Electrochemical Detection of Superoxide Anion Released by Living Cells by Manganese(III) Tetraphenyl Porphine as Superox

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doi: 10.1007/s40242-019-0006-5

Electrochemical Detection of Superoxide Anion Released by Living Cells by Manganese(III) Tetraphenyl Porphine as Superoxide Dismutase Mimic CUI Min1, REN Jujie1*, WEN Xiaofang1, LI Na1, XING Yifei1, ZHANG Cong1, HAN Yuanyuan1 and JI Xueping2* 1. Department of Chemistry, School of Sciences, Hebei University of Science and Technology, Shijiazhuang 050018, P. R. China; 2. Department of Medical Chemistry, Hebei Medical University, Shijiazhuang 050017, P. R. China Abstract Superoxide anion, one of the most active reactive oxygen species, is associated with the development of many diseases. So monitoring superoxide anion in living cells is of great significance for the pathological research of many diseases. In this work, a new non-enzymatic sensor for the detection of superoxide anion(O •− 2 ) was developed, which was fabricated by the nanocomposites composed of manganese(III) tetraphenyl porphine(MnTPP) as superoxide dismutase mimic and electrochemical reduced graphene oxide(ERGO) as electrode support material to modify the glassy carbon electrode(GCE). The electrochemical behavior of the fabricated electrode(MnTPP/ERGO/GCE) was performed by electrochemical impedance spectroscopy(EIS) and cyclic voltammetry(CV), which revealed that MnTPP/ERGO/GCE possessed good catalytic ability to the electrochemical reduction of O •− The 2 . MnTPP/ERGO/GCE showed excellent electroanalysis performance towards O•− using the technique of differential 2 pulse voltammetry(DPV) with a linear relationship in the range of 0.2―110.0 μmol/L, a sensitivity of 445 μA·L·mmol‒1·cm‒2 and a detection limit of 0.039 μmol/L(S/N=3). The real-time monitoring of O•− 2 from MCF-7 breast cancer cells stimulated by zymosan was realized in this work, which indicates that the MnTPP/ERGO/GCE hold potential application for electrochemical quantification of superoxide anions in biological applications. Keywords Superoxide anion; Electrochemical sensor; Manganese(III) tetraphenyl porphine; Electrochemical reduced graphene oxide; MCF-7 breast cancer cell

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Introduction

Superoxide anion(O•− 2 ) is the primary or essential specie of reactive oxygen species(ROS), which is closely related to various physiological and pathological processes[1,2]. Excessive accumulation of O•− 2 may damage biological membranes, tissues and organisms, which could lead to the development of various diseases, such as neurodegenerative diseases, autoimmune diseases, diabetes and cancer[3―5]. So it is necessary to build a fast and accurate method for the sensitive detection of O•− 2 in human body or living cells. Up to date, various methods have been developed for the detection of O•− 2 including electron spin resonance[6,7], spectrophotometry[8,9], chemiluminescence[10,11], chromatography[12,13], fluorescence[14,15] and electrochemical method[16―20]. Owing to the high activity and short •− half-life of O•− 2 , it is very difficult to detect O2 accurately. Although several conventional methods mentioned above are available for the detection of O•− 2 , elect