Electrostatic assembly of polyaniline and platinum-poly(amidoamine) dendrimers hybrid nanocomposite multilayer, and its electrocatalysis towards CO and O-2

The electrostatic layer-by-layer assembly method was successfully used in a multilayer buildup of polyaniline (PANT) and platinum nanocrystals encapsulated in the carboxyl-terminated poly(amidoamine) dendrimers (generation 4.5 G4.5COOH) (Pt-G4.5COOH NPs) on solid substrates. Multilayer growth was monitored by ultraviolet-visible (UV-vis) absorption spectroscopy. The AFM observation revealed a molecularly smooth (PANI/Pt-G4.5COOH NPs) multilayer film which is rougher and thicker than the multilayer of PANT and G4.5COOH (G4.5COOH/PANI)(m). The PANI/Pt-G4.5COOH NPs multilayers show a fast surface-confined electron-exchange process at the Au electrode in an acid solution, and remains stable, reversible and electroactive, even in neutral solution. Furthermore, the multilayers show a strong elect rocatalytic response towards CO oxidation and O-2 reduction, and the catalytic capability can be easily tuned by the control of multilayer thickness.

Surface-modified Nafion (R) membrane by casting proton-conducting polyelectrolyte complexes for direct methanol fuel cells

Surface-modified Nafion (R) membrane was prepared by casting proton-conducting polyelectrolyte complexes on the surface of Nafion (R). The casting layer is homogeneous and its thickness is about 900 nm. The proton conductivity of modified Nafion (R) is slightly lower than that of plain Nafion (R); however, its methanol permeability is 41% lower than that of plain Nafion (R). The single cells with modified Nafion (R) exhibit higher open circuit voltage (OCV = 0.73 V) and maximal power density (P-max = 58 mW cm(-2)) than the single cells with plain Nafion (R) (OCV = 0.67 V, P x = 49 mW cm-2). It is a simple, efficient, cost-effective approach to modifying Nafion (R) by casting proton-conducting materials on the surface of Nafion (R).

Loosely packed self-assembled monolayer of N-hexadecyl-3,6-di(p-mercaptophenylacetylene)carbazole on gold and its application in biomimetic membrane research

Dithiols of N-hexadecyl-3,6-di(p-mercaptophenylacetylene)carbazole (HDMC) have been synthesized and employed to form self-assembled monolayers (SAMs) on gold. One characteristic of the HDMC molecule is its peculiar molecular structure consisting of a large and rigid headgroup and a small and flexible alkyl-chain tail. HDMC adsorbates can attach to gold substrates by a strong Au-S bond with weak van der Waals interactions between the alkyl-chain tails, leading to a loosely packed hydrophobic SAM. In this way we can couple hybrid bilayer membranes (HBMs) to gold surfaces with more likeness to a cell bilayer than the conventional HBMs based on densely packed long-chain alkanethiol SAMs. The insulating properties and stability of the HDMC monolayer as well as the HDMC/lipid bilayer on gold have been investigated by electrochemical techniques including cyclic voltammetry and impedance spectroscopy. To test whether the quality of the bilayer is sufficiently high for biomimetic research, we incorporated the pore-forming protein a-hemolysin) and the horseradish peroxidase into the bilayers, respectively.

Electrochemistry and electrogenerated chemiluminescence of SiO2 nanoparticles/tris(2,2 '-bipyridyl)ruthenium(II) multilayer films on indium tin oxide electrodes

In this paper, a simple method of preparing {SiO2/Ru-(bPY)(3)(2+)}(n) multilayer films was described. Positively charged tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) and negatively charged SiO2 nanoparticles were assembled on ITO electrodes by a layer-by-layer method. Electrochemical and electrogenerated chemiluminescence (ECL) behaviors of the {SiO2/Ru(bpy)(3)(2+)}(n) multilayer film-modified electrodes were studied. Cyclic voltammetry, UV-visible spectroscopy, quartz crystal microbalance, and ECL were adopted to monitor the regular growth of the multilayer films. The multilayer films containing Ru(bpy)(3)(2+) was used for ECL determination of TPA, and the sensitivity was more than 1 order of magnitude higher than that observed for previous reported immobilization methods for the determination of TPA. The multilayer films also showed better stability for one month at least. The high sensitivity and stability mainly resulted from the high surface area and special structure of the silica nanoparticles.

