Electrospray Ionization with High-Resolution Mass Spectrometry as a Tool for Lignomics: Lignin Mass Spectrum Deconvolution
Electrospray Ionization with High-Resolution Mass Spectrometry as a Tool for Lignomics: Lignin Mass Spectrum Deconvolution
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DOI：
10.1007/s13361-018-1916-z
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发表时间：
2018-05-01
影响因子：
3.2
通讯作者：
Kubatova, Alena
中科院分区：
文献类型：
--
作者：
Andrianova, Anastasia A.;DiProspero, Thomas;Kubatova, Alena
表征木质素、木质纤维素及其降解产物的能力对于开发新的可再生原料至关重要。电喷雾电离高分辨飞行时间质谱仪(ESI-HR TOF-MS)是对木质组学工具包的扩展，旨在同时检测低分子木质素和高相对分子质量木质素。采用一系列单芳烃、双芳烃和三芳烃木质素模型化合物以及硫酸盐碱木质素，研究了不同电解液和不同电离条件对离子形成和电离效果的影响。与以往的研究相反，正电离模式被发现对甲氧基取代芳烃和多酚更有效，即结构上与天然木质素相似的多种多样的分子量物种。本文首次报道了在100mmoL L-1甲酸存在下，木质素在电喷雾正离子注入模式下有效地形成多电荷物种，并伴随着随后的光谱去卷积。根据质量分析仪的不同，开发的方法可以检测相对分子质量在150至9000 Da或更高的木质素物种。测得的M-n和M-w值分别为1500和2500 Da，与凝胶渗透色谱测定的结果吻合较好。此外，去卷积的电喷雾质谱与基质辅助激光解吸电离(MALDI)-高分辨飞行时间质谱仪(MALDI-HR TOF-MS)得到的谱相似，但具有更高的信噪比。离子迁移率ESI-HR Q-TOF-MS证实了多电荷物种的形成。
The capability to characterize lignin, lignocellulose, and their degradation products is essential for the development of new renewable feedstocks. Electrospray ionization high-resolution time-of-flight mass spectrometry (ESI-HR TOF-MS) method was developed expanding the lignomics toolkit while targeting the simultaneous detection of low and high molecular weight (MW) lignin species. The effect of a broad range of electrolytes and various ionization conditions on ion formation and ionization effectiveness was studied using a suite of mono-, di-, and triarene lignin model compounds as well as kraft alkali lignin. Contrary to the previous studies, the positive ionization mode was found to be more effective for methoxy-substituted arenes and polyphenols, i.e., species of a broadly varied MW structurally similar to the native lignin. For the first time, we report an effective formation of multiply charged species of lignin with the subsequent mass spectrum deconvolution in the presence of 100 mmol L-1 formic acid in the positive ESI mode. The developed method enabled the detection of lignin species with an MW between 150 and 9000 Da or higher, depending on the mass analyzer. The obtained M-n and M-w values of 1500 and 2500 Da, respectively, were in good agreement with those determined by gel permeation chromatography. Furthermore, the deconvoluted ESI mass spectrum was similar to that obtained with matrix-assisted laser desorption/ionization (MALDI)-HR TOF-MS, yet featuring a higher signal-to-noise ratio. The formation of multiply charged species was confirmed with ion mobility ESI-HR Q-TOF-MS.