mass spectrometry; internal energy; matrix-assisted laser desorption/ionization; MALDI; matrix
Abstract :
[en] In this paper, we report the measurement of the degree of analyte fragmentation in AP-MALDI as a function of the matrix and of the laser fluence. The analytes include p-OCH3-benzylpyridinium, three peptides containing the sequence EEPP (which cleave very efficiently at the E-P site), and three deoxynucleosides (dA, dG, and dC), which lose the neutral sugar to give the protonated base. We found that the matrix hardness/softness was consistent when comparing the analytes, with a consensus ranking from hardest to softest: CHCA >> DHB > SA approximate to THAP > ATT > HPA. However, the exact ranking can be fluence-dependent, for example between ATT and HPA. Our goal here was to provide the scientific community with a detailed dataset that can be used to compare with theoretical predictions. We tried to correlate the consensus ranking with different matrix properties: sublimation or decomposition temperature (determined using thermogravimetry), analyte initial velocity, and matrix proton affinity. The best correlation was found with the matrix proton affinity.
Disciplines :
Chemistry
Author, co-author :
Schulz, Eric; Johann-Wolfgang Goethe University Frankfurt > Institute of Pharmaceutical Chemistry > Instrumentelle Analytik
Karas, Michael; Johann-Wolfgang Goethe University Frankfurt > Institute of Pharmaceutical Chemistry > Instrumentelle Analytik
Rosu, Frédéric ; Université de Liège - ULiège > Chimie physique, spectrométrie de masse
Gabelica, Valérie ; Université de Liège - ULiège > Chimie physique, spectrométrie de masse
Language :
English
Title :
Influence of the matrix on analyte fragmentation in atmospheric pressure MALDI
Publication date :
2006
Journal title :
Journal of the American Society for Mass Spectrometry
ISSN :
1044-0305
eISSN :
1879-1123
Publisher :
Elsevier Science, New York, United States - New York
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