六甲氧基甲基三聚氰胺-多元醇-丙烯酸酯混杂聚合体系的研究

六甲氧基甲基三聚氰胺 (HMMM) 多元醇 丙烯酸酯 酸催化剂混杂聚合体系在高温下同时进行缩聚和自由基聚合并表现出协同效应 .体系中的活泼亚甲基在HMMM的催化下被空气氧化成过氧化氢物 ;过氧化氢物在酸催化下分解成自由基进而引发自由基聚合反应 .研究结果表明 ,体系中存在固化加速的协同效应 ;同时体系中还存在热互补效应 ,丙烯酸酯的自由基聚合反应放出的热可以传递给缩聚反应 ,满足缩聚反应吸热的要求 .混杂聚合得到的高分子合金膜具有优良的机械性能和耐溶剂性能 ,这是由于在混杂聚合过程中形成了互穿聚合物网络 (IPN)结构 .使用潜酸催化剂作为酸的来源 ,可以提高体系的储存稳定性 ;交联 引发剂的使用可以拓宽它的使用范围 ;对超枝化聚合物在混杂体系中的应用也进行了初步研究     

表面包覆改性对纳米CeO2分散性的影响

了改善纳米CeO2在Zn-Al类共晶合金中的分散性,采用超声液相包覆法对纳米CeO2进行表面活性剂表面包覆改性,并用AES测定了包覆层的厚度,用TEM研究了CeO2的团聚状况,用TGA分析了有机物包覆层的炭化温度范围,最后用FE-SEM观察了CeO2在复合材料中的分散情况。结果表明,包覆在纳米CeO2表面的厚度约为20 nm的表面活性剂层提高了微粒的分散性,而且该包覆层在495℃时已经炭化。热力学计算的结果也表明,炭化层能与氧化膜反应,该反应提高了CeO2与基体间的润湿性,并使其均匀分布在基体合金中。     

碳纳米管的共价修饰

碳纳米管(carbon nanotubes, CNTs)的溶解性和分散性较差是目前制约其广泛应用及在一些有特殊要求的领域(如生物技术)应用的主要原因之一. 对CNTs进行共价修饰是改善其溶解性和分散性的有效方法之一. 目前CNTs的共价修饰主要通过两类反应来实现: 羧基的衍生反应和直接加成反应. 介绍了基于这两种反应的几种共价修饰方法, 比较了各种修饰方法的优缺点及其对CNTs的溶解性和分散性的改善效果.     

Novel fiber-optic biosensor based on immobilized glutathione S-transferase and sol–gel entrapped bromcresol green for the determination of atrazine

The aim of this work was to investigate, for the first time, the potential of the enzyme glutathione S-transferase I (isoenzyme GST-I) for uses in analytical chemistry. A novel fiber-optic biosensor for the detection and determination of the triazine herbicide atrazine was developed based on maize GST-I expressed in E. coli. The sensing bioactive material was a three-layer mini-sandwich. The enzyme was immobilized on the outer layer that consisted of a hydrophilic polyvinylidenefluoride membrane. This membrane was supported on an inner glass disk by means of an intermediate binder sol–gel layer that incorporated bromcresol green (BCG). The biosensor operated in a static mode at 25 °C and the rate of the enzymatic reaction, using atrazine as a substrate, served as an analytical signal. A calibration curve was obtained for atrazine, with analytically useful concentration range 2.52–125 μM. The sensor detection limit was 0.84 μM. The reproducibility of atrazine sensing was in the order of ±3–5%. The method was successfully applied to the determination of this herbicide in real water samples, without sample preparation steps. Atrazine recovery ranged between 85 and 110%. No interference from other pesticides, such as alachlor and carbaryl was observed in the absence of atrazine. The immobilized enzyme retained about 75% of its original activity after 1 month use. Simply unscrewing the terminal holding ring of the probe and placing a new bioactive sandwich could easily replace a deteriorated mini-sandwich.     

