Holden Dylan T, Shira Brison A, Edwards Myles Quinn, Morato Nicolás M, Cooks R Graham
Department of Chemistry, Purdue University 560 Oval Dr West Lafayette IN 47907 USA
Purdue University, Purdue Institute for Cancer Research 201 S University St. West Lafayette IN 47907 USA.
Chem Sci. 2025 Sep 4. doi: 10.1039/d5sc04781a.
Over the past decade the use of electrospray ionization mass spectrometry (ESI-MS) has been extended from the domain of chemical analysis to that of chemical synthesis. This development was spurred by the observation of reaction acceleration (by as much as 10 times compared to analogous bulk reactions) occurring in microdroplets, entities once thought merely to deliver ionized compounds to the mass analyzer. Interest in microdroplet synthesis is fueled by the fact that many reactions proceed rapidly without catalysts or pH adjustment. In this Perspective, we explore the basis for these features and propose that field ionization (FI) followed by chemical ionization (CI) occurs in water-containing microdroplets and generates reactive intermediates that account for their unique chemistry. The implications of this proposal extend to the mechanism of ESI itself and to applications of accelerated reactions in drug discovery, green synthesis, and prebiotic chemistry.
在过去十年中，电喷雾电离质谱法（ESI-MS）的应用已从化学分析领域扩展到化学合成领域。这一发展是由在微滴中观察到的反应加速现象（与类似的本体反应相比，加速高达10倍）所推动的，微滴曾被认为仅仅是将离子化化合物输送到质量分析仪的实体。对微滴合成的兴趣因许多反应在无需催化剂或调节pH的情况下就能快速进行这一事实而得到激发。在这篇展望文章中，我们探究了这些特性的基础，并提出在含水微滴中发生场致电离（FI）继之以化学电离（CI），并生成了能够解释其独特化学性质的反应中间体。这一观点的影响延伸到ESI本身的机制以及加速反应在药物发现、绿色合成和前生命化学中的应用。
