In situ electrochemical SERS studies on electrodeposition of aniline on 4-ATP/Au surface

The electrochemical polymerization of 0.01 M aniline in 1 M H2SO4 aqueous solution on roughened Au surface modified with a self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) has been investigated by in situ electrochemical surface-enhanced Raman scattering spectroscopy (SERS). The repeat units and possible structures of the electrodeposited polyaniline (PANI) film were proposed; i.e., aniline monomer is coupled in head-to-tail predominately at the C-4 of aniline and amine of 4-ATP, and the thin PANI film is orientated vertically to substrate surface. Simultaneous Raman spectra during potential scanning indicate clearly that the ultrathin PANI film (in initial growth of the film) consists of semiquinone radical cation (IP+), para-disubstituted benzene (IP and IP+) and quinine diimine (NP) while it is oxidized, and without quinine diimine and semiquinone radical cation while reduced. Meanwhile, the results confirm that 4-ATP monolayer shows a strong promotion on the electrodeposition of aniline monomer, and a possible polymerization mechanism was proposed.

In situ ethylene homopolymerization and copolymerization catalyzed by zirconocene catalysts entrapped inside functionalized montmorillonite

Ethylene homopolymerizations and copolymerizations were catalyzed by zirconocene catalysts entrapped inside functionalized. montmorillonites that had been rendered organophilic via the ion exchange of the interlamellar cations of layered montmorillonite with hydrochlorides Of L-amino acids (AAH(+)Cl(-)) or their methyl esters (MeAAH(+)Cl(-)), with or without the further addition of hexadecyltrimethylammonium bromide (C16H33N+Me3Br-; R4N+Br-). In contrast to the homogeneous CP2ZrCl2/methylaluminoxane catalyst for ethylene homopolymerizations and copolymerizations with 1-octene, the intercalated Cp2ZrCl2 activated by methylaluminoxane for ethylene homopolymerizations and copolymerizations with 1-octene proved to be more effective in the synthesis of polyethylenes with controlled molecular weights, chemical compositions and structures, and properties, including the bulk density. The effects of the properties of the organic guests on the preparation and catalytic performance of the intercalated zirconocene catalysts were studied.

Synthesis and characterization of polypropylene/montmorillonite nanocomposites via an in-situ polymerization approach

Polypropylene/montmorillonite (PP/MMT) nanocomposites were prepared by in-situ polymerization using a MMT/MgCl2/TiCl4-EB Ziegler-Natta catalyst activated by trietbylaluminum (TEA). The enlarged layer spacing of MMT was confirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components. X-ray photoelectron spectrometry (XPS) analysis proved that TiCl4 was mainly supported on MgCl2 instead of on the surface of MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXD patterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).

Preparation and properties of polyethylene/montmorillonite nanocomposites by in situ polymerization

Polyethylene (PE)/montmorillonite (MMT) nanocomposites were prepared by in situ coordination polymerization using a MMT/MgCl2/TiCl4 catalyst activated by AI(Et),. The catalyst was prepared by first diffusing MgCl2 into the swollen MMT layers, followed by loading TiCl4 on the inner/outer layer surfaces of MMT where MgCl2 was already deposited. The intercalation of MMT layers by MgCl2 and TiCl, was demonstrated by the enlarged interlayer spacing determined by WAXD. The nanoscale dispersion of MMT layers in the polyethylene matrix was characterized by WAXD and TEM. As a consequence, the crystallinity of the nanocomposite decreased sharply, whereas the tensile strength was significantly improved compared to that of virgin polyethylene of comparable molecular weight. The confinement of the nanodispersed MMT layers to molecular chain and the strong interaction between the nanoscale MMT layers and the resin matrix were thought to account for the decrease of crystallinity and the remarkable enhancement of strength.

