Syntheses of fully sulfonated polyaniline nano-networks and its application to the direct electrochemistry of cytochrome c

Fully sulfonated polyaniline nano-particles, nano-fibrils and nano-networks have been achieved for the first time by electrochemical homopolymerization of orthanilic acid using a three-step electrochemical deposition procedure in a mixed solvent of acetonitrile (ACN) and water. The diameter of the uniform nano-particles is about 60nm, and the nano-fibrils can be organized in two-dimensional (21)) or three-dimensional (313) non-periodic networks with good electrical contact. Average distance between contacts is about 850 and 600 nm for a 2D and 3D system, respectively. The details of the poly(orthanilic acid) (POA) nano-structure were examined with a field emission scanning electron microscope (SEM). The structure and properties of POA were characterized with FTIR, UV-vis and electrochemical methods. The 3D POA nano-networks coated platinum electrode gave a direct electrochemical behavior of horse heart cytochrome c (Cyt c) immobilized on this electrode surface, a pair of well-defined redox waves with formal potential (E-ol) of -0.032 V (versus Ag/AgCl) was achieved. The interaction between Cyt c and POA makes the formal potential shift negatively compared to that of Cyt c in solution. Spectrophotometric and electrochemical methods were used to investigate the interaction of Cyt c with POA.

Controlled synthesis of 2D Au nanostructure assembly with the assistance of sulfonated polyaniline nanotubes

A wet chemical approach is used successfully to produce nanostructured Au material by the reduction of sulfonated polyaniline (SPANI) nanotubes. The Au nanostructures obtained are composed of single crystal Au nanoplates, which are aggregated layer-by-layer into stacks or edge-on-face into clusters at various conditions. The Au nanoplate diameter and thickness can be conveniently controlled in the range of 100 nm to 2 mu m and 10 to 30 nm, respectively, with no accompanying single Au nanoparticles being observed. The formation of the Au nanostructures was controlled by the degradation of SPANI. The gradually and slowly released segments of SPANI served as the reductant during the growth of the 2D Au nanostructures.

Mercaptoethane sulfonate protected, water-soluble gold and silver nanoparticles: Syntheses, characterization and their building, multilayer films with polyaniline via ion-dipole interactions

Mercaptoethane sulfonate protected, water-soluble gold and silver nanoparticles (Au-MES and Ag-MES) are synthesized by one-phase method and characterized by TEM, TGA and XPS techniques, UV-vis and FTIR spectra. Both Au-MES and Ag-MES nanoparticles are soluble in the water up to 2.0 mg/ml and the stability of AU-MES is much better than that of Ag-MES. When dissolved in the water. they behave like a polyanion and can be used to build multilayer films with polyaniline (PANI) by way of layer-by-layer. A new approach is presented to fabricate the Multilayer films of Au-MES/PANI and Ag-MES/PAN]. The assembly mechanism of these multilayer films is also discussed. We anticipate highly conducting PANI films can be obtained by doping with these nanoparticles.

Preparation of magnetic and conductive NiZn ferrite-polyaniline nanocomposites with core-shell structure

Magnetic and conductive NiZn ferrite-polyaniline nanocomposites with novel core-shell structure have been fabricated by microemulsion process. The samples were characterized by XRD, TEM, SEM, IR, UV-vis, voltage/current detector and SQUID magnetometry. The core-shell structure of nanocomposites was observed by TEM. The changes of the magnetic and conductive properties after polyaniline coating were investigated.

Mechanism and life study on polyaniline anti-corrosion coating

Solvent free polyaniline emeraldine base(EB) corrosion protection coating was prepared, employing aliphatic polyamine as solvent of EB as well as hardener of epoxy resin. This coating passed 2000h of salt fog test when the EB loading was about 1 wt%. The interaction between EB and iron indicated that EB acted as a "quasi-catalyst" to cause the formation of densed iron oxide film in the interface.

