Polysaccharide metabolism in Anacardiaceae (Asian lacquer) cross-linked polymers elucidated using in situ trimethylsilylation pyrolysis-gas chromatography–mass spectrometry

Abstract

Carbohydrates from polysaccharides in natural thermoset Anacardiaceae polymers of Gluta usitata, Toxicodendron succedaneum and Toxicodendron vernicifluum were identified using pyrolysis-gas chromatography–mass spectrometry with in situ trimethylsilylation. Pyrolysates resulting from the pyrolytic intermolecular chain scission of the polysaccharides were used to elucidate monomeric units. Polysaccharides, dispersed in the phenolic lacasse catalysed cross-linked macromolecules, showed to be metabolised through various catabolic and anabolic routes. Galactose functionalities, abundantly present in the polysaccharides were determined to be enzymatically converted to glucose-6-phosphate, followed by conversion via glycolysis and pentose phosphate pathways. Determination of specific routes of carbohydrate modification via glycolysis and pentose phosphate pathways facilitated differentiating G. usitata, T. succedaneum and T. vernicifluum polymers, based on the carbohydrate content. It was also found that uronic type acids, present as end groups of the branched polysaccharide structure, were biochemically converted to aldonic acids. Following the pentose phosphate and glycolysis routes, carbohydrates in G. usitata and T. vernicifluum polymers showed to be further modified via shikimate and cinnamate pathways to produce phenylpropanoid compounds. Parent molecules and pyrolysis products thereof were verified using analytical standards of high purity. The mass spectra and Kovats retention indices were compiled in an AMDIS library, which can be made available on request.