苯乙烯-双烯A交联共聚凝胶、溶胶的生成与转化

本文结合提取、凝胶色谱等方法测定了苯乙烯-双烯A交联共聚过程的转化率曲线。通过研究发现,凝胶在交联共聚一开始就产生,且整个反应过程都在不断地生成;转化率40％以前几乎无溶胶生成,此后生成的溶胶仍不断地向凝胶转化;刚生成溶胶时其分子量高、分布窄,其后分子量变低、分布变宽;T_g以上温度的热处理发生进一步聚合反应,当双烯A摩尔浓度<3.3×10~(-4)时,溶胶分数增加,A-MA摩尔浓度>5.0×10~(-4)时,凝胶分数增加,这是双烯A悬吊双键及单体苯乙烯进一步反应的结果。     

镁铝氢氧化物正电溶胶结构研究

镁铝氢氧化物正电溶胶结构研究韩书华，张春光，侯万国，孙德军，王果庭（山东大学胶体与界面化学研究所，济南，２５０１００）关键词镁铝氢氧化物，正电溶胶，共沉淀镁铝氢氧化物是一种层状的氢氧化物。Ｂｕｒｂａ等［１］提出将镁铝氢氧化物与钠质蒙脱土作用可得到抑制...     

溶胶-凝胶法制备Fe2(MoO4)3超微粒子催化剂

以硝酸铁和钼酸铵为原料，采用溶胶－凝胶法和微波加热技术制备了F 2(MoO4)3超微子催化剂，使用DTA－TG，IR，XRD以及BET比表面测试等手段，考察了制备条件对复合氧化物超微粒子形成、晶相和比表面积的影响。同时测试了该样品对甲苯选择性氧化制苯甲醛的催化性能。结果表明：制备Fe2(MoO4)2超微粒子的适宜条件为：初始溶液pH=1.0,mol柠檬酸：mol(铁＋钼）＝0．4。在此条件下制得的干凝胶，经微波加热处理后粒子的比表面积为36.4m^2/g，粒径约为35nm。在由甲苯气相选择氧化制苯甲醛的反应中表现出较高的催化活性。     

Vapor‐Surface Sol‐Gel Deposition of Titania Alternated with Protein Adsorption for Assembly of Electroactive,Enzyme‐Active Films

Combining vapor‐surface sol‐gel deposition of titania with alternate adsorption of oppositely charged iron heme proteins provided ultrathin {TiO₂/protein}_n films with reversible voltammetry extended to 15 TiO₂/protein bilayers, more than twice that of more conventional polyion‐protein or nanoparticle‐protein films made by alternate layer‐by‐layer adsorption. Catalytic activity toward O₂, H₂O₂, and NO was also improved significantly compared to the conventionally fabricated films. The method involves vaporization of titanium butoxide into thin films of water, forming porous TiO₂ sol‐gel layers. Myoglobin (Mb), hemoglobin (Hb), and horseradish peroxidase (HRP) were assembled by adsorption alternated with the vapor‐deposited TiO₂ layers. Improved electrochemical and catalytic performance may be related to better film permeability leading to better mass transport within the films, as suggested by studies with soluble voltammetric probes, scanning electron microscopy (SEM) and atomic force microscopy (AFM). The electrochemical and electrocatalytic activity of the films can be controlled by tailoring the amount of water with which the metal alkoxide precursor vapor reacts and the number of bilayers deposited in the assembly.     

La2NiO4／Al2O3催化剂上CH4／CO2的重整

 通过溶胶－凝胶方法制备了尖晶石结构的La2NiO4／Al2O3催化剂，采用BET，XRD和TG表征了催化剂的孔分布、比表面积、体相组成以及凝胶样品的热失重和热分解过程．将催化剂应用于CH4／CO2重整反应制合成气，考察了惰性气体和反应温度对转化率、选择性以及积碳的影响．结果表明，在高空速（GHSV＝4．8×104ml／（g·h））下，CH4和CO2转化率分别为51％和60％，CO和H2的选择性约为98％和92％，惰性气体He的引入明显地提高了CH4和CO2的转化率．     

Development of an electrospray ionization mass spectrometric method for the quantification of theophylline in horse serum

A rapid and selective method has been developed for the determination of theophylline in horse serum by LC-ESI/MS/MS. The analytical method includes a protein precipitation extraction for sample preparation, liquid chromatography separation technique and ionspray tandem mass spectrometry. The drug was extracted from serum using a protein precipitation with acetonitrile and the supernatants were analyzed using an LC-ESI/MS/MS instrument. The chromatography was performed using a 50 x 2.1 mm C(8) analytical column and an isocratic mobile phase composes of 60:40 acetonitrile-0.5% formic acid in water with a flow rate fixed at 350 microL/min. A linear (weighted 1/concentration) relationship was used to perform the calibration over an analytical range of 0.1-20 ppm. The intra-batch precision and accuracy at LLOQ, medium and high concentration were 11.7, 6.9 and 5.4% and 95.8, 107.8 and 95.8%, respectively, and the inter-batch precision and accuracy at LLOQ, medium and high concentration were 10.4, 7.9 and 7.3% and 97.3, 105.2 and 95.9%, respectively. This LC-ESI/MS/MS method for the determination of theophylline in horse serum has been proved to within generally accepted criteria used for bioanalytical assay and was used successfully during clinical investigation.     