Nanocomposite multilayer film of preyssler-type polyoxometalates with fine tunable electrocatalytic activities

Through layer-by-layer (LBL) assembly technique, iron oxide (Fe3O4) nanoparticles coated by poly (diallyldimethylammonium chloride) (PDDA) and Preyssler-type polyoxometalates (NH4)(14)NaP5W30O110.31H(2)O (P5W30) were alternately deposited on quartz and ITO substrates, and 4-aminobenzoic acid modified glassy carbon electrodes. Thus-prepared multilayer films were characterized by UV-visible spectroscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry. It was proved that the multilayer films are uniform and stable. And the electrocatalytic activities of the multilayer films can be fine-tuned by adjusting the assembly conditions in the LBL assembly process, such as the pH of the assembly solution. The multilayer films fabricated from P5W30 solutions dissolved in 0.1 M H2SO4 exhibit high electrocatalytic response and sensitivity toward the reduction of two substrates of important analytical interests, HNO2 and IO3- whereas the films assembled with P5W30 solutions dissolved in 1.0 M H2SO4 show remarkable electrocatalytic activity for the hydrogen evolution reaction (HER). Furthermore, the electrocatalytic properties of the HER of the latter film can be obtained from the former film upon exposure to 1.0 M H2SO4 for several hours.

Electrochemical and electrogenerated chemiluminescence of clay nanoparticles/Ru(bpy)(3)(2+) multilayer films on ITO electrodes

The electrochemical and electrogenerated chemiluminescence of Ru(bpy)(3)(2+) immobilized in {clay/Ru(bpy)(3)(2+)}(n) multilayer films by layer-by-layer assembly were investigated. The stable multilayer films of clay and Ru(bpy)(3)(2+) were assembled by alternate adsorption of negatively charged clay platelets and positively charged Ru(bpy)(3)(2+) from their aqueous dispersions. UV-vis spectroscopy, quartz crystal microbalance (QCM), cyclic voltammetry, and electrogenerated chemiluminescence (ECL) were used to monitor the immobilization of Ru( bpy)(3)(2+) and the regular growth of the {clay/Ru( bpy)(3)(2+)}(n) multilayer films. The multilayer films modified electrode was used for the ECL detection of tripropylamine ( TPA) and oxalate. The proposed novel immobilized method exhibited good stability, reproducibility and high sensitivity for the determination of TPA and oxalate, which mainly resulted from the contributing of clay nanoparticles with appreciable surface area, special structural features and unusual intercalation properties.

Fabrication and characterization of DNA/QPVP-Os redox-active multilayer film

Calf thymus DNA was immobilized on functionalized glassy carbon, gold and quartz substrates, respectively, by the layer-by-layer (LBL) assembly method with a polycation QPVP-Os, a quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) as counterions. UV-visible absorption and surface plasmon resonance spectroscopy (SPR) showed that the resulting film was uniform with the average thickness 3.4 nm for one bilayer. Cyclic voltammetry (CV) showed that the total surface coverage of the polycations increases as each QPVP-Os/DNA bilayer added to the electrode surface, but the surface formal potential of Os-centered redox reaction shifts negatively, which is mainly attributed to the intercalation of redox-active complex to DNA chain. The electron transfer kinetics of electroactive QPVP-Os in the multilayer film was investigated by electrochemical impedance experiment for the first time. The permeability of Fe(CN)(6)(3-) in the solution into the multilayer film depends on the number of bilayers in the film. It is worth noting that when the multilayer film is up to 4 bilayers, the CV curves of the multilayer films display the typical characteristic of a microelectrode array.

Modeling of organic light-emitting diodes with graded concentration in the emissive multilayer

We model the electrical behavior of organic light-emitting diodes whose emissive multilayer is formed by blends of an electron transporting material, tris-(8-hydroxyquinoline) aluminum (Alq(3)) and a hole transporting material, N,N-'-diphenyl-N,N-'-bis(1,1(')-biphenyl)-4,4-diamine. The multilayer is composed of layers of different concentration. The Alq(3) concentration gradually decreases from the cathode to the anode. We demonstrate that these graded devices have higher efficiency and operate at lower applied voltages than devices whose emissive layer is made of nominally homogeneous blends. Our results show an important advantage of graded devices, namely, the low values of the recombination rate distribution near the cathode and the anode, so that electrode quenching is expected to be significantly suppressed in these devices.

