Relaxation time and conductivity of comb-like gel polymer electrolytes

Using the copolymer of acrylonitrile (AN), methyl methacrylate (MMA), and poly(ethylene glycol) methyl ether methacrylate as a backbone and poly(ethylene glycol) methyl ether (PEGME) with 1100 molecular weight as side chains, comb-like gel polymers and their Li salt complexes were synthesized. The dynamic mechanical properties and conductivities were investigated. Results showed that the gel copolymer electrolytes possess two glass transitions: alpha-transition and beta-transition. Based on the time-temperature equivalence principle, a master curve was constructed by selecting T. as reference temperature. By reference to T-0 = 50 degrees C, the relation between log c, and c was found to be linear. The master curves are displaced progressively to higher frequencies as the content of plasticizer is increased. The relation between log tau(p) and the content of plasticizer is also linear.

Weak epitaxy growth affording high-mobility thin films of disk-like organic semiconductors

Thin films of phthalocyanine compounds show weak epitaxial growth on a monodomain film of a rod-like molecule (see figure). The resulting organic electronic devices exhibit high charge carrier mobilities close to those of the single-crystal devices.

Active site structure of NO decomposition on perovskite(-like) oxides: An investigation from experiment and density functional theory

Active site structure for NO decomposition carried out on perovskite-like oxides were discussed based on the N-2 yield measured from LaSrNi1-x,AlxO4 with different B-site cations and from La2-ySryCuO4 with different crystal phases. Results show that the active site contains two oxygen vacancies, two transition metals, and one lattice-oxygen, with the oxygen vacancy locating on the apex of MO6 octahedron, and the lattice oxygen locating between the two transition metals (i.e., M-O-M plane). Density functional theory (DFT) analysis to the structure shows that this new active site is the most active structure for NO adsorbing, and hence, for NO decomposition. The similar trend of the relative energies that are required for the formation of oxygen vacancies with f form (calculated from DFT), the amount of oxygen vacancies, and the activities (N-2 yield) certifies this result further.

Carbon nanotubes and glucose oxidase bionanocomposite bridged by ionic liquid-like unit: Preparation and electrochemical properties

For their biocompatibility and potential bionanoelectronic applications, integration of carbon nanotubes (CNTs) with biomolecules such as redox enzyme is highly anticipated. Therein, CNTs are expected to act not only as an electron transfer promoter, but also as immobilizing substrate for biomolecules. In this report, a novel method for immobilization of biomolecules on CNTs was proposed based on ionic interaction, which is of universality and widespread use in biological system. As illustrated, glucose oxidase (GOD) and single-walled carbon nanotubes (SWNTs) were integrated into a unitary bionanocomposite by means of ionic liquid-like unit on functionalized SWNTs. The resulted bionanocomposite illustrated better redox response of immobilized GOD in comparison of that prepared by weak physical absorption without ionic interaction. As a potential application of concept, the electrochemical detection of glucose was exemplified based on this novel bionanocomposite.

Self-assembly of crystalline-coil diblock copolymer in solvents with varying selectivity: From spinodal-like aggregates to spheres, cylinders, and lamellae

We have investigated systematically the morphology of thin films spin-coated from solutions of a semicrystalline diblock copolymer, poly(L-lactic acid)-block-polystyrene (PLLA-b-PS), in solvents with varying selectivity. In neutral solvents (chloroform and tetrahydrofuran (THF)), a spinodal-like pattern was obtained and the pattern boundary was sharpened by diluting the solution. Meanwhile, loose spherical associates, together with larger aggregates composed of these associates by unimer bridges, formed partly due to crystallization of the PLLA blocks in relatively concentrated solutions. In slightly PS-selective solvent (e.g., benzene), both loose and compact spherical micelles were obtained, depending on the polymer concentration, coexisting with unimers. When enhancing the selectivity with mixed solvents, for example, mixing the neutral solvent and the slightly selective solvent with a highly PS-selective solvent, CS2, loose assemblies (nanorods in CS2/THF mixtures and polydisperse aggregates in CS2/benzene mixtures) and well-developed lamellar micelles were obtained.

