Surface‐confined electropolymerization of pyronin Y in the graphene composite paper structure for the amperometric determination of dopamine

Surface‐confined electropolymerization allowed us to easily prepare homogeneous polymer composite paper structures. The fabrication of freestanding graphene (Gr)‐based composite electrodes is very important for many modular approaches in electrochemical applications, such as fuel cells, supercapacitors, and sensors. A Gr composite paper electrode doped with polymeric films of pyronin Y was fabricated by two repetitive simple applications: vacuum filtration and surface‐confined electropolymerization. The characterization of this composite paper was done with scanning tunneling microscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, powder X‐ray diffraction spectroscopy, Raman spectroscopy, UV–visible absorption spectroscopy, four‐point probe conductivity measurement, cyclic voltammetry, and electrochemical impedance spectroscopy. The freestanding composite paper demonstrated good electrocatalytic activity for the electrooxidation of dopamine; this indicated that this composite paper could be used for the amperometric quantification of dopamine in real samples. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45139.     

Electrochemical formation of poly(thionine) thin films: The effect of amine group on the polymeric film formation of phenothiazine dyes

The electropolymerization of thionine in an aqueous solution has been carried out by using both cycling voltammetry and chronoamperometry experiments. Electropolymerization has been applied at various pHs by using different working electrodes. The characterization of poly(thionine) thin films is performed by using cyclic voltammetry, current–time transients, atomic force microscopy, scanning tunnelling microscopy, ATR‐FTIR, and UV–vis absorption spectroscopy techniques. It is deduced from current–time transients and morphological data that poly(thionine) film forms with random adsorption process and exhibits an irregular polymeric film. Poly(thionine) film formation was compared with that of previously published results of phenothiazine derivatives of poly(azure A) and poly(methylene blue). It has been concluded that type of amine functional group of phenothiazine dyes is very effective on the formation of polymeric film structure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39686.     

Preparation and characterization of PS‐PMMA/ZnO nanocomposite films with novel properties of high transparency and UV‐shielding capacity

High transparent and UV‐shielding poly (styrene)‐co‐poly(methyl methacrylate) (PS‐PMMA)/zinc oxide (ZnO) optical nanocomposite films were prepared by solution mixing using methyl ethyl ketone (MEK) as a cosolvent. The films were characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet–visible (UV–vis) spectra, high‐resolution transmission electron microscopy (HR‐TEM), and atomic force microscope (AFM). Cross‐section HR‐TEM and AFM images showed that the ZnO nanoparticles were uniformly dispersed in the polymer matrix at the nanoscale level. The XRD and FTIR studies indicate that there is no chemical bond or interaction between PS‐PMMA and ZnO nanoparticles in the nanocomposite films. The UV–vis spectra in the wavelength range of 200–800 nm showed that nanocomposite films with ZnO particle contents from 1 to 20 wt % had strong absorption in UV spectrum region and the same transparency as pure PMMA‐PS film in the visible region. The optical properties of polymer are greatly improved by the incorporation of ZnO nanoparticles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

In situ polymerization and characterization of polyester‐based polyurethane/nano‐silica composites

Polyester‐based polyurethane/nano‐silica composites were obtained via in situ polymerization and investigated by Fourier‐transform infrared spectroscopy (FTIR), or FTIR coupled with attenuated total reflectance (FTIR‐ATR), Transmission electron microscopy (TEM), atomic force microscopy (AFM), an Instron testing machine, dynamic mechanical analysis (DMA) and ultraviolet‐visible spectrophotometry (UV‐vis). FTIR analysis showed that in situ polymerization provoked some chemical reactions between polyester molecules and nano‐silica particles. FTIR‐ATR, TEM and AFM analyses showed that both surface and interface contained nano‐silica particles. Instron testing and DMA data showed that introducing nano‐silica particles into polyurethane enhanced the hardness, glass temperature and adhesion strength of polyurethane to the substrate, but also increased the resin viscosity. UV‐vis spectrophotometry showed that nano‐silica obtained by the fumed method did not shield UV radiation in polyurethane films. Copyright © 2003 Society of Chemical Industry     

Poly(glutamic acid) nanofibre modified glassy carbon electrode: Characterization by atomic force microscopy, voltammetry and electrochemical impedance

