Formation and Electronic Structure of an Atypical Cu A Site

Matthew O. Ross, Oriana S. Fisher, Marcos N. Morgada, Matthew D. Krzyaniak, Michael R Wasielewski, Alejandro J. Vila, Brian M. Hoffman, Amy C. Rosenzweig

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

PmoD, a recently discovered protein from methane-oxidizing bacteria, forms a homodimer with a dicopper Cu A center at the dimer interface. Although the optical and electron paramagnetic resonance (EPR) spectroscopic signatures of the PmoD Cu A bear similarities to those of canonical Cu A sites, there are also some puzzling differences. Here we have characterized the rapid formation (seconds) and slow decay (hours) of this homodimeric Cu A site to two mononuclear Cu 2+ sites, as well as its electronic and geometric structure, using stopped-flow optical and advanced paramagnetic resonance spectroscopies. PmoD Cu A formation occurs rapidly and involves a short-lived intermediate with a max of 360 nm. Unlike other Cu A sites, the PmoD Cu A is unstable, decaying to two type 2 Cu 2+ centers. Surprisingly, NMR data indicate that the PmoD Cu A has a pure σ u ∗ ground state rather than the typical equilibrium between σ u ∗ and π u of all other Cu A proteins. EPR, ENDOR, ESEEM, and HYSCORE data indicate the presence of two histidine and two cysteine ligands coordinating the Cu A core in a highly symmetrical fashion. This report significantly expands the diversity and understanding of known Cu A sites.

Original languageEnglish
Pages (from-to)4678-4686
Number of pages9
JournalJournal of the American Chemical Society
Volume141
Issue number11
DOIs
Publication statusPublished - Mar 20 2019

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Electron Spin Resonance Spectroscopy
Electronic structure
Paramagnetic resonance
Proteins
Methylococcaceae
Optical flows
Methane
Histidine
Dimers
Ground state
Cysteine
Bacteria
Ligands
Nuclear magnetic resonance
Spectroscopy
Spectrum Analysis

ASJC Scopus subject areas

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

Cite this

Ross, M. O., Fisher, O. S., Morgada, M. N., Krzyaniak, M. D., Wasielewski, M. R., Vila, A. J., ... Rosenzweig, A. C. (2019). Formation and Electronic Structure of an Atypical Cu A Site Journal of the American Chemical Society, 141(11), 4678-4686. https://doi.org/10.1021/jacs.8b13610

Formation and Electronic Structure of an Atypical Cu A Site . / Ross, Matthew O.; Fisher, Oriana S.; Morgada, Marcos N.; Krzyaniak, Matthew D.; Wasielewski, Michael R; Vila, Alejandro J.; Hoffman, Brian M.; Rosenzweig, Amy C.

In: Journal of the American Chemical Society, Vol. 141, No. 11, 20.03.2019, p. 4678-4686.

Research output: Contribution to journalArticle

Ross, MO, Fisher, OS, Morgada, MN, Krzyaniak, MD, Wasielewski, MR, Vila, AJ, Hoffman, BM & Rosenzweig, AC 2019, ' Formation and Electronic Structure of an Atypical Cu A Site ', Journal of the American Chemical Society, vol. 141, no. 11, pp. 4678-4686. https://doi.org/10.1021/jacs.8b13610
Ross, Matthew O. ; Fisher, Oriana S. ; Morgada, Marcos N. ; Krzyaniak, Matthew D. ; Wasielewski, Michael R ; Vila, Alejandro J. ; Hoffman, Brian M. ; Rosenzweig, Amy C. / Formation and Electronic Structure of an Atypical Cu A Site In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 11. pp. 4678-4686.
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