光固化环氧丙烯酸酯/SiO2杂化材料的研究

用FTIR、SEM、DSC和TGA表征了光固化环氧丙烯酸酯／SiO2杂化材料[(EA-TMSPM)／SiO2]，研究了盐酸、γ-甲基丙烯酰氧丙基三甲氧基硅烷(TMSPM)和无机物浓度对(EA-TMSPM)／SiO2结构与性能的影响。结果表明，无机物浓度高的(EA-TMSPM)／SiO2杂化体系中SiO2粒子尺寸略大于无机物浓度低的体系；盐酸和无机物浓度的增加，都可以增强杂化材料的耐磨性。     

Solid Phase Extraction and Simultaneous Spectrophotometric Determination of Trace Amounts of Copper and Iron Using Mixture of Ligands

 A novel sensitive and simple method for rapid and selective extraction, preconcentration and determination of iron (as its bathophenanthroline complex) and copper (as its neocuproine complex) using octadecyl silica cartridges and dual wavelength spectrophotometry is presented. The dual wavelength method (533 nm for the iron-bathophenanthroline and 454 nm for the copper-neocuproine as the analytical wavelength) is used to eliminate spectral interferences. Extraction efficiency and the influence of flow rates of sample solution and eluent, pH, amount of neocuproine, bathophenanthroline and hydroxylamine hydrochloride, type and least amount of eluent for elution of iron and copper complexes from cartridge, break-through volume and limit of detection are evaluated. The effects of various cationic and anionic interferences on percent recovery of iron and copper are also studied. Extraction efficiencies >95% are obtained by elution of cartridges with minimal amount of organic solvent. Iron and copper were determined in the range of 3–100 ng mL⁻¹. The limits of detection are 0.98 and 1.13 ng mL⁻¹ for iron and copper, respectively. The proposed method is applied successfully to the determination of both analytes in river, tap and well water samples. Author for correspondence. E-mail: yyamini@modares.ac.ir Received September 18, 2002; accepted December 12, 2002 Published online May 5, 2003     

以催化油浆窄馏分为添加剂的Al－MCM－41分子筛的合成

 采用阳离子表面活性剂十六烷基三甲基溴化铵为模板剂，以正硅酸乙酯为硅源，以硫酸铝为铝源，水热合成了以催化油浆窄馏分为添加剂的高比表面积Al－MCM－41介孔分子筛，并利用XRD，HREM，TG－DTA及N2吸附－脱附等测试手段对合成样品进行了表征．合成的Al－MCM－41分子筛的比表面积和孔体积分别达到1295m2／g和1．5cm3／g，其平均孔径为4．3nm．重点研究了Al－MCM－41分子筛结晶度、晶胞参数、比表面积、孔体积及平均孔径等结构性质随催化油浆窄馏分添加量及其组成的变化规律，并从合成机理上进行了解释．     

Study of modified silicas by inverse gas chromatography part II: Influence of chain length on surface properties of silicas grafted withα−ω diols

Summary The surface properties of silicas modified with – diols having between 4 and 16 carbon atoms were investigated by inverse gas chromatography. It is shown, that the value of the dispersive component of the surface energy does not change monotonously: a minimum value is recorded when the surface is covered by a monolayer of methylene groups. Further, when measuring the adsorption enthalpies of polar probes, an alternation of their H values is observed: grafts having an odd number of carbon atoms systematically show higher H values than the others. A trans-trans configuration of the grafted chains which allows optimum interactions is proposed, suggesting a preferential diesterification reaction of both terminal hydroxyl groups of odd diols.     

Donator-Acceptor Komplex Chromatographie Tetrachlorphthalimidopropylsilica,eine neue,chemisch gebundene Phase,geeignet zur Trennung von Kohleverflüssigungsprodukten und anderen technischen aromatischen Gemischen mit der Hochleistungsflüssigkeitschromatographie

Summary The preparation of a new tetrachlorophthalimidophase for HPLC is described. The capacity ratios (k) of about forty aromatics and twenty nitrogen-containing aromatics were determined. Most of the compounds used were alkylated. It was shown that the aromatics were eluted according to the number of rings, only slightly influenced by the substituents. A similar elution order was not observed with the heteroaromatics. The performance of the stationary phase is demonstrated, performing separations of coal liquids and other aromatic mixtures.

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Donator-Acceptor Komplex Chromatographie Tetrachlorphthalimidopropylsilica, eine neue, chemisch gebundene Phase, geeignet zur Trennung von Kohleverflüssigungsprodukten und anderen technischen aromatischen Gemischen mit der Hochleistungsflüssigkeitschromatographie

Zusammenfassung Es wird die Synthese einer neuen Tetrachlorphthalimid-Phase für die HPLC beschrieben. Anhand von Elutionsversuchen mit über vierzig Aromaten und zwanzig N-Heteroaromaten, die größtenteils alkyliert waren, konnte gezeigt werden, daß kondensierte Aromaten unabhängig vom Alkylierungsgrad streng nach der Zahl der aromatischen Ringe eluiert werden, was für die Heterocyclen nicht zutrifft. Die Kapazitätsverhältnisse (k) der untersuchten Verbindungen werden angegeben. Die Leistungsfähigkeit der Phase wird an der chromatographischen Trennung von Kohleverflüssigungsprodukten und anderen komplexen, aromatischen Gemischen demonstriert.

