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Formation of odd‐electron product ions in collision‐induced fragmentation of electrospray‐generated protonated cathinone derivatives: aryl α‐primary amino ketones
Author(s) -
Fornal Emilia
Publication year - 2013
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.6635
Subject(s) - chemistry , fragmentation (computing) , protonation , aryl , electrospray , ion , cathinone , medicinal chemistry , collision induced dissociation , computational chemistry , mass spectrometry , tandem mass spectrometry , organic chemistry , chromatography , alkyl , amphetamine , neuroscience , computer science , dopamine , biology , operating system
RATIONALE Modification of the even‐electron rule for fragmentation reactions of protonated molecules (even electron ions) may be necessary to interpret the liquid chromatography/mass spectrometry (LC/MS) spectra of aryl α‐primary amino ketones as new designer drugs. METHODS Collision‐induced fragmentation of 38 protonated cathinone derivatives generated by electrospray ionisation (ESI) was examined by hybrid quadrupole time‐of‐flight mass spectrometry (Q‐TOF MS). RESULTS Q‐TOF MS revealed that odd‐electron product ions are often formed by collision‐induced dissociation (CID) of protonated aryl α‐primary amino ketones, contradicting the even‐electron rule. Radical cations were among the most characteristic and most abundant ions in the CID‐MS/MS product spectra, and were usually represented by basic peaks in the spectra. CONCLUSIONS To help elucidate the correct structures of new aryl α‐primary amino ketone drugs by LC/MS/MS, it is essential to include odd‐electron product ions in the data interpretation rules. Even and odd numbers of valence electrons in the product ions should be allowed in data interpretation. Copyright © 2013 John Wiley & Sons, Ltd.