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

doi:10.1016/j.snb.2020.128437

Sensors and Actuators B: Chemical

Volume 321, 15 October 2020, 128437

https://doi.org/10.1016/j.snb.2020.128437 Get rights and content

Highlights

•
Biomimetic electrochemical sensors based on immobilized complexes of iron and manganese with porphyrin macrocycles for hydrogen peroxide detection.
•
High sensitivity is achieved due to the electrocatalytic reduction of hydrogen peroxide with an electrochemically reduced form of MnP.
•
Low detection limit of 5⋅10⁻⁷ M and high selectivity for hydrogen peroxide in the presence of oxygen.
•
MnP electrode is investigated as an electrochemical transducer in glucose-oxidase-based biosensor.
•
Determination of hydrogen peroxide and glucose in human serum samples.

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.

Graphical abstract

Introduction

Electrochemical sensors and systems with hydrogen peroxide are an important topic in current scientific investigations because of the established role of hydrogen peroxide in diverse fields. In biological systems, it is involved in redox signaling [[1], [2], [3]] and ROS-based medicine [4]. In cells, where most hydrogen peroxide is generated through the dismutation of the superoxide radical anion originating mainly from the electron transport chain of aerobic respiration, it also contributes to oxidative stress conditions responsible for toxic effects, which damage cell components, and is also involved in a number of diseases and pathologies [1]. Furthermore, hydrogen peroxide is a redox-active product of the metabolic redox reactions catalyzed by oxidase enzymes (e.g., glucose oxidase, monoamine oxidase, glutamate oxidase). Consequently, determination of hydrogen peroxide is a strategy for the determination of glucose, monoamines, glutamate, lactate, and cholesterol. Along with its role in biological processes, hydrogen peroxide is of great interest for industrial, ecological, and analytical applications [[5], [6], [7], [8]].

These topics have motivated significant research activity in the development of sensors for hydrogen peroxide determination in various media [3,[9], [10], [11], [12], [13], [14], [15], [16], [17], [18]]. Electrochemical sensors based on modified electrodes are often the method of choice due to their widely recognized advantages such as accuracy, miniaturization potential, low costs, simple instrumentation and utilization, portability, temporal resolution, and applicability for real-time measurements and implantation. Modern electrochemical sensors for hydrogen peroxide rely on bio- and electrocatalytic reactions on the electrode surfaces modified with peroxidase enzyme, smaller biomolecular catalysts (e.g., cytochrome c, myoglobin) [10,12,19], noble metals, oxides, metal and carbonaceous electrode nanomaterials [11,[13], [14], [15],[20], [21], [22]], as well as their synergy [12,[23], [24], [25]]. Modifying the electrodes makes it possible to decrease the overpotential of the hydrogen peroxide reduction or oxidation, increase currents, and improve the selectivity of the determinations.

