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Equilibrium conditions in laser-desorbed plumes: thermodynamic properties of α-cyano- 4-hydroxycinnamic acid and protonation of amino acids

机译:激光解吸羽流中的平衡条件:α-氰基-4-羟基肉桂酸的热力学性质和氨基酸质子化

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摘要

The equilibrium nature of a plume of laser desorbed material is explored through the application of a simple equilibrium model to the ion signals observed in 355 nm laser desorption/ionization mass spectra of mixtures of the MALDI matrix α-cyano-4-hydroxycinnamic acid (αCHCA) with the amino acids glycine, alanine, valine, isoleucine, and phenylalanine. In these studies it is found that there are systematic and predictable increases in the relative yield of protonated amino acid with increases in amino acid gas-phase basicity. In addition, the thermodynamic values extracted from the equilibrium plot are shown to be in good agreement with values obtained from computational investigation of plausible αCHCA proton donor species. These results are supportive of a picture wherein the laser-desorbed material is viewed as a dense plume in which facile charge transfer occurs leading, ultimately, to a thermodynamically equilibrated distribution of proton donor and proton acceptor species.
机译:通过将简单的平衡模型应用于MALDI基质α-氰基-4-羟基肉桂酸(αCHCA)混合物在355 nm激光解吸/电离质谱图中观察到的离子信号,探索了激光解吸材料羽流的平衡性质。 )氨基酸甘氨酸,丙氨酸,缬氨酸,异亮氨酸和苯丙氨酸。在这些研究中,发现随着氨基酸气相碱度的增加,质子化氨基酸的相对产率有系统的和可预测的增加。此外,从平衡图中提取的热力学值显示与从合理的αCHCA质子供体物种的计算研究中获得的值高度一致。这些结果支持了图片,其中将激光解吸的材料视为致密的羽状物,在其中发生容易的电荷转移,最终导致质子供体和质子受体物种的热力学平衡分布。

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