Single‐Source Precursors For Synthesizing Bifunctional Periodic Mesoporous Organosilicas

A new class of bifunctional periodic mesoporous organosilicas (PMOs) composed of organosilicate building blocks with two different silicon sites have been synthesized from the single‐source bifunctional organosilica precursors tris(triethoxysilylethyl)ethoxysilane and bis(triethoxysilylethyl)diethoxysilane, respectively denoted MT³‐PMO and DT²‐PMO. The synthesis of these PMOs is achieved by the co‐assembly of a triblock‐copolymer Pluronic P123 template with the bifunctional organosilica precursor under acid‐catalyzed and inorganic‐salt‐assisted conditions. After template removal through solvent extraction, the MT³‐PMO and DT²‐PMO so obtained show well‐ordered mesopores and display large pore diameters (6–7 nm) and pore volumes (0.6–0.8 cm³ g^–1) with a narrow pore‐size distribution and high surface areas (700–800 m³ g^–1).     

Highly Efficient Orange and Green Solid‐State Light‐Emitting Electrochemical Cells Based on Cationic IrIII Complexes with Enhanced Steric Hindrance

Highly efficient orange and green emission from single‐layered solid‐state light‐emitting electrochemical cells based on cationic transition‐metal complexes [Ir(ppy)₂sb]PF₆ and [Ir(dFppy)₂sb]PF₆ (where ppy is 2‐phenylpyridine, dFppy is 2‐(2,4‐difluorophenyl)pyridine, and sb is 4,5‐diaza‐9,9′‐spirobifluorene) is reported. Photoluminescence measurements show highly retained quantum yields for [Ir(ppy)₂sb]PF₆ and [Ir(dFppy)₂ sb]PF₆ in neat films (compared with quantum yields of these complexes dispersed in m‐bis(N‐carbazolyl)benzene films). The spiroconfigured sb ligands effectively enhance the steric hindrance of the complexes and reduce the self‐quenching effect. The devices that use single‐layered neat films of [Ir(ppy)₂sb]PF₆ and [Ir(dFppy)₂sb]PF₆ achieve high peak external quantum efficiencies and power efficiencies of 7.1 % and 22.6 lm W^–1) at 2.5 V, and 7.1 % and 26.2 lm W^–1 at 2.8 V, respectively. These efficiencies are among the highest reported for solid‐state light‐emitting electrochemical cells, and indicate that cationic transition‐metal complexes containing ligands with good steric hindrance are excellent candidates for highly efficient solid‐state electrochemical cells.     

Radiochemical proton activation analysis for the determination of cadmium and lead in sediment reference materials

Proton activation analysis was used for the determination of cadmium and lead in three sediment reference materials. The method is based on the^111,112Cd(p, xn)¹¹¹ In and the^206,207,208Pb(p, xn)²⁰⁶Bi reactions.¹¹¹In and²⁰⁶Bi were chemically separated by anion exchange. The results obtained were taken into account for the certification of the materials and are in the excellent agreement with the certified values.     

Electrochemical C-V Characteristics and Photoluminescence of a-C∶N Films

Amorphous carbon (a-C) films and amorphous carbon films incorporating with the nitrogen (a-C∶N) were deposited on silicon substrates in a radio-frequency driven plasma enhanced chemical vapour deposition system, while the surface electrical properties of films were investigated by electrochemical capacitance-voltage measurements. It was examined the effect of the interface defects on the properties and deduced that the conducting type of a-C∶N films was n-type. Subsequently, a comparative studies of a-C and a-C∶N films were performed by photoluminescence spectra depending on the temperature. With the decrease of the temperature, the main band with peak energy of 2.48 eV in the a-C∶N films was more intense compared with the other three bands caused by amorphous C in the a-C films.     

Synthesis of molecular imprinted organic-inorganic hybrid polymer binding caffeine

Random copolymers of poly{(methacrylamide)-co-(vinyl trimethoxysilane)} and poly{(methacrylic acid)-co-(vinyl trimethoxysilane)} were synthesized via a free radical polymerization reaction. Acid catalyzed sol-gel process of tetraethylorthosilicate (TEOS) with aforementioned polymers in the presence of methyl xanthine class of alkaloid like caffeine resulted in the formation of highly transparent monoliths. Solvent extraction of the template leaves behind the recognition sites intact with high selectivity towards the print molecule. The ionic and non-specific adsorptions, which are considered to be the main disadvantages of the molecularly imprinted polymers (MIP), are prevented to a considerable extent by the end capping of surface silanol groups. The template binding efficiencies of MIP were determined by HPLC analysis.     

