Solvent dependent swelling behaviour of poly(<Emphasis Type="Italic">N</Emphasis>-vinylcaprolactam) and poly(<Emphasis Type="Italic">N</Emphasis>-vinylcaprolactam-<Emphasis Type="Italic">co</Emphasis>-itaconic acid) gels and determination of solubility parameters

Swelling behaviour of poly(N-vinylcaprolactam) (PVC) and poly(N-vinylcaprolactam-co-itaconic acid) (P(VC-co-IA)) gels was investigated in different solvents (water, ethanol, methanol, isopropyl alcohol (IPA), chloroform, toluene, acetone) and in binary solvent mixtures (ethanol/chloroform, ethanol/methanol, IPA/chloroform, ethanol/water, IPA/water). Gels were synthesised in ethanol by the free radical cross-linking polymerisation method at 60°C for 24 h in the presence of azo-bis(isobutyronitrile) and allyl methacrylate as the initiator and cross-linker, respectively. And also, ethanol/distilled water mixture (?_r = 4:1) was used as the synthesis medium to determine its effect on the swelling of gels. It was found that the presence of water in the synthesis medium significantly affected the equilibrium swelling value (ESV) and the swelling tendency of gels both in solvents and in solvent mixtures. All gels synthesised in ethanol showed the highest swelling in chloroform. The gels synthesised in the ethanol/water mixture displayed different swelling behaviour. In this case, while chloroform was still valid for maximum swelling of PVC, P(VC-co-IA) had the highest swelling in methanol. Solubility parameters of gels were predicted by the van Krevelen-Hoftyzer (VKH) and Hoy methods (group contribution methods) and theoretical calculations verified the experimental swelling order.     

Surfactant-assisted synthesis of polyaniline nanofibres without shaking and stirring: effect of conditions on morphology and conductivity

Polyaniline (PANI) nanofibres were synthesised by the chemical oxidative polymerisation method using ammonium peroxydisulphate (APS) as an oxidant/initiator. In this work, a surfactant-assisted method without shaking and stirring was used for the synthesis of PANI nanofibres. The effect was investigated of various parameters such as monomer/oxidant ratio, polymerisation temperature, and the presence of surfactant (Triton X-100 as a non-ionic surfactant) on the morphology and electrical conductivity of nanofibres. The morphology of PANI nanofibres was characterised by scanning electron microscopy and transmission electron microscopy. The results demonstrate that the morphology of PANI nanofibres was significantly influenced by the aniline/APS mole ratio, polymerisation temperature and presence of the surfactant during synthesis. The results showed that more regular and consistent nanofibres were obtained using a monomer/oxidant ratio of 4 at ambient temperature of polymerisation. PANI nanofibres with diameters in the range of 10?C100 nm and length up to several ??m were obtained. PANI nanofibres were also characterised using FTIR and UV-VIS absorption spectroscopy. The electrochemical behaviour of PANI nanofibres was studied by cyclic voltammetry. It was found that the electrical conductivity of PANI nanofibres increased with the increasing monomer/oxidant ratio and decreasing polymerisation temperature, respectively.     

聚苯胺对钯催化甲酸电氧化反应的促进作用

钯基纳米材料是甲酸电氧化反应的优良催化剂.本工作制备了两个系列钯基催化剂,并考察了聚苯胺对钯上甲酸电氧化反应的助催化作用.一种是以聚苯胺为基底,在其表面电沉积钯纳米粒子,制得nPANI/Pd催化剂(n表示聚合苯胺的循环数);另一种是直接在商业Pd/C催化剂表面电聚合苯胺,制得Pd/C/nPANI催化剂.结果显示,聚苯胺单独存在时对甲酸电氧化反应没有催化活性,但其可对钯上甲酸电氧化反应呈现明显的促进作用,且促进作用与聚苯胺的厚度(聚合循环数)密切相关.在两个系列催化剂中,15PANI/Pd和Pd/C/20PANI显示出最高的催化性能.15PANI/Pd中钯的质量比催化活性是纯钯催化剂的7.5倍; Pd/C/20PANI中钯的质量比催化活性和本征催化活性分别是商业Pd/C催化剂的2.3和3.3倍.钯催化性能的提升与聚苯胺和钯纳米粒子间的电子效应有关.     