The development of non-enzymatic sensors based on biomimetic molecular complexes is expected to make use of the synergic effect of the above-mentioned materials and combine their advantages, while being at the same time more robust, flexible, easy-to-use, and not consuming noble metals [9,[26], [27], [28], [29], [30]]. In natural redox biological transformations, metalloproteins with iron, copper, and Fe/Cu active site tetrapyrrolic complexes mediate oxygenation reactions with oxygen and hydrogen peroxide terminal oxidants [31]. By analogy with natural systems, a biomimetic electrocatalytic reduction of hydrogen peroxide using metal complexes with N₄-macoheterocycles as electrocatalysts is a candidate for the development of electrochemical sensors for hydrogen peroxide [9]. Along with the central metal of the complex, substituents of the tetrapyrrolic macroheterocycle may contribute to the redox properties of the complex as well as steric interactions and arrangements, which makes it possible to modify the sensor properties with respect to detection limit, sensitivity, and selectivity [32]. As far as hydrogen peroxide sensing is concerned, most work has been performed with iron porphyrin complexes, since these macroheterocycles are direct analogues of the hemes in HRP, cyt c, and other redox hemoproteins. There is also growing interest in manganese porphyrins as biomimetic components and sensor materials in electrochemical and electrocatalytic systems because of the essential role of manganese in redox biological processes in photosystem II and non-heme manganese catalase enzymes, the possibility of tuning the environment of the central metal ion, the ability of the manganese ion to change oxidation states, and its interactions with various oxygen-containing species such as oxygen, superoxide, and hydrogen peroxide [33,34]. Moreover, manganese porphyrins may be advantageous in comparison with Fe and Cu porphyrin complexes for the construction of in vivo sensors and with respect to applications in biological systems, since Fe and Cu porphyrin complexes have been shown to participate in the Fenton reaction, react with H₂O₂ to form HO, inducing cell death, being cytotoxic [35]. Unlike Fe and Cu porphyrins, MnTMPyP does not participate in the Fenton reaction and does not exhibit cytotoxicity. However, unlike the iron and cobalt complexes, only a few examples of manganese macrocycles have been reported as catalysts of the molecular oxygen reduction reaction, the epoxidation reaction, as well as the superoxide dismutase mimic, and as scavengers of the reactive oxygen species [8,[35], [36], [37], [38], [39]]. However, it has been assumed that biomimetic iron and manganese complexes have similar intermediates in the reaction with oxygen and incompletely reduced oxygen species [39]. It has been shown that manganese tetrakis(sulphonatophenyl)porphyrin complex has a higher peroxidase-like activity in the spectrophotometric determination of hydrogen peroxide than a number of Fe-, Co-, Cu- Zn- and metal-free porphyrins [40].

Recently we performed an investigation on a series of water-soluble manganese porphyrins in the electrocatalytic reduction of oxygen and hydrogen peroxide in aqueous solutions, where the electrode support did not essentially influence the redox properties of the complexes, and where we discussed possible intermediates and mechanisms of the reactions [41]. This study revealed prospects of the Mn(III) meso-tetra(N-methyl-4-pyridyl) porphyrin complex for the biomimetic electrochemical sensing of hydrogen peroxide based on the electrocatalytic reduction reaction. However, the distinction in the properties of metal complexes with tetrapyrrolic ligands in the bulk dissolved and adsorbed states suggest a difference in their electrocatalytic properties and is worth investigating [[42], [43], [44], [45]]. To the best of our knowledge, this is the first detailed study of the sensor based on the electrocatalytic properties of the Mn porphyrin in reduction of hydrogen peroxide as applied for the analysis of biological media. In this investigation, we study and compare the immobilization and biomimetic sensor properties of complexes of Mn and Fe with porphyrin macrocycles for a non-enzymatic selective electrocatalytic determination of hydrogen peroxide. Properties of the modified electrode as an electrochemical transducer for the oxidase biosensor and an analysis of biological media are also shown and discussed.

Section snippets

Materials and solutions

Mn(III) meso-tetraphenylporphine chloride, MnTPP, Mn(III) meso-tetra(N-methyl-4-pyridyl) porphine pentachloride, MnTMPyP, Fe(III) meso- tetra(N-methyl-4-pyridyl) porphine pentachloride, Fe(III)TMPyP, and Fe(III) meso-tetraphenylporphine chloride, Fe (III)TPP with a purity of > 95 % were purchased from Frontiers Scientific Inc., Fig. 1. All other chemicals of analytical reagent grade, Nafion solution (5 wt. % in mixture of lower aliphatic alcohols and water), glucose oxidase from Aspergillus

Immobilization of manganese and iron porphyrin complexes on GCEs

In a previous study, the higher electrocatalytic activity of manganese porphyrin complexes with positively charged electron-withdrawing N-methyl-4-pyridyl meso-substituents of the macrocycle in the biomimetic oxygen and hydrogen peroxide reduction reactions in solutions was demonstrated [41] (additional information is provided in section S1 and Fig. S1 in the supporting information). In the present study, the immobilization and hydrogen peroxide sensing properties of the porphyrin complexes

Conclusions

Non-enzymatic biomimetic sensors for hydrogen peroxide based on a series of immobilized porphyrin complexes of iron and manganese were prepared and investigated. The influence of the meso-substituents of the macroheterocyclic porphyrin ligand, composition of the adsorption solution, Nafion membrane, and amino acids on the properties of the sensors were studied. The MnTMPyP complex achieved the best sensor performance for the determination of hydrogen peroxide in the presence of oxygen with a

