Preparation, structures, and electrochemistry of a new polyoxometalate-based organic/inorganic film on carbon surfaces

The preparation, structure, and electrochemical and electrocatalytical properties of a new polyoxometalate-based organic/inorganic film, composed of cetyl pyridinum 11-molybdovanadoarsenate (CPMVA) molecules, have been studied. Cyclic potential scanning in acetone solution led to a stable CPMVA film formed on a highly oriented pyrolytic graphite (HOPG) surface. X-ray photoelectron spectroscopy, scanning tunneling microscopy, and cyclic voltammetry were used for characterizing the structure and properties of the CPMVA film. These studies indicated that self-aggregated clusters were formed on a freshly cleaved HOPG surface, while a self-organized monolayer was formed on the precathodized HOPG electrode. The CPMVA film exhibited reversible redox kinetics both in acidic aqueous and in acetone solution, which showed that it could be used as a catalyst even in organic phase. The CPMVA film remained stable even at pH > 7.0, and the pH dependence of the film was much smaller than that of its inorganic film (H4AsMo11VO40) in aqueous solution. The CPMVA film showed strong electrocatalysis on the reduction of bromate, and the catalytic currents were proportional to the square of the concentration of bromate. The new kind of polyoxometalate with good stability may have extensive promise in catalysis.

The synthesis of phenyl-capped trianiline and teraaniline by a modified-pseudo-high dilution technique and their UV-Vis spectral studies

Phenyl-capped trianiline and tetraaniline in the leucoemeraldine oxidation state were synthesized through a modified-pseudo-high-dilution technique. The chemical oxidation process of these compounds were studied by UV-Vis spectra. It was found that phenyl-capped trianiline in the leucoemeraldine oxidation state was oxidized to its EB form and then decomposed, Phenyl-capped tetraaniline was oxidized to its EB form and then to the pernigraniline oxidation state.

Morphology, thermal behavior, and mechanical properties of PA6/UHMWPE blends with HDPE-g-MAH as a compatibilizing agent

A functionalized high-density polyethylene (HDPE) with maleic anhydride (MAH) was prepared using a reactive extruding method. This copolymer was used as a compatibilizer of blends of polyamide 6 (PA6) and ultrahigh molecular weight polyethylene (UHMWPE). Morphologies were examined by a scanning electron microscope. It was found that the dimension of UHMWPE and HDPE domains in the PA6 matrix decreased dramatically, compared with that of the uncompatibilized blending system. The size of the UHMWPE domains was reduced from 35 mu m (PA6/UHMWPE, 80/20) to less than 4 mu m (PA6/UHMWPE/HDPE-g-MAH, 80/20/20). The tensile strength and Izod impact strength of PA6/UHMWPE/HDPE-g-MAH (80/20/20) were 1.5 and 1.6 times as high as those of PA6/UHMWPE: (80/20), respectively. This behavior could be attributed to chemical reactions between the anhydride groups of HDPE-g-MAH and the terminal amino groups of PA6 in PA6/UHMWPE/HDPE-g-MAH blends. Thermal analysis was performed to confirm that the above chemical reactions took place during the blending process. (C) 2000 John Wiley & Sons, Inc.

Voltammetric study of the sodium ion transfer across micro-water/1,2-dichloroethane interface facilitated by terminal-vinyl liquid crystal crown ether

Sodium ion transfer across micro-water/1,2-dichloroethane (DCE) interface facilitated by a novel ionophore, terminal-vinyl liquid crystal crown ether (LCCE) was studied by cyclic voltammetry. LCCEs have potential applications because of their physicochemical properties and the utilization of crown ethers as selective ionophoric units in other functionalized compounds are interesting. Host-guest-type behavior for such compounds in the liquid-crystalline state is studied. The experimental results suggest that the transfer of the sodium ion facilitated by LCCE was controlled by diffusion of LCCE from bulk solution of DCE to the interface. The diffusion coefficient of LCCE in DCE was calculated to be equal to (3.62 +/- 0.20) x 10(-6) cm(2)/s. Steady-state voltammograms are due to sodium ion transfer facilitated by the formation of 1: 1 metal (M)-LCCE complex at the interface and the mechanism tends to be transfer by interfacial complexation or dissociation (TIC or TID). The stability constant of the complex formed was determined to be log beta(o) = 5.5 in DCE phase. The influence of parameters such as concentration of sodium ion and concentration of LCCE on the sodium ion transfer was investigated.

