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A Heme–Peptide Metalloenzyme Mimetic with Natural Peroxidase‐Like Activity
Author(s) -
Nastri Flavia,
Lista Liliana,
Ringhieri Paola,
Vitale Rosa,
Faiella Marina,
Andreozzi Concetta,
Travascio Paola,
Maglio Ornella,
Lombardi Angela,
Pavone Vincenzo
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201003485
Subject(s) - chemistry , guaiacol , peroxidase , abts , heme , catalysis , enzyme , hydrogen peroxide , stereochemistry , combinatorial chemistry , horseradish peroxidase , biocatalysis , cofactor , artificial enzyme , organic chemistry , reaction mechanism , antioxidant , dpph
Mimicking enzymes with alternative molecules represents an important objective in synthetic biology, aimed to obtain new chemical entities for specific applications. This objective is hampered by the large size and complexity of enzymes. The manipulation of their structures often leads to a reduction of enzyme activity. Herein, we describe the spectroscopic and functional characterization of Fe III –mimochrome VI, a 3.5 kDa synthetic heme–protein model, which displays a peroxidase‐like catalytic activity. By the use of hydrogen peroxide, Fe III –mimochrome VI efficiently catalyzes the oxidation of several substrates, with a typical Michaelis–Menten mechanism and with several multiple turnovers. The catalytic efficiency of Fe III –mimochrome VI in the oxidation of 2,2′‐azino‐di(3‐ethyl‐benzothiazoline‐6‐sulfonic acid (ABTS) and guaiacol ( k cat / K m =4417 and 870 m M −1 s −1 , respectively) is comparable to that of native horseradish peroxidase (HRP, k cat / K m =5125 and 500 m M −1 s −1 , respectively). Fe III –mimochrome VI also converts phenol to 4‐ and 2‐nitrophenol in the presence of NO 2 − and H 2 O 2 in high yields. These results demonstrate that small synthetic peptides can impart high enzyme activities to metal cofactors, and anticipate the possibility of constructing new biocatalysts tailored to specific functions.