Confining conducting polyaniline in a stable inorganic network

Water soluble conducting polyaniline with electrical conductivity of 10(-1)-10(-2) S/cm was prepared employing dopant induced water solubility technology. The water resistance of the conducting film was significantly improved employing,sol-gel hybrids method, especially when the conductive polyaniline loading was below 30 wt%. The reason for the improvement is that the conducting polyaniline chains are confined in a stable inorganic network.

Conductive hybrids from water-borne conductive polyaniline and (3-glycidoxypropyl)trimethoxysilane

Free-standing conductive films of organic-inorganic hybrids were prepared employing the sol-gel process of (3-glycidoxypropyl)trimethoxysilane (GPTMS) and water-borne conductive polyaniline (cPANI) in water/ethanol solution. The hybrids displayed a percolation threshold for electrical conductivity at a volume fraction of 2.1% polyaniline (PANI); the maximum conductivity of the hybrids reached 0.6 S/cm. GPTMS showed good compatibility with water-borne cPANI during the sol-gel process, and freestanding conductive films were obtained at room temperature. Transmission electron microscopy images of the hybrids indicated that the cPANI was dispersed in the inorganic phase in nanoscale. Because of good confinement of cPANI chains in the inorganic network, water resistance of the hybrid films was significantly improved compared with that of pure cPANI; the electrical conductivity of the films kept stable for 6-7 days soaking in water, whereas it decreased sharply for 1 day soaking for the pure cPANI.

Surface plasmon resonance studies on the electrochemical doping/dedoping processes of anions on polyaniline-modified electrode

The combination of in situ surface plasmon resonance (SPR) with electrochemistry was used to investigate the electrochemical doping/dedoping processes of anions on a polyaniline (PAn)-modified electrode. Electrochemical SPR characteristics of the PAn film before and after doping/dedoping were revealed. The redox transformation between the insulating leucoemeraldine, and the conductive emeraldine, corresponding to the doping/dedoping of anion, can lead to very distinct changes in both the resonance minimum angle and the shape of SPR curve. This is ascribed to the swelling/shrinking effect, and the change of the PAn film in the imaginary part of the dielectric constant resulted from the transition of the film conductivity. In situ recording the time evolution of reflectance change at a fixed angle permits the continuous monitoring of the kinetic processes of doping/dedoping anions. The size and the charge of anions, the film thickness, as well as the concentration of anions are shown to strongly influence the rate of ingress/egress of anions. The time differential of SPR kinetic curves can be well applied in the detecting electroinactive anion by flow injection analysis. The approach has higher sensitivity and reproducibility compared with other kinetic measurements, such as those obtained by amperometry.

Morphology and thermal properties of conductive polyaniline/polyamide composite films

Polyaniline (PANI) in an emeraldine-base form, synthesized by chemical oxidation polymerization, was doped with camphor sulfonic acid (CSA). The conducting complex (PANI-CSA) and a matrix, polyamide-66, polyamide-11, or polyamide-1010, were dissolved in a mixed solvent, and the blend solution was dropped onto glass and dried for the preparation of PANI/polyamide composite films. The conductivity of the films ranged from 10(-7) to 10(0) S/cm when the weight fraction of PANI-CSA in the matrices changed from 0.01 to 0.09, and the percolation threshold was about 2 wt %. The morphology of the composite films before and after etching was studied with scanning electron microscopy, and the thermal properties of the composite films were monitored with differential scanning calorimetry. The results indicated that the morphology of the blend systems was in a globular form. The addition of PANI-CSA to the films resulted in a decrease in the melting temperature of the composite films and also affected the crystallinity of the blend systems.