Morphology, structure, and properties of in situ compatibilized linear low-density polyethylene/polystyrene and linear low-density polyethylene/high-impact polystyrene blends

Blends of linear low-density polyethylene (LLDPE) with polystyrene (PS) and blends of LLDPE with high-impact polystyrene (HIPS) were prepared through a reactive extrusion method. For increased compatibility of the two blending components, a Lewis acid catalyst, aluminum chloride (AlCl3), was adopted to initiate the Friedel-Crafts alkylation reaction between the blending components. Spectra data from Raman spectra of the LLDPE/PS/AlCl3 blends extracted with tetrahydrofuran verified that LLDPE segments were grafted to the para position of the benzene rings of PS, and this confirmed the graft structure of the Friedel-Crafts reaction between the polyolefin and PS. Because the in situ generated LLDPE-g-PS and LLDPE-g-HIPS copolymers acted as compatibilizers in the relative blending systems, the mechanical properties of the LLDPE/PS and LLDPE/HIPS blending systems were greatly improved. For example, after compatibilization, the Izod impact strength of an LLDPE/PS blend (80/20 w/w) was increased from 88.5 to 401.6 J/m, and its elongation at break increased from 370 to 790%. For an LLDPE/HIPS (60/40 w/w) blend, its Charpy impact strength was increased from 284.2 to 495.8 kJ/m(2). Scanning electron microscopy micrographs showed that the size of the domains decreased from 4-5 to less than 1 mum, depending on the content of added AlCl3.

In situ controllable synthesis of polyoxometalate nanoparticles in polyelectrolyte multilayers

Size-controlled Ag3PW12O40 nanoparticles have been synthesized in situ in polyelectrolyte multilayer thin films via layer-by-layer self-assembly.

Hybrid organic-inorganic compounds doped with terbium carboxyl complexes produced in situ via a sol-gel approach

In situ synthesis of terbium carboxyl complexes in an organic-inorganic hybrid matrix by a sol-gel process has been proposed. The formation of terbium carboxyl complexes in the hybrid matrix is confirmed by the luminescence spectra and IR spectra. It is observed that the location at the amino group in aminobenzoic acid has a large effect on the luminescence properties and lifetimes. Furthermore, the emission intensity decreases with increasing temperature.

In situ study of nanostructure and morphological development during the crystal-mesophase transition of poly(di-n-hexylsilane) and poly(di-n-butylsilane) by X-ray and hot-stage AFM

Nanostructure and morphology and their development of poly(di-n-hexylsilane) (PDHS) and poly(di-n-butylsilane) (PDBS) during the crystal-mesophase transition are investigated using small angle X-ray scattering (SAXS), wide angle X-ray diffraction and hot-stage atomic force microscopy. At room temperature, PDHS consists of stacks of lamellae separated by mesophase layers, which can be well accounted using an ideal two-phase model. During the crystal-mesophase transition, obvious morphological changes are observed due to the marked changes in main chain conformation and intermolecular distances between crystalline phase and mesophase. In contrast to PDHS, the lamellae in PDBS barely show anisotropy in dimensions at room temperature. The nonperiodic structure and rather small electronic density fluctuation in PDBS lead to the much weak SAXS. The nonperiodic structure is preserved during the crystal-mesophase transition because of the similarity of main chain conformation and intermolecular distances between crystalline phase and mesophase.

Structural electrochemical study of hemoglobin by in situ circular dichroism thin layer spectroelectrochemistry

Secondary and tertiary or quaternary structural changes in hemoglobin (HB) during an electroreduction process were studied by in situ circular dichroism (CD) spectroelectrochemistry with a long optical path thin-layer cell. By means of singular value decomposition least-squares analysis, CD spectra in the far-UV region give two similar a components with different CD intensity, indicating slight denaturation in the secondary structures due to the electric field effect. CD spectra in the Soret band show a R --> T transition of two quaternary structural components induced by electroreduction of the heme, which changes the redox states of the center ion from Fe3+ to Fe2+ and the coordination number from 6 to 5. The double logarithmic analysis shows that electroreduction of hemoglobin follows a chemical reaction with R --> T transition. Some parameters in the electrochemical process were obtained: formal potential, E-0t = -0.167 V; electrochemical kinetic overpotential, DeltaE(0) = -0.32 V; standard electrochemical reaction rate constant, k(0) = 1.79 x 10(-5) cm s(-1); product of electron transfer coefficient and electron number, alphan=0.14; and the equilibrium constant of R --> T transition, K-c = 9.0.

