Study of polyaniline conducting/electroactive polymer as sensor for some agricultural phosphorus pesticides

Abstract  

Due to their wide applications as insecticides, pesticides, chemical warfare agents, etc., detection of organophosphorus compounds is of great importance. This paper deals with application of polyaniline conducting polymer (PANi) as a sensor material for detection of some agricultural organophosphorus compounds that are commonly used as insecticides and pesticides. The compounds employed in this investigation are dichlorvos, trichlorophon, and chlorpyrifos. The effects of some important parameters such as concentration, thickness of the polymer film, etc., on electrical conductivity and conductivity stability for these compounds have also been investigated. In situ electrical conductivity measurements were performed using a standard direct-current (DC) four-point probe technique. It was found that adsorption and desorption of these compounds on PANi film cause measurable change in the resistance of conducting polymers.     

Electroanalysis of some common pesticides using conducting polymer/multiwalled carbon nanotubes modified glassy carbon electrode

The cyclic voltammetric behaviour of three common pesticides such as isoproturon (ISO), voltage (VOL) and dicofol (DCF) was investigated at glassy carbon electrode (GCE), multiwalled carbon nanotubes modified GCE (MWCNTs/GCE), polyaniline (PANI) and polypyrrole (PPY) deposited MWCNT/GCE. The modified electrode film was characterized by scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The electroactive behaviour of the pesticides was realized from the cyclic voltammetric studies. The differential pulse voltammetric principle was used to analyze the above-mentioned pesticides using MWCNT/GCE, PANI/MWCNT/GCE and PPY/MWCNT/GCE. Effects of accumulation potential, accumulation time, Initial scan potential, amplitude and pulse width were examined for the optimization of stripping conditions. The PANI/MWCNT/GCE performed well among the three electrode systems and the determination range obtained was 0.01-100 mgL(-1) for ISO, VOL and DCF respectively. The limit of detection (LOD) was 0.1 microgL(-1) for ISO, 0.01 microgL(-1) for VOL and 0.05 microgL(-1) for DCF on PANI/MWCNT/GCE modified system. It is significant to note that the PANI/MWCNT/GCE modified system results in the lowest LOD in comparison with the earlier reports. Suitability of this method for the trace determination of pesticide in spiked samples was also realized.     

Study of a nanocomposite based on a conducting polymer: polyaniline

A simple way to obtain a conducting nanocomposite is described, and the conducting particles are characterized. Core-shell particles [polystyrene-polyaniline (PANI)] have been obtained by the dispersion process from three types of polystyrene latexes: a no-cross-linked core stabilized by a nonylphenolethoxylate (NP40) and two cross-linked cores stabilized by NP40 and a mixture NP40/Surfamid (a surfactant bearing an amide group). The surface of these particles has been extensively characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and scanning electron microscopy. A maximum coverage of 94% was obtained for the high PANI content as revealed by XPS analysis. A better coverage was obtained for the cross-linked polystyrene latex stabilized by the Surfamid. The amide group of this surfactant allows the H-bonding formation with the PANI backbone and, thus, improves the conductivity. It was shown that a uniform coverage of the core particles was not required to ensure a good conductivity.     

Coating of zinc ferrite particles with a conducting polymer, polyaniline

Particles of zinc ferrite, ZnOFe2O3, were coated with polyaniline (PANI) phosphate during the in situ polymerization of aniline in an aqueous solution of phosphoric acid. The PANI-ferrite composites were characterized by FTIR spectroscopy. X-ray photoelectron spectroscopy was used to determine the degree of coating with a conducting polymer. Even a low content of PANI, 1.4 wt%, resulted in the 45% coating of the particles' surface. On the other hand, even at high PANI content, the coating of ferrite surface did not exceeded 90%. This is explained by the clustering of hydrophobic aniline oligomers at the hydrophilic ferrite surface and the consequent irregular PANI coating. The conductivity increased from 2 x 10(-9) to 6.5 S cm(-1) with increasing fraction of PANI phosphate in the composite. The percolation threshold was located at 3-4 vol% of the conducting component. In the absence of any acid, a conducting product, 1.4 x 10(-2) Scm(-1), was also obtained. As the concentration of phosphoric acid increased to 3 M, the conductivity of the composites reached 1.8 S cm(-1) at 10-14 wt% of PANI. The ferrite alone can act as an oxidant for aniline; a product having a conductivity 0.11 S cm(-1) was obtained after a one-month immersion of ferrite in an acidic solution of aniline.     

