Open Access. Powered by Scholars. Published by Universities.®
Articles 1 - 2 of 2
Full-Text Articles in Medicine and Health Sciences
Hydroxyl Radical Formation In The Gas Phase Oxidation Of Distonic 2-Methylphenyl Radical Cations, Matthew Prendergast, Phillip A. Cooper, Benjamin B. Kirk, Gabriel Da Silva, Stephen J. Blanksby, Adam J. Trevitt
Hydroxyl Radical Formation In The Gas Phase Oxidation Of Distonic 2-Methylphenyl Radical Cations, Matthew Prendergast, Phillip A. Cooper, Benjamin B. Kirk, Gabriel Da Silva, Stephen J. Blanksby, Adam J. Trevitt
Adam Trevitt
The reactions of distonic 4-(N,N,N-trimethylammonium)-2-methylphenyl and 5-(N,N,N-trimethylammonium)-2-methylphenyl radical cations (m/z 149) with O 2 are studied in the gas phase using ion-trap mass spectrometry. Photodissociation (PD) of halogenated precursors gives rise to the target distonic charge-tagged methylphenyl radical whereas collision-induced dissociation (CID) is found to produce unreactive radical ions. The PD generated distonic radicals, however, react rapidly with O2 to form [M + O2]•+ and [M + O2 - OH]•+ ions, detected at m/z 181 and m/z 164, respectively. Quantum chemical calculations using G3SX(MP3) and M06-2X theories are deployed to examine key decomposition pathways of the 5-(N,N,N-trimethylammonium)-2-methylphenylperoxyl radical and rationalise …
Ultraviolet Action Spectroscopy Of Iodine Labeled Peptides And Proteins In The Gas Phase, Benjamin B. Kirk, Adam J. Trevitt, Stephen J. Blanksby, Yuanqi Tao, Benjamin N. Moore, Ryan Julian
Ultraviolet Action Spectroscopy Of Iodine Labeled Peptides And Proteins In The Gas Phase, Benjamin B. Kirk, Adam J. Trevitt, Stephen J. Blanksby, Yuanqi Tao, Benjamin N. Moore, Ryan Julian
Adam Trevitt
Structural investigations of large biomolecules in the gas phase are challenging. Herein, it is reported that action spectroscopy taking advantage of facile carbon-iodine bond dissociation can be used to examine the structures of large molecules, including whole proteins. Iodotyrosine serves as the active chromophore, which yields distinctive spectra depending on the solvation of the side chain by the remainder of the molecule. Isolation of the chromophore yields a double featured peak at 290 nm, which becomes a single peak with increasing solvation. Deprotonation of the side chain also leads to reduced apparent intensity and broadening of the action spectrum. The …