Highly enantioselective synthesis of organic compound using right- and left-handed helical silica

Highly enantiomerically enriched (up to 96-97% ee) 5-pyrimidyl alkanol was obtained by the addition of diisopropylzinc to pyrimidine-5-carbaldehyde in the presence of the artificially designed chiral inorganic material, right- and left-handed helical silica.     

Analysis of gases containing inorganic and organic compounds using a combination of a thick-film capillary column and a packed adsorption column

A gas chromatographic system consisting of one multiport valve, two (hot-wire and flame-ionization) detectors and two analytical columns (one thick-film capillary and one packed adsorption column) is used for the analysis of gas samples containing a number of inorganic compounds (hydrogen, argon, oxygen, nitrogen, carbon monoxide, and carbon dioxide) and organic compounds. Examples include samples containing hydrocarbons up to n-nonane and benzene and toluene. The system also permits the analysis of more complicated samples containing, for example, alcohols, in addition to hydrocarbons.     

Characterization of ABTS at a Polymer‐Modified Electrode

ABTS, 2,2′‐azinobis(3‐ethylbenzothiazoline‐6‐sulfonate), a colorless dianion that forms a colored radical upon oxidation, was characterized with electrochemistry and spectroscopy and demonstrated to be a detectable analyte in a polymer‐modified spectroelectrochemical sensor. Three positively charged polymers were incorporated into a thin film on an indium tin oxide (ITO) optically transparent electrode and used to concentrate ABTS at the electrode surface. Of the three films, poly(vinylbenzyl trimethyl ammonium chloride)‐poly(vinyl alcohol) (PVTAC‐PVA), poly(diallyldimethylammonium chloride)‐silica (PDMDAAC‐SiO₂), and quaternized poly(4‐vinyl‐N‐methylpyridinium nitrate)‐silica (QPVP‐SiO₂), PVTAC‐PVA demonstrated the best ability to absorb ABTS. Within 20 min, a change of 0.2 absorbance units at 417 nm and 13.6 μA/cm² in anodic peak current density in cyclic voltammetry at a scan rate of 0.025 V/s were observed.     

Electro-optic effects of colloidal crystals of polymer-modified silica spheres immobilized with gelator

Electro-optic responses of colloidal crystals consist of poly(maleic anhydride-co-styrene)-modified silica spheres (P(MA-ST)/SiO₂) in acetonitrile and the crystals immobilized with a gelator, N-benzyloxycarbonyl-L-isoleucilaminooctadecane (Z-L-Ile-C-18), are studied by reflected-light intensity measurements and time-resolved reflection spectroscopy. Application of an alternating electric field deforms P(MA-ST)/SiO₂ crystal lattices reversibly. The response waveforms from the crystals are dependent on the frequency and strength of the applied electric field; similar dependencies have been qualitatively observed for the colloidal crystals consisting of polystyrene or silica spheres in aqueous media in our previous studies. Both gelated and ungelated P(MA-ST)/SiO₂ crystals change the reflection intensity, however, the amplitude is larger for the latter. The small response for the gelated P(MA-ST)/SiO₂ crystals is attributed to the higher elastic modulus (G). The G value of the gelated P(MA-ST)/SiO₂ crystals in acetonitrile is estimated from the change in the inter-sphere distance to be 8.0 Pa, which is about 2.3 and 2.4 times larger than that for ungelated P(MA-ST)/SiO₂ crystals in acetonitrile and colloidal silica crystals in aqueous media, respectively.     

气相白炭黑表面处理率的影响因素及判定

气相白炭黑是一种二氧化硅纳米材料，气相白炭黑的最主要应用是用于硅橡胶的补强，但气相白炭黑在硅橡胶中很难分散，影响了补强效果，本文用六甲基二硅氮烷对白炭黑进行表面处理并对白炭黑表面处理率问题做一些探讨。     

SO_4~(2-)/SiO_2表面酸性的红外光谱和密度泛函理论研究

对介孔SiO2及硫酸根促进的SiO2样品进行了原位吡啶吸附红外光谱测试,分别建立了硫酸根促进前后的SiO2表面原子簇模型,用密度泛函理论对其吡啶吸附行为进行了计算,分析了SO42-/SiO2表面酸性产生的机理.实验和计算结果表明,SO42-/SiO2表面不存在Lewis酸中心,原位红外谱图中表征Lewis酸性的特征峰对应于氢键吸附吡啶的环振动,这种氢键作用因SiO2表面的硫酸根促进而得到加强.HSO4-螯合结构为SO42-/SiO2表面Brφnsted酸中心,其酸强度强于表面磺酸基团修饰的介孔SiO2材料SO3H-MSU,而弱于HZSM-5.SO42-/SiO2的酸催化活性源于其表面的Brφnsted酸性.     