Preparation and characterization of poly(ethyl acrylate)/bentonite nanocomposites by in situ emulsion polymerization

Transparent poly(ethyl acrylate) (PEA)/bentonite nanocomposites containing intercalated-exfoliated combinatory structures of clay were synthesized by in situ emulsion polymerizations in aqueous dispersions containing bentonite. The samples for characterization were prepared through direct-forming films of the resulting emulsions without coagulation and separation. An examination with X-ray diffraction and transmission electron microscopy showed that intercalated and exfoliated structures of clay coexisted in the PEA/bentonite nanocomposites. The measurements of mechanical properties showed that PEA properties were greatly improved, with the tensile strength and modulus increasing from 0.65 and 0.24 to 11.16 and 88.41 MPa, respectively. Dynamic mechanical analysis revealed a very marked improvement of the storage modulus above the glass-transition temperature. In addition, because of the uniform dispersion of silicate layers in the PEA matrix, the barrier properties of the materials were dramatically improved. The permeability coefficient of water vapor decreased from 30.8 x 10(-6) to 8.3 x 10(-6) g cm/cm(2)s cmHg. (C) 2002 Wiley Periodicals, Inc.

In situ analysis of electropolymerization of aniline by combined electrochemistry and surface plasmon resonance

The combination of electrochemistry with surface plasmon resonance (SPR) has been used to characterize the growth of polyaniline (PAn) on a gold electrode surface during potential cycling. Potential-modulated SPR characteristics of the PAn film were also revealed. The potential switch between the oxidized and reduced states of PAn can lead to a large change of SPR response due to the variation in the imaginary part of the dielectric constant of PAn film resulting from the transition of the film in conductivity. The redox transition of the PAn film during potential cycling is very profitable to the SPR measurements. Two modes of SPR measurement, SPR angular scan (R-theta) and the time evolution of the reflectivity change at a fixed angle (R-t), were displayed to study the growth process of the PAn film. The angle shift of the resonance minimum recorded at each cathodic limit of cyclic potential scanning allows for the unambiguous measurement of the film growth. During cyclic potential scanning, the R-t curve was repeatedly modulated with the direction of the potential ramp as a result of the redox switch of the PAn film, and the amplitude of potential-modulated reflectivity change was well correlated with the cyclic number. The time differential of the R-t curve permits continuous monitoring of the film growth process. These results illustrate that the combined technique is suitable for studying the electropolymerization process of a conducting polymer.

Conformational transition of DNA in electroreduction studied by in situ UV and CD thin layer spectroelectrochemistry

Electrochemically induced three conformational transitions of calf thymus DNA from B-10.4 to Z(10.2)-DNA and from B-10.2 to B-10.4 and to C-DNA in 10 mM phosphate buffer solution (pH 7.21) at glassy carbon electrode are found and studied by in situ circular dichroism (CD) thin layer spectroelectrochemistry with singular value decomposition least square (SVDLS) analysis. It indicates that the so-called B-10.2 form and the C-form of DNA may be composed of B-10.4 and left-A DNA and of B-10.4 and right-A DNA, respectively. The irreversible electrochemical reduction of adenine and cytosine groups in the DNA molecule is studied by UV-Vis spectroelectrochemistry. Some electrochemical parameters alphan = 0.17, E-0' = -0.70 V (vs. Ag/AgCl), and the standard heterogeneous electron transfer rate constant, k(0) = 1.8 x 10(-5) cm s(-1) are obtained by double logarithmic analysis and non-linear regression. (C) 2000 Elsevier Science B.V. All rights reserved.

In situ synthesis of terbium-benzoic acid complex in sol-gel derived silica by a two-step sol-gel method

Terbium complexes with benzoic acid and its derivatives o-hydroxybenzoic acid and p-hydroxybenzoic acid were in situ synthesized in sol-gel derived silica matrix via a two-step sol-gel process. The formation process of the complex was characterized by fluorescence spectra, absorption spectra and IR spectra. The gels that contain in situ synthesized complexes exhibit the characteristic emission bands of terbium ion. The fluorescence lifetimes of Tb3+ in the silica gels are longer than those in the pure complexes and in the solutions that contain the corresponding complexes. (C) 2000 Elsevier Science Ltd. All rights reserved.