Glassy carbon electrodes (GCE) were modified with poly(glutamic acid) acid films prepared using three different procedures: glutamic acid monomer electropolymerization (MONO), evaporation of poly(glutamic acid) (PAG) and evaporation of a mixture of poly(glutamic acid)/glutaraldehyde (PAG/GLU). All three films showed good adherence to the electrode surface. The performance of the modified GCE was investigated by cyclic voltammetry and differential pulse voltammetry, and the films were characterized by atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS). The three poly(glutamic acid) modified GCEs were tested using the electrochemical oxidation of ascorbic acid and a decrease of the overpotential and the improvement of the oxidation peak current was observed. The PAG modified electrode surfaces gave the best results. AFM morphological images showed a polymeric network film formed by well-defined nanofibres that may undergo extensive swelling in solution, allowing an easier electron transfer and higher oxidation peaks.     

Electrochemical synthesis and in situ spectroelectrochemistry of conducting polymer nanocomposites. I. polyaniline/TiO2, polyaniline/ZnO,and polyaniline/TiO2+ZnO

The polyaniline (PAn), polyaniline/titanium dioxide (PAn/TiO₂), polyaniline/zinc oxide (PAn/ZnO), and a novel conducting polymer nanocomposites, polyaniline/titanium dioxide + zinc oxide (PAn/TiO₂+ZnO), were synthesized by in situ electropolymerization and potential cycling on gold electrode. The PAn and nanocomposite films were characterized by cyclic voltammetry, Fourier transform infra‐red (FTIR) spectroscopy, in situ resistivity measurements, in situ UV–Visible, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The differences between cathodic and anodic peaks of three redox couples were obtained for PAn and polymeric nanocomposite films. During cathodic and anodic scans, the shift of potential was observed for polymer nanocomposite films. The characteristic FTIR peaks of PAn were found to shift to lower wavelengthsin polymer nanocomposite films. These observed effects have been attributed to interaction of TiO₂, ZnO, and TiO₂+ZnO particles with PAn molecular chains. Significant differences from in situ resistivity of PAn and nanocomposite films were obtained. The resistance of PAn/TiO₂, PAn/ZnO, and PAn/TiO₂+ZnO films were found to be smaller than the PAn film. The in situ UV–Visible spectra for Pan and polymer nanocomposite films were studied. The results show the intermediate spectroscopic properties between PAn and polymer nanocomposite films. The morphological analyses of PAn and nanocomposite films have been investigated. The nanocomposites SEM and TEM micrographs suggest that the inorganic semiconductor particles were incorporated in organic conducting polymer, which consequently modifies the morphology of the films significantly. POLYM. COMPOS., 35:351–363, 2014. © 2013 Society of Plastics Engineers     

Electropolymerization of PoPD from aqueous solutions of sodium dodecyl benzene sulfonate at conducting glass electrode

Electropolymerization of poly‐(o‐phenylenediamine) (PoPD) film was performed in a micellar aqueous solution containing sodium dodecyl benzene sulfate (SDBS) by cyclic voltammetry at conducting glass electrode. The experimental results showed that the anionic micelle, i.e., SDBS, can greatly catalyze the electropolymerization reaction of oPD and reduce its oxidation potential from 0.97 to 0.74 V (vs. saturated calomel electrode). In the anionic micellar media, the local concentration of o‐phenylenediamine (oPD) on the surface of electrode may be increased, and the oPD cation radicals are more stabilized in the hydrophobic microcircumstance of micelle, which is available to avoid hydrolysis degradation of PoPD and enhance the stability of the PoPD film. The spectroscopy and morphology of the films were characterized by FTIR spectroscopy and atomic force microscopy, respectively. The results suggested the possible presence of columnar structures when the electropolymerization is performed in the micellar medium. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1928–1932, 2007     

Syntheses and electrochromic and fluorescence properties of three double dithienylpyrroles derivatives

Three double dithienylpyrroles derivatives have been successfully prepared by performing a Knorr–Paal condensation between 1,4-di(thiophen-2-yl) butane-1,4-dione and various aromatic diamines. Additionally, their corresponding polymer films were synthesized via electropolymerization. Their electrochemical, spectroelectrochemical and electrochromic behaviors were further investigated by thermogravimetric analysis, scanning electron microscopy, cyclic voltammetry, UV–vis absorption and fluorescence emission spectra. Scanning electron microscopy and thermogravimetric analysis demonstrated that the polymer films possessed homogeneous, compact and smooth layer structures and thermal stabilities (up to nearly 180 °C). Cyclic voltammograms and UV–vis absorption spectra studies showed that the polymer films have stable, well-defined, reversible redox processes, low optical band gaps (E_g < 2.2 eV) and multicolor electrochromic behaviors. Additionally, the fluorescence spectra study showed that all of the monomers and polymers exhibited different intensity emission bands at different wavelengths.     

