非对映选择性合成科涅克内酯

反式取代的γ 丁内酯是重要的有机合成中间体[1],已有多种合成路线见诸报道[2～ 4 ].这些方法各有特色 ,但也存在原料难以得到、合成路线冗长、反应条件苛刻、立体选择性不高、总产率低等不足 .我们以巴豆酸甲酯 ( 1)为原料 ,经 5步反应立体选择性地合成了 (± ) 反 科涅克内酯 ( 5 ) .反应式如下 :　　岛津ＩＲ 44 0型红外光谱测定仪 ,ＫＢｒ压片 .ＶａｒｉａｎＥＡ 3 60Ｌ型核磁共振仪 ,ＣＤＣｌ3为溶剂 ,ＴＭＳ为内标 .ＫｙＫｙ ＱＰ 10 0 0Ａ型气相色 质联用仪 ,电离方式为ＥＩ ,电子能量 70ｅＶ .ＶａｒｉａｎＳＰ 3 40 0型色谱仪 ,固…     

Comparative surface plasmon resonance and enzyme-linked immunosorbent assay characterisation of a monoclonal antibody with N-acyl homoserine lactones

This study shows the detection of (N-acyl) homoserine lactones (AHLs or HSL) with monoclonal antibodies via a surface plasmon resonance (SPR)-based immunosensor in comparison to conventional microtiter plate-based enzyme-linked immunosorbent assay (ELISA). An HSL derivative, named HSL2 (Table 1), was attached to bovine serum albumin (BSA) and the conjugate (HSL2-BSA-r2) was either covalently immobilised on the SPR sensor chip surface via free amino groups or via adsorption on the ELISA polystyrene plate surface. With a newly developed rat monoclonal antibody (mAb HSL1/2 2C10), AHLs were detected sensitively in a competitive format with SPR and ELISA. Well comparable experiments between SPR and ELISA could be obtained in buffers. Moreover, the SPR sensor surface with the immobilised conjugate HSL2-BSA-r2 could be regenerated at least 340 times (regeneration cycles) without loss of activity. The measurement time per cycle was approximately 15 min. The competitive detection format for SPR and ELISA allowed the detection in the μg L⁻¹ range.     

川芎中内酯类化学成分的提取与溶剂萃取分离方法研究

以川芎中4种主要内酯的总量为指标,系统地研究了乙醇浓度、乙醇用量、回流次数、回流温度、萃取溶剂种类和用量等因素对水浴回流法提取川芎内酯的影响,确定了川芎内酯的最佳提取工艺:10倍量体积分数75%的乙醇,60℃水浴中回流提取两次,乙酸乙酯作萃取溶剂,萃取溶剂的最佳用量为11mL/g药材。经反相高效液相色谱法测定,溶剂萃取后的提取物中4种主要内酯(洋川芎内酯-H、洋川芎内酯-I、瑟丹酸内酯和蒿本内酯)的总量为24%~30%。     

Synthesis of macrocyclic lactones with methoxysulfonyl side chain

Two representative macrocyclic lactones with methoxysulfonyl side chain（5a and 5b）were synthesized employing Michael addition with acrolein and ring enlargement as the key steps,starting from potassium,α-oxocycloaikylsulfonates（1）in total yields of 45 and 57%,respectively.     

Conversions of Coumarins Accompanied by Intermediate Opening and Recyclization of the Lactone Ring. 2. Study of the Interaction of Malonic Acid Hydrazide and Amide Derivatives with 3-Acyl(3-cyano, 3-ethoxycarbonyl)Coumarins

Reaction between the N,N′-diisopropylidene and N,N′-diacetyl derivatives of malonic acid dihydrazide and 3-acyl(3-cyano, 3-ethoxycarbonyl)coumarins under the conditions of the Michael reaction lead to the formation of N′-isopropylidene and N′-acetyl derivatives of coumarin-3-carboxylic acid hydrazide. Ethoxycarbonylacethydrazide reacts in an analogous manner. Special features have been studied of the interaction of malonic acid amide derivatives with unsubstituted coumarin and with coumarins containing electron-withdrawing groupings in position 3 of the ring. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1502–1514, October, 2005.     

鸡蛋壳制备葡萄糖酸钙的研究

葡萄糖酸钙是一种溶解度高,生理宽容性大的钙营养剂和抗过敏药,广泛用作食品添加剂及医药制剂供口服或静脉注射.目前常用的生产方法主要是生物发酵法,其缺点是工艺复杂, 生产周期长且易造成污染.本研究以葡萄糖酸δ内酯作为葡萄糖酸的来源,利用蛋壳中所含高达93%的CaCO3[1]进行中和反应制备葡萄糖酸钙,探索了一条变废为宝,工艺简单,成本低,污染小的葡萄糖酸钙生产路线.     

Boron‐functionalized poly(3‐hydroxybutyrate)s from hydroboration of poly(allyl‐β‐hydroxyalkanoate)s: Synthesis and insights into the microstructure

The controlled ring‐opening polymerization of racemic allyl‐β‐butyrolactone (rac‐BL^allyl) in toluene or in bulk, catalyzed by the discrete β‐diiminate zinc amido [(BDI^iPr)Zn(N(SiMe₃)₂)] ( 1 ) or {amino‐methoxy‐bis(phenolate)}yttrium amido [(ONOO^tBu)Y(N(SiHMe₂)₂)(THF)] ( 2 ) complexes, in association with an alcohol, gave poly(β‐hydroxyalkanoate)s (PHAs) with allylic side chains. These PHAs^allyl exhibit either a slightly isotactic‐enriched (P_m = 0.61) or highly syndiotactic‐enriched (P_r = 0.82) backbone structure, respectively, with high molar mass (M _n up to 21,100 g mol^?1) and narrow molar mass distribution values (1.05 < M _w/M _n < 1.28), as evidenced by detailed ¹³C NMR and size exclusion chromatography analyses. Postpolymerization rhodium‐catalyzed hydroboration of the resulting PHAs^allyl with pinacolborane quantitatively afforded the corresponding PHAs^boron. Introduction of boron into the pendant chains did not alter neither the structure of the polymer backbone nor the macromolecular features (M _n, M _w/M _n, and stereoregularity). However, differential scanning calorimetry analyses revealed a significant increase of the glass transition temperature on modifying the allyl for the boron function in these PHAs. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of 13-amino telekin derivatives and their cytotoxic activity

Telekin is a eudesmane sesquiterpene-lactone naturally occurring in many medicinal plants with antitumour and anti-inflammatory activity. In this study, a series of 13-amino derivatives of telekin have been synthesised through Michael addition reaction, and their relative configurations were exemplified by the single crystal X-ray diffraction of the dimethylamine adduct. The in vitro cytotoxicity against three tumour cell lines of these amine derivatives was evaluated. The piperidine and 4-hydroxypiperidine adducts displayed stronger cytotoxic activity than telekin.