Attempt to incorporate ferrocenecarboxylic acid into polypyrrole during the electropolymerization of pyrrole in chloroform: its application to the electrocatalytic oxidation of ascorbic acid

 In this work, polypyrrole films with ferrocenecarboxylic acid incorporated (PPy/FCA) were prepared on a glassy carbon (GC) electrode in chloroform as an aprotic solvent with low dielectric constant, convenient for the preparation of the films by a precipitation mechanism. The electrochemical behaviour of the PPy/FCA-coated GC electrode was studied by cyclic voltammetry in aqueous solution with low pH. The results obtained show that the electrochemical response of FCA incorporated in polypyrrole is consistent with a reversible surface oxidation. An obvious electrocatalytic effect of PPy/FCA on the oxidation of ascorbic acid is observed in aqueous solution. Received: 30 July 1998 / Accepted: 3 March 1999     

蒽醌/聚吡咯复合膜修饰电极的电化学行为和电催化活性

在水溶液中制备了掺杂蒽醌磺酸盐(AQS)的聚吡咯(PPy)/玻碳复合膜修饰电极,采用循环伏安法和旋转圆盘电极技术研究了该修饰电极在不同pH值溶液中的电化学行为以及在pH=5.5的磷酸盐缓冲溶液中对氧还原反应的电催化性能和动力学.结果表明,与裸玻碳电极相比,PPy膜的存在不仅降低了AQS的反应电位和峰电位差,而且增大了其氧化还原反应的峰电流,H2AQ/HAQ-氧化还原对的电离常数为9.5.AQS/PPy膜修饰电极上氧的还原主要是两电子还原为H2O2的不可逆过程,H2AQ对氧还原反应起主要催化作用,还原过程符合异相氧化还原催化机理.该修饰电极具有良好的电化学重现性.     

碳纳米管/聚二烯丙基二甲基氯化铵/磷钼酸复合膜的组装及其在溴酸盐检测中的应用

通过静电层层组装技术在玻碳(GC)电极表面制备{多壁碳纳米管(MWCNT)/聚二烯丙基二甲基氯化铵(PDDA)}n多层膜,并采用循环伏安法在多层膜的表面电化学修饰一层磷钼酸(PMo12)膜,构筑GC/{MWCNT/PDDA}n-PMo12复合膜修饰电极.利用SEM对比观察{MWCNT/PDDA}n和{PDDA/MWCNT}n-PMo12的微观结构,并研究该复合膜修饰电极的电化学及其对溴酸盐(BrO3-)电催化还原性质.在此基础上研发一种基于GC/{MWCNT/PDDA}n-PMo12复合膜修饰电极的电流型BrO3-传感器,该传感器表现出明显增大的响应电流.在最优的实验条件下,采用电流时间曲线(i-t)法考察该复合膜修饰电极对BrO3-的安培响应.实验结果表明,该传感器在BrO3-浓度为50～400nmol/L的范围内具有良好的线性关系,相关系数R2为0.9950,响应时间为1.53s,检出限为20nmol/L,灵敏度为13.81mA(mmol/L)-1cm-2.     

新型聚N，N-二甲基苯胺/多壁碳纳米管修饰电极的制备、表征与应用

采用多壁碳纳米管(MWNT)改性聚N,N-二甲基苯胺(PDMA)膜,制备了新型复合膜修饰玻碳电极,并用SEM、电化学方法对修饰电极进行表征。 结果表明,无论MWNT是以掺杂还是先滴涂MWNT再聚合DMA多层修饰方式,均会改变PDMA膜的形貌和电化学性能。 复合膜修饰电极比单一PDMA膜修饰电极大幅度提高了比表面积和电活化面积,同时使PDMA和MWNT更好地协同发挥其优良的电化学特性。 实验结果表明,层层修饰制备的聚N,N-二甲基苯胺/多壁碳纳米管复合膜修饰电极对香草醛的电化学响应远大于基体电极和其它方法制备的修饰电极,电催化作用显著提高,其过电位降低了148 mV,氧化峰电流约增加了6倍;其电极反应是吸附控制的不可逆氧化过程,转移电子数n为2,质子数m为1,传递系数α为0.4062,吸附量为Γ=3.527×10-9 mol/cm2;检出下限为8.0×10-7 mol/L,样品平均回收率为99.87%。     

