{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,17]],"date-time":"2025-10-17T00:29:06Z","timestamp":1760660946959,"version":"build-2065373602"},"reference-count":41,"publisher":"Wiley","issue":"9","license":[{"start":{"date-parts":[[2020,6,21]],"date-time":"2020-06-21T00:00:00Z","timestamp":1592697600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["41603092"],"award-info":[{"award-number":["41603092"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["analyticalsciencejournals.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["J Mass Spectrom"],"published-print":{"date-parts":[[2020,9]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Kinetic isotope effects (KIEs) occurring in mass spectrometry (MS) can provide in\u2010depth insights into the fragmentation behaviors of compounds of interest in MS. Yet, the fundamentals of KIEs in collision\u2010induced dissociation (CID) in tandem mass spectrometry (MS\/MS) are unclear, and information about chlorine KIEs (Cl\u2010KIEs) of organochlorines in MS is particularly scarce. This study investigated the Cl\u2010KIEs of dichloromethane, trichloroethylene, and tetrachloroethylene during CID using gas chromatography\u2010electron ionization triple\u2010quadrupole MS\/MS. Cl\u2010KIEs were evaluated with MS signal intensities. All the organochlorines presented large inverse Cl\u2010KIEs (&lt;1, the departures of Cl\u2010KIEs from 1 denote the magnitudes of Cl\u2010KIEs), 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\u2010ion and inter\u2010ion Cl\u2010KIEs were studied, within the ranges of 0.820\u20131.020 and 0.797\u20131.016, respectively, showing both normal and inverse Cl\u2010KIEs depending on collision energies. The observed Cl\u2010KIEs 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\u2010KIEs are dominated by critical energies at low internal energies of precursor ions, resulting in normal Cl\u2010KIEs; while at high internal energies, the Cl\u2010KIEs are controlled by rotational barriers (or looseness\/tightness of transition states), which lead to isotope\u2010competitive reactions in dechlorination and thereby inverse Cl\u2010KIEs. It is concluded that the Cl\u2010KIEs 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\u2010KIEs of organochlorines during CID and may be conducive to elucidating the underlying mechanisms of KIEs in collision\u2010induced and photo\u2010induced reactions in the actual world.<\/jats:p>","DOI":"10.1002\/jms.4521","type":"journal-article","created":{"date-parts":[[2020,4,4]],"date-time":"2020-04-04T16:30:52Z","timestamp":1586017852000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Energy\u2010dependent normal and unusually large inverse chlorine kinetic isotope effects of simple chlorohydrocarbons in collision\u2010induced dissociation by gas chromatography\u2010electron ionization\u2010tandem mass spectrometry"],"prefix":"10.1002","volume":"55","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6951-4497","authenticated-orcid":false,"given":"Caiming","family":"Tang","sequence":"first","affiliation":[{"name":"State Key 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