Biomimetic sensor based on Mn(III) meso-tetra(N-methyl-4-pyridyl) porphyrin for non-enzymatic electrocatalytic determination of hydrogen peroxide and as an electrochemical transducer in oxidase biosensor for analysis of biological media

Abstract

Bioinspired molecular complexes that mimic the enzymatic catalysis of redox transformations offer a versatile platform for the development of non-enzymatic mediatorless sensors with high sensitivity, selectivity, and robustness without the use of precious metals. The aim of this study was to prepare and investigate biomimetic sensors based on the electrocatalytic reduction of hydrogen peroxide and oxygen by a series of immobilized complexes of iron and manganese with porphyrin macrocycles for the detection of hydrogen peroxide and glucose. The influence of substitution of the macroheterocyclic ligand, composition of the adsorption solution, Nafion membrane, and amino acids on the properties of the sensors was studied. Optimized sensor function is based on the electrogenerated reduced form of Mn(II) meso-tetra(N-methyl-4-pyridyl) porphyrin as a catalyst and allows high sensitivity of the hydrogen peroxide detection of 1.8 A M−1 cm−2 and 0.071 A M−1 cm−2 to be achieved in the lower and higher concentration ranges, respectively, with a low detection limit of 5⋅10−7 M at physiological pH 7.4 and in the presence of oxygen. The MnTMPyP electrode was investigated as an electrochemical transducer in the glucose-oxidase-based biosensor. The sensors were successfully applied for the detection of hydrogen peroxide and glucose in human serum samples. Along with a simple fabrication procedure and robustness of the sensor, the biomimetic electrocatalytic properties of the MnTMPyP complex facilitate excellent performance of the proposed sensors for hydrogen peroxide and glucose determination in biological media, emphasizing the importance of bioinspired electrocatalytic metalloporphyrin complexes for the development of sensors and point-of-care devices.