Ultrathin multilayer films incorporating Keggin-type heteropolyanion clusters

Two new ultrathin multiplayer films have been successfully prepared fi-om Keggin-type heteropoly acids H-4[SiW12O40] and H-3[PMo12O40] with polyelectrolytes PEI, PSS, and PAH, using the electrostatic layer-by-layer self-assembly, technique. The XR results reveal their film thickness at nanoscale (similar to 20 nm). According to the AFM images, it is believed that the surface roughness (rough degree of film surface) of the polyelectrolyte-polyoxometalate film greatly depends on the kind of polyoxometalates.

Multilayer assembly of Mn-substituted Keggin-type [ZnW11O39Mn(H2O)](8-) on chemically modified glassy carbon electrode and its electrocatalytic properties

Through layer-by-layer assembly, undecatungstozincates monosubstituted by transition metals Mn, ZnW11 Mn (H2O) O-39(8-) was successfully immobilized on a glassy carbon electrode surface grafted covalently by 4-aminobenzoic acid. The electrochemical behavior of these polyoxometalates was investigated. Cyclic voltammetry proves the uniform growth of the film. They exhibit some special electrochemical properties in the films, different from those in homogeneous aqueous solution. The effect of pH on the redox behavior of ZnW11Mn(H2O)O-39(8-) in the film was discussed in detail. The multilayer film electrodes have an excellent electrocatalytic response to the reduction of H2O2 and BrO3-, and to the oxidation of ascorbic acid.

Simple preparation method of multilayer polymer films containing Pd nanoparticles

A simple route to the fabrication of multilayer films containing Pd nanoparticles is described. Following layer-by-layer assembly of PdCl42- and polycation, QPVP-Os (a quaternized poly(4-vinylpyridine) complexed with [Os(bpy)(2)Cl](2+/+)), on 4-aminobenzoic acid-modified glassy carbon electrodes, the three-dimensional Pd nanoparticle multilayer films are directly formed on electrode surfaces via electrochemical reduction of PdCl42- sandwiched between polymers. The growth of PdCl42- is easy on electrode surfaces by electrostatic interaction, and the assembly processes are monitored by cyclic voltammetry and UV-vis spectroscopy. The depth profile analyses by X-ray photoelectron spectroscopy verify the constant composition of the Pd nanoparticle multilayer films. Atomic force microscopy proves that the as-prepared Pd nanoparticles are uniformly distributed with an average particle diameter of 3-7 mn. The resulting Pd nanoparticle multilayer-modified electrode possesses high catalytic activity for the reduction of dissolved oxygen and oxidation of hydrazine compounds in aqueous solution.

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.

Electrostatic layer-by-layer assembly of polycation and DNA multilayer films by real-time surface plasmon resonance technique

The assembly of alternating DNA and positively charged poly(dimethyldiallylammonium chloride) (PDDA) multilayer films by electrostatic layer-by-layer adsorption has been studied. Real time surface plasmon resonance (BIAcore) technique was used to characterize and monitor the formation of multilayer films in solution in real time continuously. The results indicate that the uniform multilayer can be obtained on the poly(ethylenimine) (PEI) coated substrate surface. The kinetics of the adsorption of DNA on PDDA surface was also studied by real-time BIAcore technique, and the observed rate constant was calculated using a Langmuir model (k(obs) = (1.28 +/- 0.08) x 10(-2) s(-1)).

Characterization of multilayer film using electrochemical impedance spectroscopy

A new multilayer film fabricated based on electrostatic attraction in this laboratory was firstly characterized by the electrochemical impedance spectroscopy. The relationship between the charge-transfer resistance and double-layer capacitance with the number of layers was obtained through analyzing the impedance data. It demonstrated that the multilayer film showed a unique structure with the film growth. Compared to other electrochemical methods, the electrochemical impedance spectroscopy was proved to be a very sensitive and useful technique for characterizing the multilayer films.

Formation and characterization of heteropolyacid/polycation multilayer films on gold electrode

Ultrathin multilayer films of a polybasic lanthanide heteropoly tungstate-molybdate complex and a cationic polymer of quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) have been fabricated on a gold electrode precoated with a cysteamine self-assembled monolayer. The multilayer films have been characterized by optical spectroscopy, small-angle X-ray diffraction, and electrochemical methods (cyclic voltammetry and electrochemical impedance). Especially, the electrochemical impedance spectroscopy is developed to monitor the layer deposition processes. It provides important information such as double-layer capacitance and charge-transfer resistance. All obtained results reveal regular film growth with each layer adsorption. (C) 2001 The Electrochemical Society.

Multilayer assemblies of colloidal ZnS doped with silver and polyelectrolytes based on electrostatic interaction

Multilayer assemblies of silver doped ZnS colloid and polycation were fabricated by a self-assembly technique exploiting electrostatic interaction. UV/Vis spectra showed the uniform deposition process and X-ray photoemission spectroscopy (XPS) confirmed the coexistence of silver. It was found that the emission spectra of the silver doped ZnS colloid red-shifted to 528 nm comparing with undoped ZnS colloid. However, the most important finding was that the luminescence intensity of doped ZnS assembled in films was much stronger than that of undoped ZnS in films and that of doped ZnS in the spin-casting film. The mechanism of the enhancement luminescence was discussed. (C) 1998 Elsevier Science S.A. All rights reserved.

