Adsorption efficiency of poly(malachite green) films towards oxidation of ascorbic acid

Thickness of poly(malachite green) films electropolymerized on a glassy carbon electrode surface, the concentration of ascorbic acid, pH value of the solution, and accumulation time were found to affect the adsorption-controlled anodic peak current of ascorbic acid on this polymer film coated electrode. Adsorption efficiency, defined as the ratio of the active sites in polymer films to the amount of adsorbed ascorbic acid molecules, was then proposed and estimated from the comparison of mathematically simulated cyclic voltammograms with experimental ones. The concentration of ascorbic acid is the greatest parameter affected the adsorption efficiency. Poly(malachite green) film electropolymerized on the glassy carbon electrode was found to be not totally active towards oxidation of ascorbic acid when the concentration of ascorbic acid is too high or when the poly(malachite green) film is too thick. The potential shift of ascorbic acid on the modified electrodes was also discussed.     

Voltammetric resolution of dopamine in the presence of ascorbic acid and uric acid at poly (calmagite) film coated carbon paste electrode

The poly (calmagite) film was synthesized on the surface of carbon paste electrode by electrochemical method. The synthesized polymer film coated electrode exhibits excellent electrocatalytic activity towards the detection of dopamine at neutral pH. The scan rate effect was found to be adsorption controlled electrode process. The concentration effect of dopamine was studied. The redox peak potentials of dopamine were depend on pH. This polymer film coated electrode was very good at simultaneous study of dopamine in the presence of high concentrated ascorbic acid and uric acid. The incorporation study was done by varying the concentration of one species while other two are kept constant. The proposed method was applied to the detection of dopamine in injection samples.     

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.     

A modified composite film electrode of polyoxometalate/carbon nanotubes and its electrocatalytic reduction

Keggin-type polyoxometalate (H₄SiMo₁₂O₄₀) and carbon nanotubes (CNTs) coated by poly(allylamine hydrochloride) (PAH) were alternately deposited on glassy carbon (GC) electrodes by an electrochemical growth method in acidic aqueous solution. The preparation of the film electrode was simple and convenient. Thus-prepared multilayer films and the electrochemical behavior of the composite film modified electrode were characterized by UV–vis spectroscopy and cyclic voltammetry. It was shown that the multilayer films are uniform and stable. The resulting multilayer film modified electrode behaves as an electrochemical sensor because of its low overpotential for the catalytic reduction of S₂O₈ ²⁻ and NO₂ ⁻ in acidic aqueous solution.     

Layer‐by‐layer self‐assembled multilayer films of single‐walled carbon nanotubes and tin disulfide nanoparticles with chitosan for the fabrication of biosensors

In this study, multilayer films containing chitosan, tin disulfide (SnS₂) nanoparticles, and single‐walled carbon nanotubes were prepared on glassy carbon electrodes with the use of a layer‐by‐layer assembly technique. The resulting films were characterized with cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy, and ultraviolet–visible absorption spectroscopy. The results of CV and EIS indicates that the peak currents and charge‐transfer resistance all had linear responses to the number of assembled layers. The multilayer‐film‐modified electrode showed excellent electrocatalytic properties for some species, such as dopamine hydrochloride (DA), ascorbic acid (AA), and uric acid (UA). The well‐separated voltammetric signals of DA, UA, and AA could be obtained on the assembled multilayer‐film‐modified electrode, and the peak‐to‐peak potential separations were 171, 136, and 307 mV for DA–UA, DA–AA, and UA–AA on CV, respectively. These facts showed that the multilayer‐film‐modified electrode could be used as a new sensor for the simultaneous detection of DA and UA in the presence of AA in a real sample. In addition, the multilayer films were stable, selective, and reproducible. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

聚ABSA修饰电极对多巴胺、抗坏血酸、尿酸的同时测定

采用电聚合的方法制备了聚对氨基苯磺酸修饰电极（pABSA/GCE）,并采用循环伏安法和线性扫描方法分别对多巴胺（DA）,抗坏血酸（AA）,尿酸（UA）以及三者的混合液进行了测定,研究了该修饰电极的电化学行为。结果表明,pABSA/GCE对AA,DA,UA有良好的电催化作用。在混合液的测定中,三者可以很好的分离,AA-DA、DA-UA、AA-UA的峰电位差分别为265 mV,146 mV和411 mV。该pABSA/GCE修饰电极既用于混合液中AA、DA和UA的分别测定也可以用于三者的同时测定,电极重现性和稳定性良好。     

PEDOT/Palladium composite material: synthesis, characterization and application to simultaneous determination of dopamine and uric acid