E-beam crosslinked,biocompatible functional hydrogels incorporating polyaniline nanoparticles

PANI aqueous nanocolloids in their acid-doped, inherently conductive form were synthesised by means of suitable water soluble polymers used as stabilisers. In particular, poly(vinyl alcohol) (PVA) or chitosan (CT) was used to stabilise PANI nanoparticles, thus preventing PANI precipitation during synthesis and upon storage. Subsequently, e-beam irradiation of the PANI dispersions has been performed with a 12 MeV Linac accelerator. PVA-PANI nanocolloid has been transformed into a PVA-PANI hydrogel nanocomposite by radiation induced crosslinking of PVA. CT-PANI nanoparticles dispersion, in turn, was added to PVA to obtain wall-to-wall gels, as chitosan mainly undergoes chain scission under the chosen irradiation conditions. While the obtainment of uniform PANI particle size distribution was preliminarily ascertained with laser light scattering and TEM microscopy, the typical porous structure of PVA-based freeze dried hydrogels was observed with SEM microscopy for the hydrogel nanocomposites. UV?visible absorption spectroscopy demonstrates that the characteristic, pH-dependent and reversible optical absorption properties of PANI are conferred to the otherwise optically transparent PVA hydrogels. Selected formulations have been also subjected to MTT assays to prove the absence of cytotoxicity.     

Polyaniline precipitation in aqueous medium: from bulk aggregates to nanoparticles

A postsynthetic self-assembly system was designed to investigate a construction process from suspended polyaniline (PANI) molecules to condensed aggregates. The conventionally synthesized PANI was dissolved in polar solvent and introduced into acidic medium with electrolytes similar to the aniline chemical oxidative polymerization (COP) medium. In this way, reaction interference that is usually encountered in the COP process could be avoided, and influences of medium conditions including organic electrolytes on the self-assembly behaviors of PANI were studied. It was discovered that, in a static aqueous medium with moderate pH and rich electrolytes, PANI molecules composed of bulk aggregates could self-assemble into well-dispersed nanoparticles with few structural changes. Electrostatic force is considered to dominate the self-assembly of PANI molecules as compared with other noncovalent interaction or the effect of soft templates such as ionic liquid and surfactant. The results are supposed to provide better understanding on the formation mechanism of micro/nanostructured PANI.     

Template-free enzymatic synthesis of electrically conducting polyaniline using soybean peroxidase

Synthesis of polyaniline (PANI) catalyzed by soybean peroxidase at 1 °C in either aqueous or partially organic media, was studied as a function of pH and reaction media. Kinetic studies indicated that, unlike chemical polymerization, enzymatic polymerization of aniline showed neither induction period nor auto acceleration. The redox reversibility and chemical structure of the synthesized PANI was strongly dependent on the starting pH of the reaction medium. UV-vis, FT-IR, WAXD and TGA analysis are used to explain how the enzymatic reaction conditions influence both the chemical structure and physical properties of the PANI. Optimal reaction conditions are outlined for the direct enzymatic synthesis of electrically conductive emeraldine salt with yield as high as 71%.     

Comparative study of 2‐amino and 3‐aminobenzoic acid copolymerization with aniline synthesis and copolymer properties

Polyanilines soluble in an aqueous basic medium were synthesised by copolymerization of aniline (ANI) with both 2 and 3‐aminobenzoic acids (ABA). Different composition copolymers were prepared by varying the ANI/ABA feed ratio. Poly(aniline‐co‐2‐aminobenzoic acid) (PANI2ABA) and poly(aniline‐co‐3‐aminobenzoic acid) (PANI3ABA) displayed differences in their properties, such as specific charge and fluorescence behavior because the reactivity of 2‐aminobenzoic (2ABA) and 3‐aminobenzoic (3ABA) acids are very different. The new materials were characterized by X‐ray photoelectron, Fourier transform infrared, and Raman spectroscopies. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5587–5599, 2004     

