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Full-Text Articles in Social and Behavioral Sciences
Concerted Ho2 Elimination From Alpha-Aminoalkylperoxyl Free Radicals: Experimental And Theoretical Evidence From The Gas-Phase Nh2 Chco2 - + O2 Reaction, Gabriel Da Silva, Benjamin Kirk, Celli Lloyd, Adam Trevitt, Stephen Blanksby
Concerted Ho2 Elimination From Alpha-Aminoalkylperoxyl Free Radicals: Experimental And Theoretical Evidence From The Gas-Phase Nh2 Chco2 - + O2 Reaction, Gabriel Da Silva, Benjamin Kirk, Celli Lloyd, Adam Trevitt, Stephen Blanksby
Adam Trevitt
We have investigated the gas-phase reaction of the α- aminoacetate (glycyl) radical anion (NH2 •CHCO2−) with O2 using ion trap mass spectrometry, quantum chemistry, and statistical reaction rate theory. This radical is found to undergo a remarkably rapid reaction with O2 to form the hydroperoxyl radical (HO2 •) and an even-electron imine (NHCHCO2−), with experiments and master equation simulations revealing that reaction proceeds at the ion−molecule collision rate. This reaction is facilitated by a low-energy concerted HO2 • elimination mechanism in the NH2CH(OO•)CO2− peroxyl radical. These findings can explain the widely observed free-radical-mediated oxidation of simple amino acids to amides …
Branching Fractions Of The Cn + C3h6 Reaction Using Synchrotron Photoionization Mass Spectrometry: Evidence For The 3-Cyanopropene Product, Adam Trevitt, Talitha Selby, Craig Taatjes, Satchin Soorkia, J Savee, D L Osborn, S R Leone
Branching Fractions Of The Cn + C3h6 Reaction Using Synchrotron Photoionization Mass Spectrometry: Evidence For The 3-Cyanopropene Product, Adam Trevitt, Talitha Selby, Craig Taatjes, Satchin Soorkia, J Savee, D L Osborn, S R Leone
Adam Trevitt
The gas-phase CN + propene reaction is investigated using synchrotron photoionization mass spectrometry (SPIMS) over the 9.8 - 11.5 eV photon energy range. Experiments are conducted at room temperature in 4 Torr of He buffer gas. The CN + propene addition reaction produces two distinct product mass channels, C3H3N and C4H5N, corresponding to CH3 and H elimination, respectively. The CH3 and H elimination channels are measured to have branching fractions of 0.59 + 0.15 and 0.41 + 0.10, respectively. The absolute photoionization cross sections between 9.8 and 11.5 eV are measured for the three considered H-elimination coproducts: 1-, 2-, and …
Isolation And Characterization Of Charge-Tagged Phenylperoxyl Radicals In The Gas Phase: Direct Evidence For Products And Pathways In Low Temperature Benzene Oxidation, Benjamin Kirk, David Harman, Hilkka Kenttamaa, Adam Trevitt, Stephen Blanksby
Isolation And Characterization Of Charge-Tagged Phenylperoxyl Radicals In The Gas Phase: Direct Evidence For Products And Pathways In Low Temperature Benzene Oxidation, Benjamin Kirk, David Harman, Hilkka Kenttamaa, Adam Trevitt, Stephen Blanksby
Adam Trevitt
The phenylperoxyl radical has long been accepted as a critical intermediate in the oxidation of benzene and an archetype for arylperoxyl radicals in combustion and atmospheric chemistry. Despite being central to many contemporary mechanisms underpinning these chemistries, reports of the direct detection or isolation of phenylperoxyl radicals are rare and there is little experimental evidence connecting this intermediate with expected product channels. We have prepared and isolated two charge-tagged phenyl radical models in the gas phase [i.e., 4-(N,N,N-trimethylammonium)phenyl radical cation and 4-carboxylatophenyl radical anion] and observed their reactions with dioxygen by ion-trap mass spectrometry. Measured reaction rates show good agreement …