     

Determination of paraquat in human blood plasma using reversed-phase ion-pair high-performance liquid chromatography with direct sample injection

This report describes the determination of paraquat (PQ) in human blood plasma samples by a direct-injection reversed-phase ion-pair chromatographic method. Blood plasma filtrate was injected directly into the LiChrospher® RP-18 alkyl-diol silica (ADS) precolumn integrated in a column switching system using a mixture of 3% 2-propanol and 10 mM sodium octane sulfonate (SOS) in a 0.05 M phosphate buffer (pH 2.8). After washing with this phase, the ADS precolumn was back-flushed with the analytical mobile phase consisting of 40% of methanol and 10 mM SOS in a 0.05 M phosphate buffer (pH 2.8) at a flow rate of 1.0 ml min⁻¹, in order to carry the analyte to a conventional reversed-phase analytical column, where the separation of PQ was achieved and finally detected by UV at 258 nm. The recoveries of PQ from human blood plasma samples ranged between 95.0 and 99.5% at nine different concentrations (from 0.05 to 3.00 μg of PQ ml⁻¹) with coefficients of variation <2.5% (n=3). The precision expressed as relative standard deviation was below 3.5% for between-day and below 4.3% for within-day measurements (n=5). The detection limit (signal-to-noise ratio, S/N>3) was 0.005 μg ml⁻¹ with an injection volume of 200 μl. The proposed method is promising for the identification and quantification of PQ at low concentration levels and is suitable for its analysis in human blood plasma samples from intentional or accidental poisonings cases with a sample throughput of 5 samples per hour.     

Carbenium ion pairs on silica: UV-spectroscopic and electrokinetic measurements of triarylmethylium/halide-aerosil in 1,2-dichloroethane

The interaction of carbenium ion pairs with silica is studied by means of UV-spectroscopy, electrokinetic and adsorption measurements using triphenylmethyl derivatives, (RC₆H₄)₃CX, (X=F, Cl, Br, SCN, OH; R=Cl, I, H, CH₃, C(CH₃)₃, OCH₃, N(CH₃)₂) in interaction with silica particles suspended in 1,2-dichloroethane. The adsorption of triarylmethyl-halides onto silica is accompanied by the heterolytic dissociation of the tertiary carbonhalogen bond. The degree of ionization depends on the basicity of the counter anion and acidity of the cation, respectively. The influences of both concentration and structure of triarylmethyl halides on the zeta-potential are discussed with regard to steric and electronic factor. The zeta-potential values of the adsorbates decrease significantly, as compared with the free silica surface, from a certain triarylmethyl halide concentration where ionization takes place, to a constant level which is characteristic of the carbenium ion pair. These constant zeta-potential values of the adsorbates depend on the basicity of the counter ion and the _p Hammett constants of the ring substitutents, with exclusion of sterically hindered substituents and salt derivatives, e.g., crystal violet and malachite green.     

Synthesis and characterization of nanoparticulate MnS within the pores of mesoporous silica

Mesoporous silica was loaded with nanoparticulate MnS via a simple post-synthesis treatment. The mesoporous material that still contained surfactant was passivated to prevent MnS formation at the surface. The surfactant was extracted and a novel manganese ethylxanthate was used to impregnate the pore network. This precursor thermally decomposes to yield MnS particles that are smaller or equal to the pore size. The particles exhibit all three common polymorphs. The passivation treatment is most effective at lower loadings because at the highest loadings (SiO₂:MnS molar ratio of 6:1) large particles (>50 nm) form at the exterior of the mesoporous particles. The integrity of the mesoporous network is maintained through the preparation and high order is maintained. The MnS particles exhibit unexpected ferromagnetism at low temperatures. Strong luminescence of these samples is observed and this suggests that they may have a range of important application areas.     

High-performance liquid chromatography of sulfonamides and quinolones on p-tert-butyl-calix[6]arene-bonded silica gel stationary phase

The high-performance liquid chromatographic behavior of some sulfonamides and quinolones was studied on a p-tert-butyl-calix[6]arene-bonded silica gel stationary phase. The effect of mobile phase variables such as methanol content, ionic strength and pH on their chromatographic behavior was investigated. The retention behavior of sulfonamides on the stationary phase was compared with that on both Zorbax C₁₈-bonded silica gel and γ-(ethylenediamino)propyltriethoxylsilane-bonded silica gel (diamino-bonded phase). The retention mechanism of sulfonamides and quinolones on the stationary phase was also discussed. The results indicate that the stationary phase behaves as a reversed-phase packing and its separation selectivity is much better than that of not only Zorbax C₁₈ phase but also diamino-bonded phase. Some sulfonamides and quinolones were separated on the stationary phase, but the separation of sulfonamides is far more successful.     

One-phase supported titanium-based catalysts for polymerization of ethylene. III. ESR spectra of the ternary system Sio2—R3Al—TiCl4

The ternary catalyst systems based on activated silica, aluminum alkyl, and titanium tetrachloride were polymerized in an ethylene gas-phase polymerization process, and further studied using ESR spectroscopy. Two types of titanium (III) ESR-active centers were observed and a linear dependence between the concentration of that characterized by a rhombic anisotropic signal with g₁ = 1.962, g₂ = 1.945, and g₃ = 1.913 values and catalyst productivity was found. © 1993 John Wiley & Sons, Inc.