Open AccessKinetics for tautomerizations and dissociations of triglycine radical cations
Author(s) -
ChiKit Siu,
Junfang Zhao,
Julia Laskin,
Ivan K. Chu,
Alan C. Hopkinson,
K. W. Michael Siu
Publication year - 2009
Publication title -
journal of the american society for mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.961
H-Index - 127
eISSN - 1879-1123
pISSN - 1044-0305
DOI - 10.1016/j.jasms.2009.01.014
Subject(s) - chemistry , protonation , tautomer , radical ion , hydrogen atom , fragmentation (computing) , proton , ion , density functional theory , kinetics , computational chemistry , stereochemistry , group (periodic table) , organic chemistry , operating system , physics , quantum mechanics , computer science
Fragmentations of tautomers of the alpha-centered radical triglycine radical cation, [GGG(*)](+), [GG(*)G](+), and [G(*)GG](+), are charge-driven, giving b-type ions; these are processes that are facilitated by a mobile proton, as in the fragmentation of protonated triglycine (Rodriquez, C. F. et al. J. Am. Chem. Soc. 2001, 123, 3006-3012). By contrast, radical centers are less mobile. Two mechanisms have been examined theoretically utilizing density functional theory and Rice-Ramsperger-Kassel-Marcus modeling: (1) a direct hydrogen-atom migration between two alpha-carbons, and (2) a two-step proton migration involving canonical [GGG](*+) as an intermediate. Predictions employing the latter mechanism are in good agreement with results of recent CID experiments (Chu, I. K. et al. J. Am. Chem. Soc. 2008, 130, 7862-7872).
Accelerating Research
Robert Robinson Avenue,
Oxford Science Park, Oxford
OX4 4GP, United Kingdom
Address
John Eccles HouseRobert Robinson Avenue,
Oxford Science Park, Oxford
OX4 4GP, United Kingdom