Electrochemical preparation of poly(N‐acetylaniline)/poly‐(4‐styrenesulfonic acid‐co‐maleic acid) composite film towards ascorbic acid sensing

Poly(N‐acetylaniline)/poly(4‐styrenesulfonic acid‐co‐maleic acid) (PNAANI/PSSMA) composite film was prepared by cyclic voltammetry (CV), and was characterized by FTIR and X‐ray photoelectron spectrum (XPS). The electroactivity of the composite film was high in neutral and basic solutions, and it had been used for amperometric determination of ascorbic acid (AA). Compared with pure PNAANI film, the catalytic activity of the composite film was much better. AA was detected amperometrically in sodium citrate buffer at a potential of 0.3 V (versus SCE). The response current was proportional to the concentration of ascorbic acid in the range of 4.7 × 10^?6 to 5.0 × 10^?5M and 5.0 × 10^?5 to 2.5 × 10^?3M, respectively, with the detection limit of 1.9 × 10^?6 mol L^?1 at a signal to noise ratio 3. In addition, the stability and reusability of the composite film were performed well, and it was satisfying to be used for determination of AA in real fruit juice samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyaniline Langmuir-Blodgett film modified glassy carbon electrode as a voltammetric sensor for determination of Ag ions

A highly sensitive electrochemical sensor made of a glassy carbon electrode (GCE) coated with a Langmuir-Blodgett film (LB) containing polyaniline (PAn) doped with p-toluenesulfonic acid (PTSA) (LB/PAn-PTSA/GCE) has been used for the detection of trace concentrations of Ag⁺. UV-vis absorption spectra indicated that the PAn was doped by PTSA. The surface morphology of the PAn LB film was characterized by atomic force microscopy (AFM). The electrochemical properties of this LB/PAn-PTSA/GCE were studied using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry. The LB/PAn-PTSA/GCE was used as a voltammetric sensor for determination of trace Ag⁺ at pH 5.0 using linear scanning stripping voltammetry. Under the optimal experimental conditions, the stripping current was proportional to the Ag⁺ concentration over the range from 6.0 × 10⁻¹⁰ mol L⁻¹ to 1.0 × 10⁻⁶ mol L⁻¹, with a detection limit of 4.0 × 10⁻¹⁰ mol L⁻¹. The high sensitivity, selectivity, and stability of this LB/PAn-PTSA/GCE also demonstrated its practical utility for simple, rapid and economical determination of Ag⁺ in water samples.     

Effects of dopants on percolation behaviors and gas sensing characteristics of polyaniline film

Effects of dopants on the correlation between the polyaniline (PAn) film resistance (R) and the reduction charge (Q) injected to the PAn film was investigated in dry acetonitrile solutions during electrochemical reduction by using the double potential step method. The R-Q correlation behaves as S-type curves, leading to the determination of the critical reduction charge (Q_c). The latter represents the reduction charge required for the formation of a continuous partially reduced phase in the PAn film. It was observed that the PAn film doped with sodium dodecylbenzene sulphate (SDBS) yielded a smaller Q_c than that doped with perchlorate, when the PAn films were electrochemically reduced under given conditions. The resistance of the pre-doped PAn film will increase significantly when the film is injected with reduction charge more than Q_c. Hence, a smaller Q_c means that the film can respond to very light reduction (or dedoping), being indicative of better sensing ability toward alkaline and reducing gases. This was confirmed by the increased sensitivity of the PAn/SDBS sensor toward 100 ppm NH₃ vapor, compared with the PAn/ClO₄⁻ sensor.     

