Analyte-substrate interactions at functionalized tip electrospray ionization mass spectrometry: Molecular mechanisms and applications
Analyte-substrate interactions at functionalized tip electrospray ionization mass spectrometry: Molecular mechanisms and applications
复制标题
功能化尖端电喷雾电离质谱分析物-底物相互作用：分子机制和应用
DOI：
10.1002/jms.4300
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发表时间：
2018
影响因子：
2.3
通讯作者：
Hu Bin
中科院分区：
文献类型：
--
作者：
Yao Ya-Nan;Hu Bin
传统的电喷雾离子化质谱（ESI-MS）通常使用毛细管尖端进行样品引入和离子化。近年来，使用非毛细管基底尖端的ESI-MS吸引了越来越多的兴趣，因为它可以从复杂样品中分离和富集分析物，因为分析物-基底相互作用。在这项工作中，模型混合物和功能化的尖端被用来研究分析物-底物相互作用的分子机制。将混合物直接加载在基底尖端上，然后通过监测每个分析物的选择离子色谱（SIC）响应来研究分析物的时间响应。结果表明，当基体溶液负载于基体表面时，所有的分析物都被一起喷射出来，然后观察到分析物的顺序电离。分析物的顺序电离受到分析物-基质相互作用的影响，这导致相互作用较弱的分析物移动更快，而相互作用较强的分析物保留在基质上。分析物-底物相互作用的主要分子机制被揭示为疏水相互作用和静电相互作用。此外，基于机理的见解，功能化尖端进一步应用于从复杂样品中快速提取目标分析物，具有良好的分析性能。总之，本研究的分析物-基质相互作用的机制和应用是有用的理解的基本原理和功能化尖端电喷雾电离（TESI）的进一步发展。
Conventional electrospray ionization mass spectrometry (ESI‐MS) commonly uses capillary tip for sample introduction and ionization. In recent years, ESI‐MS using noncapillary substrate tips has attracted growing interest as it allows separation and enrichment of analytes from complex samples due to analytes‐substrate interactions. In this work, model mixtures and functionalized tips were employed to investigate the molecular mechanism of the analyte‐substrate interactions. The mixtures were directly loaded on substrate tips, and then temporal responses of analytes were investigated by monitoring selected ion chromatogram (SIC) responses of each analyte. It is found that all analytes are sprayed out together when bulk solution loaded substrate surface and then sequential ionization of analytes were observed. Sequential ionization of analytes was affected by the analytes‐substrate interactions which caused analytes of weaker‐interaction to be faster moved and the analytes of stronger‐interactions to be retained on the substrate. The main molecular mechanisms of analyte‐substrate interactions were revealed to be hydrophobic interactions and electrostatic interactions. Furthermore, based on the mechanistic insights, functionalized tips were further applied for rapid extractive sampling of target analytes from complex samples with good analytical performances. Overall, this study on the mechanism and applications of analyte‐substrate interactions is useful for understanding the fundamental principles and further developments of functionalized tip electrospray ionization (TESI).