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 Roberts, Christina M. Sorensen, Simone Raugei, Thomas C. Squier, Wendy J. Shaw

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

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(PPh 2NAPPA)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(PPh 2NAPPA-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(PPh 2NAPPA)2]2+ (APPA=4-aminophenyl propionic acid).

Original languageEnglish
Pages (from-to)1510-1514
Number of pages5
JournalChemistry - A European Journal
Volume20
Issue number6
DOIs
Publication statusPublished - Feb 3 2014

Fingerprint

Electrocatalysts
Nickel
Peptides
Enzymes
Coordination Complexes
Metal complexes
Catalysts
Propionic acid
Scaffolds (biology)
Hydrogen production
Scaffolds
Metals

Keywords

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

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Reback, M. L., Buchko, G. W., Kier, B. L., Ginovska-Pangovska, B., Xiong, Y., Lense, S., ... Shaw, W. J. (2014). Enzyme design from the bottom up: An active nickel electrocatalyst with a structured peptide outer coordination sphere. Chemistry - A European Journal, 20(6), 1510-1514. https://doi.org/10.1002/chem.201303976

Enzyme design from the bottom up : An active nickel electrocatalyst with a structured peptide outer coordination sphere. / Reback, Matthew L.; Buchko, Garry W.; Kier, Brandon L.; Ginovska-Pangovska, Bojana; Xiong, Yijia; Lense, Sheri; Hou, Jianbo; Roberts, John; Sorensen, Christina M.; Raugei, Simone; Squier, Thomas C.; Shaw, Wendy J.

In: Chemistry - A European Journal, Vol. 20, No. 6, 03.02.2014, p. 1510-1514.

Research output: Contribution to journalArticle

Reback, ML, Buchko, GW, Kier, BL, Ginovska-Pangovska, B, Xiong, Y, Lense, S, Hou, J, Roberts, J, Sorensen, CM, Raugei, S, Squier, TC & Shaw, WJ 2014, 'Enzyme design from the bottom up: An active nickel electrocatalyst with a structured peptide outer coordination sphere', Chemistry - A European Journal, vol. 20, no. 6, pp. 1510-1514. https://doi.org/10.1002/chem.201303976
Reback, Matthew L. ; Buchko, Garry W. ; Kier, Brandon L. ; Ginovska-Pangovska, Bojana ; Xiong, Yijia ; Lense, Sheri ; Hou, Jianbo ; Roberts, John ; Sorensen, Christina M. ; Raugei, Simone ; Squier, Thomas C. ; Shaw, Wendy J. / Enzyme design from the bottom up : An active nickel electrocatalyst with a structured peptide outer coordination sphere. In: Chemistry - A European Journal. 2014 ; Vol. 20, No. 6. pp. 1510-1514.
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