Pyrolysis field ionization mass spectrometry of carbohydrates: Part b: Polysaccharides

The application of pyrolysis in combination with field ionization (FI) mass spectrometry for the characterization and identification of polysaccharides is reported. Polysaccharides such as xylan, agarose and alginic acid, which contain monomer subunits of different elemental composition, can be differentiated in a straightforward manner by the field ionization spectra of their Curie-point pyrolysates. Polysaccharides with hexosyl subunits, such as cellulose, galactan, laminaran and mannan, were pyrolysed by Curie-point pyrolysis and show photographically recorded FI spectra which differ in the relative heights of their pyrolysis peaks. Characteristic pyrolysis products are formed, which can be identified or assigned structures on the basis of accurate mass measurements, direct isotopic determination and by analogy with established chemical procedures and mechanisms.Oven pyrolysis of polysaccharides combined with electrical detection of the FI spectra at low mass resolution gives a higher sensitivity and better reproducibility for all peaks over the whole mass range. From sample amounts of about 40 μg, spectra are obtained by raising the oven temperature by 0.4°C/s. Utilizing repetitive magnetic scanning, registration and signal processing by the data system, the standard deviation of the peak heights for five repeated measurements is about 10%. Accumulation of about 30 spectra in a limited mass range on a multi-channel analyser gives results which vary by about 2–3% on average, despite a lower sample consumption (20–30 μg). Oven pyrolysis between 250 and 400°C yields significant differences in the spectra of differently linked mannans and allows an unequivocal differentiation of these isomers. Following FI, field desorption (FD) spectra were obtained from pyrolysis products condensed on the emitter surface by heating of the emitter wire between 10 and 30 mA. The cations of alkali metals, such as Na*, K* and Cs*, can be registered in this way. Most interesting is the detection of the molecular ions of monomer and oligomer subunits of the polysaccharides as complementary analytical information in the FD mode. Obviously, condensation of these neutral, thermal products on the emitter surface occurs without field ionization and desorption is initiated by supply of thermal energy to the adsorbed sample layer.