CRediT authorship contribution statement

Ruiqin Peng: Data curation, Funding acquisition, Investigation. Andreas Offenhäusser: Conceptualization, Resources, Visualization. Yuri Ermolenko: Conceptualization, Methodology, Data curation, Investigation. Yulia Mourzina: Conceptualization, Methodology, Supervision, Data curation, Validation, Investigation, Visualization.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

Dr. R. Peng acknowledges the Helmholtz–OCPC Postdoc Program (20181032) for the financial support. The authors thank E. Brauweiller-Reuters for the SEM studies.

Ruiqin Peng graduated from the Shandong Normal University (Ms.Sc.) in 2012. He received his Ph.D. in material science and engineering (2016) from the Harbin Institute of Technology. His research interests refer to electrochemical sensors and their analytical application.

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Yuri Ermolenko received his PhD in radiochemistry in 1982 from Leningrad State University. Since then he has worked at the Faculty of Chemistry of St. Petersburg (Leningrad) State University. In 2000, he received his DSc degree in radiochemistry and solid-state chemistry from St. Petersburg (Leningrad) State University. Since 2001, he has been professor of radiochemistry and solid-state chemistry. His main scientific interests are in the field of solid-state chemistry and the development of new sensor materials.

Andreas Offenhäusser studied physics and completed his PhD dissertation in 1989 at the University of Ulm. For 2 years, he worked in the field of power transistors at Robert Bosch GmbH in Reutlingen, Germany. From 1992 until 1994 he performed a post doctoral study at the Frontier Research Program at RIKEN, Japan. Afterwards, he worked as a group leader at the Max-Planck-Institute for Polymer Research in Mainz, Germany. Since 2001, Prof. Offenhäusser is director of the Institute of Biological Information Processing (IBI-3, Bioelectronics) at the Forschungszentrum Jülich and Professor of Experimental Physics at the Rheinisch-Westfälische Technische Hochschule (RWTH) Aachen.

Yulia Mourzina received a PhD in analytical chemistry from St. Petersburg State University in 1994. Currently, she is a senior scientist at the Institute of Biological Information Processing (IBI-3, Bioelectronics), Forschungszentrum Jülich, Germany. Her main research interests are electrochemical (bio)sensors.

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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

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials and solutions

Immobilization of manganese and iron porphyrin complexes on GCEs

Conclusions

CRediT authorship contribution statement

Declaration of Competing Interest

Acknowledgements

Sens. Actuators B Chem.

Sens. Actuators B Chem.

Biosens. Bioelectron.

Sens. Actuators B Chem.

J. Electroanal. Chem.

Electrochim. Acta

Sens. Actuators B Chem.

Biosens. Bioelectron.

Sens. Actuators B Chem.

Sensors and Actuators B-Chemical

Sens. Actuators B Chem.

Bioelectrochemistry

Electrochim. Acta

Sens. Actuators B Chem.

Sens. Actuators B Chem.

Sens. Actuators B Chem.

Electrochim. Acta

J. Inorg. Biochem.

Coord. Chem. Rev.

J. Electroanal. Chem.

Int. J. Electrochem. Sci.

Sens. Actuators B Chem.

Electrochim. Acta

Sens. Actuators B Chem.

Sens. Actuators B Chem.

Sens. Actuators B Chem.

Arch. Biochem. Biophys.

Biosens. Bioelectron.

Anal. Chim. Acta

Free Radic. Biol. Med.

Redox signaling by reactive Electrophiles and oxidants

Chem. Rev.

Detection of hydrogen peroxide in Photosystem II (PSII) using catalytic amperometric biosensor

Front. Plant Sci.

Reactive oxygen species (ROS)-Based nanomedicine

Chem. Rev.

Bioinspired manganese and Iron complexes for enantioselective oxidation reactions: ligand design, catalytic activity, and beyond

Acc. Chem. Res.

The atmospheric chemistry of hydrogen peroxide: a review

Ann. Chim.

Interconnection of reactive oxygen species chemistry across the interfaces of atmospheric, environmental, and biological processes

Acc. Chem. Res.