Bola型阴离子表面活性剂与溴化十二烷基三乙铵混合体系的表面性质与聚集行为

研究了具有简单结构的bola型阴离子表面活性剂二十酸二钠（C_(20)Na_2)与 阳离子型普通表面活性剂溴化十二烷基三乙铵（C_(12)Et_3）混合体系的表面性质 ，发现混合体系的cmc和γ_(cmc)比C_(12)Et_3单一体系未有显著降低。以负染色 ，FF-TEM，动态光散射（DLS）及粘度方法研究了混合体系的聚集行为，发现混合 体系中同时形成球形囊泡和管状聚集体，提出了产生这种聚集行为的机制。     

Synthesis, characterization, antitumor activity of nickel(Ⅱ) and cobalt (Ⅱ) complexes of 2,2''''-diamino-4,4''''-bithiazole and their interaction with dGMP

New complexes,of bis(2,2'-diamino-4,4'-bithiazole)sulfate nickel(Ⅱ) and bis(2,2'-diami-no-4,4'-bithiazole)sulfate cobalt(Ⅱ),have been prepared.The complexes were characterized by infrared and UV-Vis spectroscopy,1H NMR,elemental analyses and molar conductivity.The effect of these complexes on the DNA synthesis of sarcoma 180 cells has been studied by the technique of isotopic liquid scintillation.The results indicated that complexes show ability to inhibit DNA synthesis of the tumor cells.In order to provide a molecular basis for understanding the biological effects,the probe,[trana-en2Os(η2-H2)](CF3SO3)2 (en,ethylenediamine) as a monitor was first used to explore interaction of the complexes with 2'-deoxyguanosine-5'-monophosphate (dGMP).     

SELECTIVE SEPARATION OF WATER-ETHANOL MIXTURES THROUGH COPOLYMERIC MEMBRANES: Ⅰ. ACRYLIC ACID AND ACRYLONITRILE COPOLYMER AND ITS IONIZED MEMBRANES

The copolymer of acrylic acid and acrylonitrile has been synthesized and pervaporation properties of the copolymeric membranes have been investigated. In order to elucidate the influence of membrane-permeate interaction on the pervaporation of water-ethanol mixtures and to prepare much improved membranes, the membranes have been treated with alkali metal, alkali earth metal and transition metal salt aqueous solutions. The treated membranes (ionized membranes) exhibited higher separation factors than the untreated membranes. The separation factors of various alkali metal cation membranes decreased in the following order : Li~+>Na~+>K~+, and the permeation rates showed an opposite tendency. The dependence of pervaporation behavior on the copolymer composition ,feed concentration and operating temperature have been studied with both ionized and non-ionized membranes. The apparent activation energies of water and ethanol permeation were calculated.     

以β-二酮连接的含生色团丙烯酰类单体及其饱和模型化合物的荧光行为

通过合成一系列同一分子中既含有给电子性荧光生色团又含缺电子性碳碳双键的烯类单体, 发现这类单体在相同生色团浓度下的荧光强度均明显低于相应的饱和模型化合物或聚合物[1～3]. 这种现象称为荧光结构自猝灭效应(SSQE), 以区别于浓度自猝灭现象. 对于电子状态与之相反的单体, 即含受电子性荧光生色团的乙烯基醚类单体, 也观察到了SSQE[4,5]. 进一步的研究结果表明, SSQE是光照条件下分子内电子给受体之间电荷转移作用的结果, 分子中电子给受体间的间隔基长度和溶剂的性质等都对SSQE有显著的影响[6]. 以往合成的含给生色团的丙烯酰类单体, 其电子给受体间是通过饱和脂肪链相连, 当生色团和受电子性碳碳双键之间以β-二酮结构相连时, 这类单体的荧光性质如何, 是否发生SSQE是我们的关注所在. 另一方面, β-二酮类化合物在一定波长光照射条件下, 常发生烯醇式与酮式的互变异构化. 虽然已有许多文献报道有关烯醇式-酮式互变异构过程中各种光谱的变化以及用核磁、红外、紫外等光谱手段研究烯醇式-酮式互变异构动力学, 但有关β-二酮类化合物互变异构过程中荧光光谱的变化的报道却很少[7～11]. 本文合成了以β-二酮连接的含二甲氨基苯基生色团的烯类单体, 1-(4-二甲氨基苯基)-4-甲基-4-戊烯-1,3-二酮(DMPDK)及其饱和模型化合物1-(4-二甲氨基苯基)-1,3-丁二酮(DMBDK), 研究了其光谱性质及光致互变异构行为.     

