The influence of hard-segments on two-phase structure and shape memory properties of PCL-based segmented polyurethanes

Poly(epsilon-caprolactone)-based segmented polyurethanes (PCLUs) were prepared from poly(epsilon-caprolactone) diol, diisocyanates (DI), and 1,4-butanediol. The DIs used were 4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluenediisocyanate (TDI), iso-phorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI). Differential scanning calorimetry, small-angle X-ray scattering, and dynamic mechanical analysis were employed to characterize the two-phase structures of all PCLUs. It was found that HDI- and MDI-based PCLUs had higher degree of microphase separation than did IPDI- and TDI-based PCLUs, which was primarily due to the crystallization of HDI- and MDI-based hard-segments. As a result, the HDI-based PCLU exhibited the highest recovery force up to 6 MPa and slowest stress relaxation with increasing temperature. Besides, it was found that the partial damage in hard-segment domains during the sample deformation was responsible for the incomplete shape-recovery of PCLUs after the first deformation, but the damage did not develop during the subsequent deformation.

Polyelectrolyte complexes based on chitosan and poly(L-glutamic acid)

Polyelectrolyte complexes (PECs) were prepared by mixing aqueous solutions of chitosan (CS) and poly(L-glutamic acid) (PLGA) at various pH. It was found that the stoichiometry of the PECs depends on pH.An investigation of the PECs using Fourier transform infrared spectroscopy proved that the formation of the complexes is due to electrostatic interaction between –NH3 + groups of CS and –COO− groups of PLGA. The solid PECs were characterized using wide-angle X-ray diffraction, which suggested that a strong interaction occurs between the two polymers at pH = 4 or 5 and relatively weak interaction at pH = 3. These results were further confirmed by thermogravimetric analysis data. Transmission electron microscopy showed that the complexes have a spherical shape. The effect of ionic strength on the size of the PECs was also studied using dynamic light scattering. It was found that the size of the PECs is dependent on pH.

Single-wall carbon nanotube-based voltammetric sensor and biosensor

The pH-sensitive property of the single-wall carbon nanotube modified electrode based oil the electroactive group on the single-wall carbon nanotube was explored by differential pulse voltammetry technique. In pH range 1-13 investigated in Britton-Robinson (B-R) buffer, the anodic peak shifted negatively along with the increase of pH exhibiting a reversible Nernstian response. Experiments were carried out to investigate the response of the single-wall carbon nanotube (SWNT) modified electrode to analytes associated with pH change. The response behavior of the modified electrode to ammonia was studied as an example. The potential response could reach equilibrium within 5 min. The modified electrode had good operational stability. Voltammetric urease and acetylcholinesterase biosensors were constructed by immobilizing the enzymes with sol-get hybrid material. The maximum potential shift could reach 0.130 and 0.220V for urea and acetylthiocholine, respectively. The methods for preparing sensor and biosensor were simple and reproducible and the range of analytes could be extended to substrates of other hydrolyases and esterases.

Synthesis, structure and norbornene polymerization behavior of neutral palladium complexes

A series of neutral palladium(II) complexes bearing non-symmetric bidentate pyrrole-iminato or salicylaldiminato chelate ligands have been synthesized, and the structure of representative complexes (3a, 4a, and 5a) have been confirmed by X-ray crystallographic analysis. These palladium complexes have been investigated as catalysts for the polymerization of norbornene. Using modified methylaluminoxane (MMAO) as a cocatalyst, these complexes display high activities and produce vinyl-addition polynorborenes. Catalytic activity of up to 8.52 x 10(3) kg/mol(Pd) h has been observed. Wide-angle X-ray diffraction (WAXD) has been used to investigate the polymer microstructure and it has been found that they are non-crystalline.

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.

Preparation and characterization of ultrathin multilayer films based on polyoxometalate Mo8V2O28 center dot 7H(2)O

The ultrathin multilayer films of sphere-shaped polyoxomolybdate Mo8V2O28.7H(2)O (abbreviated to Mo8V2) and poly(allylamine hydrochloride) (DAH) have been prepared by the layer-by-layer (LbL) self-assembly method. The (Mo8V2/DAH)(m) multilayer films have been characterized by X-ray photoelectron spectra (XPS) and atomic force microscopy (AFM). The electrochemistry behavior of the film at room temperature was investigated.