Charge compensation dynamics in a soluble copolymer of poly(aniline) and poly(phenylene sulfide)

Poly(phenylene sulfide phenyleneamine), PPSA, is a copolymer of poly(aniline) and poly(phenylene sulfide), soluble in conventional organic solvents as tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, and cyclohexanone. In this research, its electrochemical behavior has been studied in acetonitrile in the presence of different electrolytes, where the loss of electroactivity was observed after few cycles. In this paper, the charge compensation dynamics of PPSA is analyzed through electrochemical quartz crystal microbalance experiments and electroacoustic impedance measurements. Raman spectroscopy data have shown that once the oxidation of the sulfur atom occurs, a loss of electroactivity is observed, being not possible to recover the pristine state of the polymer. Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data obtained for the fully oxidized polymer are consistent with the formation of a networked polymer due to the electrophilic attack of the positive sulfur atom on the activated aromatic rings. Electrochemical quartz crystal microbalance results clearly show that the degree of irreversibility fully depends on the chemical nature of the anions with a negligible participation of the cations of the electrolytic solution. This work is in memoriam of Prof. Dr. Francisco C. Nart, dearest friend and colleague, whose scientific skills and enthusiasm will always be remembered.     

六甲氧基甲基三聚氰胺-多元醇-丙烯酸酯混杂聚合过程热互补效应的研究

六甲氧基甲基三聚氰胺（HMMM）－多元醇－丙烯酸酯－酸催化剂的混合体系在较高温度下同时进行缩聚和自由基聚合并表现出协同效应，DSC研究结果表明，丙烯酸酯在HMMM和酸的催化作用下可在较低温度下发生自由基聚合反应，并把反应释放出来的大量的热量有效地传递给缩聚发反应，满足缩聚反应吸热的要求，从而节省固化所需要的能量，为了提高储存稳定性。本文以潜酸催化剂作为酸的来源，对该混杂聚合体系进行了研究，仍有明显的热互补效应。     

Determination of Organophosphorus Pesticides in Soil by MMSPD-GC-NPD and Confirmation by GC-MS

A novel method, modified matrix solid-phase dispersion (MMSPD), has been developed for quantitative analysis of organophosphorus pesticide residues in soil. It was based on matrix solid-phase dispersion (MSPD) and continuous liquid-solid extraction (continuous LSE), using Florisil as sorbent and dichloromethane as the recycling solvent. Two soils with different texture and physicochemical properties were studied to validate the method. The effect of residence time of pesticides in soil was also studied. MMSPD was compared with MSPD and continuous LSE respectively. Determination was carried out by gas chromatography with nitrogen-phosphorus detection (GC-NPD). The method gave recoveries ranging from 72–105% with relative standard deviations (RSDs) lower than 15% for the pesticides studied. The limits of detection (LODs) ranged from 0.1 to 0.6 ng g⁻¹. Two pesticide residues have been detected in real soil samples from Fujian, China, using MMSPD. The pesticides were confirmed by gas chromatography-mass spectrometry (GC-MS) in a selected-ion monitoring (SIM) mode. Revised: 4 and 9 April 2006     

Importance of the Debye interaction in organic solutions: Henry's law constants for polar liquids in nonpolar solvents and vice versa

Henry's law constants have been determined for -butyrolactone (BL), ethyl acetate (EA), and 2-methyl-3-pentanol (MEP) in mixtures of iso-octane (ISO) and toluene (TOL), for BL, EA, TOL, and ISO in cinnamaldehyde (CIN) and for TOL and ISO in each other and in BL. From these data and published vapor pressures, the activity coefficients at infinite dilution and the standard molar Gibbs free energy of transfer, G ₂ ⁰ of the solutes from dilute solution in ISO to dilute solution in each solvent medium have been calculated. The different behavior patterns of BL and EA are attributed to differences in their abilities to exist in different conformations possessing different dipole moments. For polar solutes, G ₂ ⁰ decreases with increasing polarizability of the solvent and with increasing dipole moment of the solute, suggesting increased contributions from dipole-induced dipole (Debye) interactions. The sigmoidal plot of G ₂ ⁰ against the change in pair potential energy calculated from the classical expressions suggests that G ₂ ⁰ seriously underestimates the strength of the Debye interactions in comparison with the London interactions.     

WO3/(TiO2-SiO2)催化剂的表面分散状态及催化性能的研究

用气相流动吸附法制备复合载体,用浸渍法制备WO3/(TiO2-S iO2)催化剂.应用LRS和TPR技术研究WO3在复合载体TIO2-S iO2表面的分散状态,发现TiO2在S iO2表面的分散可增强WO3与载体之间的相互作用,提高WO3在载体表面的分散阈值.另外TPR实验证明,TiO2的存在不仅大大改善WO3的分散状态,而且使WO3在TiO2-S iO2的还原温度升高,WO3与载体之间的作用增强.负载于经TiO2调变的S iO2上的催化剂其HDS、HYD、BHD活性高于负载于单纯S iO2上的催化剂的活性.