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.

Template-free fabrication of hexagonal ZnO microprism with an interior space

Well-faceted hexagonal ZnO microprisms with regular interior space have been successfully prepared by a template-free hydrothermal synthetic route. The morphologies of the products depend on the experimental conditions such as the solvent, the concentration of ammonia aqueous solution, and the reaction temperature. Through manipulation of the aging time, the as-prepared ZnO can be controlled as a monodispersed hexagonal twinning solid or as hollow microprisms. Moreover, the evolution process of the hollow ZnO nanoarchitecture after reaction for 2, 6, 12, and 24 h has been investigated by field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). A possible growth mechanism has also been proposed and discussed. Furthermore, the photoluminescence (PL) measurement exhibits the unique emitting characteristic of hollow ZnO nanostructures.

Synthesis, properties, and gas permeation performance of cardo poly(arylene ether sulfone)s containing phthalimide side groups

Novel bisphenol monomers (1a-d) containing phthalimide groups were synthesized by the reaction of phenolphthalein with ammonia, methylamine, aniline, and 4-tert-butylanilne, respectively. A series of cardo poly (arylene ether sulfone)s was synthesized via aromatic nucleophilic substitution of 1a-d with dichlorodiphenylsulfone, and characterized in terms of thermal, mechanical and gas transport properties to H-2, O-2, N-2, and CO2. The polymers showed high glass transition temperature in the range 230-296 degrees C, good solubility in polar solvents as well as excellent thermal stability with 5% weight loss above 410 degrees C. The most permeable membrane studied showed permeability coefficients of 1.78 barrers to O-2 and 13.80 barrers to CO2, with ideal selectivity. factors of 4.24 for O-2/N-2 pair and 28.75 for CO2/CH4 pair. Furthermore, the structure-property relationship among these cardo poly(arylene ether sulfone)s had been discussed on solubility, thermal stability, mechanical, and gas permeation properties. The results indicated that introducing 4-tert-butylphenyl group improved the gas permeability of polymers evidently.

Facile synthesis and characterization of hyperbranched poly(ether amide)s generated from Michael addition polymerization of in situ created AB(2) monomers

A new straightforward strategy for synthesis of novel hyperbranched poly (ether amide)s from readily available monomers has been developed. By optimizing the reaction conditions, the AB(2)-type monomers were formed dominantly during the initial reaction stage. Without any purification, the AB(2) intermediate was subjected to further polymerization in the presence (or absence) of an initiator, to prepare the hyperbranched polymer-bearing multihydroxyl end-groups. The influence of monomer, initiator, and solvent on polymerization and the molecular weight (MW) of the resultant polymers was studied thoroughly. The MALDI-TOF MS of the polymers indicated that the polymerization proceeded in the proposed way. Analyses of H-1 NMR and C-13 NMR spectra revealed the branched structures of the polymers obtained. These polymers exhibit high-moderate MWs and broad MW distributions determined by gel permeation chromatography (GPC) in combination with triple detectors, including refractive index, light scattering, and viscosity detectors. In addition, the examination of the solution behavior of these polymers showed that the values of intrinsic viscosity [eta] and the Mark-Houwink exponent a were remarkably lower compared with their linear analogs, because of their branched nature.

Nature of the ring-banded spherulites in blends of aromatic poly(ether ketone)s

The ring-banded spherulites in liquid crystalline poly(aryl ether ketone) (LC-PAEK) and poly(aryl ether ether ketone) (PEEK) blends with a higher content (>50%) of LC-PAEK are investigated by polarizing light microscopy (PLM) and atomic force microscopy (AFM) techniques. The results indicate that the light core and rings of the ring-banded spherulites under PLM are mainly composed of an LC-PAEK phase, while the dark rings consist of coexisting phases of PEEK and a small amount of LC-PAEK. The formation of the ring-banded spherulites is attributable to structural discontinuity caused by a rhythmic radial growth.

Ordering-induced micro-bands in thin films of a main-chain liquid crystalline chloro-poly(aryl ether ketone)

Micro-banded textures developed from thin films of a main-chain thermotropic liquid crystalline chloro-poly(aryl ether ketone) in the melt were investigated using transmission electron microscopy (TEM). selective area electron diffraction, and atomic force microscopy techniques. The micro-banded textures were formed in the copolymer thin films after annealing at temperatures between 320 and 330degreesC, where a highly ordered smectic crystalline phase is formed without mechanical shearing. The micro-banded textures displayed a sinusoidal-like periodicity with a spacing of 150 nm and an amplitude of 2 rim. The long axis of the banded texture was parallel to the b-axis of an orthorhombic unit cell. In the convex regions, the molecular chains exhibited a homeotropic alignment, i.e. the chain direction was parallel to the film normal. In the concave re-ions, the molecular chains possessed a tilted alignment. In addition to the effects of annealing temperatures and times, the thickness of the film played a vital role in the formation of the banded texture. A possible formation mechanism of this banded texture vas also suggested and discussed. It was suggested that the micro-bands were formed during cooling.

