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Collision‐induced dissociation of [U VI O 2 (ClO 4 )] + revisited: Production of [U VI O 2 (Cl)] + and subsequent hydrolysis to create [U VI O 2 (OH)] +
Author(s) -
Tatosian Irena J.,
Iacovino Anna C.,
Van Stipdonk Michael J.
Publication year - 2018
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.8135
Subject(s) - chemistry , dissociation (chemistry) , ion , mass spectrometry , analytical chemistry (journal) , molecule , collision induced dissociation , tandem mass spectrometry , organic chemistry , chromatography
Rationale In a previous study [ Rapid Commun Mass Spectrom . 2004;18:3028–3034], collision‐induced dissociation ( CID) of [U VI O 2 (ClO 4 )] + appeared to be influenced by the high levels of background H 2 O in a quadrupole ion trap. The CID of the same species was re‐examined here with the goal of determining whether additional, previously obscured dissociation pathways would be revealed under conditions in which the level of background H 2 O was lower. Methods Water‐ and methanol‐coordinated [U VI O 2 (ClO 4 )] + precursor ions were generated by electrospray ionization. Multiple‐stage tandem mass spectrometry (MS n ) for CID and ion‐molecule reaction (IMR) studies was performed using a linear ion trap mass spectrometer. Results Under conditions of low background H 2 O, CID of [U VI O 2 (ClO 4 )] + generates [U VI O 2 (Cl)] + , presumably by elimination of two O 2 molecules. Using low isolation/reaction times, we found that [U VI O 2 (Cl)] + will undergo an IMR with H 2 O to generate [U VI O 2 (OH)] + . Conclusions With lower levels of background H 2 O, CID experiments reveal that the intrinsic dissociation pathway for [U VI O 2 (ClO 4 )] + leads to [U VI O 2 (Cl)] + , apparently by loss of two O 2 molecules. We propose that the results reported in the earlier CID study reflected a two‐step process: initial formation of [U VI O 2 (Cl)] + by CID, followed by a very rapid hydrolysis reaction to leave [U VI O 2 (OH)] + .