UV/Vis Action Spectroscopy and Structures of Tyrosine Peptide Cation Radicals in the Gas Phase |
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Authors: | Emilie Viglino Dr Christopher J Shaffer Prof?Dr Franti?ek Ture?ek |
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Institution: | Department of Chemistry, University of Washington, Seattle, WA, USA |
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Abstract: | We report the first application of UV/Vis photodissociation action spectroscopy for the structure elucidation of tyrosine peptide cation radicals produced by oxidative intramolecular electron transfer in gas‐phase metal complexes. Oxidation of Tyr‐Ala‐Ala‐Ala‐Arg (YAAAR) produces Tyr‐O radicals by combined electron and proton transfer involving the phenol and carboxyl groups. Oxidation of Ala‐Ala‐Ala‐Tyr‐Arg (AAAYR) produces a mixture of cation radicals involving electron abstraction from the Tyr phenol ring and N‐terminal amino group in combination with hydrogen‐atom transfer from the Cα positions of the peptide backbone. |
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Keywords: | copper complexes electron transfer gas-phase chemistry peptides UV/Vis spectroscopy |
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