Preparation and characterization of conducting poly(acryloyl chloride)‐g‐ polypyrrole copolymer

The electroactive copolymer of poly(acryloyl chloride) (PAC) and polypyrrole (PPy) can be synthesized by electrochemical polymerization using a polymer precursor which contains a pyrrole moiety in its side chain. Poly(acryloyl pyrrole) (PAP) was synthesized chemically with acryloyl chloride and potassium pyrrole salt and characterized using FT‐IR and ¹H‐NMR spectroscopy. PAP dissolved in dimethyl formamide (DMF), was spin‐coated on a platinum electrode and polymerized electrochemically in the electrolytic mixture solution consisting of acetonitrile, 0.1 M pyrrole, and 0.1 M lithium perchlorate. Constant potential electrolysis showed that pyrrole groups in the precursor were oxidized to form PPy, that is, they acted as grafting centers at which the PPy grew. Scanning electron microscopy (SEM) results and conductivity measurements supported the formation of the graft copolymer. The morphological feature of PAC‐g‐PPy copolymer films showed homogeneous structure, but that of PAC/PPy composite films showed irregular structure. The maximum conductivity of the final products was about 1 S/cm. Copyright © 2002 John Wiley & Sons, Ltd.     

Electrochemical impedance spectroscopy and in situ UV‐vis spectroelectrochemistry studies of Poly(N‐vinyl carbazole)/ Polydimethylsiloxane composite electrodes

Poly(N‐vinyl carbazole)/polydimethylsiloxane (PNVCz/PDMS) composite electrodes were prepared by electrochemical polymerization of NVCz monomer onto PDMS‐coated platinum (Pt) and glassy carbon (GC) electrode surfaces to investigate the influence of the insulating constituent, PDMS and process temperature on the capacitive performance of the coated layers. The electrochemical properties of the bilayer coatings were studied by electrochemical impedance spectroscopy and UV‐vis spectroelectrochemistry measurements. The low‐frequencies capacitance values of composite electrodes indicated that the capacitive behaviors of the composites decreased with increasing PDMS content (from 5.0 to 10.0; in wt/v%) in coating solutions at 25 °C, and with decreasing coating temperatures (from 25 °C to ? 15 °C) of PDMS and PNVCz and, more resist PDMS/PNVCz layers formed. Copyright © 2011 John Wiley & Sons, Ltd.     

ELECTRICALLY CONDUCTIVE COMPOSITE PREPARED BY ELECTROCHEMICAL POLYMERIZATION OF PYRROLE IN POLY-(p- PHENYLENE TEREPHTHALAMIDE) MATRIX

The preparation of PPy/PPTA conductive composite films by electrochemical method is presented.The first step is to cast a thin layer of poly (p-phenylene-terephthalamide) (PPTA) on a slice of Pt working electrode. The second step is to electrochemically polymerize pyrrole on the PPTA/Pt working electrode. Both of the electrical conductivity and the mechanical properties of the PPy/PPTA composite film are better than those of the pure PPy film, and the film has excellent flexibility at low temperature, even in liquid nitrogen.The SEM picture of the cross-section of PPy,/PPTA composite film showed that the two components were well mixed.Cyclic voltammograms of PPy,/PPTA film in aqueous solution showed that the conductive films could be reduced and reoxidized.     

All-solid-state planar miniature ion-selective chloride electrode

All-solid-state ion-selective electrodes with plastic membrane (poly(vinyl chloride) (PVC), bis(2-ethylhexyl) sebacate (DOS), methyltri-n-tetradecylammonium chloride (MTTACl)), a conducting poly(pyrrole) (PPy) film doped either with chloride ions (PPyCl) or hexacyanoferrate(II) ions (PPyFeCN), and glassy carbon (GC) or screen-printed graphite layer (S-PG) as an inner electric contact were investigated. All the electrodes show close to Nernstian response, but their lifetimes vary. The at least 2-months lifetime of screen-printed electrodes is only achieved for the electrodes containing PPyFeCN (cation-exchanging film). Shorter lifetime of other screen-printed electrodes, i.e. without PPy, or with PPyCl (anion-exchanging film), was attributed to the diffusion of anionic products of the hydrolysis of organic components of the graphite paste used to prepare the electric contact. The properties of miniature, screen-printed electrodes comprising PPyFeCN solid contact, were comparable to those ion-selective electrodes with PPy solid contact (regardless the ion-exchanging characteristic of the polymer) deposited on GC electric contact.     

