Electrochemical polymerisation of aniline on conducting textiles of polyester covered with polypyrrole/AQSA

Polyaniline (Pani) has been electrochemically polymerised on conducting textiles of polyester covered with polypyrrole (Ppy)/anthraquinone sulphonic acid (AQSA), obtaining a double conducting polymer layer. Electrochemical syntheses have been performed by means of cyclic voltammetry (CV) and potentiostatic methods. Pani morphology varies with the method of synthesis as it has been corroborated by scanning electron microscopy. EDX analyses have been performed to study zonal composition of the samples. Surface resistivity measurements have been carried out with a 4-point probe equipment. Electrochemical impedance spectroscopy (EIS) and CV have been employed to characterise the electroactivity of the samples in solutions with different pH values. X-Ray photoelectron spectroscopy (XPS) was employed in order to determine the doping level of polyaniline films and the oxidation state of the sample. With the potentiodynamic synthesis the doping level was higher than that obtained with potentiostatic synthesis, however, polymer overoxidation appeared.     

Surface (XPS,SIMS) chemical investigation on poly(pyrrole‐3‐acetic acid) films electrosynthesized on Ti and TiAlV substrates for the development of new bioactive substrates

Electropolymerization of pyrrole‐3‐acetic acid was performed by cyclic voltammetry on titanium and Ti90Al6V4 substrates with the aim of developing a multilayer structure for applications in advanced biomaterials. The polymeric films obtained were characterized by both XPS and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). Information on the poly(pyrrole‐3‐acetic acid) (PPy‐3‐acetic) surface structure was achieved by a detailed XPS analysis of C 1s and N 1s signals. The number of COOH groups was quantified by XPS coupled to a chemical derivatization reaction in which esterification with trifluoroethanol was exploited so that the presence of fluorine (or the CF₃ component in C 1s spectra) could be used as a marker for COOH groups. As a result, it was found that more than 90% of the monomer units along PPy‐3‐acetic chains bear carboxylic functionalities, of which 60% are protonated and 40% are present as carboxylate groups. Some decarboxylation occurs with film ageing. The PPy‐3‐acetic films were also investigated by ToF‐SIMS in the negative ion mode, thus obtaining, for the first time, interesting information on the structure of the top surface layers of a polymer belonging to the polypyrrole family. In particular, clusters of peaks related to PPy‐3‐acetic oligomers were detected and the decarboxylation phenomenon on top of the polymer surface was confirmed. Copyright © 2005 John Wiley & Sons, Ltd.     

有机溶液中添加水对聚吡咯电化学性能的影响

采用电势阶跃技术, 于Pt微盘电极上在含水体积分数分别为0, 2%, 4%, 6%和8%的0.1 mol/L Pyrrole+0.1 mol/L LiClO₄的碳酸丙烯酯(PC)溶液中合成了聚吡咯(PPy)膜. 采用循环伏安法、计时电流法考察了不同含水比例条件下聚吡咯的电化学行为, 采用扫描电镜对其表面形貌进行了观察分析. 研究结果表明, 最佳的含水体积分数为6%. 在此条件下聚合得到的PPy量大, 具有较高的电化学容量、较好的电化学反应可逆性.     

Crown-tetrathiafulvalenes attached to a pyrrole or an EDOT unit: synthesis, electropolymerization and recognition properties