Polypyrrole/polyaniline conductive films obtained electrochemically on polycarbonate‐coated platinum electrodes

In this study, two‐component free‐standing films were obtained by coating a polycarbonate (PC)‐coated Pt electrode first with polypyrrole (PPy) in an organic medium and then polyaniline (PAn) in an aqueous medium using an electrochemical technique. The amount of PPy and PAn contained in the films was controlled by varying the electrolysis time. The PC/PPy/PAn films were characterized by cyclic voltammetry, conductivity, FTIR and UV–visible spectrophotometry, and thermogravimetric analysis. The resistance change of the films was determined in the temperature range of ?15 to 120 °C and their temperature sensor properties were investigated. © 2002 Society of Chemical Industry     

Spectroelectrochemistry of pyrrole oligomers in the presence of acrylamide

Soluble pyrrole oligomers were characterized during electropolymerization of pyrrole in the presence of acrylamide (in acetonitrile) which stabilizes radical cations of pyrrole allowing the reaction to be followed by spectroscopic and spectroelectrochemical means. The role of the applied electrical conditions and the effect of the presence of acrylamide on the formation of pyrrole oligomers in solution, and on the resulting polymer on an electrode surface (both Pt and indium tin oxide), were investigated. The soluble and insoluble products were characterized using UV‐visible and FTIR spectroscopy, cyclic voltammetry and a four‐point probe technique. Polypyrrole and poly(pyrrole–acrylamide) free‐standing films had conductivity values of about 90 and 1 S cm^?1, respectively. Spectroscopic, cyclovoltammetric and conductivity results support the incorporation of acrylamide into intermediate species that may have useful application in industry. © 2002 Society of Chemical Industry     

Hydrolysis of the 4-cyanopyridine on a Au(111) electrode studied by vibrational spectroscopies

The adsorption of 4-cyanopyridine on a Au(111) electrode is studied by cyclic voltammetry, FTIR and Sum Frequency Generation (SFG). This subject needs insight because potential-dependent irreversible reactions occur on the electrode. The present study is the continuation of a previous one which dealt with the potential-dependent orientation of 4-cyanopyridine (4-CP) on Au(111) electrodes. In this paper we are considering the hydrolysis of 4-CP into isonicotinamide occurring competitively to the reorientation of the 4-CP molecule. This results in the dissociation of the CN group into CONH₂. We show that in a perchlorate supporting test electrolyte, the adsorbed cyanopyridine adlayer is progressively hydrolyzed when the electrode potential is successively swept negatively then positively between −0.8 and +0.6 V (Ag | AgCl). The product and the mechanism of the hydrolysis reaction are identified thanks to the use of in situ FTIR. SFG spectroscopy is used in the 850–1100 cm⁻¹ range to address the question of the very slow kinetics of the reaction.     

Electrosynthesis and characterization of o‐phenylenediamine oligomers

The contribution of electrochemical methods to the development of conducting polymers has been most relevant, although the electropolymerization mechanism has not yet been totally elucidated. The formation of a high‐density oligomeric region in the electrode–solution interface has been clearly established as formed by oligomers with different chain lengths. It has been confirmed that, depending on the variables governing the process (applied potential, electrolysis time, concentration, etc), it is possible to control to some extent the oligomer to be generated. In this present work, the electrosynthesis of oligomers of o‐phenylenediamine is proposed. A saturated solution of the monomer was electrolysed at 0.95 V versus SCE over 1 min, using stainless steel as the working electrode material. Under these conditions, a mixture of the dimer and tetramer, relatively easy to separate by thin layer chromatography, was deposited. The products were characterized by mass spectrometry, UV–vis spectroscopy, elemental analysis and ¹H NMR spectroscopy. This approach allows the synthesis of oligomers in a fast and simple way. In addition, the product is directly obtained on the electrode surface, hence making its separation and purification very straightforward. Copyright © 2004 Society of Chemical Industry     

