Rapid communications in mass spectrometry : RCM, 2009
An intramolecular transacylation reaction was observed in the mass spectrometry of molecules cont... more An intramolecular transacylation reaction was observed in the mass spectrometry of molecules containing both benzoyl and carboxymethyl groups on an aromatic heterocyclic core. The reaction is triggered by a dissociative protonation on the heterocyclic ring at the atom (carbon or nitrogen) that bonds to the benzoyl group, leading to an intermediate ion-neutral complex. The incipient benzoyl cation in the complex migrates to attack the carboxyl group of the neutral partner at the carbonyl or hydroxyl oxygen under thermodynamic or kinetic control, respectively. Elimination of benzoic acid followed by loss of carbon monoxide takes place as a result of the transacylation.
The specificity and selectivity of LC-MS-MS is illustrated to explain why LC-MS-MS has become the... more The specificity and selectivity of LC-MS-MS is illustrated to explain why LC-MS-MS has become the method of choice for quantitation within the pharmaceutical industry. Two assays are described that demonstrate the facility with which new ion trap technology can utilize the selectivity and sensitivity of LC-MS-MS to quantitate trace level components within complex matrices, in particular human plasma. One assay undergoes a validation procedure and demonstrates the utility of this new technology for drug quantitation within a regulated environment.
Rapid communications in mass spectrometry : RCM, 2009
An intramolecular transacylation reaction was observed in the mass spectrometry of molecules cont... more An intramolecular transacylation reaction was observed in the mass spectrometry of molecules containing both benzoyl and carboxymethyl groups on an aromatic heterocyclic core. The reaction is triggered by a dissociative protonation on the heterocyclic ring at the atom (carbon or nitrogen) that bonds to the benzoyl group, leading to an intermediate ion-neutral complex. The incipient benzoyl cation in the complex migrates to attack the carboxyl group of the neutral partner at the carbonyl or hydroxyl oxygen under thermodynamic or kinetic control, respectively. Elimination of benzoic acid followed by loss of carbon monoxide takes place as a result of the transacylation.
The specificity and selectivity of LC-MS-MS is illustrated to explain why LC-MS-MS has become the... more The specificity and selectivity of LC-MS-MS is illustrated to explain why LC-MS-MS has become the method of choice for quantitation within the pharmaceutical industry. Two assays are described that demonstrate the facility with which new ion trap technology can utilize the selectivity and sensitivity of LC-MS-MS to quantitate trace level components within complex matrices, in particular human plasma. One assay undergoes a validation procedure and demonstrates the utility of this new technology for drug quantitation within a regulated environment.
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Papers by Jack Cunniff