Polyaniline doped with poly(acrylamidomethylpropanesulphonic acid): electrochemical behaviour and conductive properties in neutral solutions

Poly(2-acrylamido-2-methyl-1-propanesulphonic acid) (PAMPSA)-doped polyaniline (PANI) layers are synthesised in the presence of sulphuric and perchloric acids. The effects of the inorganic acid as well as of the electrochemical synthetic procedure (potentiostatic and potentiodynamic deposition) and thickness of the polymer layers are studied. The focus is directed towards the pH dependence of the electrochemical redox activity and conductivity of the PAMPSA-doped PANI layers obtained under different conditions. Ascorbic acid oxidation is used as a test reaction to study the electrocatalytic behaviour of various PAMPSA-doped PANI layers in neutral solution. It is found that the type of inorganic component present in the polymerisation solution has a marked effect on the extent of doping in acidic solutions as well as on the redox electroactivity in neutral solutions. A comparison between potentiostatically and potentiodynamically synthesised layers at pH 7 shows a markedly lower conductance and lower extent of redox charge preservation in the case of potentiodynamic synthesis. The PANI electrocatalytic activity for ascorbic acid oxidation is also dependent on the polymer electrodeposition procedure, with potentiostatically synthesised layers exhibiting better electrocatalytic performance.     

一种水中可溶性导电聚苯胺的制备与表征

分别以聚乙二醇(PEG)的水、乙醇溶液为反应媒介, 制备了Keggin结构杂多酸(H₄SiW₁₂O₄₀)掺杂的导电聚苯胺材料. 此聚苯胺经IR, XRD, UV-Vis光谱进行了表征, 并采用标准的四探针法对其电导率进行了测定. 同时系统地研究了杂多酸、氧化剂和单体的比例、反应混合体系温度的改变等对所合成聚苯胺的产率、导电率、水中溶解性等方面的影响. 结果表明, 在PEG乙醇溶液中制备的聚苯胺比在水溶液中制备的有较高的产率、电导率和溶解率. 其最高电导率可达到1.87 S/cm, 溶解率可达53%.     

溶剂散逸自组装法制备具有电致收缩性能的聚苯胺/聚氨酯凹透镜阵列

以水珠为模板,采用溶剂散逸自组装法制备了表面具有特殊形貌的有序多孔膜. 以此多孔膜为模板制备了聚苯胺/聚氨酯（PANI/PU）的凹透镜阵列. 采用红外光谱（FTIR）和扫描电子显微镜（SEM）对界面聚合得到的PANI/PU纳米复合物的结构和凹透镜阵列的形貌进行了表征,研究了不同合成条件对纳米复合物导电性能的影响,并对PANI/PU凹透镜阵列的电学和光学性能进行了研究. 结果表明,PANI/PU凹透镜阵列同时具有导电性、电致收缩性和光衍射性质;其收缩率与外加电压成反比,而透光率与收缩率成正比.     

Reduction of silver nitrate by polyaniline nanotubes to produce silver-polyaniline composites

Polyaniline (PANI) nanotubes were prepared by oxidation of aniline in 0.4 M acetic acid. They were subsequently used as a reductant of silver nitrate in 1 M nitric acid, water or 1 M ammonium hydroxide at various molar ratios of silver nitrate to PANI. The resulting PANI-silver composites contained silver nanoparticles of 40–60 nm size along with macroscopic silver flakes. Under these experimental conditions, silver was always produced outside the PANI nanotubes. Changes in the molecular structure of PANI were analyzed by FTIR spectroscopy. Silver content in the composites was determined as a residue by thermogravimetric analysis, and confirmed by density measurements. The highest conductivity of a composite, 68.5 S cm⁻¹, was obtained at the nitrate to PANI molar ratio of 0.67 in water. Also, the best reaction yield was obtained in water. Reductions performed in an acidic medium gave products with conductivity of 10⁻⁴–10⁻² S cm⁻¹, whereas the reaction in alkaline solution yielded non-conducting products.     

