含己烷雌酚的聚磷酸酯的合成及其抗肿瘤活性研究

合成了３种主链含己烷雌酚的生物可降解的聚磷酸酯，结构经ＩＲ，＾１ＨＮＭＲ和元素分析鉴定，通过水接触角的测定研究了聚合物的亲水－疏水性能，以ｐＨ值变化表征了聚合物的体外水解速率。初步的体外实验表明，此类聚磷酸酯具有较好的体外抗艾氏腹水癌活性。     

Chemical Constituents from the Root of Antidesma Pentandrum var. Barbatum

Investigation of the root extract of Antidesma pentandrum var. barbatum led to the isolation of seven new compounds, antidesmol ( 1 ), antidesmanins E ( 2 ) and F ( 3 ), antidesnone ( 4 ), antidesnol ( 5 ), barbatumols A ( 6 ) and B ( 7 ), together with 14 known compounds including sodium aristolochate‐I ( 10 ) and aristolochic acid‐I methyl ester ( 11 ).     

Preparation and characterization of rosin glycerin ester and its bromide

Rosin glycerin ester and its bromide were prepared from natural renewable rosin, glycerin and liquid bromine which were first subjected to an esterification reaction, followed by an addition reaction. Their structures were characterized by an infrared (IR) spectrum and their thermal resistance was conducted with thermal gravity (TG) and differential scanning calorimetry (DSC). It showed that the bromide in the rosin glycerin ester decomposed faster than the ester; hence it may be used as fire-resistant material.     

Complete immiscibility in binary cholesteryl-n-carboxylic acid ester/stearic acid monolayers at the water/air interface

Applying different surface and spreading techniques to form binary monolayers in a different mixing state, the mixing behavior of the three binary systems cholesteryl formiate/stearic acid, cholesteryl acetate/stearic acid, and cholesteryl-n-propionate/stearic acid were investigated and compared.Analyzing the force ()/area (a) isotherms and the equilibrium spreading pressures (^e of the binary monolayers, it can be concluded that the components of the three binary systems do not mix within the whole concentration range. The lipids in the binary monolayers are completely immiscible.     

Synthesis, conformation and PKC isozyme surrogate binding of indolinelactam-Vs, new conformationally restricted analogues of (−)-indolactam-V

New conformationally restricted analogues of tumor promoter (−)-indolactam-V (1), indolinelactam-Vs (8, 11) and their hexyl derivatives at position 1 or 7 (9, 10, 12, 13), were synthesized from 1. (3R)-Indolinelactam-V (8) adopted a conformation similar to the twist form of 1 with a cis amide, while the conformation of (3S)-indolinelactam-V (11) was close to that of the sofa form of 1 with a trans amide. 7-Hexyl derivatives of 8 and 11 (10, 13) showed binding affinities for C1 domains of protein kinase C (PKC) isozymes compared to 1, but exhibited little selectivity among these PKC isozymes. However, introduction of the hexyl group at position 1 of 8 and 11 significantly enhanced their binding selectivity for novel PKC isozymes. The best selectivity for novel PKC isozymes was observed in (3S)-1-hexylindolinelactam-V (12) with a sofa-like conformation. These results suggest that a sofa-restricted analogue of 1 with a hydrophobic chain at an appropriate position would be a promising lead for designing agents with a high selectivity for novel PKC isozymes.     

A novel method for asymmetric synthesis of both enantiomers of α-substituted carboxylic acid derivatives from optically active 1-chlorovinyl p-tolyl sulfoxides and lithium ester enolates with 1,4-chiral induction from the sulfur chiral center

Treatment of optically active 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from symmetrical ketones and (R)-(−)-chloromethyl p-tolyl sulfoxide in three steps, with lithium enolate of carboxylic acid tert-butyl esters gave optically active adducts having a substituent at the α-position with high 1,4-chiral induction from the sulfur chiral center in high yields. The adducts were converted to optically active esters and carboxylic acids having a chiral center at the α-position. When this addition reaction was carried out with the ester enolate generated from excess carboxylic acid tert-butyl ester with LDA in the presence of HMPA, the diastereomer of the adduct was obtained. By using the two reaction conditions for the generation of the ester enolates, a new method for asymmetric synthesis of both enantiomers of carboxylic acid derivatives having a substituent at the α-position from the one chiral source, (R)-(−)-chloromethyl p-tolyl sulfoxide, was realized.     

