一缩二乙二醇二缩水甘油醚的合成

以一缩二乙二醇和环氧氯丙烷为原料、三氟化硼乙醚络合物为催化剂合成一缩二乙二醇二缩水甘油醚(DGEG)。讨论了催化剂用量、原料配比、碱金属氢氧化物以及成环反应温度对产物收率的影响。同时 ,用傅立叶红外光谱对其进行了分析与表征。当三氟化硼乙醚络合物用量为 3份、环氧氯丙烷与一缩二乙二醇的物质的量比为 8∶1、用氢氧化钾在 30℃左右进行成环反应时 ,可以得到低粘度、高收率的产物。     

From Molecular Clusters to Metal Nanoparticles

Different methods to prepare supported metal nanoparticles of uniform size are discussed. (i) Supported ruthenium particles were generated from Ru and Ru-Fe bimetallic molecular metal carbonyl cluster precursors (MCC). (ii) Gold nanoparticle formation in the supercage of Y zeolite was studied on Au/NaY, Au/HY and Au-Fe/HY system. (iii) Palladium nanoparticles were grown in liquid phase then deposited on an SiO₂ support or they were grown on the support surface in a solid-liquid interfacial layer. The particle size control was more efficient in the latter two cases than in the preparation starting from MCC.     

Enzymatic esterification of glycerol I. Lipase-catalyzed synthesis of regioisomerically pure 1,3-sn-diacylglycerols

Regioisomerically pure 1,3-sn-diacylglycerols are conveniently prepared in high yields (>80%) and in large quantities by enzymatic esterification of glycerol in the presence of various 1,3-selective lipases(Chromobacterium viscosum, Rhizopus delemar, Rhizomucor miehei) and a variety of different acyl donors like free fatty acids, fatty acid alkyl esters and vinyl esters. All reactions are carried out in aprotic organic solvents of low water content, namelyn-hexane, diethyl ether or tBuOMe. The creation of an artificial interphase between the solvent-immiscible hydrophilic glycerol and the hydrophobic reaction media by the adsorption of glycerol onto a solid support prior to use was essential for the success of these transformations. The effects of reaction conditions and the regioselectivities of the lipases on the product yields are described in detail.     

Catalytic wall reactor: Catalytic coatings of stainless steel by VOx/TiO2 and Co/SiO2 catalysts

Catalytic wall (structured) reactors and structured supports are suitable to study the catalytic properties of nanosized materials. The coating of metallic (aluminum and stainless steel) plates by thin layers of active phase is presented in two cases, VO_x/TiO₂ and Co/SiO₂, catalysts used in the oxidative dehydrogenation (ODH) of propane and in Fischer–Tropsch synthesis (FTS) of clean fuels, respectively. The preparation of coated plates and their characterisation by various methods of physicochemical analysis are described. Both chemical and physical methods were used for coating. VO_x/TiO₂ layers were obtained by grafting of Ti (on Al or stainless-steel plates) and V (on TiO₂) alkoxides and use of sol–gel media or suspension. A silica primer was deposited (on stainless-steel plate) by plasma-assisted chemical vapour deposition (PACVD) onto which Co oxide and silica were coprecipitated from sol–gel. The catalytic experiments in the respective reactions were carried out in special plate reactors and compared with those of catalytic powders. The study shows that the coating of a metallic substrate by a catalyst is not straightforward and requires specific studies dealing with both chemistry (chemical affinity between substrate and catalytic layers) and catalytic engineering (catalytic performance in taylor-made reactors).     

基于稀疏表示的单帧运动图像盲复原

提出一种基于稀疏表示的单帧运动盲复原方法,它充分利用自然图像中存在的各种先验知识进行求解。该方法分为模糊核估计和图像修复两个阶段。在估计模糊核时,它运用shock滤波器从模糊图像中预测出清晰边缘,以此指导全局图像的复原,并运用多尺度策略来解决大模糊核问题。在图像修复阶段,运用稀疏表示理论对复原图像进行降噪和重建,最终提高图像复原质量。实验结果表明,在不同噪声和模糊核条件下,该算法能有效消除运动模糊。     

Flexibilized Copolyimide Adhesives

Two copolyimides, LARC-STPI and STPI-LARC-2, with flexible backbones were prepared and characterized as adhesives. The processability and adhesive properties were compared to those of a commercially available form of LARC-TPI.

Lap shear specimens were fabricated using adhesive tape prepared from each of the three polymers. Lap shear tests were performed at room temperature, 177°C, and 204°C before and after exposure to water-boil and to thermal aging at 204°C for up to 1000 hours.

The three adhesive systems possess exceptional lap shear strengths at room temperature and elevated temperatures both before and after thermal exposure. LARC-STPI, because of its high glass transition temperature provided high lap shear strengths up to 260°C. After water-boil, LARC-TPI exhibited the highest lap shear strengths at room temperature and 177°C, whereas the LARC-STPI retained a higher percentage of its original strength when tested at 204°C [68% versus 50% (STPI-LARC-2) and 40% (LARC-TPI)].

These flexible thermoplastic copolyimides show considerable potential as adhesives based on this study and because of the ease of preparation with low cost, commercially available materials.     

新型三硅氧烷表面活性剂的合成与表征

合成了一种新型的三硅氧烷表面活性剂Me3SiOSiMeROSiMe3[R=(CH2)3NHCH2CH(OH)CH2(OCH2CH2)xOCH3,x=1,2]。通过低聚乙二醇单甲醚和环氧氯丙烷在相转移催化剂(P.T.C)的存在下合成出低聚乙二醇甲醚缩水甘油醚,产物再与氨丙基三硅氧烷进行开环反应,得到目标产物。通过气相色谱(GC)和氢核磁共振(1HNMR)确定了目标产物的纯度与结构。     

茶袋法固相合成胸腺五肽肽库

利用组合化学技术,采用简便的茶袋法固相合成制备胸腺五肽D型氨基酸取代类似物肽库,共合成32条肽。粗肽得率平均在54%左右。通过高效液相色谱分离得到纯肽,经质谱及HPLC分析,所制类似物相对分子质量与胸腺五肽一致,精制后的肽得率平均在36%左右。     

微波诱导稀土固体超强酸SO4^2-／TiO2／Ce^4＋催化合成乙酸正丁酯

本文探讨了标题合成方法中合成反应条件对酯收率的影响。其最佳反应条件为：n(醇)：n(酸)=2．5：1．0，固体超强酸用量为反应物总质量的2．0％，微波辐射功率528W，辐射时间20min，酯收率达89．5％。用IR等手段对产品进行了确证。     

Synthesis and Characterization of Segmented Block Copolymers Based on Hydroxyl‐Terminated Liquid Natural Rubber and α,ω‐Diisocyanato Telechelics

Summary: Segmented block copolymers, consisting of non‐polar soft segments from hydroxyl‐terminated liquid natural rubber (HTNR) and polar hard segments from α,ω‐diisocyanato telechelics obtained by “criss‐cross”‐cycloaddition, have been synthesized. The block copolymer formation took place under relatively mild reaction conditions at 80 °C in dichloroethane in the presence of dibutyltin dilaurate as a catalyst. The resulting block copolymers were characterized by spectroscopic techniques (¹H NMR, FTIR, UV‐vis spectroscopy) as well as GPC for molar mass determination. The block copolymers were compression molded in a hot stage press, and the resulting samples were characterized by DSC and stress‐strain measurement. The solubility and phase morphology of the materials have also been studied.

Segmented block copolymer from HTNR and α,ω‐diisocyanato telechelics