Theoretical study of the influence of monomer excess on the structure and properties of polyaniline oligomers

Polyaniline is among the most intensely investigated polymers because of its exceptional properties affording its current and potential applications. The structure and energy spectra of isolated oligomers and infinite chains in different oxidation states and degrees of protonation have been discussed at length from experimental and theoretical perspectives. The reaction environment effect, however, has received less attention and, particularly, the influence of monomer excess has been completely neglected in theoretical studies. Experimental measurements show that residual aniline is always detected in emeraldine samples obtained at low pH. Upon addition of oxidant to emeraldine PANI samples, post-polymerization due to the presence of excess monomers occurs. This is an indication of the formation of aniline-PANI complexes in the reaction medium. The presence of aniline monomers should affect the PANI chain arrangement and optical/conducting characteristics. Therefore, model clusters of aniline with neutral or singly protonated emeraldine tetramers in explicit water medium and periodic boundary conditions are addressed in this paper using a Monte Carlo/AMBER96/AM1 computational protocol to simulate the absorption spectra. The monomer impact on the structure, energy characteristics, and UV/vis spectra of the polymer are discussed.     

Characterization of stainless steel electrode modified by a thin film of polyaniline containing pt particles and its electrocatalytic activity for methanol oxidation

The catalytic behavior of stainless steel (SS) electrode modified by a thin film of polyaniline (PANI) containing platinum particles was studied for electrooxidation of methanol and compared with a platinated Pt/PANI electrode in acidic aqueous solution. Cyclic voltammetry (CV), chronoamperometry, CO stripping techniques were used to investigate electrochemical properties and electrocatalytic activity of SS/PANI/Pt and Pt/PANI/Pt electrodes. The morphology and particle size of Pt catalysts were characterized by Transmission Electron Microscopy (TEM) measurement. The effects of various parameters such as thickness of polymer film, medium temperature and stability of the modified electrodes on methanol oxidation were also investigated. The results indicated that the modified SS electrode exhibited a considerably high electrocatalytic activity on the methanol oxidation as well as the modified Pt electrode.     

Poly(tetrafluoroethylene) composite membranes coated with urchin-like polyaniline hiberarchy: Preparation and properties

Spiny polyaniline (PANI) spheres (urchin-like) were coated on a poly(tetrafluoroethylene) (PTFE) membrane via a counter-diffuse interfacial oxidation polymerization of aniline in an aqueous medium. The produced composite membrane has both unexpected superhydrophilicity and conductivity. The microstructure and morphology of the composite membrane were characterized by FTIR, UV-vis, XRD, TGA, and SEM. Effects of reagent concentrations and polymerization time on the membrane morphology and properties were studied systematically. A possible formation mechanism of the urchin-like polyaniline nanospheres on PTFE surface has been briefly discussed. The co-effect of both spherical micelles formed by Nafion and nanofibrous micelles formed by aniline/p-toluenesulfonic acid was considered to be a reason to produce the urchin-like PANI nanospheres. The PTFE/Nafion/PANI composite membrane showed a convertible hydrophilic/hydrophobic feature via adjusting acidity/alkalinity of an aqueous medium and also was able to adsorb heavy metal-ions from the medium.     

Composite layers consisting of polyaniline and poly(o-phenylenediamine): Electrochemical deposition, electrochromic and electrocatalytic properties

The composite polymer layers consisting of polyaniline (PANI) and poly(o-phenylenediamine) (poly(o-PDA)) were electrodeposited on a platinum electrode by simultaneous electrochemical oxidation of corresponding monomers from aquaeous hydrochloric solutions. The growth of PANI and poly(o-PDA) occurs separately resulting in layers with two distinct, finely distributed phases. The first deposited layers are composed mainly of poly(o-PDA) and become richer in PANI as the electropolymerization proceeds. The aniline/o-PDA copolymer was not formed during electrodeposition, as evidenced by cyclic voltammetry and Fourier-transformed IR spectroscopy. It was demonstrated that the electrochromic properties of resulting composite layers are the combination of yellow/brown-reddish and green/dark blue observable color transitions which are characteristics of poly(o-PDA) and PANI, respectively. Electrocatalytic properties of the electrosynthesized composite layers were investigated on quinone/hydroquinone (Q/H₂Q) redox system and it was shown that the composite layers increase the heterogeneous electron transfer rate with a magnitudes ranging from those obtained on pure poly(o-PDA) to those obtained on pure PANI layer.     