Nano-Particles by Wet Chemical Processing in Commercial Applications

Nano-sized materials produced by wet chemical processing have a wide range of industrial applications. For example, a solution of monodisperse SiO₂-particles for single-layer anti-reflection coating on glass was developed. Although being porous, the anti-reflection coating shows excellent mechanical stability which is sufficient for commercial applications. The coating sol is used to produce cover glass with high transmission for solar energy systems, e.g. photovoltaic modules.Nano-sized materials made by sol–gel processes are not limited to niche applications. Inorganic metal oxide coatings on thin mica platelets are the basis for pearl lustre pigments. The inorganic layers, consisting of titanium dioxide or iron oxides, are obtained by a wet chemical procedure. The well-defined layer thickness, varying from 50 to 300 nm, determines the optical properties of the pearlescent pigment. By using synthetic SiO₂ platelets instead of natural mica, impressive angle-dependant colour effects can be achieved. Synthetic SiO₂ platelets are also produced by a sol–gel coating technique.Special spherical silica particles made by a wet chemical processing are used in cosmetic applications. The size distribution determines the skin feeling of the formulation. In addition, specific colour or anti-wrinkle effects can be achieved.     

Investigation of the porosity of silica and alumina with chemically bonded polystyrene

The effect of modification of porous silica and alumina with a copolymer of styrene and vinylsilane on the porosity of oxides have been investigated by means of low temperature nitrogen sorption. Only small changes of the specific surface area and of the specific pore volume were observed on modification of oxides with non-cross-linked copolymer. The specific surface area significantly increased after the cross-linking of the deposited polymeric layer while the specific pore volume remains almost unaffected. A broad hysteresis loop appears in the nitrogen sorption isotherm for the alumina modified with the cross-linked polymer. The porosity of oxides modified by chemisorption method differed strongly from that observed for composites modified by physisorption of polymer.     

Microstructural Analysis of the Effects of Poly(ethylene glycol) on an Acid Catalyzed Sol-Gel Derived Ceramic Material

Ceramic materials have been derived from an acid catalyzed sol-gel process. The addition of different molecular weights and concentrations of polyethylene glycol (PEG) to the sol mixture modifies the phase behaviour of the sol-gel process. The resulting gel is burned at 973 K to make porous ceramic materials. Nitrogen adsorption-desorption isotherms are used to assess the effects of PEG on the internal structure of the burned ceramic material. These isotherms indicate an extensive pore network exists consisting of micropores and mesopores. In the micropore region of the isotherms, the _S-plot analysis reveals changes in specific primary micropore volumes, specific total pore volumes, specific external surface areas and specific SPE surface area when PEG is added in the sol-gel process. The average pore width and the overall mesopore size distribution curves shift to higher pore size values and ranges on addition of PEG to the sol-gel mixture. The presence of PEG during the sol-gel process leads to an apparent narrowing of the micropore size distribution. The results of this work clearly indicate that the molecular weight and the concentration of a polymer, such as PEG, influences the eventual internal structure of a ceramic after burning.     

Synthesis and characterization of stereoregular poly(methyl methacrylate)–silica hybrid utilizing stereocomplex formation

Stereoregular poly(methyl methacrylate) (PMMA)–silica nanocomposites were prepared using stereocomplex formation between i-PMMA and s-PMMA by an in situ method. The methodology adopted here is the simultaneous formation of organic gel and inorganic gel, the so-called interpenetrating polymer network (IPN) formation. The gelation of i- and s-PMMA were performed by stereocomplex formation with the associated segments forming the crosslinking points in the presence of tetramethoxysilane (TMOS). The effects of the i/s-ratio, PMMA concentration, molecular weight, and solvent nature on the hybrid materials formation were addressed. The presence of the stereocomplex in the silica matrix was confirmed by DSC and solvent extraction methods. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 785–794, 2004