Photoluminescence of organic-inorganic hybrid SiO2 xerogels

Organic-inorganic hybrid SiO2 xerogels were prepared by the sol-gel method under various preparation conditions and compositions by using tetraethoxysilane (TEOS), (3-aminopropyl) triethoxysilane (A-PS), (3-glycidoxypropyl) trimethoxysilane (GPS), organic acid (CH3COOH) and inorganic acids (HCl, HNO3, H2SO4) as the main precursors. Luminescence and FT-IR spectra were used to characterize the resulted hybrid SiO2 xerogels. The result of FT-IR spectrum shows that the xerogels are composed of non-crystalline -Si-O-Si- networks containing some organic groups such as -NH, -CH and -OH. Under the excitation of 365 nm, all the hybrid xerogels exhibit strong luminescence in the blue region, but the emission intensity and position depend on the starting precursor compositions to a large extent. Suitable amount of polyethylene glycol (PEG500 and PEG10000) in the hybrid xerogels can enhance the emission intensity. Additionally, the emission intensity of the hybrid xerogels increases with heat treatment temperature in the range of ambient to 200degreesC, and vacuum condition is also able to enhance the emission intensity.

Characterization of organic-inorganic multilayer films by cyclic voltammetry, UV-Vis spectrometry, X-ray photoelectron spectroscopy, small-angle X-ray diffraction and electrochemical impedance spectroscopy

We have employed several techniques, including cyclic voltammetry, UV-Vis spectrometry, small-angle X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy, to characterize the formation processes and interfacial features of ultrathin multilayer films of silicotungstate and a cationic redox polymer on cysteamine-coated Au electrodes self-assembled monolayers. All of these techniques confirm that the multilayer films are built up stepwise as well as uniformly in a layer-by-layer fashion. In particular, the electrochemical impedance spectroscopy is successfully used to monitor the multilayer deposition processes. It has been proved that the electrochemical impedance spectroscopy is a very useful technique in characterization of multilayer films because it provides valuable information about the interfacial impedance features.

An organic-inorganic vanadium oxide with one-dimensional ladder-type structure: hydrothermal synthesis, structure and characterization of [V4O10(o-phen)(2)]

A novel organic-inorganic hybrid vanadium oxide [V4O10(o-phen)(2)], involving all vanadium atoms present in +5 oxidation, has been hydrothermally synthesized and characterized by elemental analysis, IR, UV-vis, ESR, XPS spectra and TG-DTA thermal analysis. The single-crystal X-ray diffraction shows that the red-brown crystal is formed in the triclinic system, space group P (1) over bar, a = 9.782(2), b = 6.5124(14), c = 19.765(4) Angstrom, alpha = 89.94(2)degrees, beta = 100.66(2)degrees, gamma = 89.86(2)degrees. The title compound exhibits an infinite one-dimensional ladder-type tetravanadate skeleton with organonitrogen donors of o-phenanthroline ligands coordinated directly to the vanadium oxide framework.

Photoluminescent organic-inorganic composite films layer-by-layer self-assembled from the rare-earth-containing polyoxometalate Na-9[EuW10O36] and poly(allylamine hydrochloride)

Photoluminescent organic-inorganic composite films incorporating the rare-earth-containing polyoxometalate Na-9[EuW10O36] (EW) and poly(allylamine hydrochloride) (PAH) have been prepared by the layer-by-layer self-assembly method. UV-vis spectroscopy and ellipsometry were used to follow the fabrication process of the EW/PAH composite films. The experimental results show that the deposition process is linear and highly reproducible from layer to layer. An average EW/PAH bilayer thickness of ca. 2.1 nm was determined by ellipsometry. In addition, scanning electron microscopy and atomic force microscopy images of the EW/PAH composite films indicate that the film surface is relatively uniform and smooth. The photoluminescent properties of these films were investigated by fluorescence spectroscopy.

An organic-inorganic hybrid ultrathin film: preparation and characterization of copper phthalocyanine derivative-ferric oxide nanoparticles

A nanoparticulate ferric oxide-copper tris(2,4-di-tert-amylphenoxy)-8-quinolinolylphthalocyanine hybrid ultrathin film was constructed from alternate layers by the Langmuir-Blodgett technique. The composition, morphology and structure of the film were studied by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy, atomic force microscopy, small-angle X-ray diffraction, visible spectroscopy and polarized UV-Vis spectroscopy. All the above analyses suggest that the thin film is a kind of one-dimensional superlattice, composed of organic and inorganic components. The XPS data reveal that the nanoparticulate ferric oxide exists as an alpha-Fe2O3 phase in the films. Gas-sensing measurements show that the hybrid LB film has very fast response-recovery characteristics towards 2 ppm C2H5OH vapor.

