Two-dimensional ESEEM spectroscopy of nitrogen hyperfine couplings in methemerythrin and azidomethemerythrin

Sergei A. Dikanov, Roman M. Davydov, Astrid Gräslund, Michael K. Bowman

Research output: Contribution to journalArticlepeer-review

Abstract

The application of a two-dimensional ESEEM spectroscopy, known as HYSCORE, to the study of the hyperfine couplings from the nitrogens of histidine and azide ligands in mixed-valent states of methemerythrin and azidomethemerythrin produced by low-temperature (77 K) γ-irradiation is described. The HYSCORE spectra contain groups of well-separated cross-peaks from directly coordinated and remote histidine nitrogens, and from nitrogens of the azide ligand. The observation of cross-features correlating double-quantum transitions allows direct estimation of the hyperfine couplings from all coordinated histidine nitrogens of semimethemerythrin which vary between 5 and 15 MHz as well as their changes upon azide binding. The results obtained show that two-dimensional spectroscopy provides significantly more information compared to one-dimensional techniques for the characterization of the paramagnetic centers involving large numbers of magnetically nonequivalent nuclei. This work forms the basis for the application of two-dimensional ESEEM in conjunction with low-temperature reduction for the detailed characterization of nitrogen coordination in diiron centers in proteins of unknown crystal structure.

Original languageEnglish (US)
Pages (from-to)6797-6805
Number of pages9
JournalJournal of the American Chemical Society
Volume120
Issue number27
DOIs
StatePublished - Jul 15 1998
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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