Construction of a Zinc Porphyrin鈥揊ullerene-Derivative Based Nonenzymatic Electrochemical Sensor for Sensitive Sensing of Hydrogen Peroxide and Nitrite

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• 作者：Hai Wu ; Suhua Fan ; Xiaoyan Jin ; Hong Zhang ; Hong Chen ; Zong Dai ; Xiaoyong Zou
• 刊名：Analytical Chemistry
• 出版年：2014
• 出版时间：July 1, 2014
• 年：2014
• 卷：86
• 期：13
• 页码：6285-6290
• 全文大小：367K
• ISSN：1520-6882

文摘

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鈥揻ullerene (C₆₀) derivative (ZnP鈥揅₆₀), which was designed and synthesized according to the conformational calculations and the electronic structures of two typical ZnP鈥揅₆₀ derivatives of para-ZnP鈥揅₆₀ (ZnP_p鈥揅₆₀) and ortho-ZnP鈥揅₆₀ (ZnP_o鈥揅₆₀). The two derivatives were first investigated by density functional theory (DFT) and ZnP_p鈥揅₆₀ with a bent conformation was verified to possess a smaller energy gap and better electron-transport ability. Then ZnP_p鈥揅₆₀ was entrapped in tetraoctylammonium bromide (TOAB) film and modified on glassy carbon electrode (TOAB/ZnP_p鈥揅₆₀/GCE). The TOAB/ZnP_p鈥揅₆₀/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 渭A mM^鈥? and a limit of detection (LOD) as low as 0.81 渭M. The electrocatalytic oxidation of nitrite showed a linear range from 2.0 渭M to 0.164 mM, with a sensitivity of 249.9 渭A mM^鈥? and a LOD down to 1.44 渭M. Moreover, the TOAB/ZnP_p鈥揅₆₀/GCE showed excellent stability and reproducibility, and good testing recoveries for analysis of the nitrite levels of river water and rainwater. The ZnP_p鈥揅₆₀ can be used as a novel material for the fabrication of nonenzymatic electrochemical sensors.