HIGH-PERFORMANCE LIQUID-CHROMATOGRAPHY CHEMICAL IONIZATION MASS-SPECTROMETRIC ANALYSIS OF PYROLYSATES OF AMYLOSE AND CELLULOSE

In-source pyrolysis chemical Ionization mass spectrometry (PyCIMS) of polysaccharides shows a number of ion series that correspond to anhydrooligosaccharides and oligosaccharides with attached sugar ring-cleavage fragments. To confirm that these observed Ion series are produced upon pyrolysis and not by cluster formation or fragmentation in the Ion source, off-line Curie point pyrolysates of amylose and cellulose were prepared, and their condensates were per-O-benzoylated. The desorption chemical Ionization (DCI) mass spectra of the pyrolysates show Ion series that correspond to those in the PyCI mass spectra, taking into account mass changes upon derivatization. Chromatographic separation (high-performance liquid chromatography (HPLC)) of these derivatized pyrolysates Indicates a range of Isomeric products corresponding to each of the major ions found In the DCI mass spectra. The fact that the retention times of the main peaks in the dimer and the trimer region of the amylose and cellulose pyrolysates In the chromatograms are quite different confirms that the conformation of the glycosldic bonds Is preserved upon pyrolysis. © 1990, American Chemical Society. All rights reserved.