Poly(phenylene sulfide-tetraaniline): The soluble conducting polyaniline analogue with well-defined structures

A novel conducting polymer poly(phenylene sulfide-tetraaniline) (PPSTEA), with tetraaniline (TA) and phenylene sulfide (PS) segments in its repeat unit, has been synthesized through an acid-induced polycondensation reaction of 4-methylsulfinylphenyl-capped tetraaniline. The new polymer, which represents the first soluble conducting polyaniline analogue with well-defined structure, has high molecular weight, good solubility in common solvents, and good film-forming properties. Its electrical property is analogous to polyaniline. The conductivity of preliminarily, protonic-doping PPSTEA is up to 10 degrees S/cm. This synthetic strategy appears to be general for developing novel well-defined polyaniline analogue containing much longer fixed conjugation length.

Multilayer assemblies of tungstodiphosphate anions on 1,7-diaminoheptane modified glassy carbon electrode and the electrocatalytic reduction to iodate

1,7-Diaminoheptane (DAH) had been covalently grafted on glassy carbon electrode by amino cation radical formation, which resulted in a stable cationic monolayer under proper pH conditions. Dawson-type tungstodiphosphate anion, P2W18O626- and small molecule, Ru(NH3)(6)(3+) were alternately assembled on the DAH modified electrode through layer-by-layer electrostatic interaction. Thus-prepared multilayer film had been characterized by cyclic voltammetry and X-ray photoelectron spectroscopy. The P2W18O626- multilayers exhibit high electrocatalytic response and sensitivity towards the reduction of iodate. With the increase of the number of P2W18O626- the catalytic current was enhanced and the catalytic potential shifted positively. Iodate in table salt was determined at the modified electrode containing three layers of P2W18O626- with satisfactory results. The multilayer electrode is promising as an electrochemical sensor for the detection of trace iodate.

Synthesis of poly(ether ether ketone)s with high content of sodium sulfonate groups as gas dehumidification membrane materials

Sodium sulfonate-functionalized polyether ether ketone)s derived from Bisphenol A with a degree of sulfonation up to 2.0 were synthesized by aromatic nucleophilic polycondensation of various amounts of 5,5-carbonylbis(2-fluorobenzenesulfonate) (1), 4,4'-diflurobenzophenone (2) and Bisphenol A (2). Copolymers showed excellent thermal stability and good mechanical properties. The selectivity of water vapor over nitrogen of membranes prepared from copolymers 3a and 3h was determined to be 3.43 x 10(6) and 1.05 x 10(7), respectively.

Electrochemical behavior of heteropoly acid anions adsorbed in electrodes modified with mesoporous molecular sieve silica

Heteropoly acid H4SiW12O48 (denoted as SiW12) was assembled with the mesoporous materials MCM-41 modified with 3-aminopropyltriethoxysilane (APTES) (denote MCM-41((m))). The electrochemical behavior of SiW12/MCM-41((m)) complexes-based electrode indicated SiW12 anion was adsorbed by MCM-41((m)). In MCM-41((m)) electrode, large voltammetric waves, showing that the electrostatic bound ions adsorbed in MCM-41((m)) were electrochemically active. The potential application as amperometric sensors for nitrite is anticipated.

Synthesis of monodisperse pheyl-capped oligoaniline pentamer and hexamer in the leucoemeraldine oxidation state and EB state and its UV studies

Aniline pentamer and hexamer in the leucoemeraldine oxidation state were synthesized through a novel method. The method was accomplished by the reaction of parent aniline tetramer in the pernigraniline oxidation state with diphenylamine and N-phenyl-1,4-phenylenediamine in the leucoemeraldine oxidation state respectively. The oligomers in the leucoemeraldine oxidation state were characterized by IR, NMR, elemental analysis and MALDI-MS. Aniline pentamer and hexamer in the emeraldine oxidation state were synthesized by the oxidation of Ag2O in DMF. It was found that some fragmentation occurred when the pentamer and hexamer were oxidized by (NH4)(2)S2O8 and FeCl3. 6H(2)O. The pentamer and hexamer in the emeraldine oxidation state was studied by UV/Vis spectra. The relative intensity of exciton peak for pentaaniline showed a little increase compared with that of hexaaniline.

Cobalt(II)hexacyanoferrate film modified glassy carbon electrode for construction of a glucose biosensor

An amperometric glucose biosensor was constructed based on a glassy carbon electrode modified with a Cobalt(II)hexacyanoferrate film which catalyzes electroreduction of hydrogen peroxide. Gelatin was used as immobilization matrix. Interference could be effectively eliminated by the combination of low detection potential with a Nafion coating. A low applied potential can avoid oxidation of interferences such as ascorbic acid, uric acid, p-acetyl-aminophenol, etc.. Nafion coating prevents interferences from access to the electrode surface by electrostatic repulsion. A wide linear range of detection was obtained. Analytical performance parameters are given and kinetic analysis discussed.

