Ontology highlight
ABSTRACT:
SUBMITTER: Wang Y
PROVIDER: S-EPMC5528148 | biostudies-literature | 2017 May
REPOSITORIES: biostudies-literature
Wang Ying Y Olankitwanit Arnon A Rajca Suchada S Rajca Andrzej A
Journal of the American Chemical Society 20170522 21
We report a large kinetic isotope effect at 298 K, k<sub>H</sub>/k<sub>D</sub> ≈ 150, associated with an intramolecular 1,5-hydrogen atom transfer (1,5-HAT) in the decay of a PEGylated carbazyl (aminyl) radical in solution. The experimental observations surprisingly combine the hallmarks of tunneling, including large KIEs and unusual activation parameters, with linear Arrhenius and Eyring plots over an exceptionally wide temperature range of 116 K. ...[more]