Surprising arching sheet-like dendrites growing from BaF2 nanocubes

BaF2 nanocubes were prepared from quaternary reverse micelles of cetyl trimethyl ammonium bromide (CTAB), n-butanol, n-octane, and water. Interestingly, there are arching sheet-like dendrites growing between two neighbouring sides of these cubes. X-ray powder diffraction (XRD) analysis showed that the products were BaF2 single phase. Scanning electron microscopy (SEM) or transition electron microscopy (TEM) was used to estimate the size of the final products. The results showed that the shape and size of particles were strongly dependent on the reaction conditions, such as the temperature and reaction time. When the reaction temperature was 25 degreesC, we obtained cuboid-like particles with 'clean' surfaces (no dendrites growing on them), and when the temperature was 35 degreesC, we obtained nanocubes with dendrites growing from them between the neighbouring sides. The influence of reaction time at a temperature of 35 degreesC is also discussed.

Reversible B/Z-DNA transition under the low salt condition and non-B-form polydApolydT selectivity by a cubane-like europium-L-aspartic acid complex

We report here that a cubane-like europium-L-aspartic acid complex at physiological pH can discriminate between DNA structures as judged by the comparison of thermal denaturation, binding stoichiometry, temperature-dependent fluorescence enhancement, and circular dichroism and gel electrophoresis studies. This complex can selectively stabilize non-B-form DNA polydApolydT but destabilize polydGdCpolydGdC and polydAdTpolydAdT. Further studies show that this complex can convert B-form polydGdCpolydGdC to Z-form under the low salt condition at physiological temperature 37 degrees C, and the transition is reversible, similar to RNA polymerase, which turns unwound DNA into Z-DNA and converts it back to B-DNA after transcription. The potential uses of a left-handed helix-selective probe in biology are obvious. Z-DNA is a transient structure and does not exist as a stable feature of the double helix. Therefore, probing this transient structure with a metal-amino acid complex under the low salt condition at physiological temperature would provide insights into their transitions in vivo and are of great interest.

An one-pot epitaxial growth method to synthesize cactus-like ZnO

In this work, we have developed a one-pot, morphology controlled epitaxial growth method to synthesize novel cactus-like ZnO in solution. Utilizing zinc acetate and hexamethylenetetramine as the precursors, ZnO nanorods synthesized in the first step remained in the solution, without any separation, served directly as the matrix for the epitaxial growth in the second step. Control experiments revealed that a proper mass of precursors added in the second step was crucial to form cactus-like ZnO. The as-synthesized ZnO was single crystalline and possessed three photoluminescence emissions centered at 390, 425 and 490 run. Finally, a possible mechanism for the epitaxial growth ZnO was proposed and discussed.

Hydrothermal syntheses and crystal structures of new cage-like mixed-valent polyoxovanadates

Three new cage-like mixed-valent polyoxovanadates [Ni(1,10'-phen)(3)](2)[V10O26] 1, [Zn(2,2'-biPY)(3)](3)[V15O36Cl](.)3H(2)O (2) and [Co(2,2'-biPY)(3)](3)[V15O36Cl](.)3H(2)O (3) have been hydrothermally synthesized for the first time and characterized by elemental analyses, IR, EPR spectra, TG analyses and single crystal X-ray diffraction. The polyoxoanion of I exhibits an interesting empty ellipsoidal [V-2(IV) V-8(V) O-26](4-) 'host' shell, while the oxo vanadium clusters of 2 and 3 possess a spherical [V-8(IV) V-7(V) O36Cl](6-) cage with a Cl- ion encapsulated. The structure-directing role of organic templates (1,10'-phen and 2,2'-bipy) on the formation of the polyoxoanion structures is discussed.

An unusual organic-inorganic chain-like hybrid complex [(CuCl)(2)(o-phen)](infinity) (o-phen=o-phenanthroline)

A novel organic-inorganic hybrid complex [(CuCl)(2) (o-phen)](infinity) 1 (o-phen = o-phenanthroline) has been hydrothermally synthesized and structurally characterized by elemental analyses, XPS spectrum, TG analysis, and single-crystal X-ray diffraction. Compound I crystallizes in the monoclinic system, space group P2(1)/n, a = 3.7285(7) Angstrom, b = 19.603(4) Angstrom, c = 16.757(3) Angstrom, beta = 95.83(3)degrees, V = 1218.4(4) Angstrom(3), Z = 4, lambda(MoKalpha) = 0.71073 Angstrom (R(F) = 0.0643 for 2559 reflections). Data were collected on an R-axis RAPID diffractometer at 293 K in the range of 1.60 < θ < 27.48degrees. The title compound exhibits a one-dimensional chain-like scaffolding constructed by the unusual [Cu3Cl3] hexagon motifs by, sharing opposite edges. Only Cu(1) sites of the [Cu3Cl3] hexagon are coordinated with N donors of o-phen groups. Furthermore, the three-dimensional supermolecular architecture is formed by C-H...Cl hydrogen bonds between o-phen groups and CuCl chains.

