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Abstract

A thermogravimetric/mass spectrometric (TG/MS) system was used to characterize the thermolysis reactions of (4-O-methyl-D-glucurono)-D-xylan. The mass spectrometric peaks, measured as function of time, were attributed to water, methanol, carbon monoxide, carbon dioxide, formaldehyde, formic acid, acetic acid, acetone, acrolein, 2-furaldehyde, and 3-hydroxy-2-penteno-1,5-lactone. The time derivative of the thermogravimetric curve (DTG) consisted of two partially overlapping peaks, indicating a multistep mechanism. The mass spectrometric intensities of the peaks assigned to methanol and 2-furaldehyde coincided with the first DTG peak, suggesting that the first DTG peak represents both dehydration and fragmentation pathways. Methanol, water, formyl group, and carbon dioxide contributed to both of the DTG peaks. This indicates that the dehydration, decarboxylation, and decarbonylation took place in two steps. The compounds observed only in the second DTG peak and later (acetone, formic acid, formaldehyde, acrolein, acetic acid, and 3-hydroxy-2-penteno-1,5-lactone) are probably products of reactions which occur after the collapse of the original polysaccharide structure.