Siloxane-Based Nanobuilding Blocks by Reaction Between Silanediol and Trifunctional Silicon Alkoxides

The preparation of nanostructured organic-inorganic materials by assembling of nanobuilding blocks allows controlling the extent of phase interaction, which in its turn governs structure-properties relationships. We present here the synthesis of siloxane-based nanobuilding blocks prepared by reacting diphenylsilanediol with vinyltriethoxysilane and triethoxysilane. The reaction products were obtained by non-hydrolytic condensation between silanediol and ethoxide groups in inert atmosphere, in the presence of pyridine, triethylamine or butyl lithium. Different synthetic conditions were examined by means of ATR-FTIR and NMR spectroscopies, showing the formation of siloxane bonds. In the case of triethoxysilane the reaction carried out in the presence of pyridine leads to Si–H bond preservation in the final product. Air stable products with improved Si–O–Si hydrolytic stability can be obtained by removal of the base after the reaction completion. The condensation products can be described as a mixture of siloxane rings involving difunctional and trifunctional silicon units.     

Compositional Profiles in Silica-Based Sol-Gel Films Doped with Erbium and Silver, by RBS and ERDA

Photosensitive organic-titania hybrid materials have been prepared from metal alkoxides and various organic ester compounds with double bonds. The refractive index of the film increases with the decrease of the concentration of the organic ester compound, and the highest refractive index of 1.62 is obtained when 2-hydroxymethyl acrylate (HOA) is used as the organic ester and the molar ratio of HOA to Ti is 0.5. The material with the highest refractive index is exposed to femtosecond pulse using the multi-beam laser interference technique. After laser irradiation, the irradiated parts of the material are photopolymerized and periodic structures can be obtained by development of the unirradiated parts. In the case of laser irradiation of 120 J total energy for 5 min, the periodic structure obtained corresponds to 2D photonic crystal structure which is composed of two parts; the material with the highest refractive index and the air.     

Surface solid-state interactions in copper-nickel-cement catalysts for hydrogenation of oxygen

The surface phase composition of alumocalcium cement-supported CuO and CuO-NiO catalysts prepared by chemical mixing has been studied using the method of thermo-vacuum curves of electric conductivity. The deactivation of these catalysts due to overheating to 800 °C under conditions of hydrogenation of oxygen is rationalized by the partial extraction of CuO (and NiO) from the stabilizing structure of the support solid solutions and by sintering of the extracted oxides and the reduced metallic phase. Complete regeneration of the CuO-NiO-talum catalysts can be achieved if a considerable amount (20%) of copper hydroxocarbonate is added.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1559–1562, September, 1994.     

The Electrochemical Behavior of Keggin Polyoxometalate Modified by Tricyclic,Aromatic Entity

The inorganic‐organic hybrid polyoxometalates (POMs), (pbpy)₄H[PMo₁₂O₄₀(VO)] ( 1 ) and (pbpy)₄H₄[SiMo₁₂O₄₀] ( 2 ) (pbpy=5‐phenyl‐2‐(4‐pyridinyl)pyridine), have been synthesized and were, respectively, used as a solid bulkmodifier to fabricate a three‐dimensional bulk‐modified carbon paste electrode (CPE) by direct mixing. The electrochemical behavior and electrocatalysis of 1 and 2 modified CPE ( 1 ‐CPE and 2 ‐CPE) have been studied in detail. Both 1 ‐CPE and 2 ‐CPE show remarkable stability that can be ascribed to the doped organic conjugated pbpy, which is very important for practical applications in electrode modification.     

