Cysteine radical cation

A distonic structure probed by gas phase IR spectroscopy

Rajeev K. Sinha, Philippe Maître, Susanna Piccirillo, Barbara Chiavarino, Maria Elisa Crestoni, Simonetta Fornarini

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

The interest in the radical cations of amino acids is twofold. On the one hand, these species are relevant in enzymatic catalysis and in oxidative damage of proteins. On the other hand, as constituents of peptides and proteins, they aid the mass spectrometric characterization of these biomolecules, yielding diagnostic fragmentation patterns and providing complementary information with respect to the one obtained from even electron ions. The cysteine radical cation has been obtained by S-NO bond cleavage of protonated S-nitrosocysteine and thoroughly characterized by IRMPD spectroscopy, both in the 1000-2000 cm-1 range (the highly structurally diagnostic, so-called ' fingerprint’ range) and in the 2900-3700 cm-1 spectral range, encompassing O-H and N-H stretching vibrations. In this way the distonic structure in which the charge is on the NH3 group and the spin is on the sulfur atom is unambiguously demonstrated. This tautomer is a local minimum on the potential energy surface, at 29.7 kJ mol-1 with respect to the most stable tautomer, a captodative structure allowing extensive delocalization of charge and spin.

Original languageEnglish
Pages (from-to)9794-9800
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume12
Issue number33
DOIs
Publication statusPublished - 01-01-2010

Fingerprint

tautomers
cysteine
Cysteine
Cations
Infrared spectroscopy
Gases
vapor phases
proteins
cations
Potential energy surfaces
Biomolecules
Sulfur
spectroscopy
Catalysis
Stretching
catalysis
peptides
amino acids
cleavage
fragmentation

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Sinha, R. K., Maître, P., Piccirillo, S., Chiavarino, B., Crestoni, M. E., & Fornarini, S. (2010). Cysteine radical cation: A distonic structure probed by gas phase IR spectroscopy. Physical Chemistry Chemical Physics, 12(33), 9794-9800. https://doi.org/10.1039/c003576a
Sinha, Rajeev K. ; Maître, Philippe ; Piccirillo, Susanna ; Chiavarino, Barbara ; Crestoni, Maria Elisa ; Fornarini, Simonetta. / Cysteine radical cation : A distonic structure probed by gas phase IR spectroscopy. In: Physical Chemistry Chemical Physics. 2010 ; Vol. 12, No. 33. pp. 9794-9800.
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Sinha, RK, Maître, P, Piccirillo, S, Chiavarino, B, Crestoni, ME & Fornarini, S 2010, 'Cysteine radical cation: A distonic structure probed by gas phase IR spectroscopy', Physical Chemistry Chemical Physics, vol. 12, no. 33, pp. 9794-9800. https://doi.org/10.1039/c003576a

Cysteine radical cation : A distonic structure probed by gas phase IR spectroscopy. / Sinha, Rajeev K.; Maître, Philippe; Piccirillo, Susanna; Chiavarino, Barbara; Crestoni, Maria Elisa; Fornarini, Simonetta.

In: Physical Chemistry Chemical Physics, Vol. 12, No. 33, 01.01.2010, p. 9794-9800.

Research output: Contribution to journalArticle

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