Tandem mass spectrometry of poly(ethylene imine)s by electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI)
Tandem mass spectrometry of poly(ethylene imine)s by electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI)
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DOI：
10.1002/jms.2032
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发表时间：
2012-01-01
影响因子：
2.3
通讯作者：
Schubert, Ulrich S.
中科院分区：
文献类型：
--
作者：
Altuntas, Esra;Knop, Katrin;Schubert, Ulrich S.
在这方面的贡献，线性聚（乙烯亚胺）（PEI）聚合物，这是在基因传递中的重要性，详细研究了通过使用电喷雾电离四极杆飞行时间（ESI-Q-TOF）和基质辅助激光解吸/电离飞行时间（MALDI-TOF）质谱（MS）。通过活性阳离子开环聚合（CROP）和随后在酸性条件下的水解，使用取代的2-恶唑啉的聚合来合成具有不同端基的所分析的PEI。本研究的主要目标是以详细的方式识别线性PEI聚合物，以获得有关其断裂途径的信息。为此，通过使用ESI-Q-TOF和MALDI-TOF MS结合碰撞诱导解离（CID）实验对三种不同的线性PEI进行详细表征。在ESI-MS以及MALDI-MS分析中，所获得的PEI光谱导致所研究的PEI的拟合质量分布。在串联质谱分析中，根据质子化母峰得到的裂解产物，提出了通过四元环状过渡态的电荷远程重排的1，2-氢化物移位以及电荷诱导裂解反应为主要裂解机制。此外，提出异裂和均裂裂解作为替代裂解途径。此外，提出了1，4-氢消除来解释从钠化母峰获得的不同碎片产物。版权所有（C）2012约翰威利父子有限公司
In this contribution, linear poly(ethylene imine) (PEI) polymers, which are of importance in gene delivery, are investigated in detail by using electrospray ionization-quadrupole-time of flight (ESI-Q-TOF) and matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry (MS). The analyzed PEIs with different end groups were synthesized using the polymerization of substituted 2-oxazoline via a living cationic ring-opening polymerization (CROP) and a subsequent hydrolysis under acidic conditions. The main goal of this study was to identify linear PEI polymers in a detailed way to gain information about their fragmentation pathways. For this purpose, a detailed characterization of three different linear PEIs was performed by using ESI-Q-TOF and MALDI-TOF MS in combination with collision-induced dissociation (CID) experiments. In ESI-MS as well as MALDI-MS analysis, the obtained spectra of PEIs resulted in fitting mass distributions for the investigated PEIs. In the tandem MS analysis, a 1,2-hydride shift with a charge-remote rearrangement via a four-membered cyclic transition state, as well as charge-induced fragmentation reactions, was proposed as the main fragmentation mechanisms according to the obtained fragmentation products from the protonated parent peaks. In addition, heterolytic and homolytic cleavages were proposed as alternative fragmentation pathways. Moreover, a 1,4-hydrogen elimination was proposed to explain different fragmentation products obtained from the sodiated parent peaks. Copyright (C) 2012 John Wiley & Sons, Ltd.