Immunosensors based on layer-by-layer self-assembled Au colloidal electrode for the electrochemical detection of antigen

Colloidal Au particles have been deposited on the gold electrode through layer-by-layer self-assembly using cysteamine as cross-linkers. Self-assembly of colloidal Au on the gold electrode resulted in ail easier attachment of antibody, larger electrode surface and ideal electrode behavior. The redox reactions of [Fe(CN)(6)]-/[Fe(CN)(6)](3-) on the gold surface were blocked due to antibody immobilization, which were investigated by cyclic voltammetry and impedance spectroscopy. The interaction of antigen with grafted antibody recognition layers was carried out by soaking the modified electrode into a phosphate buffer at pH 7.0 with various concentrations of antigen at 37degreesC for 30 min. Further, an amplification strategy to use biotin conjugated antibody was introduced for improving the sensitivity of impedance measurements. Thus, the sensor based oil this immobilization method exhibits a large linear dynamic range, from 5 - 400 mug/L for detection of Human IgG. The detection limit is about 0.5 mug/L.

Concentration and time dependant behavior of chlorpromazine interaction with supported bilayer lipid membrane

The interaction of chlorpromazine (CPZ) with supported bilaver lipid (dipalmitoyphosphatidylcholine) membrane (s-BLM) on the glassy carbon electrode (GCE) was investigated using cyclic voltammetry and ac impedance spectroscopy. The experimental data, based on the voltammetric response of Ru(NH3)(6)(3+) associated with the oxidation of CPZ on the electrode, indicated that the interaction of CPZ with s-BLM was concentration and time dependant. The interaction between them could be divided into three stages by the concentration of CPZ: low, middle and high concentration. At the first stage, s-BLM was not affected by CPZ and the interaction was only a penetration of a small quantity of CPZ molecule into s-BLM. At the second stage, the defects formed in s-BLM due to the penetration of more CPZ molecule into s-BLM. At the last stage, a high CPZ:lipid ratio reached in s-BLM, resulting in the solubilization of s-BLM. The interaction time had different effect at three stages.

Nonisothermal crystallization behavior of glass-bead-filled polypropylene

The effects of the glass-bead content and size on the nonisothermal crystallization behavior of polypropylene (PP)/glass-bead blends were studied with differential scanning calorimetry. The degree of crystallinity decreased with the addition of glass bead, and the crystallization temperature of the blends was marginally higher than that of pure PP at various cooling rates. Furthermore, the half-time for crystallization decreased with an increase in the glass-bead content or particle size, implying the nucleating role of the glass beads. The nonisothermal crystallization data were analyzed with the methods of Avrami, Ozawa, and Mo. The validity of various kinetic models for the nonisothermal crystallization process of PP/glass-bead blends was examined. The approach developed by Mo successfully described the nonisothermal crystallization behavior of PP and PP/glass-bead blends. Finally, the activation energy for the nonisothermal crystallization of pure PP and PP/glass-bead blends based on the Kissinger method was evaluated.

Carbazole-based hole-transporting materials for electroluminescent devices

Two kinds of carbazole-based molecules connected with diphenylamine and carbazole are synthesized by modified Ullmann reaction. Comparative study on their thermal stability, redox behavior, hole injection and transport properties are present. The results demonstrate that the carbazole-based molecules are very promising hole-transporting materials for electroluminescent devices.

Langmuir-Blodgett films based on europium-substituted heteropolytungstate and their luminescence properties

Several new hybrid organic-inorganic Langmuir-Blodgett (LB) films containing europium-substituted hetero-polytungstate Eu (XW11O39)(2)''(-) (X=Ge, Si, B) were successfully obtained using LB technique. When the heteropolytungstate anions are dissolved in the subphase, dimethyldioctadecylammonium bromide compression isotherms have been modified, which shows that the polyanions interact with the monolayer. Y-type LB films were obtained from the systems. Low-angle X-ray has shown that these LB films have well-defined lamella. The LB films were characterized by luminescence spectra and the characteristic luminescence behavior for europium-substituted heteropolytungstate complexes and their LB films were discussed. The results of excitation spectra indicate that the energy could be effectively transferred from ligands to the Eu3+ ions in the LB films and the luminescence efficiency could be greatly increased. The results of luminescence spectra indicate that the formations of hybrid organic-inorganic LB films have a great effect on the luminescence of europium-substituted heteropolytungstate. The lifetime shortening was observed in LB films.