Phenolphthalein immobilized membrane for an optical pH sensor

A phenolphthalein immobilized cellulose membrane for an optical pH sensor was described. The phenolphthalein was first reacted with the formaldehyde to produce a series of prepolymers with many hydroxymethyl groups. In this paper, the prepolymers was abbreviated to phenolphthalein-formaldehyde (PPF). Then the PPF was covalently immobilized to the diacetylcellulose membrane via hydroxymethyl groups. Finally the membrane was hydrolyzed in the 0.1 M NaOH solution for 24 h to reduce the response time. Advantageous features of the pH-sensitive membrane include (a) a large dynamic range from pH 8.0 to 12.50, or even broader, (b) rapid response time (2-30 s), (c) easy of fabrication, and (d) a promising material for determination of high pH values. The immobilized PPF has a broader dynamic range from 8.0 to 12.50 than the free phenolphthalein from pH 8.0 to 11.0, and this was due to the newly produced methylenes in our investigation.

Self-assembled multilayer films of europium-substituted polyoxometalate and their luminescence properties

A new kind of hybrid self-assembled film was obtained by means of alternating deposition of the polyoxometalate (POM), K-13[Eu(SiW11-O-39)(2)], and polyacrylamide (PAA) on the 3-aminopropylsilanized precursor film. The experimental results showed that the polyanions were successfully incorporated into the self-assembled multilayers of the polyacrylamide. The scanning electron microscopy (SEM) was taken to study the surface morphology of the film. The X-ray photoelectron spectra (XPS) verified that the polyoxometalates were incorporated into the multilayer films with a certain adsorption interaction. The effects of the polyacrylamide on the luminescence of the polyoxometalate were discussed in detail. The luminescence spectra showed that the energy was transferred from the ligands to the Eu3+ ions in the self-assembled films.

Extraction and separation of cadmium(II), iron(III), zinc(II), and europium(III) by Cyanex302 solutions using hollow fiber membrane modules

The mass transfer behaviors of Cd(II), Fe(III), Zn(II), and Eu(III) in sulfuric acid solution using microporous hollow fiber membrane (HFM) containing bis(2,4,4-trimethylpentyl)monothiophosphinic acid (commercial name Cyanex302) were investigated in this paper. The experimental results showed that the values of the mass transfer coefficients (K-w) decreased with an increase of H+ concentration and increased with an increase of extractant Cyanex302 concentration. The mass transfer resistance of Eu3+ was the largest because K-w value of Eu3+ was the smallest. The order of mass transfer rate of metal ions at low pH was Cd > Zn > Fe > Eu. Mixtures of Zn2+ and Eu3+ or of Zn2+ and Cd2+ were well separated in a counter-current circulation experiment using two modules connected in series at different initial acidity and concentration ratio. These results indicate that a hollow fiber membrane extractor is capable of separating the mixture compounds by controlling the acidity of the aqueous solution and by exploiting different mass transfer kinetics. The interfacial activity of Cyanex302 in sulfuric acid solution was measured and interfacial parameters were obtained according to Gibbs adsorption equation.

Stable multilayer films based on photoinduced interaction between polyoxometalates and diazo resin

Ultrathin multilayers films consisting of Keggin anion [PMo12O40](3-) and diazo resin were first prepared by the electrostatic layer-by-layer self-assembly method. This film material could be stabilized by the photoinduced interaction between Keggin anion and diazo resin. IR spectra and X-ray photoelectron spectra revealed the occurrence of the partial transformation from ionic bond to covalent bond between layers of the film under irradiation by UV light. Such transformation increases the stability of the film, which was demonstrated by AFM images and the etching experiments with organic solvent.

Synthesis and characterization of the nanoporous ultrathin multilayer films based on molybdenum polyoxometalate (Mo-36)(n)

Ultrathin multilayer films of the wheel-shaped molybdenum polyoxometalate cluster (Mo-36)(n) and poly(allylamine hydrochloride) (PAH) have been prepared by the layer-by-layer (LbL) self-assembly method. The ((Mo-36)(n)/PAH)(m) multilayer films have been characterized by Xray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). UV-VIS measurements reveal regular film growth with each (Mo-36)(n) adsorption. The electrochemical behavior of the film at room temperature was investigated.