Palladium (Pd) incorporated poly (3,4-ethylenedioxythiophene) (PEDOT) films were synthesized through an electrochemical route and characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The electrochemical study showed catalytic oxidation of dopamine (DA) with optimum loading of Pd. DA and uric acid (UA) were detected using differential pulse voltammetry (DPV). In the presence of ascorbic acid (AA), DA-AA showed peak potential separation of 0.19 V while 0.32 V between UA-AA on Pd-incorporated PEDOT. These peak separations are large enough for sensing DA and UA in the presence of AA. DA and UA exhibited linear calibration plots and the minimum detection limits are 0.5 and 7 μM respectively. On Pd-PEDOT, the reversibility of DA oxidation was found to increase compared to bare glassy carbon electrode (GCE) and PEDOT modified GCE. Fouling effects were also found to be minimal making Pd-PEDOT composite suitable for electroanalysis.     

Preparation,optimization, and voltammetric characteristics of poly(o‐phenylenediamine) film as a dopamine‐selective polymeric membrane

Poly(o‐phenylenediamine) films were electrochemically prepared on gold electrodes from the corresponding monomer in an aqueous solution at a constant potential. The polymeric films prepared in this one‐step procedure were found to be thin and insoluble in the aqueous solution. Cyclic and differential pulse voltammetric techniques were used to examine the permeation properties of ascorbic acid and dopamine at the resultant polymeric film electrode. Then, the effects of the chemical and electrochemical variables (e.g., film thickness, polymerization potential, concentrations of monomer and electrolyte) on the permselectivity characteristics of the polymeric film were systematically investigated and the optimal values for each parameter were determined. Furthermore, it was found that the optimized polymer electrode was found to be stable for the successive runs. As a result, it is claimed that poly(o‐phenylenediamine) film can be used as a dopamine‐selective polymeric membrane. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 327–332, 2001     

Preparation and electrochemical behavior of dopamine-selective polymeric membrane

Summary o-toluidine was polymerized electrochemically using constant-potential electrolysis at a gold electrode surface. Electrochemical behavior of dopamine and ascorbic acid at the polymer electrode prepared in this manner was examined by cyclic and differential pulse voltammetry techniques. The influence of chemical and electrochemical variables on dopamine selectivity of the polymer electrode was systematically investigated and the optimal values for each parameter were determined. Experimental results showed that optimized polymeric membrane exhibited selectivity for dopamine while blocking ascorbic acid. Therefore, it is claimed that poly (o-toluidine) film can be used as a dopamine-selective polymeric membrane in the presence of ascorbic acid. Key Words: poly (o-toluidine); selective membrane; dopamine Received: 22 November 1999/Revised version: 25 January 2000/Accepted: 10 February 2000     

Characterization and electrochemical studies of Nafion/nano-TiO2 film modified electrodes

A nano-TiO₂ film from stable aqueous dispersion has been modified on a glassy carbon electrode (GCE), and was characterized by scanning electron microscopy (SEM) and surface-enhanced Raman spectroscopy (SERS). This nanostructured film exhibits an ability to improve the electron-transfer rate between electrode and dopamine (DA), and electrocatalyze the redox of DA. The electrocatalytical behavior of DA was examined by cyclic voltammetry (CV). Combined with Nafion, the bilayer-modified electrode (N/T/GCE) gives a sensitive voltammetric response of DA regardless of excess ascorbic acid (AA). Electrochemical impedance spectroscopy (EIS) at a fixed potential was performed at variously treated GCEs. The mechanism of the electrode reaction of DA at N/T/GCE and the equivalent circuits of different GCEs have been proposed.     

Electrochemical preparation and electrocatalytic properties of PEDOT/ferricyanide film-modified electrodes

The poly(3,4-ethylenedioxy thiophene) (PEDOT)/ferricyanide (FCN) film was synthesized by a potentiostatic and also using potentiodynamic methods namely cyclic voltammetric and chronoamperometric techniques. The EQCM technique was used to study the mechanism of the incorporation of ferricyanide ions on the PEDOT film. The UV-vis absorption results too confirmed the presence of ferricyanide with the PEDOT film. The electrocatalytic oxidation of ascorbic acid was carried out on a glassy carbon electrode modified with the PEDOT/FCN film through cyclic voltammetry, chronoamperometry and rotating disk electrode (RDE) voltammetry as diagnostic techniques. It was found that the catalytic current depended on the concentration of ascorbic acid. The number of electron transfer involved in the rate-determining step was found to be 1 and transfer coefficient (α) equal to 0.476. The diffusion coefficient of ascorbic acid was also estimated through the chrono amperometric and rotating disk electrode methods. The D values of ascorbic acid obtained by through the cyclic and chronoamperometric methods were found to be 4.4103 × 10⁻⁶ and 4.9595 × 10⁻⁶ cm² s⁻¹, respectively. This modified electrode was also used for the simultaneous determination of ascorbic acid and dopamine.     

