Radicals formed by the reaction of electrons with amino acids and peptides in a neutral aqueous glass

M. D. Sevilla, Virginia Brooks

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

The reactions of electrons with a number of amino acids, N-acetylamino acids, N-acetylpeptides, and peptides in a neutral aqueous glass (12 M LiCl-D2O) have been investigated by electron spin resonance spectroscopy. Electron attachment to the amino acids, glycine and alanine, at 77°K results in immediate deamination. For amino acids with more reactive side groups, e.g., glutamic acid, anion radicals are found with the electron localized on the side group. For all peptides we find immediate N-terminal deamination upon electron attachment at 77°K. Where glycine is at the N terminal, upon warming to the softening point of the glass, deamination is followed by abstraction from an α-carbon position. Stable anions are found for N-acetylamino acids and N-acetylpeptides after electron attachment. These anions undergo deamination of a secondary amine group upon warming to 165°K. Further warming results in hydrogen abstraction to form an α-carbon radical. These results are compared to those found in an alkaline glass (8 M NaOD). It is found that changes in protonation at nitrogen sites greatly affect stability and hyperfine splittings of radicals produced after electron attachment. McLachlan spin density calculations confirm the experimental result that deprotonation at the nitrogen in peptide α-carbon radicals can significantly alter the α-carbon proton splitting. Finally, the results found in this study are discussed in terms of other recent work utilizing pulse radiolysis, product analysis, and esr. Good agreement is found between the various techniques.

Original languageEnglish (US)
Pages (from-to)2954-2959
Number of pages6
JournalJournal of Physical Chemistry
Volume77
Issue number25
StatePublished - 1973
Externally publishedYes

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electron attachment
Peptides
peptides
amino acids
Amino acids
Amino Acids
Glass
Electrons
glass
carbon
Carbon
glycine
anions
heating
Anions
electrons
Negative ions
nitrogen
Glycine
glutamic acid

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Radicals formed by the reaction of electrons with amino acids and peptides in a neutral aqueous glass. / Sevilla, M. D.; Brooks, Virginia.

In: Journal of Physical Chemistry, Vol. 77, No. 25, 1973, p. 2954-2959.

Research output: Contribution to journalArticle

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