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 d etermined by time-of-flight secondary ion mass spectrometry under impact of similar to 25 keV Xe+ and SF5+ ion beams and similar to 100 MeV Cf-252 fis sion fragments. Matrix-embedded samples, dissolved in a large surplus of al pha-cyano-4-hydroxycinnamic acid, were prepared by nebulizer spray depositi on, neat samples by the droplet technique. It is shown that the status of t he sample can be assessed by evaluating the matrix-specific features of the mass spectra. The beneficial effect of matrix isolation was small for angi otensin 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 fact or 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 fiss ion fragments were qualitatively similar. Quantitative differences include the following: with fast projectiles the yields were about 10-30 times high er than with slow ions, but similar for negative ion emission under SF5+ bo mbardment; the analyte-to-matrix yield ratios were higher with slow ions an d 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 strongl y reduced the yield of protonated analyte molecules ejected by slow ion imp act, but not of deprotonated species. Hence protonation seems to correlate with sample "wetness" or the presence of volatile proton-donating additives . (J Am Soc Mass Spectrom 2000, 11, 553-563) (C) 2000 American Society for Mass Spectrometry.