ETS and DEAS Studies of the Reduction of Xenobiotics in Mitochondrial Intermembrane Space.

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.