Investigation of charge transport properties in conducting copolymers of aniline with 3‐aminobenzenesulfonic acid for their applications as antistatic encapsulation materials blended with low‐density polyethylene

The electrostatic charge dissipative (ESD) properties of conducting self‐doped and PTSA-doped copolymers of aniline (AA), o‐methoxyaniline (methoxy AA) and o‐ethoxyaniline (ethoxy AA) with 3‐aminobenzenesulfonic acid (3‐ABSA) blended with low‐density polyethylene (LDPE) were investigated in the presence of external dopant p‐toluenesulfonic acid (PTSA). Blending of copolymers with LDPE was carried out in a twin‐screw extruder by melt blending by loading 1.0 and 2.0 wt% of conducting copolymer in the LDPE matrix. The conductivity of the blown polymers blended with LDPE was in the range 10^?12–10^?6 S cm^?1, showing their potential use as antistatic materials for the encapsulation of electronic equipment. The DC conductivity of all self‐doped homopolymers and PTSA‐doped copolymers was measured in the range 100–373 K. The room temperature conductivity (S cm^?1) of self‐doped copolymers was: poly(3‐ABSA‐co‐AA), 7.73 × 10^?4; poly(3‐ABSA‐co‐methoxy AA), 3.06 × 10^?6; poly(3‐ABSA‐co‐ethoxy AA), 2.99 × 10^?7; and of PTSA‐doped copolymers was: poly(3‐ABSA‐co‐AA), 4.34 × 10^?2; poly(3‐ABSA‐co‐methoxy AA), 9.90 × 10^?5; poly(3‐ABSA‐co‐ethoxy AA), 1.10 × 10^?5. The observed conduction mechanism for all the samples could be explained in terms of Mott's variable range hopping model; however, ESD properties are dependent upon the electrical conductivity. The antistatic decay time is least for the PTSA‐doped poly(3‐ABSA‐co‐AA), which has maximum conductivity among all the samples. © 2013 Society of Chemical Industry     

Design,synthesis and characterization of a novel self‐doped polyaniline derivative

A type of self‐doped polyaniline derivative was successfully synthesized using an oxidative coupling polymerization approach. The structure of the electroactive polymer was investigated using Fourier transform infrared and ¹H NMR spectroscopy and gel permeation chromatography. Its thermal and spectral properties were characterized using thermogravimetric analysis and UV‐visible spectroscopy. The electrochemical activity of the polymer was studied using cyclic voltammetry (CV) in 1.0 mol L^?1 H₂SO₄ solution with various scan rates. The peak current increases linearly with scan rate from 10 to 120 mV s^?1, which indicates that the electrode reaction is controlled by a surface process. In addition, the self‐doped characteristic was investigated using CV in 1.0 mol L^?1 KCl solution with pH value changing from 1 to 12, and the results indicate that the polymer has excellent electrochemical activity even in neutral and alkaline environments. Copyright © 2010 Society of Chemical Industry     

Molecularly imprinted electrochemical sensor for the determination of ampicillin based on a gold nanoparticle and multiwalled carbon nanotube‐coated pt electrode

A novel molecularly imprinted electrochemical sensor was developed for the sensitive and selective determination of ampicillin (AMP). The sensor was prepared on a platinum electrode modified with multiwalled carbon nanotubes (MWCNTs), gold nanoparticles (AuNPs), and a thin film of molecularly imprinted polymers (MIPs). MWCNTs and AuNPs were introduced to enhance the sensor's electronic transmission and sensitivity. The molecularly imprinted polymer (MIP) was synthesized using AMP as the template molecule, methacrylic acid as functional monomer, and ethylene glycol maleic rosinate acrylate (EGMRA) as cross‐linker. The performance of the proposed imprinted sensor was investigated using cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). The results showed that the imprinted film displayed a fast and sensitive response to AMP. Under optimal conditions, response peak current had a linear relationship with the concentration of AMP in the range of 1.0 × 10^?8 mol/L to 5.0 × 10^?6 mol/L and a detection limit of 1.0 × 10^?9 mol/L (S/N = 3). This imprinted sensor was used to detect AMP in food samples with recoveries of 91.4–105%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40613.     

