Conductive polyaniline/silica hybrids from sol-gel process

A hybrid material with a conductive organic network in an inorganic matrix has been prepared by in-situ hydrolysis/polycondensation of TEOS in an aqueous solution of a solubilized polyaniline. Due to intense hydrogen bonding (indicated by Si-29 NMR and FTIR) the conductive polymer is very well dispersed in the silica matrix. The Figure shows SEM images of a 46/54 wt.-% hybrid at two temperatures (left 20 degreesC, right 100 degreesC).

Formation of ordered arrays of gold nanoparticles from CTAB reverse micelles

In this presentation, a reverse micelle technique was described to create colloid gold nanoparticles and their self-organization into superlattices. Gold nanoparticles were prepared by the reduction of HAuCL4 in CTAB/octane + 1-butanol/H2O reverse micelle system using NaBH4 as reducing agent. Dodecanethiol (C12H25SH) was used to passivate the gold nanoparticles immediately after formation of the gold colloid. After re-dispersing in toluene under ultrasonication, a supernatant containing nearly monodispersed dodecanethiol-capped gold nanoparticles was obtained. Self-organization of the gold nanoparticles into 1D, 2D and 3D superlattices was observed on the carbon-coated copper grid by TEM. UV-vis absorption spectra were also used to characterize the gold colloids with and without dodecanethiol capping. (C) 2001 Elsevier Science B.V. All rights reserved.

Electrochemiluminescence of tris(2,2 '-bipyridine)ruthenium(II) immobilized in poly(p-styrenesulfonate)-silica-Triton X-100 composite thin-films

The electrochemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium(ii) [Ru(bpy)(3)(2+)] immobilized in poly(p-styrenesulfonate) (PSS)-silica-Triton X-100 composite films was investigated. The cooperative action of PSS, sol-gel and Triton X-100 attached Ru(bpy)(3)(2+) to the electrode strongly, and the presence of Triton X-100 prevented drying fractures of the sol-gel films during gelation and even on repeated wet-dry cycles. The modified electrode was used for the ECL detection of oxalate, tripropylamine (TPA) and NADH in a flow injection analysis (FIA) system with a newly designed flow cell. The detection scheme exhibited good stability, short response time and high sensitivity. Detection limits were 0.1, 0.1 and 0.5 mu mol L-1 for oxalate, TPA and NADH, respectively, and the linear concentration range extended from 0.001 to 1 mmol L-1 for the three analytes. Applications of the flow cell in ECL and electrochemical detection, as well as the immobilization of reagents based on the cooperative action, are suggested.

Novel, covalently bonded hybrid materials of europium (terbium) complexes with silica

New kinds of hybrid materials containing covalently bonded Eu3+ (Tb3+) bipyridine complexes in a silica network have been prepared and their luminescence properties reported.

Preparation and luminescence properties of lanthanide complexes and their silica-based composites

Binary complexes of europium and terbium with N-propyl-4-carboxyphthalimide (NP) were prepared and characterized. The luminescence behaviors of the lanthanide complexes as well as their doped silica-based composites were investigated by fluorescence spectra. The results indicated that the lanthanide complexes showed fewer emission lines and slightly lower intensities in silica matrix than that of corresponding pure complexes. The lifetimes of the lanthanide complexes became longer when they were incorporated in silica matrix. (C) 2001 Elsevier Science B.V. All rights reserved.

Preparation of poly(4-vinylpyridine)/silica hybrids supported cyclopentadienyltitanium trichloride (CpTiCl3) catalyst and styrene polymerization

Poly(4 - vinylpyridine)/silica( PVP/SiO2) organic - inorganic nanoscale hybrid was prepared using sol - gel method, in which PVP was used as an organic component and TEOS as a SiO2 precusor, This hybrid was used as CpTiCl3 support. The XPS and IR measurements showed that two kinds of catalytic active site were formed through analyzing the interaction mode between support and CpTiCl3. The results of styrene polymerization showed that syndiotactic was the highest at 50 degreesC. The catalytic activity was 1.09 x 10(6) g PS/ (mol Ti . h) at 70 degreesC when n(Al)/n(Ti) = 1500. GPC results showed a bimodal molecular weight distribution.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 7. Phase structures in a series of copolyethers containing odd and even numbers of methylene units of different compositions