New poly(butylene succinate)/layered silicate nanocomposites. II. Effect of organically modified layered silicates on structure,properties, melt rheology,and biodegradability

A series of new poly(butylene succinate) (PBS)/layered silicate nanocomposites were prepared successfully by simple melt extrusion of PBS and organically modified layered silicates (OMLS). Three different types of OMLS were used for the preparation of nanocomposites: two functionalized ammonium salts modified montmorillonite and a phosphonium salt modified saponite. The structure of the nanocomposites in the nanometer scale was characterized with wide-angle X-ray diffraction and transmission electron microscopic observations. With three different types of layered silicates modified with three different types of surfactants, the effect of OMLS in nanocomposites was investigated by focusing on four major aspects: structural analysis, materials properties, melt rheological behavior, and biodegradability. Interestingly, all these nanocomposites exhibited concurrent improvements of material properties when compared with pure PBS. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3160–3172, 2003     

A relaxed model and its homogenization for nematic liquid crystals in composite materials

We analyse a model for equilibrium configurations of composite systems of nematic liquid crystal with polymer inclusions, in the presence of an external magnetic field. We assume that the system has a periodic structure, and consider the relaxed problem on the unit length constraint of the nematic director field. The relaxation of the Oseen–Frank energy functional is carried out by including bulk as well as surface energy penalty terms, rendering the problem fully non‐linear. We employ two‐scale convergence methods to obtain effective configurations of the system, as the size of the polymeric inclusions tends to zero. We discuss the minimizers of the effective energies for, both, the constrained as well as the unconstrained models. Copyright © 2004 John Wiley & Sons, Ltd.     

Femtochemistry of Guest Molecules Hosted in Colloidal Zeolites

The ultrafast deprotonation of 2‐(2′‐hydroxyphenyl)benzothiazole (HBT) hosted in nanometer‐sized FAU and MFI zeolites is reported. Samples are prepared via in‐situ incorporation of HBT in the precursor colloidal solutions resulting in the formation of nanometer‐sized zeolites under hydrothermal treatment. The diameter of the zeolite particles formed in the crystalline suspensions is determined by dynamic light scattering and high‐resolution transmission microscopy to lie in the range 40–100 nm. It is shown that the HBT loading does not influence the degree of the zeolite crystallinity but does change the size and the morphology of the individual zeolite nanoparticles. Colloidal suspensions containing the crystalline nanoparticles are well suited for optical investigations since they are sufficiently transparent and clear. The photochemical properties of the HBT guest in the zeolite‐host systems are studied with femtosecond transient transmission spectroscopy. Depending on the acid–base properties either the enol or the keto tautomer of HBT is found to be hosted in the internal voids of the zeolites; upon UV excitation, the HBT‐keto tautomer is converted to the enol form in both MFI‐ and FAU‐type hosts. The HBT photoconversion takes place via an ultrafast deprotonation within 1.5 ps as detected by femtosecond transient absorption spectroscopy.     

Water‐Stable,Magnetic Silica–Cobalt/Cobalt Oxide–Silica Multishell Submicrometer Spheres

A method to produce monodisperse magnetic composite spheres with diameters from less than 100 nm to more than 1 μm in water solution is reported. The spheres consist of a dielectric silica core and a cobalt/cobalt oxide shell which can be protected from further oxidation with an outer shell of silica or, alternatively, they can be covered with the polymer polyvinylpyrrolidone as a stabilizer. The formation of a uniform magnetic shell proceeds with the adsorption of metallic cobalt seeds, produced by the reduction of cobalt chloride with sodium borohydride, on a self‐assembled layer of polyelectrolytes on the silica core. In the second step, an outer silica shell can be formed by the hydrolysis and condensation of (3‐aminopropyl)trimethoxysilane and tetraethoxysilane. The double‐shell composite spheres show excellent sphericity, monodispersity, and a magnetic hysteresis loop at room temperature.     

THERMAL AND THERMO-ELASTIC-PLASTIC RESPONSE OF CERAMIC-METAL FUNCTIONALLY GRADED MATERIALS—THERMAL SHOCK PROBLEM

The thermal and thermo-elastic-plastic response of newly developed ceramic-metalfunctionally graded materials under a thermal shock load is studied.The materials are heated at the ce-ramic surface with a sudden high-intensity heat flux input,and cooled at the metal surface with aflowing liquid nitrogen.Emphasis is placed on two aspects:(1)the influence of the graded composi-tion of the materials on the temperature and stress response;and(2)the optimum design of the gradedcomposition from a unified viewpoint of the heat insulation property and stress relaxation property.Moreover,a comparison between the thermoelastic stress and the thermo-elastic-plastic stress is alsomade to indicate the plasticity effect.