Sulfur K-Edge XAS Studies of the Effect of DNA Binding on the [Fe4S4] Site in EndoIII and MutY

Yang Ha, Anna R. Arnold, Nicole N. Nuñez, Phillip L. Bartels, Andy Zhou, Sheila S. David, Jacqueline K. Barton, Britt Hedman, Keith O. Hodgson, Edward I. Solomon

Research output: Contribution to journalArticle

10 Scopus citations

Abstract

S K-edge X-ray absorption spectroscopy (XAS) was used to study the [Fe4S4] clusters in the DNA repair glycosylases EndoIII and MutY to evaluate the effects of DNA binding and solvation on Fe-S bond covalencies (i.e., the amount of S 3p character mixed into the Fe 3d valence orbitals). Increased covalencies in both iron-thiolate and iron-sulfide bonds would stabilize the oxidized state of the [Fe4S4] clusters. The results are compared to those on previously studied [Fe4S4] model complexes, ferredoxin (Fd), and to new data on high-potential iron-sulfur protein (HiPIP). A limited decrease in covalency is observed upon removal of solvent water from EndoIII and MutY, opposite to the significant increase observed for Fd, where the [Fe4S4] cluster is solvent exposed. Importantly, in EndoIII and MutY, a large increase in covalency is observed upon DNA binding, which is due to the effect of its negative charge on the iron-sulfur bonds. In EndoIII, this change in covalency can be quantified and makes a significant contribution to the observed decrease in reduction potential found experimentally in DNA repair proteins, enabling their HiPIP-like redox behavior.

Original languageEnglish (US)
Pages (from-to)11434-11442
Number of pages9
JournalJournal of the American Chemical Society
Volume139
Issue number33
DOIs
StatePublished - Aug 23 2017

ASJC Scopus subject areas

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

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    Ha, Y., Arnold, A. R., Nuñez, N. N., Bartels, P. L., Zhou, A., David, S. S., Barton, J. K., Hedman, B., Hodgson, K. O., & Solomon, E. I. (2017). Sulfur K-Edge XAS Studies of the Effect of DNA Binding on the [Fe4S4] Site in EndoIII and MutY. Journal of the American Chemical Society, 139(33), 11434-11442. https://doi.org/10.1021/jacs.7b03966