A series of liquid crystalline copolyethers have been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,12-dibromododecene [coTPPs(7/12)], which represents copolyethers containing both odd and even numbers of methylene units. The molar ratio of odd to even methylene units in this series ranges from 1/9 to 9/1. The coTPPs(7/12) exhibit multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. For all these thermal transitions, a small undercooling and superheating dependence is observed upon cooling and heating at different rates. Three types of phase behaviors can be classified in coTPPs(7/12) on the basis of the structural analyses by wide-angle X-ray diffraction on powder and fiber samples and by electron diffraction experiments in transmission electron microscopy. At room temperature, highly ordered smectic and smectic crystal (SC) phases are identified in coTPPs(7/12: 1/9 and 2/8), which is similar to the homopolymer TPP(m = 12). The coTPPs(7/12: 3/7, 4/6, and 5/5) possess a hexagonal columnar (Phi(H)) phase in which the molecular and columnar axes are parallel to the fiber direction and perpendicular to the hexagonal lateral packing. The coTPPs(7/12: 6/4, 7/3, and 8/2) possess a tilted hexagonal columnar (Phi(TH)) phase with a single tilt angle which increases with the increasing composition of the seven-numbered methylene units. However, in coTPP(7/12: 9/1), a Phi(TH) phase with multiple tilt angles is found. Upon heating, phase structures in most coTPPs(7/12) involving the columnar phases enter directly into the nematic (N) phase, while the coTPP(7/12: 1/9) exhibits a highly ordered smectic F (S-F) phase before it reaches the N phase. One exception is found in coTPP(7/12: 2/8), wherein the transformation from the S-F to Phi(H) occurs prior to the N phase. Combining the copolymer phase behaviors observed with the corresponding homopolymers TPP(n = 7) and TPP(m = 12), a phase diagram describing transition temperatures with respect to the composition can be constructed.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 6. Structure changes from smectic to columnar phases in a series of copolyethers containing odd and even numbers of methylene units in equal molar composition

A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane and different alpha,omega-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(nlm) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium, Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n 11 to 5. in the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (Phi(H)) phase. A further decrease in temperature leads to a (PH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (S-F) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature Phi(H) phase to the low-temperature S-F phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

Preparation and luminescence properties of terbium-Sal complex in-situ synthesized in silica matrix by a two-step sol-gel process

In-situ synthesis of terbium complex with salicylic acid (Sal) in silica matrix was made by a two-step sol-gel process. The terbium complex with salicylic acid was formed in sol-gel derived silica gel, and confirmed by the luminescence excitation spectra and infrared(IR) spectra. As compared to the pure terbium complex powder, the silica gel containing terbium complex exhibits its characteristic emission and presents a longer fluorescence lifetime than that for the pure complex. The luminescence properties of the complex containing;silica gel were investigated and compared with that of both terbium doped the silica gel and thp pure complex powder. The reasons leading to the above results were also discussed.

Luminescence characteristics of europium and terbium complexes with 1,10-phenanthroline in-situ synthesized in a silica matrix by a two-step sol-gel process

In-situ synthesis of europium and terbium complexes with 1,10-phenanthroline (phen) in silica matrix by a two-step sol-gel process has been proposed. The formation of europium and terbium complexes with phen in sol-gel derived silica gel were confirmed by the luminescence excitation spectra. The silica gels that contain in-situ synthesized europium and terbium complex exhibit the characteristic emission bands of the rare earth ions. Furthermore. the rare earth ions present longer fluorescence lifetimes than the comparable pure complex powder and the complexes dissolved in ethanol solutions. The luminescence properties of the silica gels codoped with europium (or terbium) and phen were also investigated with respect to the gels doped with europium (or terbium). (C) 1999 Elsevier Science B.V. All rights reserved.

