In-Source Microdroplet Derivatization Using Coaxial Contained-Electrospray Mass Spectrometry for Enhanced Sensitivity in Saccharide Analysis
In-Source Microdroplet Derivatization Using Coaxial Contained-Electrospray Mass Spectrometry for Enhanced Sensitivity in Saccharide Analysis
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DOI：
10.1021/acs.analchem.1c02897
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发表时间：
2021-12-07
影响因子：
7.4
通讯作者：
Badu-Tawiah, Abraham K.
中科院分区：
文献类型：
--
作者：
Heiss, Derik R.;Badu-Tawiah, Abraham K.
在线上，基于液滴的源内化学衍生化是使用同轴流包含电喷雾电离（包含est）源来完成的，以提高糖质谱分析的灵敏度。利用电喷雾微滴提供的反应速率加速，衍生化在微秒内完成。与传统的台式衍生化相比，以最少的样品制备和很少的资源实现了方法灵敏度的显着改进。对于这项工作，形成易于电离的苯硼酸酯衍生物的几个单糖，二糖和低聚糖是实现。考察了反应的浓度和pH等参数，并采用实验设计法对离子源参数进行了优化。使用源内苯硼酸衍生化，观察到许多单糖和双糖的信号增强大于两个数量级，导致检测限为万亿分之一（皮摩尔）。此外，氨基糖，如葡萄糖胺，在负模式下不会电离，在低十亿分之一的浓度下被检测到，等压糖，如乳糖和蔗糖很容易区分。新的源内衍生化方法可用于扩展ESI-MS分析的实用性，用于过去灵敏度和可检测性有限的化合物，同时避免了资源密集型的大相衍生化过程。
Online, droplet-based in-source chemical derivatization is accomplished using a coaxial-flow contained-electrospray ionization (contained-EST) source to enhance sensitivity for the mass spectrometric analysis of saccharides. Derivatization is completed in microseconds by exploiting the reaction rate acceleration afforded by electrospray microdroplets. Significant improvements in method sensitivity are realized with minimal sample preparation and few resources when compared to traditional benchtop derivatizations. For this work, the formation of easily ionizable phenylboronate ester derivatives of several mono-, di-, and oligosaccharides is achieved. Various reaction parameters including concentration and pH were evaluated, and a Design of Experiments approach was used to optimize ion source parameters. Signal enhancements of greater than two orders of magnitude were observed for many mono- and disaccharides using in-source phenylboronic acid derivatization, resulting in parts-per-trillion (picomolar) limits of detection. In addition, amino sugars such as glucosamine, which do not ionize in negative mode, were detected at low parts-per-billion concentrations, and isobaric sugars such as lactose and sucrose were easily distinguished. The new in-source derivatization approach can be employed to expand the utility of ESI-MS analysis for compounds that historically experience limited sensitivity and detectability, while avoiding resource-intensive, bulk-phase derivatization procedures.