Negatively charged sol-gel column with stable electroosmotic flow for online preconcentration of zwitterionic biomolecules in capillary electromigration separations

A negatively charged sol-gel coating was developed for on-line preconcentration of zwitterionic biomolecules in capillary electrophoresis (CE), using asparagine and myoglobin as representative zwitterionic bioanalytes. The sol-gel coating was created by using a solution containing three precursors: mercaptopropyltrimethoxysilane (MPTMS), tetramethoxysilane (TMOS), and n-octadecyltriethoxysilane (C18-TEOS). The resulting sol-gel coating contained chemically bonded mercaptopropyl functional groups that were further oxidized by hydrogen peroxide to the corresponding sulfonic acid moieties. Such a surface-bonded sol-gel coating can carry a negative charge over a wide range of pH due to the presence of deprotonated sulfonic acid groups. Under favorable pH conditions, the negatively charged sol-gel coating can facilitate the extraction of positively charged analytes from a zwitterionic sample through electrostatic interaction. This principle was employed to extract myoglobin and asparagine by passing aqueous samples of these zwitterionic analytes through a negatively charged sol-gel column. The extracted analytes were then desorbed and focused via local pH change and stacking. The local pH change was accomplished by passing a buffer solution with a pH above the solute p/ value, while a dynamic pH junction between the sample solution and the background electrolyte was utilized to facilitate solute focusing. The sorption/desorption phenomena could, perhaps, also be explained on the basis of ion-exchange and local pH junction effects. On-line preconcentration and analysis results obtained on sulfonated sol-gel columns were compared with those obtained on an uncoated fused silica capillary of identical dimensions using conventional sample injections. Using UV detection, the presented sample preconcentration technique provided a sensitivity enhancement factor (SEF) on the order of 3 x 10(3) for myoglobin, and 7 x 10(3) for asparagine.     

High-throughput determination of atrasentan in human plasma by high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry

Atrasentan (A-147627) is an endothelin antagonist receptor being developed at Abbott Laboratories for the treatment of prostate cancer. A quick and sensitive method for the determination of atrasentan in human plasma has been developed and validated using high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry. A dual-column, single mass spectrometer system is used to provide a reliable and routine means to increase sample throughput. The analytical method involves liquid-liquid extraction and internal standard (A-166790). The plasma samples and internal standard are acidified with 0.3 M hydrochloric acid prior to being extracted into 1:1 (v/v) hexanes--methyl t-butyl ether. The organic extract was evaporated to dryness using heated nitrogen stream and reconstituted with mobile phase. Atrasentan and internal standard were separated with no interference in a Zorbax SB-C(18) analytical column with 2.1 x 50 mm, 5 microm, and a Zorbax C(8) guard column using a mobile phase consisting of 50:50 (v:v) acetonitrile--0.05 M ammonium acetate, pH 4.5, at a flow rate of 0.30 mL/min to provide 4 min chromatograms. For a 250 microL plasma sample volume, the limit of quantitation was approximately 0.3 ng/mL. The calibration was linear from 0.30 to 98.0 ng/mL (r(2) > 0.995). A significant advantage of the method is the ability to employ parallel HPLC separations with detection by a single MS/MS system to provide sensitivity and selectivity sufficient to achieve robust analytical results with a lower limit of quantitation of 0.30 ng/mL and high throughput.     

Sol—Gel Derived Carbon Ceramic Electrode Bulk—Modified with Tris（1,10—phenanthroline—5,6—dione） iron （Ⅱ）Hexafluorophosphate and Its Use as an Amperometric Iodate Sensor

A surface‐renewable tris(1, 10‐phenanthroline‐5, 6‐dione) iron (D) hexafluorophosphate (FePD) modified carbon ceramic electrode was constructed by dispersing FePD and graphite powder in methyltrimethoxysilane (MTMOS) based gels. The FePD‐modified electrode presented pH‐dependent voltammetric behavior, and its peak currents were diffusion‐controlled in 0.1 mol/L Na₂SO₄ + H₂SO₄ solution (pH = 0.4). In the presence of iodate, dear electrocatalytic reduction waves were observed and thus the chemically modified electrode was used as an amperometric sensor for iodate in common salt. The linear range, sensitivity, detection limit and response time of the iodate sensor were 5 × 10^?6–1 × 10^?2 mol/L, 7.448 μA·L/ mmol, 1.2 × 10^?6 mol/L and 5 s, respectively. A distinct advantage of this sensor is its good reproducibility of surface‐renewal by simple mechanical polishing.     

A resistive-type humidity sensor using composite films prepared from poly(2-acrylamido-2-methylpropane sulfonate) and dispersed organic silicon sol

A composite material of dispersed organic silicon sol and poly(2-acrylamido-2-methylpropane sulfonate) (poly-AMPS) was used to make humidity sensor without protective film or complicated chemical procedures. The organic silicon sol was dispersed well in the poly-AMPS without using dispersion agent. Parameters that may affect the water-resistive but humidity-sensitive characteristic of composite material, the adding amount of organic silicon sol solution and the film of thermal treatment time, were investigated. The microstructure of the material was analyzed, and the humidity sensing and electrical properties of the sensor were measured. The sensor well responded to humidity with a relatively good linearity, though it depended on the applied frequency. The temperature influence between 15 and 35 °C was within −0.17 % relative humidity (RH)/°C in the range of 30–90% RH. The activation energy was maximum around 40% RH. The sensor showed the hysteresis within 5.9%, fast response time, long-term stability (75 days at least) and satisfactory resistance to high humidity atmosphere (97% RH) and chemical environment (20% C₂H₅OH vapor). Analyzing the structure and complex impedance plots of organic silicon sol/poly-AMPS was used to explain improvement in humidity sensing properties in comparison with nano-sized SiO₂ powder/poly-AMPS films.