Microwave-assisted synthesis of high-molecular-weight poly(ether imide)s by phase-transfer catalysis

A facile and rapid polycondensation reaction of disodium bisphenol A with bis(chlorophthalimide)s was preformed with a domestic microwave oven in o-dichlorobenzene by phase-transfer catalysis. The polymerization reactions, in comparison with conventional heating polycondensation, proceeded rapidly and were completed within 25 min. The polymerizations gave the corresponding poly(ether imide)s with inherent viscosities of 0.55-0.92 dL g(-1). The effects of various factors on the polymerization, such as the amount of the catalyst, the reaction time, and the microwave power were studied. The properties of the polymers were briefly characterized.

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.

Cyclic oligomers of phenolphthalein polyarylene ether sulfone (ketone): Preparation through cyclo-depolymerisation of corresponding polymers

Cyclic oligomers of phenolphthalein polyarylene ether sulfone(ketone) were prepared through cyclo-depolymerisation of corresponding polymers using CsF as the catalyst in dipolar aprotic solvent DMAc and DMF, and a family of macrocycles containing from dimer up to at least heptamer were confirmed. by GPC, HPLC and MALDI-TOF-MS. The yields of cyclics get as high as 86.3% and 87.9% respectively.

Peripheries of molecular projection in three-dimensional space and studies of quantitative structure-activity relationships

A new index, i.e., the periphery representation of the projection of a molecule from 3D space to a 2D plane is described. The results, correlation with toxicity of substituted nitrobenzenes, obtained by using periphery descriptors are much better than that obtained by using the areas (i.e., shadows) of projections of the compounds. Even better results were achieved by using the combination of periphery descriptors and the projections areas as well as the indicated variable K reflecting the action of group NO position on the benzene ring.

Vapor permeation separation of MeOH/MTBE through polyimide/sulfonated poly(ether-sulfone) hollow-fiber membranes

Mixtures of methanol/MTBE were separated with polyimide/sulfonated poly(ether-sulfone) hollow-fiber membranes. The separation was attempted by vapor permeation instead of pervaporation, which had been used by most researchers. The separation properties of the hollow-fiber membranes and operating conditions are discussed. The results showed that separation factors of the blended polyimide/sulfonated poly(ether-sulfone) hollow-fiber membranes were extremely high for the methanol/MTBE mixtures.

Crystallization behaviors of n-nonadecane in confined space: Observation of metastable phase induced by surface freezing

Crystallization and phase transition behaviors of n-nonadecane in microcapsules with a diameter of about 5 mu m were studied with the combination of differential scanning calorimetry ( DSC) and synchrotron radiation X-ray diffraction ( XRD). As evident from the DSC measurement, a surface freezing monolayer, which is formed in the microcapsules before the bulk crystallization, induces a novel metastable rotator phase ( RII), which has not been reported anywhere else. We argue that the existence of the surface freezing monolayer decreases the nucleating potential barrier of the RII phase and induces its appearance, while the lower free energy in the confined geometry turns the transient RII phase to a " long- lived" metastable phase.

Poly(aryl ether)s containing ter- and pentafluorene pendants for efficient blue light emission

Four novel thermally stable poly(aryl ether)s, e.g., P3F, P5F, P2A3F, and P2A5K containing ter- or pentafluorene units in the side chains for efficient blue light emission have been designed and synthesized. All the polymers show the optical properties identical to the corresponding monomers and are amorphous with higher glass transition temperature (T-g) than their monomeric Counterparts. The polymer light-emitting diodes (PLEDs) were fabricated with the device structure of ITO/(PEDOT:PSS)/polymer/Ca/Al. The incorporation of diphenylamine group to oligofluorene terminals significantly reduces the hole-injection energy barrier in PLEDs. The devices based on P2A3F and P2A5F show the luminous efficiencies of 1.2 and 2.0 cd/A at a brightness of 300 cd/m(2) with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.15, 0.13) and (0.19, 0.20), respectively. All these indicate that the high-performance light-emitting polymers can be synthesized with the traditional condensation polymerization through careful design of polymer structures.