Neighboring pyrrolidine amide participation in thioether oxidation. Methionine as a "hopping" site |
| |
Authors: | Glass Richard S Schöneich Christian Wilson George S Nauser Thomas Yamamoto Takuhei Lorance Edward Nichol Gary S Ammam Malika |
| |
Institution: | Department of Chemistry and Biochemistry, The University of Arizona, Tucson, Arizona 85721, United States. rglass@u.arizona.edu |
| |
Abstract: | Methionine residues have been shown to function as efficient "hopping" sites in long-range electron transfer in model polyprolyl peptides. We suggest that a key to this ability of methionine is stabilization of the transient sulfur radical cation by neighboring proline amide participation. That is, in a model system a neighboring pyrrolidine amide lowers the oxidation potential of the thioether by over 0.5 V by formation of a two-center three-electron SO bond. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|