Study of electron transfer across the liquid/ice-like matrix interface by scanning electrochemical microscopy

In this work, we report the findings of a study on scanning electrochemical microscopy (SECM) to investigate the interfacial electron-transfer (ET) reaction between the 7,7,8,8-tetracyanoquinodimethane radical anion (TCNQ(.-)) in 1,2-dichloroethane and ferricyanide in an ice-like matrix (a mixture of insulting ice and conductive liquid) under low temperatures. Experimental results indicate that the formed liquid/ice-like matrix interface is superficially similar in electrochemical characteristics to a liquid/liquid interface at temperatures above -20 degreesC. Furthermore, imaging data show that the surface of the ice-like matrix is microscopically flat and physically stable and can be applied as either a conductive or an insulting substrate for SECM studies. Perchlorate ion was selected as the common ion in both phases, the concentrations of which controlled the interfacial potential difference. The effect of perchlorate concentration in the DCE phase on interfacial reactions has been studied in detail. The apparent heterogeneous rate constants for TCNQ(.-) oxidation by Fe(CN)(6)(3-) in another phase under different temperatures have been calculated by a best-fit analysis, where the experimental approach curves are compared with the theoretically derived relationships. Reaction rate data obey Butler-Volmer formulation before and after the freezing point, which is similar to most other known cases of ET reactions at liquid/liquid interfaces. However, there is a sharp change observed for heterogeneous rate constants around the freezing point of the aqueous phase, which reflects the phase transition. At temperatures below -20 degreesC, surface-confined voltammograms for the reduction of ferricyanide were obtained, and the ice-like matrix became an insulating one, which indicates that the aqueous phase is really a frozen phase.

Seed-mediated growth of large, monodisperse core-shell gold-silver nanoparticles with Ag-like optical properties

Large, monodisperse core-shell Au-Ag nanoparticles with Ag-like optical properties have been prepared by the seeding growth method in micellar media.

Electrocatalytic oxidation of NADH by rutin in biomembrane-like films on glassy carbon electrode

Stable lipid film was made by casting dipalmitoylphosphatidylcholine (DPPC) and rutin onto the surface of a glassy carbon (GC) electrode. The electrochemical behavior of rutin in the DPPC film was studied. The modified electrode coated with rutin gave quasi-reversible reduction-oxidation peak on cyclic voltammogram in the phosphate buffer (pH 7.4). The peak current did not decrease apparently after stored at 4 degreesC for 8 hours in refrigerator. This model of biological membrane was used to investigate the oxidation of dihydronicotinamide adenine dinucleotide (NADH) by rutin. Rutin in the film acts as a mediator. The modified electrode shows a great enhancement and the anodic peak potential was reduced by about 220 mV in the oxidation of 5 X 10(-3) mol L-1 NADN compared with that obtained at a bare glassy carbon electrode. (C) 2000 Elsevier Science S.A. All rights reserved.

The single crystal-like banded textures in the films of a thermotropic liquid crystalline poly(aryl ether ketone) containing a lateral chloro group

The banded textures in the films of a thermotropic liquid crystalline poly(aryl ether ketone) containing a lateral chloro group have been studied by means of transmission electron microscopy(TEM), electron diffraction(ED) and atomic force microscopy (AFM). The crystallization-induced Landed texture without external shear can be formed when the thin films were annealed at the temperature range(320-330 degrees C) of the liquid crystalline state from the melt, The results show that the banded regions have high orientation of single crystal based on the orthorhombic packing and the growing direction of the Lands is along the b axis of the crystals, This kind of single crystal-like bands is due to the different orientation of the packing molecular chains, The molecular chains of the dark bands in the bright field electron micrograph are perpendicular to the film plane, while the ones of the bright Lands are tilt along the b axis with the tilt angle upto +/-20 degrees.