In-situ synthesis of terbium complex with salicylic acid in silica matrix by a two-step sol-gel process

A process for in situ synthesis of terbium complex with salicylic acid by a two-step sol-gel method in silica matrix has been proposed. The luminescence properties of the silica gels codoped with terbium and salicylic acid have also been discussed with respect to that of the gel doped with terbium and that of pure terbium complex with salicylic acid.

Luminescence properties of rare-earth (Eu3+ and Tb3+) complexes with paraaminobenzoic acid and 1,10-phenanthroline incorporated into a silica matrix by sol-gel method

Ternary complexes of europium and terbium with paraaminobenzoic acid and 1,10-phenanthroline (Eu(p-ABA)(3). phen . 2H(2)O and Tb(p-ABA)(3). phen . 2H(2)O, where p-HABA = paraaminobenzoic acid and phen = 1,10-phenanthroline) were introduced into a silica matrix by sol-gel method. The luminescence behavior of the complexes in silica gels was studied in comparison with the. corresponding solid-state complexes by means of emission, excitation spectra, and Lifetimes. Within the range of effective dopant concentrations, the luminescence intensities of rare-earth complexes in silica gel increase with the increasing of their dopant concentration. The lifetimes of rare-earth ions (Eu3+ and-Tb3+) in silica gel doped with europium and terbium complexes become longer than those in pure complexes. Very small amounts of rare-earth complexes doped in silica gel matrix can exhibit excellent luminescence properties, (C) 1998 Elsevier Science Ltd.

Luminescence properties of the rare earth (Eu3+ and Tb3+) complexes with 1,10-phenanthroline incorporated in silica matrix by a sol-gel method

Europium and terbium complexes with 1,10-phenanthroline were introduced into silica gel by the sol-gel method. The luminescence behavior of the complexes in silica gels was studied compared with the corresponding solid state complexes by means of emission, excitation spectra and lifetimes. (C) 1998 Published by Elsevier Science S.A. All rights reserved.

Luminescence properties of rare earth (Eu3+ and Tb3+) complexes with conjugated carboxylic acids and 1,10-phenanthroline incorporated in silica matrix

Binary and ternary complexes of europium and terbium with conjugated carboxylic acid (nicotinic acid and 3,4-furandicarboxylic acid) and 1,10-phenanthroline were introduced into silica gel by the sol-gel method. The luminescence behavior of the complexes in silica gels was studied compared with the corresponding solid state complexes by means of emission, excitation spectra and lifetimes. The result indicated that the rare earth ions (EU3+ and Tb3+) showed fewer emission lines and slightly lower emission intensities in the silica gel than those in pure rare earth complexes. The lifetimes of rare earth ions (EU3+ and Tb3+) in silica gel doped with rare earth complexes became longer than those in pure rare earth complexes. (C) 1998 Elsevier Science S.A.

Luminescence properties of sol-gel derived silica gels doped and undoped with RE-complexes (RE=Eu, Tb)

The luminescence properties of silica gels and silica gels doped with two rare earth complexes, Eu(TTA)(3) and Tb(o-CBA)(3) (TTA=thenoyltriffuocetate, o-CBA=o-chlorobenzoic acid) are reported and discussed. Pure silica gels show a blue luminescence, and the maximum excitation and emission wavelengths depend strongly on the solvents used. Both of the studied rare earth complexes exhibit the characteristic emissions of the rare earth ions in silica gels, i.e., Eu3+5D0-->F-7(J)(J=0,1,2,3,4), Tb3+5D4-->F-7(J)(J=3,4,5,6) transitions. Compared with the pure RE-complexes powder, the silica gels doped with RE-complexes show fewer emission lines of the rare earth ions. Furthermore the rare earth ion (Tb3+) presents a longer lifetime (1346 mu s) in silica gel doped with Tb(o-CBA)3 than in pure Tb((o-CBA)(3) powder (744 mu s). The reasons responsible for these results are discussed in the context.