Pshenichnyuk Stanislav A, Modelli Alberto
Institute of Molecule and Crystal Physics, Ufa Research Centre, Russian Academy of Sciences, Prospeкt Oktyabrya 151, 450075, Ufa, Russia,
Methods Mol Biol. 2015;1265:285-305. doi: 10.1007/978-1-4939-2288-8_20.
This chapter describes the complementary experimental techniques electron transmission spectroscopy (ETS) and dissociative electron attachment spectroscopy (DEAS), two of the most suitable means for investigating interactions between electrons and gas-phase molecules, resonance formation of temporary molecular negative ions, and their possible decay through the dissociative electron attachment (DEA) mechanism. The latter can be seen as the gas-phase counterpart of the transfer of a solvated electron in solution, accompanied by dissociation of the molecular anion, referred to as dissociative electron transfer (DET). DET takes place in vivo under reductive conditions, for instance, in the intermembrane space of mitochondria under interaction of xenobiotic molecules with electrons "leaked" from the respiration chain. Experimental procedures supported by suitable quantum chemical calculations are described in detail and illustrated by an example of ETS/DEAS study of rhodanine which shows rich fragmentation under gas-phase resonance electron attachment.
本章介绍了互补的实验技术——电子透射光谱（ETS）和解离电子附着光谱（DEAS），这是研究电子与气相分子之间相互作用、临时分子负离子的共振形成以及它们通过解离电子附着（DEA）机制可能发生的衰变的两种最合适的手段。后者可被视为溶液中溶剂化电子转移的气相对应物，伴随着分子阴离子的解离，称为解离电子转移（DET）。DET在体内的还原条件下发生，例如，在外源分子与从呼吸链“泄漏”的电子相互作用时，在线粒体的膜间隙中发生。详细描述了由适当的量子化学计算支持的实验程序，并以罗丹宁的ETS/DEAS研究为例进行说明，该研究表明在气相共振电子附着下罗丹宁会发生丰富的碎片化。
