-oligosaccharides, including their sodium borodeuteride-reduced forms, by using hydrophilic interaction chromatography and negative ion mode collision induced dissociation - mass spectrometry. Non-oxidised cello-oligosaccharides showed predominantly C- and A-type cleavages. In comparison, C4-oxidised ones underwent B-/Y- and X-cleavage close to the oxidised non-reducing end, while closer to the reducing end C-/Z- and A-fragmentation predominated. C1-oxidised cello-oligosaccharides showed extensively A-cleavage. Reduced oligosaccharides showed predominant glycosidic bond cleavage, both B-/Y- and C-/Z-, close to the non-reducing end. Our findings provide signature mass spectrometric fragmentation patterns to unambiguously elucidate the catalytic behaviour and classification of LPMOs. |
Databáze: | OpenAIRE |
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