聚合物载体-稀土金属络合物的研究Ⅱ.在聚合物载体-钕络合物催化体系下丁二烯的定向聚合

本文介绍了由苯乙烯-丙烯酸共聚物载体-钕络合物组成的新型丁二烯定向聚合催化体系SAAC·Nd-Al(C_2H_5)_2Cl-Al(i-C_4H_9)_3,研究了该体系的组分、组分比对体系活性的影响,考察了不同烷基铝、聚合物载体-钕络合物的表征参数与催化活性的关系。该体系有良好的活性和定向效应。聚丁二烯的顺式-1,4结构含量高达98％。     

OSW saponins: facile synthesis toward a new type of structures with potent antitumor activities

[reaction: see text] OSW saponins, featuring a 16beta,17alpha-dihydroxycholest-22-one aglycon and an acylated beta-D-xylopyranosyl-(1-->3)-alpha-L-arabinopyranosyl residue attached to the 16-hydroxyl group, have recently been discovered from a group of lily plants, which show potent antitumor activities with a novel mechanism of action. This paper describes an aldol approach to the stereoselective construction of the 16alpha,17alpha-dihydroxycholest-22-one structure from 16alpha-hydroxy-5-androsten-17-ones and propionates. Elaboration of the aldol adducts toward OSW-1, involving installation of the isoamyl ketone side chain, inversion of the 16-hydroxyl configuration, and selective protection of the C22-oxy function, has been explored and accomplished. In particular, the present route was found convenient for the synthesis of OSW saponin analogues with a C22-ester side chain. Thus, the 23-oxa-analogue of OSW-1 (40) was prepared starting from the industrial dehydroisoandrosterone (1) in a linear eight-step sequence and in 26% overall yield. Analogues with a variety of modified side chains were prepared, via aldol condensation with propionates of varying length, thiopropionate, and acetate (for preparation of 68-75) or via aminolysis of the 22,16-lactone 26 (for preparation of the 23-N-analogues). Cross metathesis (CM) reaction was also found feasible for modification at the final stage from C22-allyl ester 70. Valuable structure-activity relationships (SAR), together with the practical synthetic approach, have thus been provided to set a new stage for further studies on this new type of antitumor structures.     

破碎-絮凝法分离细长碳纳米管与碳纤维

根据碳纤维与细长碳纳米管耐磨性能与絮凝沉降性能的差异，提出了一种有效分离细长碳纳米管与碳纤维的物理方法——破碎-絮凝法.该方法包括研磨破碎、液相分散、絮凝沉降、过滤分离等步骤，可高效去除混杂于细长碳纳米管样品中的碳纤维，同时还可去除螺旋状碳纤维及细小碳颗粒等易悬浮杂质.纯化过程对细长碳纳米管无损伤.用电子显微镜和热重分析表征了纯化效果，并初步分析了纯化机理.     

树枝状十二酯的合成

以乙二胺和丙烯酸十二酯为原料，甲醇为溶剂，采用迈克尔加成反应合成了低代的树枝状十二酯。探讨了反应条件对树枝状十二酯收率的影响。乙二胺2mL(30mmol)，n(乙二胺)：n(丙烯酸十二酯)=1：6，甲醇占反应液总体积的50％，反应温度40℃，反应时间48h，产率54．9％。     

Synthesis and Ionic Conductivity of Network Polymer Electrolytes with Internal Plasticizers

Network polymer electrolytes with free oligo(oxyethylene) chains as internal plasticizers were prepared by cross-linking poly(ethylene glycol) acrylates. The effects of salt concentration and properties of internal plasticizers on ionic conductivity were studied.     

Formation and photoluminescence of silver nanoparticles stabilized by a two-armed polymer with a crown ether core

Silver nanoparticles were synthesized by the use of a two-armed polymer with a crown ether core [poly(styrene)]-dibenzo-18-crown-6-[poly(styrene)] based on the flexibility of the polymer chains and the complex effect of crown ether with Ag(+) and Ag. The size of silver nanoparticles could be tailored by controlling the initial concentrations of the polymer and Ag(+), and the molecular weight of the polymer. The emission of silver nanoparticles was blue-shifted, and the intensity of the photoluminescence of silver nanoparticles stabilized by the polymer was significantly increased due to the complex effect between the crown ether embedded in the polymer and the silver nanoparticles.     

Systematic enantiomeric separation of [60]fullerene bisadducts possessing an inherent chiral addition pattern

The optical resolution of trans-2 and trans-3 [60]fullerene bisadducts with an inherent chiral addition pattern, modified by Bingel reaction, cycloaddition by benzyne, Prato reaction, and cycloaddition by o-quinodimethane, was systematically investigated by using chiral HPLC columns (Chiralcel OD and Chiralpak AD). The chiroptical properties of enantiomers separated were also examined.     

A simple route towards tubular ZnO

Thermal treatment of Zn(NH3)(4)2+ precursor in ethanol solvent led to the formation of the tubular ZnO which exhibited strong ultraviolet photoluminescence around 385 nm at room temperature; TEM images showed the hollow tubules with approximately 450 nm in diameter and approximately 4 microns in length were built up by ZnO polycrystals.     

Bioactive constituents from Chinese natural medicines. XIV. New glycosides of beta-carboline-type alkaloid, neolignan, and phenylpropanoid from Stellaria dichotoma L. var. lanceolata and their antiallergic activities

A new beta-carboline-type alkaloidal glycoside, glucodichotomine B, four new neolignan glycosides, dichotomosides A, B, C, and D, and a new phenylpropanoid glycoside, dichotomoside E, were isolated from a Chinese natural medicine, the roots of Stellaria dichotoma L. var. lanceolata. The structures of the new glycosides were determined on the basis of chemical and physicochemical evidence. Among them, dichotomoside D inhibited the release of beta-hexosaminidase (IC(50)=64 microM) as well as tumor necrosis factor-alpha and interleukin-4 (IC(50)=16, 34 microM) in RBL-2H3 cells. These findings suggest that dichotomoside D is more effective against the late-phase reactions in type I allergy than in the immediate phase.     

Ni-catalyzed alkylative dimerization of vinyl grignard reagents using alkyl fluorides

Alkyl halides underwent unique cross-coupling reaction with vinylmagnesium chloride in the presence of Ni catalyst to give 2-alkyl-3-butenyl Grignard reagent (1) in high yields. This reaction proceeded efficiently at 25 degrees C in THF using primary and secondary alkyl fluorides. On the other hand, PhCH=CHMgBr gave double alkylative vinyl coupling product 4 in good yield as the sole coupling product. Alkyl fluorides react as the most suitable alkylating reagent in comparison to the corresponding chlorides, bromides, and iodides.