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Title
| - Solvent Effects in Tandem Mass Spectrometry: MechanisticStudies Indicating How a Change in Solvent Conditions and pHCan Dramatically Alter CID Spectra
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Abstract
| - Dramatically different CID (collision-induced dissociation) spectra are obtained when the complex[Zn(dien-glucose)]+ is electrosprayed from acidic and basic solutions. To understand this peculiarphenomenon, an in-depth mechanistic study was performed on one of the product ions that is presentwhen the initial complex is diluted in basic solution but absent when the complex is diluted withacidic solution. On the basis of the results of this study, the differences in the CID spectra can berationalized by the fact that the complex electrosprayed from basic solution was kinetically trapped,with the deprotonation site distal from the metal center. Under acidic conditions, the deprotonationsite is at a hydroxyl group coordinated to the metal ion. A variety of experiments support thishypothesis. The studies herein underscore the importance of using identical solvent conditions whencomparing sets of CID spectra. The data also highlight a very interesting phenomenon involvingdeprotonation of a hydroxyl group, which was several atoms away from the Zn(II) metal center.
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