期刊
ANALYTICAL CHEMISTRY
卷 84, 期 16, 页码 7107-7111出版社
AMER CHEMICAL SOC
DOI: 10.1021/ac3014077
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资金
- National Research Foundation of Korea (NRF)
- Korea government (MEST) [305-20110059]
- Ministry of Education, Science and Technology, Republic of Korea
Matrix-assisted laser desorption ionization of peptides was investigated using alpha-cyano-4-hydroxycinnamic acid as the matrix. In each experiment, a set of mass spectra was collected by repetitive irradiation of a spot on a sample. Even though shot-to-shot variation in spectral pattern was significant, it was reproducible for different spots and samples. Each spectrum was tagged with the temperature in the early plume (T-early) estimated through kinetic analysis of the peptide ion survival probability. T-early decreased as the shot continued because the thermal conduction got more efficient as the sample got thinner. From each spectral set collected under various experimental conditions, a spectrum tagged with a particular T-early was selected. Then, patterns of the spectra thus selected were the same. The reaction quotient for the matrix-to-peptide proton transfer determined at a specified T-early was independent of the sample composition, indicating quasi-thermal equilibrium for this reaction. Furthermore, the van't Hoff plots were linear, also indicating quasi-thermal equilibrium. This, together with the thermal kinetics for the fragmentation of peptide and matrix ions, is responsible for the reproducibility of the mass spectral pattern at a specified T-early.
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