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The Photochemistry of N ‐ p ‐Toluenesulfonyl Peptides: The Peptide Bond as an Electron Donor
Author(s) -
Hill Roger R.,
Moore Sharon A.,
Roberts David R.
Publication year - 2005
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1562/2005-04-29-ra-507
Subject(s) - dipeptide , chemistry , intramolecular force , peptide , electron transfer , peptide bond , photochemistry , redox , combinatorial chemistry , protecting group , stereochemistry , organic chemistry , biochemistry , alkyl
The scope of photobiological processes that involve absorbers within a protein matrix may be limited by the vulnerability of the peptide group to attack by highly reactive redox centers consequent upon electronic excitation. We have explored the nature of this vulnerability by undertaking comprehensive product analyses of aqueous photolysates of 12 N‐p ‐toluenesulfonyl peptides with systematically selected structures. The results indicate that degradation includes a major pathway that is initiated by intramolecular electron transfer in which the peptide bond serves as electron donor, and the data support the likelihood of a relay process in dipeptide derivatives.