Molecularly imprinted conducting polymer based electrochemical sensor for detection of atrazine

An original electrochemical sensor based on molecularly imprinted conducting polymer (MICP) is developed, which enables the recognition of a small pesticide target molecule, atrazine. The conjugated MICP, poly(3,4-ethylenedioxythiophene-co-thiophene-acetic acid), has been electrochemically synthesized onto a platinum electrode following two steps: (i) polymerization of comonomers in the presence of atrazine, already associated to the acetic acid substituent through hydrogen bonding, and (ii) removal of atrazine from the resulting polymer, which leaves the acetic acid substituents open for association with atrazine. The obtained sensing MICP is highly specific towards newly added atrazine and the recognition can be quantitatively analyzed by the variation of the cyclic voltammogram of MICP. The developed sensor shows remarkable properties: selectivity towards triazinic family, large range of detection (10⁻⁹ mol L⁻¹ to 1.5 × 10⁻² mol L⁻¹ in atrazine) and low detection threshold (10⁻⁷ mol L⁻¹).     

Self-assembled networks of conducting polyaniline in bulk polymers: A new class of conducting polymer blends

This review of the current status of conducting polymers will focus on recent progress which demonstrates that the initial promise of the late 1970's has become reality. Conducting polymers are now available as materials with truly unique properties: They combine the important electronic and optical properties of semiconductors and metals with the attractive mechanical properties and processing advantages of polymers. Conducting polymer blends based upon polyaniline (PANI) are a new class of materials in which the threshold for the onset of electrical conductivity (σ) can be reduced to volume fractions below 1%, well below that required for classical percolation (16% by volume for globular conducting objects dispersed in an insulating matrix in three dimensions). The origin of this remarkably low threshold for the onset of electrical conductivity is the self-assembled network morphology of the PANI polyblends which forms during the course of liquid-liquid separation. Since the average density of the conducting network near threshold is small, the conductivity increases smoothly and continuously over many orders of magnitude as the concentration of conducting polymer increases above threshold. The low percolation threshold and the continuous increase of σ(f) above threshold are particularly important; as a result of this combination, conducting polyblends can be reproducibly fabricated with controlled levels of electrical conductivity while retaining the desired mechanical properties of the matrix polymer.^1-3)     

Preparation and characterization of conducting polyaniline layered magnetic nano composite polymer particles

Considering the application potentials of organic materials possessing both conducting and ferromagnetic functions in various electronic devices, an attempt was made to prepare conducting polyaniline (PANI) layered magnetic nano composite polymer particles. Two routes were used to modify magnetic Fe₃O₄ core particles. In one route, seeded emulsion polymerization of methyl methacrylate (MMA) was carried out in presence of nano‐sized Fe₃O₄ core particles. In another route, cross‐linker ethyleneglycol dimethacrylate (EGDM) was used in addition to MMA. The modified composite particles were named as Fe₃O₄/PMMA and Fe₃O₄/P(MMA‐EGDM), respectively. Finally, seeded chemical oxidative polymerization of aniline was carried out in the presence of Fe₃O₄/PMMA and Fe₃O₄/P(MMA‐EGDM) composite seed particles to obtain Fe₃O₄/PMMA/PANI and Fe₃O₄/P(MMA‐EGDM)/PANI composite polymer particles. The modification of Fe₃O₄ core particles was confirmed by electron micrographs, FTIR, UV–visible spectra, X‐ray photoelectron spectra, X‐ray diffraction pattern and thermogravimetric analyses. A comparative study showed that crosslinking of intermediate shell improved the magnetic susceptibility and electrical conductivity of PANI layered magnetic nano composite particles. Copyright © 2013 John Wiley & Sons, Ltd.     

3,4-Alkylenedioxypyrroles: functionalized derivatives as monomers for new electron-rich conducting and electroactive polymers

New functionalized derivatives of 3,4-ethylenedioxypyrrole (EDOP, 5a) and 3,4-(1,3-propylenedioxy)pyrrole (ProDOP, 5b) as especially electron-rich monomers which yield highly electroactive and stable conducting polymers useful for a diverse set of applications have been synthesized. N-Alkylations of ProDOP were carried out to yield a variety of ProDOP derivatives having alkyl, sulfonatoalkoxy, glyme, and glyme alcohol pendant chains. Iodization of EDOP and ProDOP via iodo-decarboxylation afforded iodo-functionalized derivatives useful for subsequent aryl coupling chemistry. N-Protection and formylation of EDOP, followed by Knoevenagel condensation of the resultant 2-formyl-EDOP with aryl acetonitrile derivatives, led to 1-cyano-2-(2-(3,4-ethylenedioxypyrryl))-1-(2-thienyl)vinylene (23) (Th-CNV-EDOP) and 1-cyano-2-(2-(3,4-ethylenedioxypyrryl))-1-(2-(3,4-ethylenedioxythienyl)vinylene (26) (EDOT-CNV-EDOP). A 14-crown-4-ether 34 based dioxypyrrole was synthesized with a cavity potentially useful for lithium ion coordination and sensing in the resultant electroactive polymer. C-Alkylated ProDOPs (43a, 43b, and 43c) containing octyl, ethylhexyl, and dioctyl substituents appended to the central methylene of the propylene bridge, were prepared as monomers for potentially soluble pi-conjugated polymers.     

