Enzyme design from the bottom up: an active nickel electrocatalyst with a structured peptide outer coordination sphere.
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(P(Ph)2N(Ph))2](2+) (P(Ph)2N(Ph)=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(P(Ph)2N(APPA))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.
Pacific Northwest National Labs, Richland, WA 99354 (USA).
Matthew L
ML
Reback
Garry W
GW
Buchko
Brandon L
BL
Kier
Bojana
B
Ginovska-Pangovska
Yijia
Y
Xiong
Sheri
S
Lense
Jianbo
J
Hou
John A S
JA
Roberts
Christina M
CM
Sorensen
Simone
S
Raugei
Thomas C
TC
Squier
Wendy J
WJ
Shaw
D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D055664:Electrochemical Techniques; D006859:Hydrogen / Q000737:chemistry; D006864:Hydrogenase / Q000737:chemistry; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D010455:Peptides / Q000737:chemistry*
D056831:Coordination Complexes; D010455:Peptides; D009532:Nickel; D006859:Hydrogen; D006864:Hydrogenase
electrocatalysis; hydrogen production; outer coordination sphere; peptide catalysis; synthetic enzymes