In Situ Fabrication of ZnS Semiconductor Nanoparticles in Layered Organic-inorganic Solid Template

Ordered ZnS semiconductor nanoparticles were in situ synthesized in metal halide perovskite organic/inorganic layered hybrids (CnH2n 1NH3)2ZnCl4 (n=10 and 12) by reaction of their spin-casting films with H2S gas. Transmission electron microscopy, UV-vis spectroscopy and small-angle X-ray diffraction were used to characterize the morphology and the structure of formed nanoparticles. Obtained results indicate an effective way to incorporate functional inorganic nanoparticles into structured organic matrices.     

The Efficient Synthesis of the Optically Active β‐Hydroxyl‐γ‐Butyrolactone Derivatives

The optically active β‐hydroxyl‐γ‐butyrolactones were synthesized from nonchiral starting material by employing reductive cleavage reaction, sharpless asymmetric epoxidation and dihydroxylation, and Lewis acid‐catalysed cyclization as key steps. This strategy can be used to prepare many chiral β‐hydroxyl‐γ‐butyrolactone analogues.     

Synthesis of （2R,4R）—2—N—tert—Butyloxycarbonyl Amino—4,5—epoxido—valeric Acid Methyl Ester

The stereoselective synthesis of (2R,4R)-2-N-tert-butyloxycarbonyl amino-4,5-epoxido-valeric acid methyl ester 8,which is the key intermediate for the synthesis of (2′S,2R)-3-trans-nitrocyclopropyl-alanine,was first accomplished.     

2-巯基噻唑[5，4-d]并嘧啶类化合物及其衍生物的合成

由邻硝基氯代嘧啶（3）为原料料，与多硫化钠和二硫化碳共煮，经一步反应 获得了2-巯基噻唑[5，4-d]并嘧啶（4）。由4出发，合成了一系列2位取代的衍生 物5，4和5的结构均通过了~1H NMR及元素分析确让。并对少数化合物的生物活性进 行了测试。     

纳米固体超强酸SO42-/Fe2O3的制备及其催化合成乙酸乙酯

将Fe₂O₃纳米粉体经一定浓度的H₂SO₄浸泡活化后制成纳米固体超强酸SO₄^2-/Fe₂O₃,将其用于催化合成乙酸乙酯以考察其活性。利用均匀设计分析了超强酸制备过程及酯化反应过程中各因素的影响,研究结果表明较好的制备条件是:H₂SO₄浓度:2.5mol·L^-1;浸泡时间:1h;活化温度:167℃;活化时间:1h,此时获得的固体超强酸SO₄^2-/Fe₂O₃的粒径小于50nm。当催化剂用量为冰乙酸质量的5%,n(乙醇)∶n(冰乙酸)为3∶1,反应3.5h后乙酸的转化率高于80%。该催化剂经H₂SO₄溶液浸泡、活化再生后可重新使用,推断出其酸强度H₀<-14.5。     

高效液相色谱-串联质谱法结合多糖衍生物手性固定相拆分氰戊菊酯

建立了以多糖衍生物为手性固定相的高效液相色谱-串联质谱(HPLC-MS/MS)直接拆分氰戊菊酯对映体的方法。在反相液相色谱条件下,考察了手性固定相的种类、流动相组成、柱温、流速对氰戊菊酯4个立体异构体分离的影响。同时,利用热力学方法对氰戊菊酯的立体异构体与固定相之间的色谱保留和分离的热力学机理进行了探讨。结果表明:采用Lux Cellulose-3(纤维素-三(4-甲基苯甲酸酯))手性色谱柱,在以流动相为乙腈-水(5 mmol/L甲酸铵)=(55:45,V:V)流速0.4 mL/min,柱温30℃的条件下,可在14 mins内实现氰戊菊酯4个立体异构体的基线分离。拓展了HPLC-MS/MS在菊酯类手性农药对映体分离及检测上的应用。