动态单滴法研究乳状液液膜的稳定性

乳状液液膜作为化学分离的一种手段,自七十年代发现以来已有了许多进展,但是如何将其工业化还有许多课题有待于进一步研究.目前,除了乳状液液膜的水静态渗透性质以外,对乳状液液膜的稳定性和溶胀性质的研究主要采用搅拌法.虽然得到较好的规律性,但是搅拌法具有乳状液滴粒径分布广的弱点,对于不同的搅拌方式及条件,乳状液液膜的有效面积不同,对液膜作用的机械强度不同,因此结果会有很大差别.我们自行设计的动态单滴法实验装置,可定量地研究乳状液液膜的溶胀、稳定性及水渗透性质.     

A stannylene strategy for regioselective acylation and phosphorylation of 1,2-cyclohexylidene-myo-inositol. Its convenient resolution and phosphatidylinositol synthesis

The bis(dibutylstannylene) derivative of 1,2-cyclohexylidene-myo-inositol reacted with (S)-O-acetylmandeloyl chloride and diphosphate tetraesters to give 3,6-dimandelate and 3-phosphate, respectively. Using the stannylene methodology for the optical resolution and regioselective phosphorylation of the ketal, a concise synthesis of phosphatidylinositol with the natural configuration was accomplished.     

Kinetics study of thermal decomposition of epoxy resins containing flame retardant components

Hyperbranched polyphosphate ester (HPPE) and phenolic melamine (PM) were blended in different ratios with a commercial epoxy resin to obtain a series of flame retardant resins. The thermal decomposition mechanism of their cured products in air was studied by thermogravimetric analysis and in situ Fourier-transform infrared spectroscopy. The degradation behaviours of epoxy resins containing various flame retardant components were found to be greatly changed. The incorporation of phosphorus and nitrogen compounds improved the thermal stability at elevated temperature. The kinetics of thermal decomposition was evaluated by Kissinger method, Flynn-Wall-Ozawa method and Horowitz-Metzger method. The results showed that the activation energy at lower degree of the degradation decreased by the incorporation of flame retardant components, while increased at higher degree of the degradation.     

酚醛型氰酸酯与双酚A型环氧共固化反应的FTIR研究

在恒温固化条件下,通过FTIR跟踪方法,研究了酚醛型氰酸酯与双酚A型环氧共固化反应的路径及其反应机理.共固化体系的反应过程包括在150℃及其以下温度,主要发生的是氰酸酯的三嗪环化固化反应,其中三嗪环化固化反应由于环氧的加入,反应速率被极大地提高了;同时,酚醛型氰酸酯中的氨基甲酸酯类杂质与环氧发生开环聚合反应,引起环氧官能团产生弱而持续的消耗.但在此阶段,酚醛型氰酸酯与环氧之间没有化学反应发生;在180℃及其以上温度,三嗪环和环氧发生反应,异构为异氰脲酸环结构,并进一步反应生成唑啉酮环结构,由于该反应的发生,促进了环氧官能团的消耗速度,在环氧官能团的转化率-时间图中,出现倒S曲线;在三嗪环的转化率图中,出现一个极大值后再降落的曲线.反应温度的提高有利于促进酚醛型氰酸酯与环氧之间的共固化反应,特别是当反应温度为220℃时,氰酸酯官能团和环氧官能团的消耗、三嗪环和唑啉酮环的生成均以较快的速率进行,—OCN生成三嗪环的转化率可以较容易地达到1,而唑啉酮环的转化率不超过0.5.