蒿甲醚在单壁碳纳米管修饰电极上的电催化还原

研制了单壁碳纳米管(SWCNTs)修饰玻碳电极。用交流阻抗谱法(EIS)和扫描电镜(SEM)研究了电极膜性能,应用循环伏安法(CV)、计时库仑法(CC)、计时电流法(CA)研究了蒿甲醚在修饰电极上的电化学行为。结果表明,SWCNTs修饰电极对蒿甲醚的还原有良好的电催化活性,其还原反应为双电子过程,电极反应的扩散系数及速率常数分别为6·67×10-4cm2·s-1及8·54×10-2mol·L-1·s-1。在优化实验条件下,还原峰的峰电位位于-0·85V,其峰电流与蒿甲醚浓度在6·71×10-7~2·45×10-4mol·L-1范围内呈良好线性,检出限达4·02×10-7mol·L-1,相对标准偏差(n=10)为4·2%,可用于蒿甲醚样品的含量测定。     

A glassy carbon electrode modified with antimony and poly(p-aminobenzene sulfonic acid) for sensing lead(II) by square wave anodic stripping voltammetry

We have developed a sensor for the square wave anodic stripping voltammetric determination of Pb(II). A glassy carbon electrode was modified with a thin film of an antimony/poly(p-aminobenzene sulfonic acid) composite in air-saturated aqueous solution of pH 2.0. Compared to a conventional antimony film electrode, the new one yields a larger stripping signal for Pb(II). The conditions of polymerization, the concentration of Sb(III), the pH value of the sample solution, the deposition potential and time, frequency, potential amplitude, and step increment potential were optimized. Under the optimum conditions, a linear response was observed for Pb(II) in the range of 0.5 to 150.0 μg?L^?1. The detection limit for Pb(II) is 0.1 μg?L^?1.

Cross-sensitive rare-earth metal sensors based on bidentate neutral organophosphorus compounds and chlorinated cobalt dicarbollide

A new carbon composite electrode material, based on dispersing glassy carbon (GC) microparticles into methyltrimethoxysilane-derived sol, is described in the present paper. The resulting glassy carbon ceramic composite electrodes (GCCEs) combine the electrochemical properties of GC with the advantages of composite electrodes, and thus offer high electrochemical reactivity, low background current and are easy to prepare, modify and renew. The new material has a low double-layer capacitance and a wide potential window. Scanning electron microscopy (SEM) images indicate significant difference in the structure of GCCE and carbon ceramic composite electrode (CCE). The electrochemical properties and advantages of GCCE should find broad utility in electroanalysis.     

氟尿嘧啶的电化学控制释放

本文探讨了抗癌药物氟尿嘧啶在聚吡咯膜修饰玻碳电极上的电化学控制释放，结果表明药物自膜中的释放是聚吡咯膜的电化学氧化还原过程决定的。其释放量可由还原电位进行控制，并与还原电量和膜厚呈现良好的线性关系。     

Poly(4-amino-1-1'-azobenzene-3, 4'-disulfonic acid) coated electrode for selective detection of dopamine from its interferences

