Growth of ZnO Nanotetrapods with Hexagonal Crown

ZnO nanotetrapods with hexagonal crown were synthesized on a silicon wafer by vapor transport process at a low temperature of 630 °C and normal pressure without the presence of catalysts. The results demonstrated that the as-synthesized products with slender legs and regular hexagonal crown are single crystal with wurtzite structure and preferentially grow up along 001 direction. Photoluminescence spectra revealed that the green emission originated from oxygen vacancies overwhelmed that of the near-band-edge ultraviolet peak, which suggests the peculiar-shaped nanotetrapods may have potential applications in multichannel nano-optoelectronic devices.

Anisotropic, gradient and metal-like mechanical behaviors of teeth and their implications on tooth functions

The anisotropy and gradient of the elastic modulus and the hardness of teeth were investigated by means of instrumented indentation method. Such properties are attributed to the unique microstructures of teeth based on scanning electron microscopic analysis. By comparing the relationship between the ratio of hardness to the reduced elastic modulus and the ratio of elastic unloading work to the total work of teeth in course of indentation to those of other materials, we found that the material behaviors of teeth display metal-like characteristics rather than ceramics as considered traditionally. These material behaviors and relevant functions are discussed briefly.

Determination of lead using a poly(vinyl chloride)-based crown ether membrane

A poly(vinyl chloride)(PVC)-based membrane of 15-crown-5 exhibits a good response for lead(II) ions over a wide concentration range. The response time of the sensor is 30 s and the membrane can be used for more than four months without observing any divergence. The selectivity of the sensor is comparable with those reported for other such electrodes. It was possible to determine lead in polluted waters using this electrode assembly.

Mercury selective electrochemical sensor based on a double armed crown ether as ionophore

PVC based membranes of a double armed crown ether, N, N'-dibenzyl, 1,4,10,13-tetraoxa-7, 16-diaza cyclooctadecane (I) as ionophore with sodium tetra phenyl borate (NaTPB) as anion excluder and with many plasticizing solvent mediators have been prepared and used for Hg(II) ion determination. The membrane with DBBP (dibutyl butyl phosphonate ) as plasticizer with various ingredients in the ratio PVC: I: NaTPB: DBBP (150: 12: 2: 100) shows the best results in terms of working concentration range (3.1x10-5-1.0x10-tM) with a Nernstian slope (29.0′0.5 mV/decade of activity). The electrode works in the pH range 2.1-4.5. The response time of the sensor is 15s and it can be used for about 4 months in aqueous as well as in non-aqueous medium. It has good stability and reproducibility. The potentiometric selectivity coefficient values for mono-, di-, and trivalent cations are tabulated. The sensor is highly selective for Hg2+ in the presence of normal interferents like cadmium, silver, sodium and iron.

Assembly of 12-tungstosilicic acid and 4-aminobenzo-15-crown-5 ether based on the electrostatic attraction through bridging of oxonium ions on different substrates

Based on the electrostatic attraction Keggin-type polyoxometalate H4SiW12O40 (SiW12) and small molecule 4-aminobenzo-15-crown-5 ether (4-AB15C5) were alternately deposited on poly (allylamine hydrochloride) (PAH)-derived indium tin oxide (ITO) substrate through a layer-by-layer (LBL) self-assembly, forming a supramolecular multilayer film (film-A). SiW12 was also deposited on a glassy carbon electrode (GCE) derived by 4-AB15C5 via covalent bonding in 0.1 M NaCl aqueous solution and formed a composite monolayer film (film-B). UV-vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy measurements demonstrated that the interactions between SiW12 and 4-AB15C5 in both two film electrodes were the same and caused by the bridging action of oxonium ions. But, the nanostructure in the two film electrodes was different. 4-AB15C5 in film-A was oriented horizontally to ITO substrate, however, that in film-B was oriented vertically to GCE. Namely film-A corresponded to a layer structure, and film-B corresponded to an intercalation structure.

Surface morphology evolution of poly (styrene-block-4-vinylpyridine) (PS-b-P4VP)(H+) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA) supramolecular film

Well-ordered nanostructured polymeric supramolecular thin films were fabricated from the supramolecular assembly of poly(styrene-block-4-vinylpyridine) (PS-b-P4VP)(H+) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA). A depression Of cylindrical nanodomains was formed by the block of P4VP(H+) and PMCMA associates surrounded by PS. The repulsive force aroused from the incompatibility between the block of P4VP(H+) and PMCMA was varied through changing the molecule weight (M-w) of PMCMA, the volume fraction of the block of P4VP(H+), and annealing the film at high temperature. Increasing the repulsive force led to a change of overall morphology from ordered nanoporous to featureless structures. The effects of solvent nature and evaporation rate on the film morphology were also investigated. Further evolution of surface morphologies from nanoporous to featureless to nanoporous structures was observed upon exposure to carbon bisulfide vapors for different treatment periods. The wettability of the film surface was changed from hydrophilicity to hydrophobicity due to the changes of the film surface microscopic composition.