A crown-tetrathiafulvalene electroactive receptor has been covalently linked to electropolymerizable pyrrole or 3,4-ethylenedioxythiophene monomers. The synthetic route to the monofonctionalized tetrathiafulvalene (TTF) ligand has been optimized. Two derivatives of pyrrole (N- and 3-substituted) were synthesized. The various substituted monomers have been electropolymerized to produce polypyrrole (PP) and poly(ethylenedioxothiophene) (PEDOT) films bearing the electroactive TTF moiety. The electroactivity of the polymer films is efficiently controlled by the well-defined two-step redox behavior of the TTF unit. In the case of PEDOT, an alternative post-polymerization derivatization strategy has been used, involving the grafting of the crown-TTF ligand on the previously grown PEDOT backbone. Though chemical derivatization is realized under heterogeneous conditions, in the bulk of the film, this strategy proved to be particularly efficient. These electrodes constitute the first examples of conducting polymer-based modified electrodes incorporating a TTF electrochemical probe, able to interact with a guest ion, such as Ba2+. The cation recognition properties of these various electrodes have been analyzed by cyclic voltammetry and their electroactivity in water as well as their regeneration capability have been investigated.     

Electrochemical Synthesis and Characterization of Electroactive Conducting Polypyrrole Polymers

Conducting/electroactive polypyrrole polymers are synthesized electrochemically on glassy carbon in various electrolytes (counterions). The polymers' electroactivity is measured using cyclic voltammetry. The electrolytes are chloride, nitrate, p-toluene sulfonate, dodecyl sulfate, and dodecylbenzenesulfonate of sodium and potassium ferrocyanide. It is found that the electrolyte (dopant) markedly affects the redox behavior of the polypyrrole films.     

Functionalized polypyrrole nanotube arrays as electrochemical biosensor for the determination of copper ions

A novel electrochemical biosensor based on functionalized polypyrrole (PPy) nanotube arrays modified with a tripeptide (Gly-Gly-His) proved to be highly effective for electrochemical analysis of copper ions (Cu²⁺). The vertically oriented PPy nanotube arrays were electropolymerized by using modified zinc oxide (ZnO) nanowire arrays as templates which were electrodeposited on indium–tin oxide (ITO) coated glass substrates. The electrodes were functionalized by appending pyrrole-α-carboxylic acid onto the surface of polypyrrole nanotube arrays by electrochemical polymerization. The carboxylic groups of the polymer were covalently coupled with the amine groups of the tripeptide, and its structural features were confirmed by attenuated total reflection infrared (ATR-IR) spectroscopy. The tripeptide modified PPy nanotube arrays electrode was used for the electrochemical analysis of various trace copper ions by square wave voltammetry. The electrode was found to be highly sensitive and selective to Cu²⁺ in the range of 0.1–30 μM. Furthermore, the developed biosensor exhibited a high stability and reproducibility, despite the repeated use of the biosensor electrode.     

Preparation of ultrathin polypyrrole films using an adhesion promoter

Adhesive ultrathin polypyrrole films were deposited on Si/SiO₂ substrates modified with the new adhesion promoter 11-(Pyrrol-1-yl Undecyl) TrichloroSilane (PUTS). The oxidation potential of PUTS in solution was determined electrochemically by cyclic voltammetry. Self-assembled monolayers of PUTS were investigated by cyclic voltammetry, contact angle measurements, ellipsometry, and X-ray photoelectron spectroscopy. Several oxidants for the deposition of pyrrole on adhesion promoter modified substrates were tested and a strong dependence on the obtained film morphology was found. It was possible to deposit chemically ultrathin polypyrrole films on insulating substrates.     

Synthesis and Characterization of New Adhesion Promoter for Grafting Conducting Polymer on Oxide Substrate

For grafting polypyrrole layers on oxidic substrates, the synthesis and characterization of a new adhesion promoter 11‐(pyrrol‐3‐yl) undecyl trimethoxysilane (PyTMS) were described in this article. The oxidation potential of PyTMS was determined by cyclic voltammetry. The grafting behavior of such an adhesion promoter on oxidized surface and chemical deposition of polypyrrole over the modified oxidized surface were studied. The adsorbed layer on the oxidized substrates thus formed was determined by both contact angle measurements and X‐ray photoelectron spectroscopy. Chemical polymerization of terminal pyrrole moieties on such substrates yielded adhesive polypyrrole films, and SEM image showed that the morphology of the polypyrrole films was influenced by the experimental conditions.     

