Energy-dependent normal and unusually large inverse chlorine kinetic isotope effects of simple chlorohydrocarbons in collision-induced dissociation by gas chromatography-electron ionization-tandem mass spectrometry.

Abstract

Kinetic isotope effects (KIEs) occurring in mass spectrometry (MS) can provide in-depth insights into the fragmentation behaviors of compounds of interest in MS. Yet, the fundamentals of KIEs in collision-induced dissociation (CID) in tandem mass spectrometry (MS/MS) are unclear, and information about chlorine KIEs (Cl-KIEs) of organochlorines in MS is particularly scarce. This study investigated the Cl-KIEs of dichloromethane, trichloroethylene, and tetrachloroethylene during CID using gas chromatography-electron ionization triple-quadrupole MS/MS. Cl-KIEs were evaluated with MS signal intensities. All the organochlorines presented large inverse Cl-KIEs (<1, the departures of Cl-KIEs from 1 denote the magnitudes of Cl-KIEs), showing the largest magnitudes of 0.797, 0.910, and 0.892 at the highest collision energy (60 eV) for dichloromethane, trichloroethylene, and tetrachloroethylene, respectively. For dichloromethane, both intra-ion and inter-ion Cl-KIEs were studied, within the ranges of 0.820-1.020 and 0.797-1.016, respectively, showing both normal and inverse Cl-KIEs depending on collision energies. The observed Cl-KIEs generally declined from large normal to extremely large inverse values with increasing collision energies from 0 to 60 eV but were inferred to be independent of MS signal intensities. The Cl-KIEs are dominated by critical energies at low internal energies of precursor ions, resulting in normal Cl-KIEs; while at high internal energies, the Cl-KIEs are controlled by rotational barriers (or looseness/tightness of transition states), which lead to isotope-competitive reactions in dechlorination and thereby inverse Cl-KIEs. It is concluded that the Cl-KIEs may depend on critical energies, bond strengths, available internal energies, and transition state looseness/tightness. The findings of this study yield new insights into the fundamentals of Cl-KIEs of organochlorines during CID and may be conducive to elucidating the underlying mechanisms of KIEs in collision-induced and photo-induced reactions in the actual world.