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首页> 外文期刊>Journal of mass spectrometry: JMS >Quantitative reproducibility of mass spectra in matrix-assisted laser desorption ionization and unraveling of the mechanism for gas-phase peptide ion formation
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Quantitative reproducibility of mass spectra in matrix-assisted laser desorption ionization and unraveling of the mechanism for gas-phase peptide ion formation

机译：基质辅助激光解吸电离过程中质谱的定量重现性和气相肽离子形成机理的揭示

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摘要

In a previous study on matrix-assisted laser desorption ionization (MALDI) of peptides using α-cyano-4-hydroxycinnamic acid (CHCA) as a matrix, we found that the patterns of single-shot spectra obtained under different experimental conditions became similar upon temperature selection. In this paper, we report that absolute ion abundances are also similar in temperature-selected MALDI spectra, even when laser fluence is varied. The result that has been obtained using CHCA and 2,5-dihydroxybenzoic acid as matrices is in disagreement with the hypothesis of laser-induced ionization of matrix as the mechanism for primary ion formation in MALDI. We also report that the total number of ions in such a spectrum is unaffected by the identity, concentration and number of analytes, i.e. it is the same as that in the spectrum of pure matrix. We propose that the generation of gas-phase ions in MALDI can be explained in terms of two thermal reactions, i.e. the autoprotolysis of matrix molecules and the matrix-to-analyte proton transfer, both of which are in quasi-equilibrium in the early matrix plume.
机译：在先前使用α-氰基-4-羟基肉桂酸（CHCA）作为基质的肽的基质辅助激光解吸电离（MALDI）研究中，我们发现在不同实验条件下获得的单次发射光谱的图样在温度选择。在本文中，我们报告，即使在激光注量发生变化时，绝对离子丰度在温度选择的MALDI光谱中也相似。使用CHCA和2,5-二羟基苯甲酸作为基质获得的结果与激光诱导的基质电离作为MALDI中初级离子形成机理的假设不符。我们还报告说，在这种光谱中的离子总数不受分析物的身份，浓度和数量的影响，即与纯基质的光谱中的离子总数相同。我们建议可以用两个热反应来解释MALDI中气相离子的产生，即基质分子的自动分解和基质到分析物的质子转移，这两个过程在早期基质中都处于准平衡状态。羽。

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