Peptide fragmentation assisted by surfaces treated with a low-temperature plasma in nanoESI.
Peptide fragmentation assisted by surfaces treated with a low-temperature plasma in nanoESI.
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DOI：
10.1002/anie.200803477
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发表时间：
2008-10
影响因子：
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通讯作者：
Yu Xia;Ouyang Zheng;R. Cooks
中科院分区：
文献类型：
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作者：
Yu Xia;Ouyang Zheng;R. Cooks
在此，我们讨论了在纳米电喷雾电离（nanoESI），一种广泛使用的软电离方法的特殊条件下观察到的肽片段化的机制的影响。电喷雾离子化（ESI）技术的发展极大地扩展了质谱的应用范围。[1]受影响最大的领域是肽和蛋白质分析。蛋白质或肽的质量可以通过在ESI的正离子或负离子模式下观察到的分子的丰富的多质子化或去质子化形式以直接的方式确定。肽或蛋白质的一级结构的表征，现在是蛋白质组学的中心活动之一，[2]当ESI与串联质谱中的许多活化方法中的任何一种结合时，都是可能的。[3，4]除了ESIMS在生化分析中的广泛应用外，人们对了解ESI的基本方面有着强烈的持续兴趣。尽管对于某些类型的分子，离子形成的最后阶段是否可以通过电荷残留[5]或离子蒸发模型[6]来解释仍存在争议，但人们普遍认为ESI是一种软电离方法，并且形成的离子在典型条件下不会被显著激发。[7]由于离子内能高度依赖于它们形成的环境，因此即使是“软”电离过程也可以被调整以在适当的条件下产生激发离子。例子包括在化学电离中使用试剂进行受控电离和裂解[8]，以及在基质辅助激光解吸/电离（MALDI）中选择“冷”或“热”基质[9]。在此，我们报告了在大气压下用氦低温等离子体（LTP）对nanoESI发射器进行预处理后，在nanoESI中观察到的肽片段化。我们研究了这种新的碎片化现象，
Herein, we discuss the mechanistic implications of peptide fragmentation observed under special conditions in nanoelectrospray ionization (nanoESI), a widely used soft ionization method. The development of electrospray ionization (ESI) has significantly enlarged the scope of mass spectrometry (MS).[1] The area most favorably impacted is peptide and protein analysis. The mass of a protein or peptide can be determined in a straightforward manner from the abundant multiply protonated or deprotonated forms of the molecule that are observed in the positive-or negative-ion mode of ESI. The characterization of the primary structure of a peptide or protein, now one of the central activities in proteomics,[2] is possible when ESI is coupled with any of a number of activation methods in the context of tandem mass spectrometry.[3, 4]Besides the wide adoption of ESIMS for biochemical analysis, there is a strong continuing interest in understanding the fundamental aspects of ESI. Although debate continues as to whether the final stages of ion formation can be explained by the charge-residue [5] or ion-evaporation model [6] for certain types of molecules, it is widely accepted that ESI is a soft ionization method, and that the ions formed are not excited significantly under typical conditions.[7] As ion internal energies are highly dependent upon the environment in which they are formed, even a “soft” ionization process can be tuned to give rise to excited ions under appropriate conditions. Examples include the use of reagents for controlled ionization and fragmentation in chemical ionization [8] and the selection of either “cold” or “hot” matrices [9] in matrix-assisted laser desorption/ionization(MALDI). Herein, we report the observation of peptide fragmentation in nanoESI after pretreatment of the nanoESI emitter with a helium low-temperature plasma (LTP) at atmospheric pressure. We studied this new fragmentation phenomenon for a