Synthesis and characterization of polyaniline/graphite conducting nanocomposites

A new method for the synthesis of exfoliated graphite and polyaniline (PANI)/graphite nanocomposites was developed. Exfoliated graphite nanosheets were prepared through the microwave irradiation and sonication of synthesized expandable graphite. The nanocomposites were fabricated via the in situ polymerization of the monomer at the presence of graphite nanosheets. The as-synthesized graphite nanosheets and PANI/graphite nanocomposite materials were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The conductivity of the PANI/graphite nanocomposites was dramatically increased over that of pure PANI. TGA indicated that the incorporation of graphite greatly improved the thermal stability of PANI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1972–1978, 2004     

Poly(1,8-diaminocarbazole) – A novel conducting polymer for sensor applications

A new monomer, 1,8-diaminocarbazole (DACz), has been synthesized as a missing link between two classes of electropolymerizable compounds – aromatic amines and carbazoles to combine some attractive features of both. Electropolymerization of DACz on Pt substrate carried out by cyclic voltammetry from acetonitrile and aqueous (neutral and acidic) solutions leads to formation of compact and very well adherent conducting films, electroactive in both media. In aqueous solutions poly(1,8-diaminocarbazole) (PDACz) exhibits a linear dependence of redox potential on pH. Morphology of the polymer films was studied by AFM using a tapping mode. Ability of amino groups of PDACz for post-functionalization was studied by covalent bonding of tyrosinase.     

Innovative approach for the electrochemical detection of non-electroactive organophosphorus pesticides using oxime as electroactive probe

An innovative approach for sensitive and simple electrochemical detection of non-electroactive organophosphorus pesticides (OPs) was described in this report. The novel strategy emphasized the fabrication of an oxime-based sensor via attaching pralidoxime (PAM) on graphene quantum dots (GQDs) modified glassy carbon electrode. The introduction of GQDs significantly increased the effective electrode area, and then enlarged the immobilization quantity of PAM. Thus, the oxidation current of PAM was obviously increased. Relying on the nucleophilic substitution reaction between oxime and OPs, fenthion was detected using PAM as the electroactive probe. Under optimum conditions, the difference of oxidation current of PAM was proportional to fenthion concentration over the range from 1.0 × 10⁻¹¹ M to 5.0 × 10⁻⁷ M with a detection limit of 6.8 × 10⁻¹² M (S/N = 3). Moreover, the favorable detection performance in water and soil samples heralded the promising applications in on-site OPs detection.     

Preparation of hydrogel/conducting polymer composites

The electropolymerisation of a conducting electroactive polymer (polypyrrole) within a hydrogel matrix has been investigated. Using appropriate conditions a conductive electroactive polymer can be formed and the composite structure retains the hydration/rehydration properties of the hydrogel.     

Electrochemical sensor for neurotransmitters at physiological pH using a heterocyclic conducting polymer modified electrode

We report the simultaneous determination of two neurotransmitters, norepinephrine (NEP) and serotonin (5-HT), at physiological pH using the electropolymerized film of 3-amino-5-mercapto-1,2,4-triazole modified glassy carbon (p-AMTa) electrode. A bare glassy carbon (GC) electrode fails to resolve the voltammetric signals of NEP and 5-HT due to the surface fouling caused by the oxidized products of them. However, the p-AMTa electrode not only separates the voltammetric signals of NEP and 5-HT with a potential difference of 150 mV between NEP and 5-HT but also shows higher oxidation currents for them. The simultaneous determination of NEP and 5-HT was successfully achieved at p-AMTa electrode using differential pulse voltammetry method. The amperometric current response increased linearly with increasing NEP and 5-HT concentration in the range of 1.0 × 10(-8) to 1.0 × 10(-4) M and 1.0 × 10(-8) to 5.0 × 10(-5) M, respectively, and the detection limit was found to be 1.65 × 10(-11) for NEP and 1.32 × 10(-11) M for 5-HT (S/N = 3). The p-AMTa electrode shows better recovery results for spiked NEP and 5-HT in human blood plasma samples.     

