Pesticide sensors

J.P. Hart and I.C. Hartley, Voltammetric and amperometric studies of thiocholine at a screen-printed carbon electrode chemically modified with cobalt phthalocyanine studies towards a pesticide sensor, Analyst, 119 (1994) 259-263. 

In the following section we discuss in detail about pesticide sensors type, different electrode materials used, various electrochemical techniques employed, advantages and limitations in measurements. 

In this section, we discuss about the screen printed electrode (SPE) based AChE sensors for the selective determination of OP and CA pesticides. In the past decades, several attempts were made by the researchers to develop SPE based pesticide sensors, where the enzyme AChE was immobilized either directly onto the electrode or above other matrices incorporated SPE surfaces. Both approaches resulted in the good, rapid detection of OP and CA pesticides. Earlier, Hart et al. employed AChE/SPE to detect OP and CA pesticides [21], They measured the enzyme activity from the rate of hydrolysis of acetylthiocholine iodide. Three polymers such as hydroxyethyl cellulose, dimethylaminoethyl methacrylate, and polyethyleneimine were used as enzyme immobilization matrices. Initially, electrodes were exposed to drops of water or pesticide solution, dried and their activity was screened after 24 h. They found that, when the enzyme matrix was hydroxyethyl cellulose, electrode activity inhibited both by water as well as by pesticides. While with co-polymer matrix, a significant response towards pesticides alone was observed. Further, the long-term storage stability of electrodes was highest when the enzyme matrix consisted of the co-polymer. The electrodes retained their activity for nearly one year. In contrast, the electrodes made of hydroxyethyl cellulose or polyethyleneimine possess less stability. 

As discussed in sec 3, CNTs have been extensively used to develop pesticide sensors with higher sensitivity and longer stability. In this section we discuss about the design and the development of CNT based pesticide sensors. Joshi et al. reported the detection of OP compounds at a disposable biosensor with AChE-functionalized acid purified multi-wall carbon nanotubes (MCNTs) modified SPE [10]. The degree of inhibition of AChE by OP compounds was determined by measuring the electro oxidation current of the thiocholine generated by the AChE catalyzed hydrolysis of ATCh. The large surface area and electro-catalytic activity of MWCNTs lowered the over potential for thiocholine oxidation to + 0.2 Y. Further, mediators were not used in this case and enzyme immobilization was done by physical adsorption. 

As mentioned in the previous section, the response, the stability and the enzyme activity found greatly enhanced at the MWCNT platform. Other than CNTs, AuNPs also possess some unique properties and recent years it has been widely employed in the biosensors to immobilize biomolecules. Thus in this section we discuss about the application of AuNP matrix for the immobilization of AChE for pesticide sensor development. With the use of AuNPs, the efficiency and the stability of the pesticide sensor gets greatly amplified. Moreover, the nanoparticles matrix offers much friendly environment for the immobilized enzyme and thus the catalytic activity of the enzyme got greatly amplified. Interestingly, Shulga et al. applied AChE immobilized colloidal AuNPs sensor for the nM determination of carbofuran, a CA pesticide [16], The enzyme-modified electrode sensor was also utilized for the sensitive electrochemical detection of thiocholine from the enzyme catalyzed hydrolysis of acetylthiocholine chloride (ATCl). The fabrication and the enzyme catalyzed reaction at the AuNPs coated electrode surface is shown in Fig. 6. 

Other than AUNPs, Quantum dots have also been employed in the development of pesticide sensors. Li et al. have synthesized Poly (N-vinyl-2-pyrrolione) (PVP)-capped CdS quantum dots (QCdS-PVP) from CdC and Na2S in the presence of PVP [37], AChE was immobilized onto this QCdS-PVP matrix incorporated GCE surface. The resulting GCE/ QCdS-PVP/AChE sensor was used for the detection of OP pesticides, such as trichlorfon. The enzyme immobilization procedure was described as follows. About 3 ml of QCdS-PVP was deposited on the surface of the GCE and dried in air. Then 3 ml of 0.5 mg ml"1 AChE along with 2.5% GA was deposited on the surface of the QCdS-PVP modified GCE and dried for 1 h at room temperature. TEM results show that, the QCdS-PVP particles were homogeneously distributed and they possess an average size of 2-4 nm (Fig. 9). 

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