Electrochemical Synthesis and Characterization of Poly(o-anisidine) Film with Various Dopants: A Comparative Study

In the present work, the doped (composite) films of póly(o-anisidine)–polyvinylsulphonic acid (POA-PVS), poly(o-anisidine)–toluenesulphonic acid (POA-pTS), and poly(o-anisidine)–dodecylbenzenesulphonic acid (POA-DBS) were synthesized on a platinum electrode, using electrochemical polymerization. These synthesized films were characterized by electrochemical techniques, conductivity measurement, UV-visible spectroscopy, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The optimal film growth was achieved for synthesis of the POA film in the presence of dodecylbenzenesulphonic acid (DBS). The POA-DBS composite film exhibits good electrochemical properties, conductivity with a uniformly porous surface morphology which can be used for the immobilization of biocomponent.     

Electrochemical preparation of epinephrine/Nafion chemically modified electrodes and their electrocatalytic oxidation of ascorbic acid and dopamine

Two types of epinephrine and cyclized epinephrine quinone films have been prepared using cyclic voltammetry from the epinephrine in the strong acidic solutions and neutral aqueous solutions over different scanning potential ranges. The cyclic voltammogram of the epinephrine film is characterized by one redox couple at about +0.5 V (versus Ag|AgCl) and cyclized epinephrine quinone film exhibits one redox couples at about −0.15 V (versus Ag|AgCl) .In addition to cyclic voltammetry and an electrochemical quartz crystal microbalance (EQCM) were used to study the growth mechanism of the epinephrine and cyclized epinephrine quinone molecules. The electrocatalytic oxidation of catecholamines (dopamine and norepinephrine) and also ascorbic acid were investigated in acidic aqueous solutions using epinephrine films. The rotating ring-disk electrode technique was used to investigate the mechanism of electrochemical oxidation of dopamine and ascorbic acid.     

Investigation of polymerization parameters affecting dopamine selectivity of a polymeric membrane

Summary By means of electrochemical oxidative polymerization, poly (1,3-phenylenediamine) films on a gold electrode were prepared at a potential of 0.8 V. The permeation properties of polymeric films at the different thickness were investigated by cyclic and differential pulse voltammetry techniques. Voltammetric studies showed that polymeric film at the 1.2 mC thickness exhibited selective permeation for dopamine while rejecting ascorbic acid. Then, all the polymerization parameters affecting the permselective characteristics were systematically investigated and the optimal values were determined. Moreover, stability of polymeric membrane was examined. The results showed that polymeric membrane, owing to permselective character, could be used as a dopamine selective membrane. Received: 10 December 1999/Revised version: 12 March 2000/Accepted: 27 March 2000     

Barrier films to control loss of 9,10-anthraquinone-2-sulphonate dopant from PEDOT films during electrochemical transitions

We describe a simple approach for the synthesis of stable electroactive poly[3,4-ethylene dioxythiophene] (PEDOT) in an acid medium, by incorporating a redox active dopant like 9,10-anthraquinone-2-sodium sulphonate (AQS) on a glassy carbon (GC) electrode. The modified electrode is responsive up to a pH of 7. The stability of the modified electrode during continuous electrochemical cycling is poor, due to leaching of the dopant from the PEDOT film. Efforts are made to improve the stability of the modified electrode by forming an anionic barrier film on the PEDOT-AQS interface either physically or electrochemically. The modified electrodes were monitored by cyclic voltammetry and Fourier transform-infrared (FT-IR) spectroscopy for the presence of AQS in the film.     

Electrochemistry and electrocatalysis with hemoglobin in hollow polyelectrolyte fibrous mats

To form the PS/PAH fibers, positively charged poly(allylamine hydrochloride) (PAH) was coated on the surface of polystyrene (PS) fibers. Then, the ordered Hb‐PS/PAH film was prepared by the self‐assembly of hemoglobin (Hb) on the surface of fibers and characterized by electrochemical and spectroscopic methods. Cyclic voltammetry of the self‐assembled Hb‐PS/PAH films modified on glassy carbon electrode (GCE) displayed a quasi‐reversible electrochemical response in pH 5.0 buffers. Moreover, the Hb‐PS/PAH films also exhibited the electrocatalytic activity to the reduction of H₂O₂. Consequently, the Hb‐PS/PAH films are favorable for the direct electrochemistry of heme containing proteins, suggesting their potential application as the promising sensitive biosensor. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrochemical evaluation of ferrocene carboxylic acids confined on surfactant-clay modified glassy carbon electrodes: oxidation of ascorbic acid and uric acid

