Loss of oligomer information in pyrolysis-desorption/chemical-ionization mass spectrometry of amylose, due to the influence of potassium hydroxide

Pyrolysis-desorption/chemical-ionisation mass spectrometry (PyD/CIMS), using ammonia as ionization gas, was employed to investigate the influence of potassium hydroxide on the pyrolytic behaviour of glucans. The mass spectrum of native amylose, a 1 → 4 linked α-D-glucan, revealed an ion series pointing to desorption of intact 1,6-anhydro-oligosaccharides. Ions indicating oligomers up to the nonamer were observed. Addition of trace amounts of potassium hydroxide to amylose resulted in reduction in the size of the 1,6-anhydro-oligosaccharide ions and a simultaneous increase of ions resulting from ring rearrangements. Larger amounts of potassium hydroxide led to a complete loss of mass spectral information at the oligomer level.

Similar mass spectrometric distributions in the PyD/CIMS data of a potassium hydroxide extracted tobacco fraction clearly reveal that alkali remnants must be present in this sample, which severly reduce the mass spectrometric information from polysaccharide oligomers. It is important to evaluate the role of inorganics on the thermal activation and subsequent fragmentation of biopolymers in PyD/CIMS experiments.