The Effect of Organic Modifiers on Electrospray Ionization Charge-State Distribution and Desorption Efficiency for Oligonucleotides
The Effect of Organic Modifiers on Electrospray Ionization Charge-State Distribution and Desorption Efficiency for Oligonucleotides
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DOI：
10.1007/s13361-012-0509-5
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发表时间：
2013-02-01
影响因子：
3.2
通讯作者：
Bartlett, Michael G.
中科院分区：
文献类型：
--
作者：
Chen, Buyun;Mason, Sadie F.;Bartlett, Michael G.
溶液的化学成分对寡核苷酸的电喷雾解吸效率具有至关重要的影响。研究了各种有机改性剂在寡核苷酸解吸过程中的作用的几种理化性质。反映烷基胺挥发性的亨利定律常数被发现对电喷雾电荷态分布和寡核苷酸的解吸效率具有显着影响。具有较高值的烷基胺，例如己胺、哌啶和咪唑，通过与寡核苷酸形成复合物并在气相中与其解离来减少电荷态分布，而具有极低值的烷基胺通过在电喷雾解吸过程的早期阶段促进离子发射来减少电喷雾电荷态分布。具有中等值的离子对剂不会改变寡核苷酸的电喷雾电荷状态分布，并且它们增强寡核苷酸电离的能力遵循值递减的顺序。亨利定律常数还与酸性调节剂对寡核苷酸电离效率的影响相关。使用六氟异丙醇观察到电离增强效应，这种效应归因于其低且中等的酸度。还评估了烷基胺和六氟异丙醇对寡核苷酸电喷雾电离解吸的综合影响，发现酸碱平衡在确定这些影响中起着关键作用。
The chemical composition of the solution has a critical impact on the electrospray desorption efficiency of oligonucleotides. Several physiochemical properties of various organic modifiers were investigated with respect to their role in the desorption process of oligonucleotides. The Henry's Law Constant, which reflects the volatility of alkylamines, was found to have a prominent effect on both the electrospray charge state distribution and desorption efficiency of oligonucleotides. Alkylamines with higher values such as hexylamine, piperidine, and imidazole reduced the charge state distribution by forming complexes with the oligonucleotide and dissociating from it in the gas phase, while alkylamines with extremely low values reduced the electrospray charge state distribution by facilitating ion emission at an earlier stage of the electrospray desorption process. Ion-pairing agents with moderate values do not alter the electrospray charge state distribution of oligonucleotides and their ability to enhance oligonucleotide ionization followed the order of decreasing values. The Henry's Law Constant also correlated to the impact of the acidic modifiers on oligonucleotide ionization efficiency. Ionization enhancement effects were observed with hexafluoroisopropanol, and this effect was attributed to its low and moderate acidity. The comprehensive effects of both alkylamine and hexafluoroisoproapnol on the electrospray ionization desorption of oligonucleotides were also evaluated, and acid-base equilibrium was found to play a critical role in determining these effects.