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Internal energies of analyte ions generated from different matrix‐assisted laser desorption/ionization matrices
Author(s) -
Stevenson Elizabeth,
Breuker Kathrin,
Zenobi Renato
Publication year - 2000
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/1096-9888(200008)35:8<1035::aid-jms34>3.0.co;2-v
Subject(s) - chemistry , internal energy , mass spectrometry , analyte , analytical chemistry (journal) , ion , sublimation (psychology) , fragmentation (computing) , fourier transform ion cyclotron resonance , dissociation (chemistry) , ionization , matrix assisted laser desorption/ionization , desorption , kinetic energy , chromatography , thermodynamics , organic chemistry , adsorption , psychology , physics , quantum mechanics , computer science , psychotherapist , operating system
A transfer of energy into the internal modes of the matrix and analyte is expected to occur during matrix‐assisted laser desorption/ioniziation (MALDI) processes. Both the physical and thermochemical properties of the MALDI matrix used can influence the ion internal energy and analyte ion fragmentation. Here we report the effect of several MALDI matrices on the relative internal energy of the 2′‐deoxyadenylyl‐(3′,5′)‐2′‐deoxyguanosine (AG) anion. Relative internal energies were probed by low‐energy collision‐induced dissociation in a Fourier transform ion cyclotron resonance mass spectrometer. Sublimation temperatures of the matrices under study were also determined and found to lie between 409 and 455 K. Analyte ion internal and initial kinetic energies did not correlate with matrix sublimation temperatures. In contrast, a strong correlation between the relative internal energy of the analyte anions and the gas‐phase basicity of the matrix anions was found. These results suggest that gas‐phase proton transfer reactions play an important role in MALDI analyte ion formation and influence their internal energy and fragmentation behavior. Copyright © 2000 John Wiley & Sons, Ltd.