Identification of plant polysaccharides by MALDI-TOF MS fingerprinting after periodate oxidation and thermal hydrolysis

An autoclave treatment at 121 °C on periodate-oxidized plant polysaccharides and mixes thereof was investigated for the release of oligosaccharides to obtain a generic polysaccharide depolymerization method for polysaccharides fingerprinting. Matrix-Assisted Laser Desorption Ionization Time-Of-Flight Mass Spectrometry (MALDI-TOF MS) analysis of the oligosaccharides released showed that each polysaccharide had a unique oligosaccharides profile, even the same type of polysaccharide derived from different sources and/or having different fine structures (e.g. class of (arabino)xylans, galactomannans, glucans, or pectic materials). Various polysaccharide classes present in a polysaccharide mix could be identified based on significantly different (p < 0.05) marker m/z values present in the mass spectrum. Principal component analysis and hierarchical cluster analysis of the obtained MALDI-TOF MS data highlighted the structural heterogeneity of the polysaccharides studied, and clustered polysaccharide samples with resembling oligosaccharide profiles. Our approach represents a step further towards a generic and accessible identification of plant polysaccharides individually or in a mixture.