Hydrothermal synthesis and structural characterization of a novel organic-inorganic hybrid compound {[Cu(2, 2 '-bpy)(2)](2)-Mo8O26}

A novel organic-inorganic hybrid compound {[Cu (2, 2'-bpy)(2)](2)Mo8O26} has been hydrothermally Synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group, Pna2(1), with a=2.4164 (5), b=1.8281 (4), c=1.1877 (2) nm, V=5.247(2) nm(3), Z=4, and final R-1=0.0331, wR(2)=0.0727. The structure consists of discrete {[Cu(2,2'-bpy)(2)](2)Mo8O26} clusters, constructed from a beta -octamolybdate subunit[Mo8O26](4-) covalently bonded to two [Cu(2,2'-bpy)(2)](2+) coordination complex cations via bridging oxo groups. In addition, the spectroscopic properties and thermal behavior of this compound have been investigated by spectroscopic techniques (UV-vis, IR, Raman and EPR spectra) and TG analysis.

Luminescent properties of organic-inorganic hybrid monoliths containing rare-earth complexes

Transparent organic-inorganic hybrid monoliths containing rare-earth complexes (Eu(TTA)(3)Phen, Tb(Sal)(3)) were prepared via the sol-gel technique. It could be observed by transmission electron microscopy that the fluorescent particles are distributed in the matrix at the microscopic level. The matrix is composed of organic-inorganic semiinterpenetrating networks, i.e., PHEMA-SiO2 system. The fluorescence emission spectra of samples are similar to those from corresponding powdered Eu(III) and Tb(III) complexes, and the half-widths of the strongest bands are less than 10 nm, which indicates that the monolith exhibits high fluorescence intensity and color purity. Furthermore, the fluorescence spectra exhibit no obvious change with decreasing nanoparticle size of the rare-earth complex. The fluorescence lifetimes of samples are longer than pure Eu(III), Tb(III) complexes, respectively. Samples irradiated with an UV lamp (365 nm) are still transparent but become bright red and green in color due to fluorescence of Eu(III) and Tb(III) complexes. (C) 2000 Elsevier Science B.V. All rights reserved.

Confined crystallization behavior of PCL in organic-inorganic hybrid system

poly(epsilon-caprolactone) (PCL) and silica (SiO2) organic-inorganic hybrid materials have been synthesized by sol-gel approach and the crystalline behavior of PCL in the silica networks has been investigated by differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD). The degree of PCL crystallinity in the PCL/SiO2 hybrid networks reduces with the increase of SiO2 content. PCL is in an amorphous state when the concentration of PCL is lower than 40wt% in the hybrid materials. The melting points of PCL in the networks are lower than that of pure PCL,but they almost have a same value. WAXD results show that when the PCL weight percentage is higher than 40wt% in the hybrid samples,part of PCL can crysatllize and the PCL crystallites are almost in a same size. That means the crystalline movement of PCL molecular chains is strictly confined by the porous gel. The crystalline PCL in the hybrid samples is relatively free from the composition of the materials, because the crystallization temperature and melting point of PCL of the samples are almost equal,and the crystalline PCL of different samples has the same crystalline structure and the same crystallite sizes L-110 and L-200, that means the crystalline part of PCL in the hybrid samples is unperturbed and the porous silica gel gives enough space for PCL to crystallize into the same crystalline structure and the same size crystallites.

Preparation, structures, and electrochemistry of a new polyoxometalate-based organic/inorganic film on carbon surfaces

The preparation, structure, and electrochemical and electrocatalytical properties of a new polyoxometalate-based organic/inorganic film, composed of cetyl pyridinum 11-molybdovanadoarsenate (CPMVA) molecules, have been studied. Cyclic potential scanning in acetone solution led to a stable CPMVA film formed on a highly oriented pyrolytic graphite (HOPG) surface. X-ray photoelectron spectroscopy, scanning tunneling microscopy, and cyclic voltammetry were used for characterizing the structure and properties of the CPMVA film. These studies indicated that self-aggregated clusters were formed on a freshly cleaved HOPG surface, while a self-organized monolayer was formed on the precathodized HOPG electrode. The CPMVA film exhibited reversible redox kinetics both in acidic aqueous and in acetone solution, which showed that it could be used as a catalyst even in organic phase. The CPMVA film remained stable even at pH > 7.0, and the pH dependence of the film was much smaller than that of its inorganic film (H4AsMo11VO40) in aqueous solution. The CPMVA film showed strong electrocatalysis on the reduction of bromate, and the catalytic currents were proportional to the square of the concentration of bromate. The new kind of polyoxometalate with good stability may have extensive promise in catalysis.