Facile synthesis of phenyl-capped oligoanilines using pseudo-high dilution technique

Monodispersed phenyl-capped trianiline and tetraaniline were successfully synthesized by the reactions of diphenylamine with acetaldehyde-based Sckiff's bases of N-phenyl-1,4-phenylenediamine and 1,4-phenylenediamine, respectively, in the presence of ammonium persulfate and hydrochloric acid, subsequent deprotonation and reduction with phenylhydrazine. The reaction mechanism probably involves the slow hydrolysis of the Sckiff's bases and subsequent oxidative coupling reactions of the formed ammonium salts with diphenylamine at pseudo-high dilution condition of the salts.

Electrochemical preparation and characterization of silicotungstic heteropolyanion monolayer electrostatically linked aminophenyl on carbon electrode surface

In this paper, an organic-inorganic composite film of heteropolyanion was Formed by attaching a Keggin-type heteropolyanion, SiW12O404-, on carbon electrode surface derivatized by 4-aminophenyl monolayer. The composite film thus grafted on carbon electrode surface has good stability because of the ionic bonding character between SiW12O404- and surface aminophenyl groups. X-ray photoelectron spectroscopy, scanning tunneling microscopy, and cyclic voltammetry were used to characterize the composite film. Compared with SiW12O404- electrodeposited on a bare glassy carbon electrode (GCE), the composite film gives three more sharp and well-defined redox couples attributed to two one- and two-electron processes, and the analyses of the voltammograms of SiW12O404- anion in the composite film modified on GCE shows that its surface coverage is close to a closest packing monolayer. STM characterization shows that a two-dimensional order heteropolyanion monolayer was formed on HOPG substrate. The composite film provides a favorable environment for electron and proton transfer between SiW12O404- ion and electrode surface, which may make it suitable for various applications in sensors and microelectronics devices.

Processible nanostructured materials with electrical conductivity and magnetic susceptibility: Preparation and properties of maghemite polyaniline nanocomposite films

We here present a versatile process for the preparation of maghemite/polyaniline (gamma-Fe2O3/ PAn) nanocomposite films with macroscopic processibility, electrical conductivity, and magnetic susceptibility. The gamma-Fe2O3 nanoparticles are coated and the PAn chains are doped by anionic surfactants of omega-methoxypoly(ethylene glycol) phosphate (PEOPA), 4-dodecylbenzenesulfonic acid (DBSA), and 10-camphorsulfonic acid (CSA). Both the coated gamma-Fe2O3 and the doped PAn are soluble in common organic solvents, and casting of the homogeneous solutions gives free-standing nanocomposite films with gamma-Fe2O3 contents up to similar to 50 wt %. The morphology of the gamma-Fe2O3 nanoparticles are characterized by transmission electron microscopy, UV-vis spectroscopy, and X-ray diffractometry. The gamma-Fe2O3/PAn films prepared from chloroform/m-cresol solutions of DBSA-coated gamma-Fe2O3 and CSA-doped PAn are conductive (sigma = 82-237 S/cm) and superpapamagnetic, exhibiting no hysteresis at room temperature. The zero-field-cooled magnetization experiment reveals that the nanocomposite containing 20.8 wt % gamma-Fe2O3 has a blocking temperature (T-b) in the temperature region of 63-83 K.

Amperometric glucose biosensor based on sol-gel organic-inorganic hybrid material

A new type of sol-gel organic-inorganic hybrid material was developed and used for the production of biosensors. This material is composed of silica sol and a grafting copolymer of poly(vinyl alcohol) with 4-vinylpyridine. It prevents the cracking of conventional sol-gel-derived glasses and eliminates the swelling of the hydrogel. The optimum composition of the hybrid material was first examined, and then glucose oxidase was immobilized in this matrix to demonstrate its application. The characteristics of the biosensor were studied by cyclic voltammetry and chronoamperometry. The biosensor exhibited a series of good properties: high sensitivity (600 nA mmol(-1)L(-1)), short response time (11 s) and remarkable long-term stability in storage (at least 5 months). In addition, the characteristics of the second-generation biosensor with the use of tetrathiafulvalene as a mediator mere discussed.

Probe beam deflection study on electrochemically controlled release of 5-fluorouracil

In this paper, the polypyrrole (PPy) film modified electrodes are used as an electroreleasing reservoir. The electrochemically controlled release of 5-fluorouracil (5-FU) from a PPy film modified electrode to aqueous electrolytes is studied by the in situ probe beam deflection (PBD) method combined with cyclic voltammetry (CV) and chronoamperometry (CA). The PBD results reveal that the release of 5-FU from PPy film depends on the electrochemical redox process of the PPy film electrode. The released amount is controlled by the reduction potential and is proportional to the thickness of the film. The exchange of 5-FU anions with Cl- on an open circuit is slow on the time scale of minutes, but the release of 5-FU anions can proceed quickly at -0.6 V (vs Ag/AgCl). The amount of released 5-FU decreases with the time that the PPy film is soaked in aqueous solution. (C) 1998 Elsevier Science Ltd. All rights reserved.