title: Construction of a zinc porphyrin-fullerene-derivative based nonenzymatic electrochemical sensor for sensitive sensing of hydrogen peroxide and nitrite.
abstract: Enzymatic sensors possess high selectivity but suffer from some limitations such as instability, complicated modified procedure, and critical environmental factors, which stimulate the development of more sensitive and stable nonenzymatic electrochemical sensors. Herein, a novel nonenzymatic electrochemical sensor is proposed based on a new zinc porphyrin-fullerene (C60) derivative (ZnP-C60), which was designed and synthesized according to the conformational calculations and the electronic structures of two typical ZnP-C60 derivatives of para-ZnP-C60 (ZnP(p)-C60) and ortho-ZnP-C60 (ZnP(o)-C60). The two derivatives were first investigated by density functional theory (DFT) and ZnP(p)-C60 with a bent conformation was verified to possess a smaller energy gap and better electron-transport ability. Then ZnP(p)-C60 was entrapped in tetraoctylammonium bromide (TOAB) film and modified on glassy carbon electrode (TOAB/ZnP(p)-C60/GCE). The TOAB/ZnP(p)-C60/GCE showed four well-defined quasi-reversible redox couples with extremely fast direct electron transfer and excellent nonenzymatic sensing ability. The electrocatalytic reduction of H2O2 showed a wide linear range from 0.035 to 3.40 mM, with a high sensitivity of 215.6 μA mM(-1) and a limit of detection (LOD) as low as 0.81 μM. The electrocatalytic oxidation of nitrite showed a linear range from 2.0 μM to 0.164 mM, with a sensitivity of 249.9 μA mM(-1) and a LOD down to 1.44 μM. Moreover, the TOAB/ZnP(p)-C60/GCE showed excellent stability and reproducibility, and good testing recoveries for analysis of the nitrite levels of river water and rainwater. The ZnP(p)-C60 can be used as a novel material for the fabrication of nonenzymatic electrochemical sensors.
authors.affiliation: College of Chemistry & Chemical Engineering, Fuyang Normal College , Fuyang, Anhui 236037, P.R. China.
authors.forename: Hai
authors.initials: H
authors.lastname: Wu
authors.forename: Suhua
authors.initials: S
authors.lastname: Fan
authors.forename: Xiaoyan
authors.initials: X
authors.lastname: Jin
authors.forename: Hong
authors.initials: H
authors.lastname: Zhang
authors.forename: Hong
authors.initials: H
authors.lastname: Chen
authors.forename: Zong
authors.initials: Z
authors.lastname: Dai
authors.forename: Xiaoyong
authors.initials: X
authors.lastname: Zou
mesh_terms: D002384:Catalysis; D055664:Electrochemical Techniques / Q000379:methods*; D004566:Electrodes; D037741:Fullerenes / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000032:analysis*; D057230:Limit of Detection; D008665:Metalloporphyrins / Q000737:chemistry*; D008958:Models, Molecular; D009573:Nitrites / Q000032:analysis*; D015203:Reproducibility of Results
chemical_list: D037741:Fullerenes; D008665:Metalloporphyrins; D009573:Nitrites; C017802:zinc hematoporphyrin; D006861:Hydrogen Peroxide