Influence of Dopant Ions on the Properties of Conducting Polyacrylamide/Polyaniline Hydrogels

Polyaniline-impregnated polyacrylamide conducting hydrogels have been synthesized chemically via interfacial polymerization route using different acidic doping agents like sulfuric acid (H₂SO₄), hydrochloric acid (HCl), and perchloric acid (HClO₄). The best properties were found in case of H₂SO₄-doped polyacrylamide/polyaniline sample when compared with other doping agents. The resulting hydrogel exhibits superior properties including compact structure, high crystallinity, good mechanical strength, and electrical conductivity. The maximum electrical conductivity of the order of 9.4 × 10^?5 S/cm was found in case of H₂SO₄ doped polyacrylamide/polyaniline.     

Preparation and characterization of polyaniline‐DBSNa/Fe2O3 and polyaniline‐DBSNa/CoO nanocomposites using surfactive dopant sodium dodecylbenzenesulfonate (DBSNa)

Nanocomposites of polyaniline (PAn) containing nanometer‐size Fe₂O₃ and CoO were synthesized by a chemical method using sodium dodecylbenzenesulfonate (DBSNa) as a surfactant. Characteristics of the products such as morphology, particle size, and conductivity were studied. The results indicated that these properties were dependent on the surfactant and the type and content of metallic oxide used. When the concentration of Fe₂O₃ and CoO increased from 1 to 5 g/L in the PAn‐DBSNa/Fe₂O₃ and PAn‐DBSNa/CoO composites, the conductivity decreased from 1.3 × 10^?4 to 5.1 × 10^?5 and from 1.4 × 10^?4 to 5.1 × 10^?5 S/cm, respectively, while the particle size increased from 92 to 103 and from 104 to 117 nm, respectively. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Molybdate‐doped copolymer coatings for corrosion prevention of stainless steel

The polypyrrole and polyaniline copolymer coating (PPy‐PAni) and PPy‐PAni doped with sodium molybdate copolymer coating ( ) were synthesized on stainless steel by cyclic voltammetry. The effect of molybdate on the passivation of stainless steel was investigated by linear sweep voltammetry in 0.2 mol L^?1 of oxalic acid. The corrosion prevention performances of these copolymer coatings for stainless steel were investigated by linear sweep voltammetry, electrochemical impedance spectroscopy in 1 mol L^?1 of sulfuric acid, and potentiodynamic polarization in 0.1 mol L^?1 of hydrochloric acid. Copolymer coating doped with molybdate could accelerate the formation of the passive oxide film and have better corrosion prevention efficiencies than PPy‐PAni coating on stainless steel. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40602.     

Adiabatic compressibility of polyelectrolytes: Effect of solvents on copolymers of vinyl pyrrolidone with acrylic acid and N-dimethylaminoethyl methacrylate