Preparation and luminescence properties of LB films based on 4-hexadecyloxybenzoic terbium

LB films of 4-hexadecyloxybenzoic-terbium by using the subphase containing Tb3+ were prepared. The monolayer behavior of 4-hexadecyloxybenzoic acid (HOBA) on the subphase containing rare earth ions was studied. IR and UV spectra show that the rare earth ions were bound to carboxylic acid head groups and the coordination took place between the polar head group and the rare earth ions. The luminescence spectra show that the LB films have the fine luminescence properties, and the LB films emit strong luminescence under UV light irradiation.

Studies of perchlorate triggered ion-gate behavior of sBLM by electrochemiluminescence and its application to a sensor for perchlorate

Ru(bpy)(3)(2+) electrochemiluminescence (ECL) method and electrocatalysis method were first used to study the ion-gate behavior of supported lipid bilayer membrane (sBLM). We found that sBLM, made of dimethyldioctadecylammonium bromide (a kind of synthetic lipid), showed ion-gate behavior for the permeation of Ru(bpy)(3)(2+) in the presence of perchlorate anion. There existed a threshold concentration (0.1 muM) of perchlorate anion for ion-gate opening. Below the threshold the ion-gate was closed. Above the threshold, the number of opened ion-gate sites increased with the increase of perchlorate anion concentration and leveled off at concentrations higher than 1200 muM. Based on it, a new sensor for perchlorate was developed. Furthermore, the opening and closing of the ion-gate behavior was reversible, which means the sensor can repeatedly be used.

Photoluminescent multilayer films based on polyoxometalates

Ultrathin multilayer films consisting of the polyoxotungstoeuropate cluster K-12[EuP5W30O110] (EuP5W30) and poly( allylamine hydrochloride) (PAH) have been prepared by the layer-by-layer self-assembly method. The (EuP5W30 /PAH) multilayer films have been characterized by small-angle X-ray reflectivity measurements, X-ray photoelectron spectra, and atomic force microscopy (AFM). From the AFM images, the thickness of the {PEI/PSS/PAH(EuW30/PAH)} multilayer film was estimated to be 6.5 nm, corresponding to an average thickness of ca. 1.1 nm for a EuW30/PAH layer pair. The photoluminescent behavior of the film at room temperature was investigated to show the characteristic Eu3+ emission pattern of D-5(0)-->F-7(J). The fluorescence behavior of the multilayer film is essentially identical to that of H-n[EuP5W30O110]((12-n)-) in a concentrated aqueous solution, except for the relative intensities and peak bandwidths. The occurence of photoluminescent activity confirms the potential for creating luminescent multilayers with polyoxometalates (see ref. 23).

Fabrication and electrochemical behavior of a sol-gel-derived carbon ceramic composite electrode entrapping 2 : 18-molybdodiphosphate

A new type of inorganic-organic hybrid material incorporating carbon powder and alpha -type 2:18-molybdodiphosphate (P2Mo18) in a methyltrimethoxysilane (MTMOS) based gel has been produced by a sol-gel process and used to fabricate a chemically modified electrode. The P2Mo18-doped carbon ceramic composite electrode was characterized using SEM and cyclic voltammetry. Square-wave voltammetry with an excellent sensitivity was exploited to conveniently investigate the dependence of current and half-wave potential (E-1/2) on pH. The chemically modified electrode has some advantages over the modified film electrodes constructed by the conventional methods, such as long-term stability, reproducibility, and especially repeatability of surface-renewal by simple polishing in the event of surface fouling or dopant leaching. In addition, the modified electrode shows a good catalytic activity for the electrochemical reduction of bromate in an acidic aqueous solution. (C) 2000 Elsevier Science B.V. All rights reserved.