Polythiophene gold nanoparticles composite film for application to glucose sensor

Regioregular poly‐3‐hexylthiophene (regP3HT) and dithiobissuccinimidyl propionate (DTSP) have been used to prepare bifunctionalized gold nanoparticles (Bf AuNPs). Processable properties of regP3HT have been used to obtain regP3HT‐AuNPs‐DTSP film on a gold‐coated glass surface and the succinimidyl group of DTSP in this regP3HT‐AuNPs‐DTSP/Au electrode has been utilized for covalent immobilization of glucose oxidase (GOx). The UV‐visible (UV‐vis), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) spectroscopic studies have been used to characterize regP3HT‐AuNPs‐DTSP/Au and GOx‐regP3HT‐AuNPs‐DTSP/Au electrode, respectively. This GOx‐regP3HT‐AuNPs‐DTSP/Au bioelectrode shows response time of 10 s, linearity from 25 to 300 mg/dL of glucose and the value of Michaelis‐Menten constant as 5.85 mM (105.3 mg/dL). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Optical characterization of plasma‐polymerized pyrrole‐N,N,3,5‐tetramethylaniline bilayer thin films

A capacitively coupled parallel‐plate reactor has been used to deposit plasma‐polymerized pyrrole (PPPy), plasma‐polymerized N,N,3,5‐tetramethylaniline (PPTMA), and plasma‐polymerized pyrrole‐N,N,3,5‐tetramethylaniline (PPPy‐PPTMA) bilayer thin films on to glass substrates at room temperature. To deposit the bilayer films, pyrrole monomer has been used as the mother material and N,N,3,5‐tetramethylaniline monomer has been deposited in different deposition time ratios after the pyrrole films were formed. Fourier transform infrared (FTIR) and ultraviolet–visible (UV–vis) spectroscopy techniques have been used to characterize the as‐grown thin films of about 500‐nm thick. The structural analyses by FTIR spectroscopy have indicated that the monomer has undergone the reorganization and the ring structure is retained during the plasma polymerization. From the UV–vis absorption spectra, allowed direct transition (E_qd) and allowed indirect transition (E_qi) energy gaps were determined. The E_qd for PPPy, PPTMA, and PPPy‐PPTMA bilayer films are found to be 3.30, 2.85, and 3.65 eV respectively. On the other hand, the E_qi for the same series are 2.25, 1.80, and 2.35 eV, respectively. From these results, it is seen that the energy gaps of the PPPy‐PPTMA bilayer films have been increased compared with the PPPy and PPTMA films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electrochemical copolymerization and stability of crosslinked bis[1,2‐(pyrrol)ethoxy]ethane with pyrrole

The copolymers, pyrrole‐co‐bis[1,2‐(pyrrol)ethoxy]ethane (PEE), were produced by electropolymerization in acetonitrile (containing 0.1 mol L⁻¹ lithium perchlorate). The properties and morphology of these polymers were investigated by cyclic voltammetry, UV–vis absorption spectra and scanning electron microscopy (SEM), respectively. The results exhibit that the cyclic voltammograms and rates of electropolymerization of the prepared copolymers were significantly affected by PEE concentration in water and acetonitrile solution. Higher applied potential was required for the polymerization with decreasing the ratio of pyrrole/PEE. This was ascribed to the steric hindrance of high concentration of N‐substituted groups. The SEM images of the poly(pyrrole‐co‐PEE) and PPEE films show more compact and more smooth morphology compared with that of PPy and cyclic voltammogram of the poly(pyrrole‐co‐PEE) films, which display good electrochemical stability in the mixed solution, indicating that the modification of crosslinked structure was effective for the stabilization of the redox cycles. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Formation of polyaniline layer on DNA by electrochemical polymerization

We report the electropolymerization and characterization of polyaniline (PAN) on both DNA monolayer and single poly(dG)–poly(dC) DNA molecules serving as a template. The synthesis includes the formation of an electrostatic complex between the negatively charged DNA and positively charged anilinium ions followed by electrochemical oxidation and polymerization of the anilinium ions' monomers on the DNA template. The polymerization was carried out on a flame annealed gold substrate modified with positively charged self-assembled 4-aminothiophenol (4-ATPh) monolayer. The resulting monolayers and single macromolecular composites of DNA–PAN were characterized by atomic force microscopy (AFM), cyclic voltammetry (CV) impedance and UV–vis spectroscopy.     