Stability of Mo/Si multilayer structure used in Bragg-Fresnel optics

The thermal and chemical stabilities of Mo/Si multilayer structure used in Bragg-Fresnel optics were studied to get optimal technological parameters of pattern generation. Mo/Si multilayers were annealed at temperature ranging from 360 to 770 K, treated with acetone and 5 parts per thousand NaOH solution, and characterized by small-angle x-ray diffraction technique as well as x-ray photoelectron spectroscopy, and Olympus microscopy.

Surface roughness characterization of soft x-ray multilayer films on the nanometer scale

The soft x-ray reflectivity of multilayer films is affected by the surface roughness on the transverse nanometer scale. Scanning tunneling microscopy (STM) is an ideal instrument for providing high-lateral-resolution roughness measurements for soft x-ray multilayer films that cannot be obtained with other types of instruments on the transverse nanometer scale. The surface roughnesses of Mo/Si, Mo/C, and W/Si soft x-ray multilayer films prepared by an ion-beam-sputtering technique were measured with a STM on the vertical and transverse attributes. The film roughnesses and average spatial wavelengths added to the substrates depend on the multilayer film fabrication conditions, i.e., material combinations, number of layers, and individual layer thickness. These were estimated to lead to a loss of specular reflectivity and variations of the soft x-ray scattering angle distribution. This method points the way to further studies of soft x-ray multilayer film functional properties and can be used as basic guidance for selecting the best coating conditions in the fabrications of soft x-ray multilayer films. (C) 1996 American Vacuum Society.

Preparation of a novel polysulfone/polyethylene oxide/silicone rubber multilayer composite membrane for hydrogen-nitrogen separation

A novel poly sulfone/polyethylene oxide/silicone rubber (PSOPEO/SR) multilayer composite membrane was fabricated by double coating polysulfone substrate membrane with polyethylene oxide and silicone rubber. Gas permeation experiments were performed at 30 degrees C for hydrogen and nitrogen. PSf(PEO/SR membrane displayed high and steady performance for H-2/N-2: permeances of H-2 and N-2 of 49.51 and 0.601 GPU, respectively, and H-2/N-2 ideal separation factor of 82.3. It was explained that layer interfaces due to the introduction of PEO layer act as the permselective media and are responsible for the higher H-2/N-2 ideal separation factor which has exceeded the intrinsic permselectivities of the three polymers used in this study. (c) 2005 Elsevier B.V. All rights reserved.

A novel PTFE-reinforced multilayer self-humidifying composite membrane for PEM fuel cells

A novel polytetrafluoroethylene (PTFE)-reinforced multilayer self-humidifying composite membrane is developed. The membrane is composed of Nafion-impregnated porous PTFE composite as the central layer and nanosized SiO2 supported Pt catalyst imbedded into Nafion as the two side layers. The proton exchange membrane (PEM) fuel cells employing the self-humidifying membrane (20 mu m thick) under dry H-2/O-2 gave a peak power density of 0.95 W/cm(2) and an open-circuit voltage of 1.032 V. The good membrane performance is attributed to hygroscopic Pt-SiO2 catalyst at the two side layers, which results in enhanced anode side self-humidification function and decreased cathode polarization. (c) 2005 The Electrochemical Society.

Use of an insulating mask for controlling anisotropy in multilayer electrospun scaffolds for tissue engineering.

Tissue engineering of various musculoskeletal or cardiovascular tissues requires scaffolds with controllable mechanical anisotropy. However, native tissues also exhibit significant inhomogeneity in their mechanical properties, and the principal axes of anisotropy may vary with site or depth from the tissue surface. Thus, techniques to produce multilayered biomaterial scaffolds with controllable anisotropy may provide improved biomimetic properties for functional tissue replacements. In this study, poly(ε-caprolactone) scaffolds were electrospun onto a collecting electrode that was partially covered by rectangular or square shaped insulating masks. The use of a rectangular mask resulted in aligned scaffolds that were significantly stiffer in tension in the axial direction than the transverse direction at 0 strain (22.9 ± 1.3 MPa axial, 16.1 ± 0.9 MPa transverse), and at 0.1 strain (4.8 ± 0.3 MPa axial, 3.5 ± 0.2 MPa transverse). The unaligned scaffolds, produced using a square mask, did not show this anisotropy, with similar stiffness in the axial and transverse directions at 0 strain (19.7 ± 1.4 MPa axial, 20.8 ± 1.3 MPa transverse) and 0.1 strain (4.4 ± 0.2 MPa axial, 4.6 ± 0.3 MPa, transverse). Aligned scaffolds also induced alignment of adipose stem cells near the expected axis on aligned scaffolds (0.015 ± 0.056 rad), while on the unaligned scaffolds, their orientation showed more variation and was not along the expected axis (1.005 ± 0.225 rad). This method provides a novel means of creating multilayered electrospun scaffolds with controlled anisotropy for each layer, potentially providing a means to mimic the complex mechanical properties of various native tissues.