Here, we described a new method for electrochemically selective detection of dopamine (DA). In this report, for the first time, electrochemical polymerization of 4-amino-1-1'-azobenzene-3,4'-disulfonic acid (acid yellow 9 dye (AY)) was carried out onto the surface of glassy carbon (GC) electrode and indium tin oxide coated electrode (ITO) from acidic solution containing AY monomers. A polymerized film of acid yellow on the surface of a glassy carbon electrode was characterized by cyclic voltammetry (CV). The redox response of the poly(AY) film on the GC electrode showed a couple of redox peak in 0.1M sulfuric acid solution and the pH dependent peak potential was -58mV/pH which was close to the Nernst behavior. The poly(AY) film-coated GC electrode (GC/PAY) exhibited excellent electrocatalytic activity towards the oxidations of dopamine (DA) in 0.1M phosphate buffer solution (PBS, pH 7.0) and increased the anodic peak current three time higher than bare GC electrode. GC/PAY did not reduce the considerable overpotential for oxidation of DA when compare to bare GC electrode. However, in contrast to other polymer modified electrode, due to the strong negatively charged back bone of poly(AY) highly repelled the important interference of DA, such as ascorbic acid (AA), uric acid (UA) and reduced form of nicotinamide adenine dinucleotide (NADH) in 0.1M PBS (pH 7.0) and did not showed any response for oxidation of these interferences. This behavior makes the GC/PAY for selective detection of DA in the presence of higher concentrations AA, UA and NADH. Using differential pulse voltammetry the calibration curves for DA were obtained over the range of 1-100muM with good selectivity and sensitivity. The proposed method provides a simple method for selective detection of DA from its interferences.     

Electrochemical Glutathione Sensor Based on Electrochemically Deposited Poly‐m‐aminophenol

Preparation and characterization of electrodes suitable for determination of glutathione is reported in this study. For this poly‐m‐aminophenol (PmAP), poly‐o‐aminophenol, and poly‐p‐aminophenol were electrochemically deposited from aqueous solution on the surface of glassy carbon (GC) electrode by potential cycling in the range of +0.2–+1.0 V. The modified GC electrodes were characterized by cyclic voltammetry, electrochemical impedance spectroscopy, contact angle measurement and ellipsometry. It was found that poly‐m‐aminophenol modified GC electrode (PmAP/GC‐electrode) is most suitable for electroanalytical determination of glutathione. An electroanalytical system for the determination of glutathione based on the PmAP/GC‐electrode was developed. The analytical system was characterized by low limit of detection, good stability, high sensitivity and wide linear detection range.     

Glassy carbon paste electrodes

A new carbon composite electrode material, based on mixing glassy carbon (GC) microparticles with an organic pasting liquid is described. The resulting glassy carbon paste electrode (GCPE) combines the electrochemical properties of GC with the various advantages of composite electrodes. Glassy carbon pastes (GCPs) offer high electrochemical reactivity, a wide accessible potential window, a low background current, and are inexpensive, easy to prepare, modify, and renew. The new material has a lower double-layer capacitance and a higher heterogeneous rate constant (for ferricyanide) compared to conventional carbon pastes (CPs). Scanning electron microscopy (SEM) images indicate significant differences in the structure of GCPE and carbon paste electrode (CPE). Factors influencing the electrode kinetics of GCPE surfaces are discussed. The electrochemical properties and advantages of GCPE should be of broad utility in electroanalysis.     

Stacked graphene nanofibers doped polypyrrole nanocomposites for electrochemical sensing

This publication shows a single-step electropolymerization which has been carried out by the incorporation of an anionic stacked graphene nanofiber (SGNF) dopant into a polypyrrole (PPy) film, at a disposable screen-printed electrode. The incorporation of the SGNFs into the polymer does not affect their electrochemical properties, shown through cyclic voltammetry by the earlier oxidation of guanine, when compared with that at the graphite doped PPy electrode. The SGNF/PPy composite shows a high selectivity when used in the oxidation of guanine and hydrogen peroxide, both of which are important biomarkers used for biosensing. Disposable screen-printed electrodes provide an inexpensive, sensitive and portable substitute to glassy carbon electrodes, while giving a reproducible surface; qualities essential for effective bionsensing. The production of this single-step disposable SGNF/PPy composite electrode allows for further applications in the detection of biomedically important compounds and DNA sensing.     