Polypyrrole on self-assembled monolayers of a pyrrolyl lipoic acid derivative—electrosynthesis and polymer film characterization

The electropolymerization of pyrrole on gold modified by a self-assembled monolayer (SAM) of a pyrrolyl lipoic acid derivative was investigated in detail and the results compared to those obtained on bare substrates. Both under potentiostatic and potentiodynamic control, a slight blocking action of the underlying SAM could be observed for the initial stages of polymer growth but thereafter the electrochemical features were similar to those collected for polypyrrole (PPy) deposition on bare gold. The morphology and structure of PPy films formed on the SAMs were characterized by atomic force microscopy and X-ray diffraction, which revealed that those polymer properties are much more influenced by the electrochemical mode of preparation, than by the underlying SAMs. While, when compared to PPy on bare gold, no effect has been detected on thin layers deposited at constant potential, surface areas with rather irregular morphology, as well as a small but beneficial influence in inducing order on the first few layers of the polymer film, have been observed on similar films formed by cyclic voltammetry. The typical globular morphology of PPy has always been observed for relatively thick layers in which the redox behavior, analyzed by in situ AFM, showed an increase in volume of the polymer nodules upon reduction, largely due to the SAM reorganization induced by the applied potential.     

循环伏安法制聚(1,5-萘二胺)膜及其对紫外可见光吸收的研究

利用循环伏安法合成了1,5-萘二胺(1,5DAN)聚合物膜.从反应的介质、膜的厚度以及掺杂酸的种类等方面,讨论了制备电活性聚1,5-萘二胺(P1,5DAN)膜的影响,结果发现,在酸性水溶液中,初始的电活性比较高,但是,随着循环的继续,聚合物膜的电量损耗比较大,而在乙腈溶液中电量损耗较小;同时还发现,P1,5DAN电活性膜的厚度并不随总电量的增加而增厚;活性聚合物膜是受扩散控制,扩散系数(D)与酸根离子有关.最后,结合电化学,讨论了不同掺杂状态下的紫外可见吸收光谱(UV-Vis),并用FT-IR对所合成的聚合物作了结构表征.     

Electrochemical behavior of polyaniline films in acetonitrile

The electro-oxidation and electroreduction behavior of polyaniline films in acetonitrile in the absence and presence of added acid or base were investigated using cyclic voltammetry. A general mechanism is proposed that enables the interpretation of the electroactivity loss and the catalytic and autocatalytic properties of the film. The electroactivity loss was found to be a reversible phenomenon which is accelerated in alkaline solutions through deprotonation. Electroactivity was recovered when the electroinactive films were reduced in an acidic solution. The films that lose their electroactivity on electro-oxidation were found to be conducting, and various cation radicals in the structure are believed to be responsible for this nonprotonic conductivity. The proton content of the polyaniline film was found to be crucial in determining its electrochemical and physical properties. Autocatalysis was detected when protons were produced electrolytically in situ during electropolymerization.     

Simultaneous analysis of non‐steroidal anti‐inflammatory drugs using electrochemically controlled solid‐phase microextraction based on nanostructure molecularly imprinted polypyrrole film coupled to ion mobility spectrometry

A simple, rapid, and highly sensitive method for simultaneous analysis of anti‐inflammatory drugs (naproxen, ibuprofen, and mefenamic acid) in diluted human serum was developed using the electrochemically controlled solid‐phase microextraction coupled to ion mobility spectrometry. A conducting molecularly imprinted polymer film based on polypyrrole was synthesized for the selective uptake and release of drugs. The film was prepared by incorporation of a template molecule (naproxen) during the electropolymerization of pyrrole onto a platinum electrode using cyclic voltammetry method. The measured ion mobility spectrometry intensity was related to the concentration of analytes taken up into the films. The calibration graphs (naproxen, ibuprofen, and mefenamic acid) were linear in the range of 0.1–30 ng/mL and detection limits were 0.07–0.37 ng/mL and relative standard deviation was lower than 6%. On the basis of the results obtained in this work, the conducting molecularly imprinted polymer films as absorbent have been applied in the electrochemically controlled solid‐phase microextraction and ion mobility spectrometry system for the selective clean‐up and quantification of trace amounts of anti‐inflammatory drugs in human serum samples. Scanning electron microscopy has confirmed the nano‐structure morphology of the polypyrrole film.     