The results of adiabatic compressibility measurements for two copolymers, acrylic acid-vinyl pyrrolidone (AA—VP) and N-dimethylaminoethyl methacrylate-vinyl pyrrolidone (DAM—VP), in three different solvents, namely, water, methanol, and dioxane, have been described. The molecular weight of copolymers was determined by the light scattering method and the IR and NMR spectra of the polymers and copolymers were examined to establish that the alternating acrylic acid–vinyl pyrrolidone and N-dimethylaminoethyl methacrylate–vinyl pyrrolidone structure exists in the copolymers. The AA—VP copolymer behaves as a slightly weaker acid than the homopolymer of acrylic acid, while DAM—VP copolymer is very feebly basic and has the same strength as that of the homopolymer of N-dimethylaminoethyl methacrylate. The reduced viscosity for the two copolymers in aqueous solution is very low (～0.08 dL/g for AA—VP copolymer). In methanol solution AA—VP and DAM—VP copolymers show a decrease of øK^°₂ and øV^°₂ by 61.6 × 10^?4 cc/bar/mol and 8.0 cc/mol, and 191.0 × 10^?4 cc/bar/mol and 20.0 cc/mol, respectively, over that of the values of aqueous solution. The void space around the solute is smaller in methanol than in water, and accordingly this decrease has been attributed to geometric effect. Only one copolymer, DAM—VP is soluble in dioxane, and the values are seen to have increased in this solution by 71.0 × 10^?4 cc/bar/mol and 18.7 cc/mol, respectively, compared to the values obtained from aqueous solution. The experimentally determined øK^°₂ and øV^°₂ for AA—VP and DAM—VP copolymer are 0.6 × 10^?4 cc/bar/mol, and 102.4 cc/mol and ?61.0 × 10^?4 cc/bar/mol, 94.4 cc/mol, respectively, in aqueous solution, and ?12.0 × 10^?4 cc/bar/mol, 211.0 cc/mol and ?203.0 × 10^?4 cc/bar/mol, 191.0 cc/mol, respectively, in methanol solution. In dioxane solution the values for DAM—VP copolymer are 59.0 × 10^?4 cc/bar/mol and 229.7 cc/mol, respectively. These experimentally determined values for AA—VP copolymer show an increase by 0.04 × 10^?4 cc/bar/mol, 4.4 cc/mol and 28.3 × 10^?4 cc/bar/mol, 8.0 cc/mol in aqueous and methanol solution, respectively, compared to calculated values determined on the basis of no interaction between acid and the pyrrolidone group. In contrast, the DAM—VP copolymer shows a decrease of 27.6 × 10^?4 cc/bar/mol and 10.3 cc/mol, 149.3 × 10^?4 cc/bar/mol and 20.2 cc/mol, and 23.0 × 10^?4 cc/bar/mol and 4.1 cc/mol in aqueous, methanol, and dioxane solutions, respectively. In aqueous solution these differences between calculated and observed values have been attributed to a change of water structure around the copolymer chain. A similar effect is responsible for the difference of the values in the methanol solution also. In the dioxane solution the difference is rather small, and the solvent structure has probably not altered much due to the presence of the DAM unit in the chain.     

Gas permeation property of polyaniline films

We examined the influence of polyaniline (PAn)'s unit sequence and doping with low molecular weight dopants or polymer dopants on permeation property. It was found that CO₂ permeability was increased by the formation of a quinonediimine unit in PAn with the oxidation. CO₂ sorption amount of PAn was decreased by oxidation. The increase of CO₂ permeability with oxidation, therefore, resulted from the increase of diffusivity, which was attributable to morphological variation by the increase of a quinonediimine unit. The permselectivity of PAn films was found to be remarkably improved by doping. In particular, the selectivity value of the PAn film doped with polyvinyl sulphonic acid as a polymer dopant went up to over 2,000. This remarkable increase of selectivity was found to result in the increase of selectivity, depending on diffusivity. It was also found that the permselectivity of the PAn film doped by polymer dopants was surpassed, as compared with that doped by low molecular dopants. © 1995 John Wiley & Sons, Inc.     

Preparation of poly(9‐aminoacridine)‐modified electrode and its application in the determination of dopamine and ascorbic acid simultaneously

A novel modified electrode was fabricated with 9‐aminoacridine by electropolymerization in the phosphate buffer solution (PBS) (pH 7.4) and was characterized by cyclic voltammetry (CV). The modified electrode showed excellent electrocatalytic effect and high stability toward the electrochemical oxidation of dopamine (DA) and ascorbic acid (AA). Also, it showed a high stability for the determination of DA and AA simultaneously. Well‐separated voltammetric peaks were observed for DA and AA on the modified electrode. The separation of two anodic peaks was 170 mV, which was large enough to eliminate the interference of AA and determine DA. The differential pulse voltammograms (DPV) were used for the measurement of DA by means of the poly(9‐aminoacridine)‐modified electrode in PBS at pH 7.4. A linear response toDA was observed in the concentration range from 1.5 × 10^?6 to 3.5 × 10^?3 mol L^?1 with a correlation coefficient of 0.9998 and a detection limit (S/N = 3) of 1.0 × 10^?7mol L^?1. The proposed method was used to determine DA in DA‐hydrochloride injection and showed excellent sensitivity and recovery. The ease of fabrication, good reproducibility, high stability, and low cost of the modified electrode are the promising features of the proposed sensor. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3864–3870, 2007     