Carbon nanotubes/alizarin red S–poly(vinylferrocene) modified glassy carbon electrode for selective determination of dopamine in the presence of ascorbic acid

A modified electrode was fabricated by electrochemical formation of poly(vinylferrocene) on the multi-wall carbon nanotube-alizarin red S matrix covered glassy carbon electrode. A higher electrochemical activity was obtained to the electrocatalytic oxidation of dopamine. The electrode surface was characterized electrochemically and spectroscopically. Poly(vinylferrocene) (PVF) in electrode was used as an electron transfer mediator in the electrochemical oxidation of compounds due to its perfect reversible redox properties. Multi-wall carbon nanotubes (MWCNTs) / alizarin red S (ARS)–PVF electrode was used to the determination of dopamine in the presence of ascorbic acid in 0.1 M sulphate buffer solution at pH 7. The performance of the MWCNTs/ARS–PVF electrode was evaluated by DPV and amperometry.     

聚对氨基苯磺酸/碳纳米管复合膜修饰电极对尿酸与抗坏血酸的同时测定

通过在碳纳米管修饰玻碳电极表面电聚合的方法制备了聚对氨基苯磺酸/碳纳米管复合膜修饰电极(PABSA/CNT/GC),采用扫描电镜对电极形貌进行了表征。运用循环伏安法研究了尿酸(UA)和抗坏血酸(AA)在该修饰电极上的电化学行为,在pH7.0的PBS中,UA和AA分别在0.312、-0.025 V处产生灵敏氧化峰,与其在聚氨基苯磺酸和碳纳米管单层膜修饰电极上的电化学行为相比,两者的氧化峰电流显著增加,峰电位差(ΔEpa)达到337 mV,表明碳纳米管和聚合物产生协同增效作用,探讨了其作用机理。在优化实验条件下,建立了差分脉冲伏安法同时测定UA和AA的方法,UA、AA的线性范围分别为2.5×10-7~5.0×10-4、8.0×10-6~4.0×10-3mol/L,检出限分别为7.5×10-8、5.0×10-6mol/L。该方法用于尿样中UA和AA的测定,结果令人满意。     

pMB/MWNTs/GC电极对水体中苯二酚异构体的同时测定

通过在多壁碳纳米管修饰玻碳电极上电聚合亚甲基蓝,制备了聚亚甲基蓝/碳纳米管/玻碳电极(pMB/MWNTs/GC)。用循环伏安法研究了3种苯二酚异构体在该电极上的电化学行为,结果表明,在pH7.0的磷酸盐缓冲溶液中,该修饰电极对苯二酚异构体的氧化表现出优异的电催化性能和选择性,对苯二酚、邻苯二酚和间苯二酚的氧化峰分别为0.104、0.203、0.609 V(vs.SCE),峰电位差值分别为99、406 mV。基于苯二酚异构体在pMB/MWNTs/GC修饰电极上的伏安行为,建立了苯二酚3种异构体同时分析的新方法。考察了各影响因素对测定的影响,最优实验条件下,在5.0×10-6~1.5×10-4mol.L-1范围内,3种苯二酚异构体的阳极峰电流与其浓度存在线性关系,检出限均为1.0×10-6mol.L-1。将该法用于水体及冲洗废液中苯二酚异构体含量的测定,结果满意。     

Hollow microstructures of polypyrrole doped by poly(styrene sulfonic acid)

Microstructures with hollow interiors, such as microspheres, microcrocks, microbowls, and micropumpkins, were prepared through the direct electrochemical oxidation of pyrrole in an aqueous solution of poly(styrene sulfonic acid) (PSSA). Scanning electron microscopy demonstrated that the microstructures possessed hollow interiors. The addition of polymeric doping ions made the skins of the microstructures very smooth, and several novel structures were observed. The morphology of the microstructures was simply modulated through changes in the electrochemical conditions. Raman and Fourier transform infrared characterizations indicated that the microstructures were made of conductive polypyrrole (PPy) doped by polymeric anions of poly(styrene sulfonate), and X‐ray diffraction showed that the microstructures were amorphous. Thermogravimetric analysis indicated that PPy–PSSA composite films with microstructures had higher thermal stability than pure PPy, PPy‐coated PSSA microspheres, and naphthalene sulfonic acid doped PPy microstructures. Furthermore, PPy–PSSA composite films with microstructures showed cation‐exchange behavior during the redox process in aqueous solutions of sodium dodecyl benzenesulfonate. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3170–3177, 2004