Determination of percolation threshold electroactivity and phase behavior study on conducting blends of thermotropic polyesters and polyaniline

The new thermotropic polyester/polyaniline (PIn/PAni) blends have been prepared by solution blend of synthesized liquid crystalline poly[4,4′‐bis (ω‐alkoxy) biphenylisophthalate]s having four and six methylene units in spacer (PI4 and PI6) with PAni doped with camphorsolfonic acid (CSA). The percolation threshold electroactivity of prepared blend films has been determined by cyclic voltammetry. The effect of the PAni concentration, solvent nature and polyester structure on the electroactivity of the blends has been investigated. The extremely low percolation threshold of prepared PIn/PAni‐CSA blends from dimethylformamide (DMF) and m‐cresol solution was 3% weight of PAni‐CSA. The amount of conducting polymer necessary to retard the formation of the liquid crystalline (LC) phase is up to 45% by weight. Phase behavior studies by differential scanning calorimetry and polarizing microscopy show that blends with 45% of conducting polymer are both liquid crystal and conductive. The morphology of the blends has been investigated by scanning electron microscopy. Copyright © 2004 John Wiley & Sons, Ltd.     

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     

Stability of conducting polyester/polypyrrole fabrics in different pH solutions. Chemical and electrochemical characterization

The stability of conducting fabrics of polyester (PES) covered with polypyrrole/anthraquinone sulfonic acid (AQSA) has been tested in different pH solutions (1, 7, 13) and after washing tests. It is important to determine the stability of the counter-ion in the polymer matrix, since its loss causes the decrease of the conducting properties of the fabrics. X-ray photoelectron spectroscopy (XPS) studies were done to quantify the amount of counter-ion in the polymer and to obtain the doping level (N^δ+/N). Surface resistivity changes after the different tests were measured by electrochemical impedance spectroscopy (EIS). An increase in the solution pH caused a decrease of the doping level (N^δ+/N), the release of part of the counter-ions and an increase in the surface resistivity. Cyclic voltammetry (CV) measurements showed a gradual loss of electroactivity as pH increased. The influence of the scan rate on the characterization of conducting fabrics has been also demonstrated by CV. Lower scan rates produce a more characteristic response than higher ones. Scanning electrochemical microscopy (SECM) measurements showed a loss of electroactivity when the sample was tested in the pH 13 solution, although the material continued being electroactive.     

2,2'-双氨基苯氧基二硫化物及其聚合物的合成研究

在不同的锂或锂离子二次电池正极材料中 ,新型的聚有机二硫化物有可能成为最有应用前景的电池正极材料之一 [1] ,Visco等 [2 ]首次提出利用二硫化物中双硫键的断裂与再接 (即电聚合与电解聚 )化学性能应用于锂二次电池的充放电 .目前 ,对有代表性的有机二硫化物 2 ,5 -二巯基 -1 ,3 ,4-噻二唑(DMc T)进行了大量的研究[3～ 5] ,最近又提出通过合成新的聚有机二硫化物来提高其电化学性能[6 ,7] .为了得到一种新型高电化学活性和高导电性的锂或锂离子二次电池正极材料 ,本文通过化学方法合成2 ,2 -双氨基苯氧基二硫化物 (DAPD)单体 ,并通…     

PANI膜电聚合过程及电控分离苯酚的EQCM研究

通过电沉积方法在镀铂石英晶片上制备了导电聚苯胺(PANI)膜,采用电化学石英晶体微天平(EQCM)技术探讨了苯胺聚合机制及在苯酚溶液中的氧化还原特性.在0.5 mol/L硫酸溶液中结合循环伏安法考察了PANI膜在完全还原态(L)-半氧化态(E)-完全氧化态(P)之间的电活性和稳定性;在不同浓度的苯酚溶液中结合恒电压阶跃...     