The nature of the interaction between polyaniline and 2,5-dimercapto-1,3,4-thiadiazole in electrochemical redox processes

The interaction between polyaniline (PAn) and 2,5-dimercapto-1,3,4-thiadiazole (DMcT) was investigated by means of cyclic voltammetry and UV-visible spectroscopy. The results show that the polymerization-depolymerization reaction of DMcT or its dilithium salt Li(2)DMcT is a kinetically quasi-reversible process. PAn exhibits very weak electrochemical activity in neutral propylene carbonate. After doping with protonic acid, such as hydrochloric acid or maleic acid etc., however, it shows an extensively enhanced electroactivity. For the complex system, PAn-DMcT or PAn-Li(2)DMcT, polyaniline has no catalytic activity for the electrochemical polymerization-depolymerization reaction of DMcT or DMcT(2-). Instead, the enhancement of the electrochemical redox activity of PAn-DMcT system compared with that of PAn, DMcT, Li(2)DMcT, and PAn-Li(2)DMcT comes from the protonic doping of PAn by DMcT.

Preparation and properties of conductive polyaniline/poly-omega-aminoundecanoyle fibers

Historically, polyaniline (PANI) had been considered an intractable material, but it can be dissolved in some solvents. Therefore, it could be processed into films or fibers. A process of preparing a blend of conductive fibers of PANI/poly-omega-aminoun-decanoyle (PA11) is described in this paper. PANI in the emeraldine base was blended with PA11 in concentrated sulfuric acid (c-H,SO,) to form a spinning dope solution. This solution was used to spin conductive PANI/PA11 fibers by wet-spinning technology. As-spun fibers were obtained by spinning the dopes into coagulation bath water or diluted acid and drawn fibers were obtained by drawing the as-spun fibers in warm drawing bath water. A scanning electron microscope was employed to study the effect of the acid concentration in the coagulation bath on the microstructure of as-spun fibers. The results showed that the coagulating rate of as-spun fibers was reduced and the size of pore shrank with an increase in the acid concentration in the coagulation bath. The weight fraction of PANI in the dope solution also had an influence on the microstructure of as-spun fibers. The microstructure of as-spun fibers had an influence on the drawing process and on the mechanical properties of the drawn fibers. Meanwhile, the electrically conductive property of the drawn fibers with different percentage of PANI was measured.

Morphological study on water-borne conducting polyaniline-poly(ethylene oxide) blends

Conducting polyaniline-poly(ethylene oxide) blends were prepared from their aqueous solutions. The blends displayed an electrical conductivity percolation threshold as low as 1.83 wt % of polyaniline loading. As demonstrated by scanning electron microscopy, polarized optical microscopy, and wide-angle X-ray diffraction studies, the conducting polyaniline took a fibrillar morphology in the blend, and it existed only in the amorphous phase of poly(ethylene oxide). A three-phase model combining morphological factors instead of a two-phase model was proposed to explain the low-conductivity percolation threshold.

Conducting polyaniline confined in semi-interpenetrating networks

Communication: Conducting semi-interpenetrating network composites with low conductivity percolation threshold were synthesized from waterborne conducting polyaniline (cPAn) and melamine-urea resin, A perfect network of cPAn in the composite was observed by means of TEM (see Figure). The conductivity stability of cPAn in water was improved by confining the chain mobility of cPAn via in-situ crosslinking of melamine-urea resin. Cyclic voltammetry of the composites reveals electrochemical activities and reversibilities similarly to those of pure cPAn.

Analysis of monodispersed polyaniline oligomers by matrix-assisted laser desorption ionization mass spectrometry

Monodispersed polyaniline oligomers was studied by matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF-MS), It is found that MALDI-TOF-MS is not only a direct, accurate and rapid tool for the analysis of monodispersed polyaniline oligomers, but also a useful technique for the design of synthetic route.

Preparation and properties of conducting polymer of doped polyaniline LB film

Stable monolayer of polyaniline doped with camphor sulfonic acid at the air-water interface has been obtained and has been successfully deposited by Langmuir-Blodgett technique onto CaF2 substrate. IR and UV-Vis-NIR spectra show that the doped molecules dedoped partially from the PANI backbone during the monolayer compression or deposition. Gas-sensing measurement indicates that the doped polyaniline LB film was sensitive to ethanol vapor at room temperature.