Optical and conductivity studies of Pseudo‐doped chitin‐polyaniline blend

In this article, we report the preparation and characterization of self‐doped conducting chitin, polyaniline blends by solution blending method. The characterization of the blends was done by UV–vis absorption spectrum, FTIR, and conductivity studies. Conductivity of the self doped blends increases from less than ～10^?7 S/cm to 2.15 × 10^?5 S/cm, depending on the percentage of polyaniline in the blend. Spectroscopic analysis shows interaction between chitin and polyaniline and the electronic states are similar to those of the emeraldine and protonically doped forms of polyaniline. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and Characterization of PAn-HPC/Fe3O4 and PAn-HPC/Fe2O3 Nanocomposite Using Hydroxypropylcellulose as a Steric Stabilizer

Nanocomposite of polyaniline containing Fe₃O₄ and Fe₂O₃ was synthesized by a chemical method using hydroxypropylcellulose as a steric stabilizer. The characteristics of product such as, morphology, conductivity, and particle size were studied. The results indicate that, these properties were dependent on the surfactant, amount and type of metallic oxide. When the concentration of Fe₂O₃ and Fe₃O₄ increased from 1 to 5 g/L, in PAn/Fe₂O₃ and PAn/Fe₃O₄ composites the conductivity decreased from 1.2 × 10^?6 to 1.1 × 10^?8 and 2.8 × 10^?6 to 1.1 × 10^?8S/cm, respectively, while the particle size of nanocomposite increased from 96 to 110, and 97 to 115 nm, respectively.     

Synthesis and characterization of polysaccharide based graft copolymer by using potassium peroxymonosulphate/ascorbic acid as an efficient redox initiator in inert atmosphere

Polysaccharide based graft copolymer (xanthan gum‐g‐4‐vinyl pyridine) was synthesized using potassium peroxymonosulphate/ascorbic acid redox initiator in inert atmosphere at 40°C. By studying the effect of the concentration of monomer, peroxymonosulphate (PMS), ascorbic acid (AA), xanthan gum (XOH), hydrogen ion along with effect of time and temperature on grafting characteristics: grafting ratio (%G), add on (%A), conversion (%C), efficiency (%E), homopolymer (%H), and rate of grafting (Rg), the reaction conditions for optimum grafting were determined. The optimum concentration of AA, H⁺ ion, 4‐VP for maximum grafting were found to be 10.0 × 10^?3 mol dm^?3, 2.5 × 10^?2 mol dm^?3, 10.0 × 10^?3 mol dm^?3, respectively. Maximum %G was obtained at minimum concentration of xanthan gum i.e., at 40.0 × 10^?2 g dm^?3 and at maximum concentration of PMS i.e., at 10.0 × 10^?3 mol dm^?3. The optimum temperature and time duration of reaction for maximum % of grafting were found to be 45°C and 120 min respectively. The synthesized graft copolymer was characterized by FTIR analysis. Thermogravimetric analysis showed that the xanthan gum‐g‐4‐vinyl pyridine is thermally more stable than pure gum. A probable mechanism was suggested for the graft copolymerization. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A highly selective electrochemical sensor for nifedipine based on layer‐by‐layer assembly films from polyaniline and multiwalled carbon nanotube

An uniformly distributed film consisting of polyaniline (PANI) nanoparticles and carboxylic acid functionalized multiwalled carbon nanotubes (MWNTs‐COOH) was successfully assembled on ITO plates from a layer‐by‐layer (LBL) method by using electrostatic interactions as the main driving force. The good conjugation between PANI nanoparticles and MWNTs‐COOH resulted in significant electrochemical performance variation of the obtained films. In addition, the assembled MWNT‐COOH/PANI/ITO showed synergistic effect to the electrochemical oxidation of nifedipine (NIF) when used as a sensor. Compared with bare ITO, the oxidation potential of NIF can be decreased about 170 mV on MWNT‐COOH/PANI/ITO, and the lower detection limit of NIF was as low as 1.0 × 10^?6 mol/L. In addition, the assembled electrode gave no responses to interferences such as glucose, urea, ascorbic acid, and trisodium citrate, which showed high selectivity for recognition and quantification of NIF. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43452.     