Making the liquid-phase catalytic hydrodechlorination of pce over Pd/C safer

Summary The hydrodechlorination of tetrachloroethylene in methanol (MeOH) over palladium catalysts on activated carbon (Pd/C) at 20°C and atmospheric pressure was rendered safer by using ethanol (EtOH), isopropanol (IPA) or water-alcohol mixtures as solvents. Adding water to MeOH was better than using EtOH or IPA since it resulted in a faster reaction and better stability of Pd/C, which could also be completely reactivated.     

苯胺在聚丙烯酰胺水、乙二醇溶液中的聚合研究

以聚丙烯酰胺为反应基质,分别在聚丙烯酰胺的水、乙二醇溶液中制备了掺杂态导电聚苯胺.探索了合成可溶性导电聚苯胺的最佳条件.采用红外、紫外可见光谱、X射线粉末衍射等手段对产品进行了表征.实验结果表明,在保持聚苯胺电导率基本不变的情况下,采用在聚丙烯酰胺的乙二醇溶液中制备的聚苯胺比水溶液中制备的聚苯胺有较好的溶解率.     

Influence of ethanol on the chain-ordering of carbonised polyaniline

Polyaniline (PANI) was prepared by the oxidation of aniline hydrochloride with ammonium peroxydisulphate in water or in a water-ethanol mixture. In the presence of ethanol, PANI nanotubes and nanorods were observed. Both products were carbonised in a nitrogen atmosphere at 650°C. Initial and carbonised products were characterised by scanning and transmission electron microscopies, thermogravimetric analysis and wide-angle X-ray scattering. Their molecular structure was studied by UV-VIS, infrared, and Raman spectroscopies. Carbonised sample obtained from the PANI salt prepared in the presence of ethanol exhibits Raman spectrum which corresponds to a more ordered carbon-like material than carbonised samples obtained from the PANI base and the PANI salt prepared in pure water. The influence of ethanol present in the reaction mixture on the molecular and supra-molecular structure of PANI and, consequently, on the enhancement of chainordering of carbonised PANI is discussed.     

聚苯胺/二氧化钛复合薄膜的制备及其气敏性能

室温条件下, 运用静电力自组装和原位化学氧化聚合相结合的方法制备了聚苯胺/纳米二氧化钛(PANI/TiO2)复合薄膜和聚苯胺(PANI)薄膜, 并通过XPS和SEM对薄膜进行了分析表征. 采用平面叉指电极式器件制备了PANI/TiO2复合薄膜和PANI薄膜气体传感器, 研究了其在常温下对有毒气体NH3和CO 的敏感性能. 结果表明, PANI/TiO2复合薄膜较PANI薄膜具有更优的灵敏度和响应恢复特性.     

Grafting of poly(ethylene oxide) to the surface of polyaniline films through a chlorosulfonation method and the biocompatibility of the modified films

Poly(ethylene oxide) (PEO) could be grafted on the surface of polyaniline (PANI) films by chlorosulfonating the films with chlorosulfonic acid followed by reacting the modified films with PEO in a pyridine solution. The modified PANI films were examined by X-ray photoelectron spectroscopy and water droplet contact angles. The surface of the PEO grafted to hydrophobic PANI films became hydrophilic and the amounts of bovine serum albumin and human blood plasma platelet adsorbed onto it were decreased by more than 80%. For comparison purposes, and because the water wetting angle can be used as a measure of biocompatibility, wetting angle experiments have been also carried out for Pluronic triblock copolymer grafted to PANI and PEO or Pluronic molecules entrapped on the surfaces of PANI films. PANI was selected as substrate because one can easily change its surface properties by PEO grafting and because being conductive can be used as a sensor.