Facilitated ion-transfer of sodium cation by (anthraquinone-1-yloxy) methane-15-crown-5 across the water/1,2-dichloroethane microinterface

The transfer of sodium cation facilitated by (anthraquinone-1-yloxy) methane-15-crown-5(L) has been investigated at the water/1,2-dichloroethane microinterface supported at the tip of a micropipette. The diffusion coefficient of (anthraquinone-1-yloxy) methane-15-crown-5 obtained was (3.42 +/- 0.20) x 10(-6) cm(2) s(-1). The steady-state voltammograms were observed for forward and backward scans due to sodium ion transfer facilitated by L with 1:1 stoichiometry. The mechanism corresponded to an interfacial complexation (TIC) and interfacial dissociation (TID) process. The association constant was calculated to be log beta(o) = 11.08 +/- 0.03 in the DCE phase. The association constant of other alkali metals (Li+, K+, Rb+) were also obtained.

Ordered macroporous films from self-assembly of two-armed polymer with a crown ether core

Highly ordered honeycomb-like macroporous films were obtained via self-assembly of a two-armed polymer with a crown ether core under controlled conditions. A possible mechanism is speculated, primarily based on the strong affinity between the crown ether cores. The pore size and arrangement are sensitive to the solvent evaporation rate and the solution concentration. Upon spontaneous drying, the pore diameter (D) depends on the concentration (c) by a relation of D=518c(-0.610).

Formation and photoluminescence of silver nanoparticles stabilized by a two-armed polymer with a crown ether core

Silver nanoparticles were synthesized by the use of a two-armed polymer with a crown ether core [poly(styrene)]-dibenzo-18-crown-6-[poly(styrene)] based on the flexibility of the polymer chains and the complex effect of crown ether with Ag+ and Ag. The size of silver nanoparticles could be tailored by controlling the initial concentrations of the polymer and Ag+, and the molecular weight of the polymer. The emission of silver nanoparticles was blue-shifted, and the intensity of the photoluminescence of silver nanoparticles stabilized by the polymer was significantly increased due to the complex effect between the crown ether embedded in the polymer and the silver nanoparticles.

New high-dimensional networks based on polyoxometalate and crown ether building blocks

Three novel supramolecular assemblies constructed from polyoxometalate and crown ether building blocks, [(DB18C6)Na(H2O)(1.5)](2)Mo6O19.CH3CN, 1, and [{Na(DB18C6)(H2O)(2)}(3)(H2O)(2)]XMo12O40.6DMF.CH3CN (X = P, 2, and As, 3; DB18C6 = dibenzo-18-crown-6; DMF = N,N-dimethylfomamide), have been synthesized and characterized by elemental analyses, IR, UV-vis, EPR, TG, and single crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal space group P4/mbm with a = 16.9701(6) Angstrom, c = 14.2676(4) Angstrom, and Z = 2. Compound 2 crystallizes in the hexagonal space group P6(3)/m with a = 15,7435(17) Angstrom, c = 30.042(7) Angstrom, gamma = 120degrees, and Z = 2. Compound 3 crystallizes in the hexagonal space group P6(3)/m with a = 15.6882(5) Angstrom, c = 29.9778(18) Angstrom, gamma = 120degrees, and Z = 2. Compound 1 exhibits an unusual three-dimensional network with one-dimensional sandglasslike channels based on the extensive weak forces between the oxygen atoms on the [Mo6O19](2-) polyoxoanions and the CH2 groups of crown ether molecules, Compounds 2 and 3 are isostructural, and both contain a novel semiopen cagelike trimeric cation [{Na(DB18C6)(H2O)(2)}(3)(H2O)(2)](3+). In their packing arrangement, an interesting 2-D "honeycomblike" "host" network is formed, in which the [XMo12O40](3-) (X = As and P) polyoxoanion "guests" resided.

Systematic study of the transfer of amino acids across the water/1,2-dichloroethane interface facilitated by dibenzo-18-crown-6

Facilitated ion transfer reactions of 20 amino acids with di.benzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nano-pipets were investigated systematically using cyclic voltammetry. It was found that there were only 10 amino acids, that is, Leu, Val, Ile, Phe, Trp, Met, Ala, Gly, Cys, Gln (in brief), whose protonated forms as cations can give well-defined facilitated ion transfer voltammograms within the potential window, and the reaction pathway was proven to be consistent with the transfer by interfacial complexation/dissociation (TIC/TID) mechanisms. The association constants of DB 18C6 with different amino acids in the DCE (beta(0)), and the kinetic parameters of reaction were evaluated based on the steady-state voltammetry of micro- or nano-pipets, respectively The experimental results demonstrated that the selectivity of complexation of protonated amino acid by DB18C6 compared with that of alkali metal cations was low, which can be attributed to the vicinal effect arising from steric hindrance introduced by their side group and the steric bulk effect by lipophilic stabilization.