Nanostructured hybrid organic-inorganic lanthanide complex films produced in situ via a sol-gel approach

Communication: Nanostructural hybrid organic-inorganic lanthanide complex films were prepared in situ by use of a novel sol-gel precursor containing pendant triethoxy-silyl and carboxyl groups (see Figure). The resulting transparent and crack-free films gave rise to strong red or green emission, even at low lanthanide ion concentration. Phase separation and lanthanide ion aggregation were controlled at the nanoscale.

Synthesis and luminescence properties of organic-inorganic hybrid thin films doped with Eu(III)

In this study, silica-based transparent organic-inorganic hybrid films were prepared by the sol-gel method. Tetraethoxysilane and 3-(trimethoxysilyl)propyl methacrylate were used as the inorganic and organic compounds, respectively. Lanthanide complexes [Eu(phen)(2)]Cl-3 were incorporated into the organically modified silicates (ORMOSIL) and the luminescence properties of the resultant hybrid films (ORMOSIL:[Eu(phen)(2)]Cl-3) were characterized. The relative quantum efficiency was observed higher and the lifetimes were longer in hybrid films than those in pure silica films. Furthermore, thermal stability of hybrid films incorporating various concentration of Eu(III) complex was studied. (C) 2001 Elsevier Science B.V. All rights reserved.

Synthesis, properties and crystal structure of organic-inorganic radical salt (DBTTF)(6)HPMo12O40 center dot 2H(2)O

Organic-inorganic radical salt (DBTTF)(6)PMo12O40 . 2H(2)O was synthesized by electrocrystallization and characterized by IR spectrum, electronic spectrum and ESR technology, Its magnetic property, conductivity and crystal structure were determined. The title compound crystallized in a triclinic system with P1 space group, a = 1.378 7(7), b = 1.420 4 (2), c = 1.570 2(2) nm, alpha = 104.57(1)degrees, beta = 103.41(2)degrees, gamma = 95.80(2)degrees, V = 2.853(2) nm(3) Z = 1 and a final R = 0.072 7.

Amperometric glucose biosensor based on sol-gel organic-inorganic hybrid material

A new type of sol-gel organic-inorganic hybrid material was developed and used for the production of biosensors. This material is composed of silica sol and a grafting copolymer of poly(vinyl alcohol) with 4-vinylpyridine. It prevents the cracking of conventional sol-gel-derived glasses and eliminates the swelling of the hydrogel. The optimum composition of the hybrid material was first examined, and then glucose oxidase was immobilized in this matrix to demonstrate its application. The characteristics of the biosensor were studied by cyclic voltammetry and chronoamperometry. The biosensor exhibited a series of good properties: high sensitivity (600 nA mmol(-1)L(-1)), short response time (11 s) and remarkable long-term stability in storage (at least 5 months). In addition, the characteristics of the second-generation biosensor with the use of tetrathiafulvalene as a mediator mere discussed.

Hybrid organic-inorganic phenyl monolithic column for capillary electrochromatography

A novel hybrid organic-inorganic silica-based monolithic column possessing phenyl ligands for reversed-phase (RP) capillary electrochromatography (CEC) is described. The monolithic stationary phase was prepared by in situ co-condensation of tetraethoxysilane (TEOS) with phenyltriethoxysilane (PTES) via a two-step catalytic sol-gel procedure to introduce phenyl groups distributed throughout the silica matrix for chromatographic interaction. The hydrolysis and condensation reactions of precursors were chemically controlled through pH variation by adding hydrochloric acid and dodecylamine, respectively. The structural property of the monolithic column can be easily tailored through adjusting the composition of starting sol solution. The effect of PTES/TEOS ratios on the morphology of the created stationary phases was investigated. A variety of neutral and basic analytes were used to evaluate the column performance. The CEC columns exhibited typical RP chromatographic retention mechanism for neutral compounds and had improved peak shape for basic solutes.