Interactions of Cu(I) with selenium-containing amino acids determined by NMR, XAS, and DFT studies

Hsiao-Chuan Wang, Mindy Riahi, Joshua Pothen, Craig A. Bayse, Pamela Riggs-Gelasco, Julia L. Brumaghim

Research output: Contribution to journalArticle

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Abstract

Cu(I) coordination by organoselenium compounds was recently reported as a mechanism for their prevention of copper-mediated DNA damage. To establish whether direct Se-Cu coordination may be involved in selenium antioxidant activity, Cu(I) coordination of the selenoamino acids methyl-Se-cysteine (MeSeCys) and selenomethionine (SeMet) was investigated. NMR results in D 2O indicate that Cu(I) binds to the Se atom of both MeSeCys and SeMet as well as the carboxylic acid oxygen atom(s) or amine nitrogen atoms. X-ray absorption spectroscopy (XAS) and density functional theory (DFT) results confirm Se-Cu coordination, with the identification of a 2.4 Å Se-Cu vector in both the Se-and Cu-EXAFS data. XAS studies also show Cu(I) in an unusual three-coordinate environment with the additional two ligands arising from O/N (2.0 Å). DFT models of 1:1 Cu-selenoamino acid complexes suggest that both selenoamino acids coordinate Cu(I) through the selenium and amino groups, with the third ligand assumed to be water. These compounds represent the first structurally characterized copper(I) complexes with sulfur-or selenium-containing amino acids.

Original languageEnglish (US)
Pages (from-to)10893-10900
Number of pages8
JournalInorganic Chemistry
Volume50
Issue number21
DOIs
StatePublished - Nov 7 2011
Externally publishedYes

Fingerprint

X ray absorption spectroscopy
Selenium
selenium
Selenomethionine
Density functional theory
amino acids
absorption spectroscopy
Nuclear magnetic resonance
density functional theory
Amino Acids
Atoms
nuclear magnetic resonance
Acids
Cysteine
Copper
cysteine
Organoselenium Compounds
acids
Ligands
x rays

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Wang, H-C., Riahi, M., Pothen, J., Bayse, C. A., Riggs-Gelasco, P., & Brumaghim, J. L. (2011). Interactions of Cu(I) with selenium-containing amino acids determined by NMR, XAS, and DFT studies. Inorganic Chemistry, 50(21), 10893-10900. https://doi.org/10.1021/ic201440j

Interactions of Cu(I) with selenium-containing amino acids determined by NMR, XAS, and DFT studies. / Wang, Hsiao-Chuan; Riahi, Mindy; Pothen, Joshua; Bayse, Craig A.; Riggs-Gelasco, Pamela; Brumaghim, Julia L.

In: Inorganic Chemistry, Vol. 50, No. 21, 07.11.2011, p. 10893-10900.

Research output: Contribution to journalArticle

Wang, H-C, Riahi, M, Pothen, J, Bayse, CA, Riggs-Gelasco, P & Brumaghim, JL 2011, 'Interactions of Cu(I) with selenium-containing amino acids determined by NMR, XAS, and DFT studies', Inorganic Chemistry, vol. 50, no. 21, pp. 10893-10900. https://doi.org/10.1021/ic201440j
Wang H-C, Riahi M, Pothen J, Bayse CA, Riggs-Gelasco P, Brumaghim JL. Interactions of Cu(I) with selenium-containing amino acids determined by NMR, XAS, and DFT studies. Inorganic Chemistry. 2011 Nov 7;50(21):10893-10900. https://doi.org/10.1021/ic201440j
Wang, Hsiao-Chuan ; Riahi, Mindy ; Pothen, Joshua ; Bayse, Craig A. ; Riggs-Gelasco, Pamela ; Brumaghim, Julia L. / Interactions of Cu(I) with selenium-containing amino acids determined by NMR, XAS, and DFT studies. In: Inorganic Chemistry. 2011 ; Vol. 50, No. 21. pp. 10893-10900.
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