Properties of polyaniline/carbon nanotube multilayer films in neutral solution and their application for stable low-potential detection of reduced beta-nicotinamide adenine dinucleotide

A conducting polymer, polyaniline (PANI), was successfully assembled with commercially available poly(aminobenzenesulfonic acid)-modified single-walled carbon nanotubes (PABS-SWNTs) via the simple layer-by-layer method. PABS-SWNTs inside the multilayer film can dope PANI effectively and shift its electroactivity to a neutral pH environment, pointing to their potential biological applications. The obtained PANI/PABS-SWNTs multilayer films are very stable and show a high electrocatalytic ability toward the oxidation of reduced beta-nicotinamide adenine dinucleotide (NADH) at a much lower potential (about +50 mV vs Ag/AgCl), which makes it an ideal substrate for NADH detection and offers great promise for developing dehydrogenase-based biosensors depending on NADH as a cofactor. For a six-bilayer sample, the detection limit can go down to 1 x 10(-6) M as detected by the simple cyclic voltammetry method, with a linear detection range for NADH at concentrations between 5 x 10(-6) and 1 x 10(-3) M. The substrate can be used repeatedly for consecutive detection cycles of NADH with a very stable signal.     

In situ Raman and UV-vis spectroscopic studies of polypyrrole and poly(pyrrole-2,6-dimethyl-β-cyclodextrin)

Polypyrrole (PPy) and poly(pyrrole-2,6-dimethyl-β-cyclodextrin) [P(Py-β-DMCD)] films prepared by potential cycling in aqueous acidic solutions on indium tin oxide (ITO)-coated glass and gold electrodes were studied by in situ UV-vis and Raman spectroscopy. Characteristic UV-vis and Raman bands were identified and their dependencies on the electrode potential have been discussed. Spectroelectrochemical results reveal differences both in the position of the spectral bands and their potential dependence for PPy and P(Py-β-DMCD) films indicating interactions between polymer chains and CDs during electropolymerization process. The films were also characterized by cyclic voltammetry and FT-IR spectroscopy.     

Carboxy-endcapped conductive polypyrrole: biomimetic conducting polymer for cell scaffolds and electrodes

Numerous regenerating tissues respond favorably to electrical stimulation, creating a need for a bioactive conducting platform for tissue engineering applications. The drive for biosensors and electrode coatings further requires control of the surface properties of promising conductive materials such as polypyrrole. Here we present carboxy-endcapped polypyrrole (PPy-alpha-COOH), a unique bioactive conducting polymer with a carboxylic acid layer, composed of a polypyrrole (PPy) surface modified with pyrrole-alpha-carboxylic acid (Py-alpha-COOH). This unique structure is simple to produce, provides a stable bioactive surface via covalent bonds, and preserves bulk properties such as electrical conductivity and mechanical integrity. The chemical structure of this polymer composite was characterized by angle-resolved X-ray photoelectron spectroscopy (XPS), which demonstrated the presence of carboxylic acid functionality on the top surface of conductive PPy. A four-point probe test was used to verify the similar conductivity of PPy-alpha-COOH compared to that of standard PPy. To demonstrate the potential to influence cellular activity, the carboxylic acid monolayer surface was grafted with the cell-adhesive Arg-Gly-Asp (RGD) motif. Human umbilical vein endothelial cells (HUVECs) cultured on RGD-modified PPy-alpha-COOH demonstrated significantly higher adhesion and spreading than on the negative controls PPy-alpha-COOH and unmodified PPy.