Enantioseparation of agrochemicals by gas chromatography. Exploring columns based on cyclodextrin derivatives dissolved into polysiloxanes

Abstract

The main goal of this work is to expand the availability of chiral columns for the analysis of agrochemicals by gas chromatography. A broader offer of chiral stationary phases would allow shifting toward enantioselective analytical techniques environmentally more friendly for those compounds. We prepared seven chiral capillary columns based on derivatives of either, β‐cyclodextrin or γ‐cyclodextrins dissolved at high concentrations, in two typical polysiloxanes with different polarities, demonstrating not only the significance of the chiral selector but also of the polymer solvent for achieving adequate enantioseparation of some agrochemicals. The enantiorecognition ability of each column was evaluated with 20 volatile and semivolatile agrochemicals, possessing one or two chiral centers. Besides, to elute more polar agrochemicals, as well as to enhance enantioselectivity, three derivatization procedures targeting the carboxyl and/or amine group were evaluated. The results revealed that the prepared column consisting of octakis(2,3‐di‐O‐acetyl‐6‐O‐tertbutyldimethylsilyl)‐γ‐cyclodextrin dissolved in (14%‐cyanopropyl‐phenyl)‐86%‐methyl‐polysiloxane provides the broadest enantiorecognition capacity. This column allowed the enantioseparation of seventeen chiral agrochemicals, including metalaxyl, furalaxyl, and four imidazolinones, which were not enantioseparated in the remaining columns. To the best of our knowledge, glufosinate, fluorochloridone, fenarimol, furalaxyl, and four imidazolinones were enantioseparated by gas chromatography for the first time.