Desorption Electrospray Ionization Mass Spectrometry: 20 Years.
Desorption Electrospray Ionization Mass Spectrometry: 20 Years.
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解吸电喷雾电离质谱：20 年。
DOI：
10.1021/acs.accounts.3c00382
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发表时间：
2023
影响因子：
18.3
通讯作者：
Cooks,RGraham
中科院分区：
文献类型：
--
作者：
Morato,NicolásM;Cooks,RGraham
质谱（MS）是化学科学中应用最广泛的技术之一。随着反应产物的监测、疾病生物标志物的鉴定、热力学参数的测量和结构生物学的各个方面的应用，质谱已经成为一种适用于小化合物和大分子复合物的通用分析工具。无论应用如何，从中性化合物中产生气相离子是任何质谱实验的关键步骤。然而，多年来，这种电离步骤仅限于需要气相分析物的高能方法，因此仅限于挥发性样品。在过去的几十年里，已经开发出新的方法来解决这一限制并促进生物分子的电离。电喷雾电离（ESI）是这些方法中使用最广泛的，因为它有利于从溶液中电离完整的极性化合物。20年前，我们的团队报告了一种新的电离方法，该方法使用带电溶剂喷雾来影响表面，从物体而不是溶液中产生离子，并且直接在环境环境中进行，不需要真空，几乎不需要样品制备。这种方法被称为解吸电喷雾电离（DESI），它开创了一个新的领域，将被称为环境质谱法。DESI技术的简单性和广泛适用性──以及随后开发的数十种环境电离方法──彻底改变了复杂材料有机成分的质谱分析，特别是在现场应用中。本文描述了DESI的历史，从早期电子喷雾电离（ESSI）实验观察的技术发展开始，以及导致理解其机制的研究，即“液滴吸收”现象，涉及一系列事件（即薄膜形成，固液萃取，二次液滴产生，以及这些液滴的esi样电离）。我们还概述了在过去二十年中我们集团所展示的技术的发展和应用。特别地，我们描述了(i) DESI用于组织成像，这是迄今为止其更重要的应用之一，并将其扩展到术中临床诊断；（ii）将该技术与用于现场分析的便携式仪器相结合，特别是与串联质谱（MS/MS）相结合时；（iii）与散装溶液相比，使用DESI微滴作为微容器，以数量级加速有机反应；（iv）所有这些自动化高通量实验能力的结合，旨在加速药物发现。
ConspectusMass spectrometry (MS) is one of the most widely used technologies in the chemical sciences. With applications spanning the monitoring of reaction products, the identification of disease biomarkers, and the measurement of thermodynamic parameters and aspects of structural biology, MS is well established as a universal analytical tool applicable to small compounds as well as large molecular complexes. Regardless of the application, the generation of gas-phase ions from neutral compounds is a key step in any MS experiment. However, this ionization step was for many years limited to high-energy approaches that required gas-phase analytes and thus it was restricted to volatile samples. Over the last few decades, new methodologies have been developed to address this limitation and facilitate ionization of biological molecules. Electrospray ionization (ESI) is the most broadly used of these methods, as it facilitates the ionization of intact polar compounds from solution.Twenty years ago, our group reported a new ionization method that uses a charged solvent spray to impact a surface, generating ions fromobjectsrather than justsolutionsand doing so directly in the ambient environment with no vacuum requirements and little to no sample preparation. This method was termed desorption electrospray ionization (DESI), and it initiated a new field that would come to be known as ambient mass spectrometry. The simplicity and wide applicability of the DESI technology─and the tens of ambient ionization methods developed subsequently─revolutionized the MS analysis of complex materials for their organic components, especially forin situapplications.This Account describes the history of DESI, starting with the development of the technique from early electrosonic spray ionization (ESSI) experimental observations as well as the studies leading to the understanding of its mechanism as a “droplet pick-up” phenomenon involving sequential events (i.e., thin film formation, solid–liquid extraction, secondary droplet generation, and ESI-like ionization from these droplets). We also overview the developments and applications of the technology that have been demonstrated by our group during the last two decades. In particular, we describe (i) the use of DESI for tissue imaging, one of its more significant applications to date, and its extension to intraoperative clinical diagnosis; (ii) the integration of the technology with portable instrumentation forin situanalysis, especially when coupled with tandem mass spectrometry (MS/MS); (iii) the use of DESI microdroplets as microvessels to accelerate organic reactions by orders of magnitude compared to those in bulk solution; and (iv) the combination of all these capabilities for automated high-throughput experiments aimed at accelerating drug discovery.