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9,10-Diphenylanthracene as a matrix for MALDI-MS electron transfer secondary reactions

机译:9,10-二苯基蒽作为MALDI-MS电子转移二级反应的基质

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摘要

The most common secondary-ionization mechanism in positive ion matrix-assisted laser desorption/ionization (MALDI) involves a proton transfer reaction to ionize the analyte. Peptides and proteins are molecules that have basic (and acidic) sites that make them susceptible to proton transfer. However, non-polar, aprotic compounds that lack basic sites are more difficult to protonate, and creating charged forms of this type of analyte can pose a problem when conventional MALDI matrices are employed. In this case, forming a radical molecular ion through electron transfer is a viable alternative, and certain matrices may facilitate the process. In this work, we investigate the performance of a newly developed electron-transfer secondary reaction matrix: 9,10-diphenylanthracene (9,10-DPA). The use of 9,10-DPA as matrix for MALDI analysis has been tested using several model compounds. It appears to promote ionization through electron transfer in a highly efficient manner as compared to other potential matrices. Thermodynamic aspects of the observed electron transfers in secondary-ionization reactions were also considered, as was the possibility for kinetically controlled/endothermic, electron-transfer reactions in the MALDI plume.
机译:正离子基体辅助激光解吸/电离(MALDI)中最常见的二次电离机理涉及质子转移反应,以使分析物电离。肽和蛋白质是具有碱性(和酸性)位点的分子,使其易于质子转移。然而,缺少碱性位点的非极性非质子化合物更难以质子化,当使用常规MALDI基质时,产生此类分析物的带电形式可能会带来问题。在这种情况下,通过电子转移形成自由基分子离子是可行的选择,某些基质可以促进该过程。在这项工作中,我们研究了新开发的电子转移二级反应基质:9,10-二苯基蒽(9,10-DPA)的性能。已使用几种模型化合物测试了将9,10-DPA用作MALDI分析的基质。与其他潜在的基质相比,它似乎可以通过电子转移以高效的方式促进电离。还考虑了在二次电离反应中观察到的电子转移的热力学方面,以及在MALDI羽流中进行动力学控制/吸热的电子转移反应的可能性。

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