Electrodeposited polyaniline as a fiber coating for solid-phase microextraction of organochlorine pesticides from water

The study on the performance of polyaniline as a fiber coating for solid-phase microextraction (SPME) purposes has been reported. Polyaniline coatings were directly electrodeposited on the surface of a stainless steel wire and applied for the extraction of some organochlorine pesticides (OCPs) from water samples. Analyses were performed using GC-electron capture detection (GC-ECD). The results obtained show that polyaniline fiber coating is suitable for the successful extraction of organochlorine compounds. This behavior is most probably due to the porous surface structure of polyaniline film, which provides large surface areas and allowed for high extraction efficiency. Experimental parameters such as adsorption and desorption conditions were studied and optimized. The optimized method has an acceptable linearity, with a concentration range of 1-5000 ng/L. Single fiber repeatability and fiber-to-fiber reproducibility were less than 12 and 17%, respectively. High environmental resistance and lower cost are among the advantages of polyaniline fibers over commercially available SPME fibers. The developed method was applied to the analysis of real water samples from Yangtse River and Tianmu Lake.     

Solid-state ion selective electrode based on polypyrrole conducting polymer nanofilm as a new potentiometric sensor for Zn2+ ion

A pencil graphite electrode (PGE) electrodeposited by a polypyrrole conducting polymer doped with tartrazine (termed as PGE/PPy/Tar) was prepared and used as a zinc (II) solid-state ion-selective electrode. For the preparation of the zinc sensor electrode, electrodeposition of a polypyrrole nanofilm was carried out potentiostatically (E _app?=?0.75 V vs SCE) in a solution containing 0.010 M pyrrole and 0.001 M tartrazine trisodium salt. A pencil graphite and Pt wire were used as working and auxiliary electrodes, respectively. The introduced electrode in the current paper can be fabricated simply and was found to possess high selectivity, exhibited wide working concentration range, sufficiently rapid response, potential stability, and very good sensitivity to Zn (II) ion. The sensor electrode showed a linear Nernstian response over the range of 1.0?×?10^?5 to 1.0?×?10^?1 M with a slope of 28.23 mV per decade change in zinc ion concentration. A detection limit of 8.0?×?10^?6 M was obtained. The optimum pH working of the electrode was found to be 5.0.     

Synthesis of conducting polyaniline using novel anionic Gemini surfactant as micellar stabilizer

The Gemini surfactant 9B-4-9B containing sodium sulfonate as hydrophilic head group was synthesized based on nonylphenol and characterized by FTIR, ¹H NMR spectroscopy and the surface tension measurement. The CMC and C₂₀ of the 9B-4-9B were smaller than that of sodium dodecylbenzene sulfonate and sodium dodecylsulfate, respectively, indicating excellent efficiency of micelle formation and reduced surface tension. Conducting polyaniline salts were synthesized by chemical oxidative micellar polymerization of aniline in water firstly using Gemini surfactant 9B-4-9B as the micelle stabilizer and ammonium peroxydisulfate as the oxidant at 0 °C. The stable polyaniline dispersions have been obtained when the molar ratio of the 9B-4-9B to aniline was equal to or above 0.5 used in the polymerization system. The obtained granular polyaniline particles with the size of 1-2 μm were characterized by FTIR, UV-Vis, SEM, WAXD and conductivity measurement.     

Synthesis and characterization of epoxidized polybutadiene/polyaniline graft conducting copolymer

In this article the synthesis and characterization of an elastomeric conducting material, obtained by grafting polyaniline (EB) on commercial cis‐1,4‐polybutadiene (PB), are described. PB was first partially epoxidized in chloroform solution using meta‐chloroperbenzoic acid (MCPBA). The conducting polymer was then grafted to the activated polybutadiene (EPB) via the aminolysis reaction between the polyaniline NH₂ terminal groups and the oxirane rings. The material so obtained (EPBPAN) and the epoxidized intermediate product were characterized by ¹H NMR, ¹³C NMR, Fourier transform infrared, and ultraviolet–visible spectroscopy, thermal and mechanical analysis, and electrical conductivity measurements. The effect of the sample deformation on conductivity also was analyzed. The HCl doping of the EPBPAN film induced crosslinking reactions, generated by the acid cleavage of unreacted oxirane groups. The electrical conductivity of the doped material reached values of about 10^?5 Ω^?1 cm^?1. The key characteristics of our elastomeric conducting material are its simple synthesis, its starting as a commercial product, and the solubility of its undoped form in a common low‐boiling organic solvent like chloroform. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3082–3090, 2004