Peroxide Activation Regulated by Hydrogen Bonds within Artificial Cu Proteins

J Am Chem Soc. 2017 Dec 6;139(48):17289-17292. doi: 10.1021/jacs.7b10452. Epub 2017 Nov 15.

Abstract

Copper-hydroperoxido species (CuII-OOH) have been proposed to be key intermediates in biological and synthetic oxidations. Using biotin-streptavidin (Sav) technology, artificial copper proteins have been developed to stabilize a CuII-OOH complex in solution and in crystallo. Stability is achieved because the Sav host provides a local environment around the Cu-OOH that includes a network of hydrogen bonds to the hydroperoxido ligand. Systematic deletions of individual hydrogen bonds to the Cu-OOH complex were accomplished using different Sav variants and demonstrated that stability is achieved with a single hydrogen bond to the proximal O-atom of the hydroperoxido ligand: changing this interaction to only include the distal O-atom produced a reactive variant that oxidized an external substrate.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Copper / chemistry*
  • Hydrogen Bonding
  • Ligands
  • Metalloproteins / chemistry*
  • Peroxides / chemistry*

Substances

  • Ligands
  • Metalloproteins
  • Peroxides
  • Copper