Differential pulse voltammetric determination of methyl parathion based on multiwalled carbon nanotubes–poly(acrylamide) nanocomposite film modified electrode
Highlights
► A sensitive electrochemical sensor for detecting methyl parathion in environmental samples. ► The preparation, characterization and application of this novel MWCNTs–PAAM nanocomposite. ► The MWCNTs–PAAM/GCE exhibited a high adsorption and strong affinity toward methyl parathion. ► Wide linear range and low detection limit of the proposed method for detecting methyl parathion.
Introduction
Organophosphorus (OP) pesticides have been widely used to protect agricultural crop against damaging caused by insect pests. During and after their application in agriculture, OP pesticides are transported by wind or water to environment as only a part of the applied amounts is bioactive [1], [2]. This transport results in hazardous concentrations of pesticides and their metabolites in the surface water and soils, owing to their low solubility and bioaccumulation properties [3]. Thus, extensive usage of OP compounds with high toxicity has raised serious public concern regarding a great harm to humans and the environment [4]. Their toxicity depends on inhibiting the activity of enzymes controlling the functions of the nervous system, mainly acetylcholinesterase, which results in accumulation of acetylcholine at nerve endings. Excess acetylcholine at synaptic junctions in neurons causes fasciculation and disrupts normal neural transmission, which leads to a state of hyperarousal, and paralysis of the muscles and the main respiratory center [5]. Therefore, for the sake of human health and environmental pollution control, it is vital to develop a fast, simple, and sensitive method for analysis of OP pesticides in environmental samples.
Many analytical techniques, including capillary electrophoresis [6], gas or liquid chromatography [7], [8], [9] and electrochemical method [10], [11], have been applied to develop sensitive, convenient and effective methods for OP pesticides residue analysis. Chromatography techniques operate with high sensitivity, accuracy and high throughput, instrumental analysis, but they suffer from complicated pretreatment steps using toxic organic solvent and also long analysis time, and most of them require expensive equipment [12]. Electrochemical method possesses high sensitivity, good selectivity and low-cost instrumentation. Electroanalysis can be used to give appropriate results within a short time under field conditions or on-line monitoring, which is very fit to analyze OP pesticides concentration in environmental samples.
Among the electrochemical methods, enzyme-based electrochemical biosensors have developed in the past few years to monitor OP pesticides [13], [14], [15], [16], [17]. However, the denaturation of enzymes results in the unstability and short lifetime of use for the sensor, which mostly limits the operational applications. In addition, the enzyme can be inhibited by many kinds of contamination such as heavy metals in environmental samples, which makes the direct determination of OP pesticides lack of selectivity and even leads to false positive result [18]. Therefore, in order to eliminate the influence of enzyme on the analysis of OP pesticides in environmental samples, some more effective methods were proposed to directly detect OP pesticides without using enzymes. Recently, electrochemical sensors based materials with no enzymes have been used in the fabrication of OP pesticides electrochemical sensors [10], [11], [19], [20], [21], [22], [23], [24], [25], [26], [27], [28], [29], such as ZrO2 nanoparticles [10], nanometer-sized titania [11], Pd/MWCNTs nanocomposite [19], and pSC6 modified silver [23]. ZrO2-nanoparticles modified electrode was fabricated for the detection of OP pesticides based on a strong affinity between nano-ZrO2 and OP pesticides molecules [10], [21], [22], [24]. Hu and co-workers developed a novel and simple sensor for dichlofenthion based on nanometer-sized titania photocatalysis coupled with a screen-printed carbon electrode [11]. Pd/MWCNTs nanocomposite modified electrode was developed for the determination of methyl parathion [19]. Li and co-workers presented pSC6 modified silver nanoparticles electrochemically deposited on glassy carbon electrode for electrochemical detection of methyl parathion [23].
Multiwalled carbon nanotubes (MWCNTs) as nanomaterial have attracted great attention for their unique structural, mechanical, and electrical properties since their discovery [30]. In order to introduce functional groups on MWCNTs and broaden the application fields of MWCNTs, composite materials based on the desirable merging of MWCNTs and polymers have gained growing interest [31], [32]. Recent electrochemical studies reveal that the nanocomposite of MWCNTs and polymers are very promising in the design of electrochemical sensors and biosensors [31], [32], [33], [34], [35], [36]. For example, MWCNTs and poly(methacrylic acid) (PMAA) nanocomposites prepared by free radical polymerization has been used for the detection of uric acid [32]. MWCNTs and polyaniline nanocomposites achieved by electrochemical grafting have been used for the determination of pesticides [33] and glucose [36]. In this work, a sensitive electrochemical differential pulse voltammetry method was developed for detecting methyl parathion (MP) based on MWCNTs–PAAM nanocomposite film modified glassy carbon electrode. The novel MWCNTs–PAAM nanocomposite, containing high content of amide groups, was synthesized by PAAM polymerizing at the vinyl group functionalized MWCNTs surface using free radical polymerization. The amino functionalized material exhibited good adsorption for OP pesticides molecules [37]. Similarly, the MWCNTs–PAAM/GCE showed a high adsorption and strong affinity toward MP compared with some metal ions and nitroaromatic compounds, which exist in environmental samples. The detection of MP for MWCNTs–PAAM/GCE was performed rapidly with wide linear range (5.0 × 10−9–1.0 × 10−5 mol L−1) and low detection limit of 2 × 10−9 mol L−1 (S/N = 3), which was better than some traditional materials modified electrode [1], [10], [19], [20], [23], [25], [26], [27], [28], [29]. These merits made it suitable for MP determination in environmental water samples.
Section snippets
Reagents
MWCNTs-COOH were obtained from Shenzhen Nanotech. Co., Ltd. (Shenzhen, China). Acrylamide (AAM), 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 1,3-dinitrobenzene (DNB) and ethylene glycol dimethacrylate (EGDMA) were purchased from Sigma–Aldrich Chemical Co. (USA). Methyl parathion (MP) was obtained from Dr. Ehrenstorfer GmbH Co. (Germany). 3-Aminopropyltriethoxysilane (APTES) and vinyltriethoxysilane (VTEOS) were purchased from TCI Co., Ltd. (Japan). Azodiisobutyronitrile (AIBN) was
Preparation and characterization of MWCNTs–PAAM nanocomposite
The preparation of MWCNTs–PAAM nanocomposite was illustrated in Scheme 1. Details of the preparation could be found in Section 2. The MWCNTs–PAAM nanocomposite was characterized by Fourier transform infrared spectroscopy (FT-IR spectroscopy), thermal gravimetric analysis (TGA) and scanning electron microscopy (SEM).
Conclusion
A sensitive and selective electrochemical differential pulse voltammetry method was developed for detecting MP based on MWCNTs–PAAM nanocomposite film modified glassy carbon electrode. The experimental results demonstrated that the MWCNTs–PAAM/GCE exhibited a high adsorption and strong affinity toward MP compared with some metal ions and nitroaromatic compounds. This MWCNTs–PAAM nanocomposite film electrode was proved to be a suitable sensing tool for the fast, sensitive and selective
Acknowledgments
This work is supported by the National Natural Science Foundation of China (21175044). This work is also supported by the Programs of the Science & Technology Commission of Shanghai Municipality (10JC1404000) and the Natural Science Foundation of Shanghai (11ZR1410700). We also greatly thank the Research Fund for the Doctoral Program of Higher Education (20100076110002).
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