Size-Dependent Hydrogen Atom Attachment to Gas-Phase Hydrogen-Deficient Polypeptide Radical Cations

作者:Di Stefano Luciano H; Papanastasiou Dimitris; Zubarev Roman A*
来源:Journal of the American Chemical Society, 2018, 140(2): 531-533.
DOI:10.1021/jacs.7b10318

摘要

Despite significant affinity to carbonyl oxygens, thermal hydrogen atoms attach to unmodified polypeptides at a very low rate, while the hydrogen- hydrogen exchange rate is high. Here, using the novel omnitrap setup, we found that attachment to polypeptides is much more facile when radical site is already present, but the rate decreases for larger radical ions. The likely explanation is the intramolecular hydrogen atom rearrangement in hydrogen-deficient radicals to a more stable or less accessible site.

  • 出版日期2018-1-17