We report on the electrochemical behavior of chemically modified glassy carbon (GC) electrodes by using surfactant/clay films, [cetyltrimethylammonium bromide (CTAB)/hydrotalcite-like], containing ferrocenecarboxylic (FC) or ferrocenedicarboxylic (FDC) acid. The results show that the surfactant molecules incorporated into the clay could increase the permeability and the positive surface of the film. The FDC-CTAB-clay-GC modified electrode showed greater stability and redox electroactivity than the FC-CTAB-clay-GC modified electrode. Low concentrations of ascorbic acid (H₂A) and uric acid (UA) in aqueous solution were easily oxidized on the FDC-surfactant-clay-GC modified electrode. The kinetic of the catalytic reactions were investigated by using cyclic voltammetry and rotating disk electrode. The results suggest that the oxidation of H₂A on FDC-CTAB-clay-GC electrode is limited by kinetics while the oxidation of UA is mass transport-limited. The FDC-CTAB-clay-GC modified electrode allows to determine H₂A in presence of UA, and shows good anti-fouling properties towards surface active materials.     

Preparation of l-alanine ethyl ester modified multiwalled carbon nanotubes and their chiral discrimination between d- and l-tryptophan

l-alanine ethyl ester modified multiwalled carbon nanotubes (MWNTs-Ala) were prepared and characterized with FT-IR spectroscopy. The electrochemical behavior of d- and l-tryptophan on the MWNTs-Ala coated electrode was investigated by using cyclic voltammetry. Meanwhile, in order to understand the mechanism of the electrochemical process, the electrochemical behavior of d- and l-tryptophan on the bare glassy carbon electrode and the electrode coated with MWNTs having carboxyl groups (MWNTs-COOH) was also discussed, respectively. The results showed that the electrode coated with MWNTs-Ala could recognize the d- and l-tryptophan chiral isomers due to the introduction of l-alanine ethyl ester on the MWNTs. Furthermore, the enantioselectivity of the MWNTs-Ala coated electrode was studied as functions of the solution pH and scan rate.     

Electrocatalytic properties of NDGA and NDGA/FAD hybrid film modified electrodes for NADH/NAD redox reaction

The fabrication of monolayers composed of nordihydroguaiaretic acid (NDGA), and hybrid films composed of NDGA-flavin adenine dinucleotide (FAD) adsorbed films was performed in neutral aqueous solutions to produce electrochemically active thin films exhibiting one and two redox couples, respectively. An electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ growth of the NDGA and hybrid NDGA/FAD film monolayers. The NDGA modified film electrocatalytically oxidized NADH, ascorbic acid, dopamine, and N₂H₄ in neutral aqueous solutions. Well-separated voltammetric peaks were observed for dopamine and uric acid mixtures, and also for ascorbic acid and uric acid mixtures using the NDGA/GC modified electrode. When transferred to various aqueous buffered solutions, the two redox couples of the NDGA/FAD hybrid film and their formal potentials were observed to be pH-dependent. The electrocatalytic oxidation and reduction of NADH and NAD⁺ by a NDGA/FAD hybrid film in neutral aqueous solutions was carried out, and the electrocatalytic oxidation of NADH was performed using a NDGA/FAD hybrid film.     

Highly sensitive and selective dopamine detection by an amperometric biosensor based on tyrosinase/MWNT/GCE

Dopamine (3,4-dihydroxylphenyl ethylamine) is the most significant neurotransmitter in the human nervous system. Abnormal dopamine levels cause fatal neurological disorders, and thus measuring dopamine level in actual samples is important. Although electrochemical methods have been developed for detecting dopamine with high accuracy, certain substances (e.g., ascorbic acid) in actual samples often interfere with electrochemical dopamine detection. We developed tyrosinase-based dopamine biosensor with high sensitivity and selectivity. An electrochemically pretreated tyrosinase/multi-walled carbon nanotube-modified glassy carbon electrode (tyrosinase/MWNT/GCE) was prepared as an amperometric biosensor for selective dopamine detection. For optimizing the biosensor performance, pH, temperature, and scan rate were investigated. The electrochemically pretreated tyrosinase/MWNT/GCE exhibited not only the highest sensitivity (1,323 mAM^?1 cm^?2) compared to previously reported tyrosinase-based dopamine sensors, but also good long-term stability, retaining 90% of initial activity after 30 days. Additionally, ascorbic acid, a major interfering substances, was not oxidized at the potential used to detect dopamine oxidation, and the interfering effect of 4mM ascorbic acid was negligible when monitoring 1mM dopamine. Consequently, the electrochemically pretreated tyrosinase/MWNT/GCE is applicable for highly selective and sensitive dopamine detection in actual samples including interfering substances, thereby extending the practical use to monitor and diagnose neurological disorders.