Effects of annealing treatment on the properties of MEH-PPV/titania hybrids prepared via in situ sol-gel reaction

A uniform poly[2-methoxy-5-(2′-ethylhexyloxy)-p-phenylenevinylene] (MEH-PPV)/titania hybrid film was successfully prepared by an in situ sol-gel reaction of titanium isopropoxide (TIP) in the presence of MEH-PPV/2-chlorophenol solution. The annealing treatment increased the conversion of TIP to titania as determined from evidence of the formation of Ti-O-Ti bonds in the Fourier transform infrared (FTIR) spectrum. Scanning electronic microscope (SEM) photographs showed that the morphology and distribution of titania in the hybrid film were strongly related to the amount of water in the in situ sol-gel reaction. The thermal stability of MEH-PPV/titania hybrids was enhanced by the annealing treatment. Small angle X-ray scattering (SAXS) and X-ray diffraction (XRD) analyses indicated that annealing treatment promoted the ordered aggregation of the MEH-PPV chains and crystallization of titania to a certain extent. The blue shift in Ultraviolet-visible (UV-vis) absorption of pure MEH-PPV after annealing was ascribed to the small extent of decomposition and coil conformation which occurred at high temperature. A more-obvious blue shift for the hybrids was observed, which resulted from irregular aggregation and coil conformation of the MEH-PPV chains induced by heterogeneous point, TIP (titania). The red shift in the photoluminescent (PL) emission for pure MEH-PPV resulted from a certain extent of ordered aggregation after annealing. However, only a slight red shift in the PL emission peak for the hybrids was found due to the hindrance of ordered aggregation of MEH-PPV chains in the presence of TIP (titania).     

Silica-Based and Transition Metal-Based Inorganic-Organic Hybrid Materials—A Comparison

Organically substituted metal alkoxides can be prepared by reaction of the parent alkoxides with complexing organic compounds. The chemical and structural consequences of such substitutions are discussed in this article. Examples are given showing how functional organic moieties, such as polymerizable groups, can be incorporated into sol-gel materials via the complexing ligands. Major structural differences between silica-based and metal-based hybrid materials originate from the different charge/coordination number ratios of silicon and most metals. This results in a high tendency for the molecular building blocks to aggregate. In many cases, metal oxide clusters are formed which are capped by the organic ligands. Such surface-modified clusters are themselves very valuable condensed matter units for materials syntheses.     

Electric parameters of photosystem II particles — electric light scattering study

Electric light scattering and microelectrophoresis were applied to investigate the electric moments (permanent dipole moment and electric polarizability and electrophoretic mobility of envelope-free chloroplasts and photosystem II (PS II particles. The effect of the removal of the extrinsic polypeptides (18, 24 and 33 kDa) on the electric moments was also studied. A significant difference was observed between the orientation behaviour of chloroplasts and PS II preparations. The data indicate that the permanent and induced dipole moments contribute to the orientation of the PS II particles, whereas chloroplasts possess induced dipole moment only.

NaCl and Tris treatments of PS II preparations influence both the transverse permanent dipole moment and the electric polarizability of PS II particles. The increase in the electrophoretic mobility of PS II particles on removal of the extrinsic proteins corresponds to an increase in the electric polarizability value, demonstrating its interfacial nature.     

W／O型微乳液活化能和导电机理研究

电导行为是微乳液的重要性质之一。自Lagourette和Lagues发现了W/O型微乳液电导渗透(Percolation)现象后,人们开始了微乳液导电机理的研究。较流行的观点认为,界面层中表面活性剂分子的阴离子在微乳颗粒碰撞时发生跃迁而使W/O型微乳液具有导电性。     

Structure and Electric Conductivity of (La,Sr)(Ga,Mg)O3-α Solid Electrolyte

Electric conductivity, Raman spectra, and thermal expansion of La_0.88Sr_0.12Ga_0.82Mg_0.18O_2.85 solid solution (LSGM1218) based on lanthanum gallate were studied at various temperatures, and Xray phase analysis was performed at room temperature. Dilatometric measurements showed that secondorder phase transitions occur at 775±10$ and 880± 20 K. The transition around 880 K is confirmed by Raman spectra and by a change in the conductivity activation energy in this temperature range. This transition is associated with a symmetry change in the oxygen sublattice.     

Moment characterization of localized orbitals

The parallel between orbital first and second electric moments and statistical first and second central moments is noted. Three measures of orbital spatial distribution in terms of their moments are proposed, and applied to the LMO's in a series of ten-electron hydrides. Consistent differences between bond and lone pair distributions are found. Using the statistical interpretation, for each LMO an effective solid angle around the central atom is postulated.