Enhancement of corrosion protection of mild steel by chitosan/ZnO nanoparticle composite membranes

The development of active corrosion protection systems for metallic substrates is an issue of prime importance for many industrial applications. Nanostructured chitosan/ZnO nanoparticle films were coated on mild steel by sol–gel process, dip coating technique. Sol–gel protective coatings have shown excellent chemical stability, oxidation control and enhanced corrosion resistance for metal substrates. Further, the sol–gel method is an environmentally friendly technique of surface protection which has traditionally been used for increasing corrosion resistance of metals. Films so formed were characterized by UV–vis absorption spectroscopy (UV–vis), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray fluorescence spectrometry (EDX). Corrosion protection behavior of these coated mild steel substrates in 0.1 N HCl solutions was evaluated by potentiodynamic polarisation studies (Tafel), linear polarisation studies (LPR), electrochemical impedance spectroscopy studies (EIS).     

Variation of lexan polycarbonate properties by electron beam

The modifications in microstructural, optical, and photoluminescence properties of the Lexan polycarbonate (bisphenol‐A‐polycarbonate) films exposed to different electron doses have been studied using UV–vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), positron annihilation lifetime spectroscopy, photoluminescence spectroscopy, and scanning electron microscopy (SEM). The obtained UV–vis spectroscopy results showed decrease in optical energy gap, optical activation energy, and increase in number of carbon atoms per cluster with increase in electron dose. The chemical changes in electron irradiated polymers due to chain scission and reconstruction have been observed from FTIR spectroscopy. The correlation of positron lifetime study with optical measurement is obtained, and electron irradiation‐induced microstructural modifications within the polymer is understood. SEM result shows the degradation of Lexan polymer after electron irradiation. The mechanical properties and average molecular weight of Lexan decrease after irradiation, whereas average number of chain scissions per original polymer molecule increases. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Controlling the surface wettability of poly(sulfone) films by UV‐assisted treatment: benefits in relation to plasma treatment

Hydrophilic and superhydrophilic surfaces of poly(sulfone) (PSU) thin films were prepared by UV irradiation in the presence of O₂ or acrylic acid (AA) vapor. Treated surfaces were then investigated by water contact angle measurements, Fourier transformed IR spectroscopy in attenuated total reflectance mode (FTIR‐ATR), X‐ray photoelectron spectroscopy (XPS), near‐edge X‐ray absorption fine structure (NEXAFS) and AFM. Water contact angle values of treated PSU films using either O₂ or AA vapor as the reactive atmosphere reached about 6° after more than 120 min of irradiation. FTIR‐ATR, XPS and NEXAFS analysis showed incorporation of oxygenated groups onto the surface that led to its hydrophilic characteristics. In addition, when AA vapor was used as the reactive atmosphere, a photopolymerization process of poly(acrylic acid) onto the surface of the PSU was observed. AFM analysis showed a very low level of roughness after the treatments. A comparison of UV‐assisted surface modifications of PSU films with traditional plasma treatments showed excellent qualitative agreement between the two techniques. Our results show that UV‐assisted treatments in the presence of AA vapor or O₂ are efficient ways of controlling the surface wettability and functionalities grafted on the surface of PSU films. This treatment can be considered as a permanent dry grafting method that resists aging and uses a simple experimental setup. © 2012 Society of Chemical Industry     

Poly(2,5‐dimethoxyaniline) films on mild steel for application to glucose biosensor

Poly(2,5‐dimethoxyaniline) (PDMA) films were electrochemically synthesized on mild steel from an aqueous oxalic acid solution using galvanostatic mode. These films were characterized by potential–time curve, UV‐visible absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The enzyme glucose oxidase (GOx) was entrapped into the PDMA film by a physical adsorption method. The resulting PDMA–GOx films were characterized by UV‐visible absorption spectroscopy, FTIR, and SEM. The amperometric response of the PDMA–GOx films was measured as a function of glucose concentration in phosphate buffer solution (pH 7.3). The PDMA–GOx films exhibit a fast and linear amperometric response in the range of 2–20 mM glucose. The maximum current density and Michaelis–Menten constant of PDMA/GOx films are found to be ～483 μA/cm² and 1.12 mM, respectively. The shelf stability and thermal stability of these films were also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008