Time-of-flight secondary ion mass spectrometry of matrix-diluted oligo- and polypeptides bombarded with slow and fast projectiles: positive and negative matrix and analyte ion yields, background signals, and sample aging.

Human angiotensin II, chain B of bovine insulin, and porcine insulin were determined by time-of-flight secondary ion mass spectrometry under impact of approximately 25 keV Xe+ and SF5+ ion beams and approximately 100 MeV 252Cf fission fragments. Matrix-embedded samples, dissolved in a large surplus of alpha-cyano-4-hydroxycinnamic acid, were prepared by nebulizer spray deposition, neat samples by the droplet technique. It is shown that the status of the sample can be assessed by evaluating the matrix-specific features of the mass spectra. The beneficial effect of matrix isolation was small for angiotensin but large for the insulin samples, which did not show parent peaks from neat material. Negative ion yields under SF5+ impact were up to a factor of 50 higher than with Xe+. For positive secondary ions, the enhancement was much smaller. The mass spectra produced by slow ion beams or fast fission fragments were qualitatively similar. Quantitative differences include the following: with fast projectiles the yields were about 10-30 times higher than with slow ions, but similar for negative ion emission under SF5+ bombardment; the analyte-to-matrix yield ratios were higher with slow ions and up to 250 times higher than the molar analyte concentration; for analyte ions the peak-to-background ratios were higher using slow projectiles; the fraction of carbon-rich collisionally formed molecular ions was much higher with fast projectiles. Sample aging in vacuum for up to five weeks strongly reduced the yield of protonated analyte molecules ejected by slow ion impact, but not of deprotonated species. Hence protonation seems to correlate with sample "wetness" or the presence of volatile proton-donating additives.

252Cf-plasma desorption mass spectrometry. II--A perspective of new directions.

The 252Cf-PDMS method is a 'mature' technique, having survived 20 years of research, development and application. Recent advances in the application of the method have led to the use of the technique in clinical quantitation studies, the development of a microscopic method for measuring chemical homogeneity, in situ applications where serial modifications can be made and studied in a sequential fashion and the utilization of the primary fragmentation patterns to correlate with primary structure. Future directions in research, development and application will focus more attention on the chemistry of the 252Cf-PDMS process and the understanding and control of gas-phase reactions that occur in the ejection plume. Predictions are that the application of the in situ modification technique could lead to a new approach to pharmacokinetic studies as well as cell surface interactions where 252Cf-PDMS is effectively used to expand the capabilities of in vitro studies of biological processes.

Matrix isolation applied to the 252Cf plasma-desorption mass spectrometry of underivatized oligosaccharides.

A number of different low molecular weight and volatile compounds have been tested and compared as matrices in 252Cf plasma-desorption mass spectrometry (PDMS) measurements of oligosaccharides. Some heteroaromatic amines (2-aminothiazole and 3-aminopyridine), hydroxyanthraquinones (alizarin and quinalizarin) and phthaleins (fluorescein) proved to be especially suited to enhancing the quasimolecular ion intensity of oligosaccharides. Discrimination effects could be reduced by matrix addition and thus, quantitative results of PDMS could be improved. Oligosaccharides with broad molecular weight distribution (dextrin 10 and dextran T 1.5) have been successfully analyzed by PDMS. The mass spectra obtained compared quite well with ion chromatograms of the respective oligosaccharides.

Inactivation of Saccharomyces cells by 8-methoxypsoralen plus pulsed laser irradiation in the wavelength range 308 nm-380 nm.

Two different strains of Saccharomyces cerevisiae, one diploid wild type and one haploid mutant deficient in excision repair were irradiated with laser pulses in the range 308 nm to 380 nm after 8-MOP treatment. Both the shoulder (Dq) and the final slope (Do) of the inactivation curves were dependent on wavelength which showed a broad minimum around 355 nm. No differences in inactivation were recorded after pulsed irradiations between the repetition rates of 5 Hz and 35 Hz. Irradiations with pulses of the energy density from 0.1 mJ/cm2 up to 26 mJ/cm2 resulted in a final slope increasing with pulse energy density. This was in contrast to the effects of irradiation alone.