Matrix-Assisted Variable Wavelength Laser Desorption Ionization of Peptides; Influence of the Matrix Absorption Coefficient on Expansion Cooling

Abstract

Product ion yields in the in-and post-source decays of three peptide ions, [Y 5 X + H]+ (X = Y (tyrosine), K (lysine), and R (arginine)), generated by matrix-assisted laser desorption ionization (MALDI) were measured at six wavelengths, 307, 317, 327, 337, 347, and 357 nm, using α-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB) as the matrices. The temperatures of the early and late plumes generated by MALDI were estimated via kinetic analysis of the product ion yield data. For both matrices, the temperature drop (ΔT), i.e. the difference in the temperature between the early and late plumes, displayed negative correlation with the absorption coefficient. This was in agreement with the previous reasoning that deeper laser penetration and larger amount of material ablation arising from smaller absorption coefficient would result in larger extent of expansion cooling. The results support the postulation of the expansion cooling occurring in the plume presented previously.

A Thermal Mechanism of Ion Formation in MALDI

“…Although the most important aspect of the ISD of peptide ions is the production of c-and ztype ions (52), regular b-y channels dominate in the dissociation of small peptide ions without arginine (53,54). ISD in such cases is efficient but terminates rapidly, within 100 ns (14).…”