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.

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