Enzyme design from the bottom up: An active nickel electrocatalyst with a structured peptide outer coordination sphere

Matthew L. Reback, Garry W. Buchko, Brandon L. Kier, Bojana Ginovska-Pangovska, Yijia Xiong, Sheri Lense, Jianbo Hou, John A.S. Roberts, Christina M. Sorensen, Simone Raugei, Thomas C. Squier, Wendy J. Shaw

Research output: Contribution to journalArticlepeer-review

26 Citations (Scopus)


Catalytic, peptide-containing metal complexes with a well-defined peptide structure have the potential to enhance molecular catalysts through an enzyme-like outer coordination sphere. Here, we report the synthesis and characterization of an active, peptide-based metal complex built upon the well-characterized hydrogen production catalyst [Ni(PPh 2NPh)2]2+ (PPh 2NPh=1,3,6-triphenyl-1-aza-3,6-diphosphacycloheptane). The incorporated peptide maintains its β-hairpin structure when appended to the metal core, and the electrocatalytic activity of the peptide-based metal complex (≈100,000 s-1) is enhanced compared to the parent complex ([Ni(PPh2NAPPA)2]2+; ≈50,500 s-1). The combination of an active molecular catalyst with a structured peptide provides a scaffold that permits the incorporation of features of an enzyme-like outer-coordination sphere necessary to create molecular electrocatalysts with enhanced functionality. A H2 production catalyst with a peptide-based, structured outer coordination sphere has been synthesized (see figure), making it possible to evaluate the effect of the outer coordination sphere on molecular catalysts. The resulting complex, [Ni(PPh2NAPPA-WR10)2]2+, retains the secondary structure of the peptide (WR10) and is active for H 2 production, with enhanced rates compared with the parent complex [Ni(PPh2NAPPA)2]2+ (APPA=4-aminophenyl propionic acid).

Original languageEnglish
Pages (from-to)1510-1514
Number of pages5
JournalChemistry - A European Journal
Issue number6
Publication statusPublished - Feb 3 2014


  • electrocatalysis
  • hydrogen production
  • outer coordination sphere
  • peptide catalysis
  • synthetic enzymes

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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