Application of a C6‐OH of chitosan immobilized cyclodextrin derivates on an electrochemical H2O2 biosensor

Biosensor detecting techniques have attracted much attention in the content determination of H₂O₂, which has been used illegally as a food additive. An electrochemical biosensing membrane for the detection of H₂O₂ was developed with C6‐OH of chitosan immobilized cyclodextrin derivates (6‐CD–CTS), which possessed a high cyclodextrin loading capacity (2.12 × 10^?4 mol/g), as the carrier. The biosensor was prepared through the inclusion of ferrocene as the electron mediator in a hydrophobic cavity of cyclodextrin and crosslinking catalase (CAT) to 2‐NH₂ of 6‐CD–CTS. The ferrocene‐included complex was evaluated by ultraviolet–visible spectrophotometry and thermogravimetric analysis. Its electrochemical behavior was also studied. The impact of the reaction conditions on the CAT immobilization capacity was evaluated. When previous membrane was used to detect the concentration of H₂O₂ (C_H2O2), we found that the catalysis of CAT and the signal amplification of ferrocene had a major impact on the cyclic voltammograms. The optimal working pH of the modified electrode was 7.0. The peak current (I) had a linear relationship with the H₂O₂ concentration (CH₂O₂) in the range 1.0 × 10^?4 to 1.0 × 10^?3 mol/L. The linear regression equation was I = 0.00475C_H2O2 ? 0.03025. The detection limit was 10^?6 mol/L. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41499.     

Electrically conductive composite of polyaniline and poly (p-phenylene/diphenyl ether-terephthalamide)

In order to improve the flexibility and the anti-static properties of poly-(p-phenylene-terephthalamide) (PPTA), the copolymer of p-phenylene diamine, p,p′-diaminodiphenyl ether and terephthaloyl chloride (PPDTA) was synthesized. This copolyamide PPDTA was mixed with electrically conductive polyaniline (PAn) in concentrated sulphuric acid solution, and was processed to form film, or fibre, of the new composite PAn/PPDTA with high strength and good electrical conductivity. The composite is a lyotropic liquid crystalline polymer with electrical conductivity 10^?1 S/cm. The surface morphology of the PAn/PPDTA composite consists of an oriented fibre-like texture.     

Graft copolymerization of acrylic acid onto xanthum gum using a potassium monopersulfate/Fe2+ redox pair

A previously unreported graft copolymer of xanthan gum (XOH) with acrylic acid was synthesized and the reaction conditions were optimized using a potassium monopersulfate (PMS)/Fe²⁺ redox pair. Grafting ratio, add on, and conversion increase with an increase in the ferrous ion concentration (2.0 × 10^?3 to 5.0 × 10^?3 mol dm^?3) and PMS concentration (1.0 × 10^?3 to 4.0 × 10^?3 mol dm^?3). It was observed that grafting takes place efficiently when the acrylic acid concentration and temperature were 5.0 × 10^?2 mol dm^?3 and 35°C, respectively. Samples of xanthan gum and xanthan gum–g–acrylic acid were subjected to thermogravimetric analysis with the objective of studying the effect of grafting of acrylic acid on the thermal stability of xanthan gum. The graft copolymer was found to be more thermally stable than xanthan gum. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1341–1346, 2003     

电化学聚合导电聚苯胺膜的研究

分析了恒电位法在酸性和碱性溶液中于不锈钢基体上电聚合聚苯胺的过程及其影响因素,测定了聚苯胺膜与基体的附着力、膜的导电性和防腐性.结果表明:该膜在空气中呈绿色,稳定、完整致密,导电性好,与基体的结合情况较好.阳极极化曲线测定表明,在碱性溶液中预镀后酸性溶液中聚合聚苯胺膜,其点蚀电位比酸性溶液中聚合聚苯胺膜升高1 V左右,表明前者的导电聚苯胺膜可显著提高不锈钢的抗点蚀性能,具有良好的点腐蚀防护效果.