新型类维A酸锡酯的合成、结构表征及其体外抗癌活性

用二正丁基氧化锡和类维生素A酸以摩尔比1∶2和1∶1反应,合成了两个系列的新型类维生素A酸二正丁基锡酯化合物3a~3d和4a~4d,并利用(1H,13C,119Sn)NMR和IR表征了这些化合物的结构,确定了化合物3a~3d是通过单齿配位形式与锡原子结合而成的五配位三角双锥型的配合物化合物,而化合物4a~4d的结构中存在着一个锡氧四元环,分子中的酯基为二齿配体,锡原子都是六配位扭曲八面体构型.生物活性测试表明:该类化合物对宫颈癌细胞(Hela)、肝癌细胞(LCC)、肺癌细胞(A549)等癌细胞都具有较好的抗癌活性.     

有机膦酸的核磁共振分析

使用400MHz核磁共振仪测定了羟基乙叉二膦酸(HEDP)和甲胺二甲叉膦酸(MADMP)的^1H、^13C和^31P谱．研究了P对H和C的偶合裂分,探讨了N对^1H、^13C和^31P谱的影响．发现P对邻近C、H的偶合作用很强,而N的存在使谱图变得复杂．结果表明核磁共振波谱适合于有机膦酸的结构鉴定,是剖析该类化合物的一种较好方法。     

阻燃剂对二苄基双膦酸四甲酯的研制

在催化剂的作用下,以亚磷酸三甲酯和对二氯苄为原料,合成一种高效无卤阻燃剂——对二苄基双膦酸四甲酯.当反应温度为130℃,物质的量比(亚磷酸三甲酯:对二氯苄)为2.8:1,反应时间为6h,催化剂用量为原料总质量的3％时,产率可达80％.通过高分辨质谱仪、红外光谱仪、核磁共振仪对产品结构进行了表征,通过热重分析仪对其热稳定...     

小分子有机抑制剂的合成及其对黄铁矿和毒砂的抑制性能

本文报道了小分子有机抑制剂氨基三甲叉膦酸NTP,乙二胺四甲叉膦酸EDTP和己二胺四甲叉膦酸HDTP的合成方法,对NTP,EDTP,HDTP和氨基二乙酸NDA四种化合物抑制黄铁矿、毒砂的行为以及分离这两种矿物的性能作了实验研究,并对药剂与矿物表面的作用模式以及药剂结构与性能间关系进行了研究讨论。     

链结构对聚芳酯性质的影响

本文通过几种测试手段对用低温溶液法合成的以聚对苯二甲酸氯代对苯二酚酯和聚2,5-二氯对苯二甲酸氯代对苯二酚酯为主体,分别以不同结构的双酚:4,4'-二羟基二苯醚、4,4'-二羟基联苯、双酚A和1,5-萘二酚为第三单体的芳香族共聚酯的性能进行了讨论,发现分子链结构对芳香族共聚酯的性能有很大的影响。     

循环冷却水用水质稳定剂效果的快速评价

提出了一种新的有效评价阻垢剂阻垢性能的方法——浊度法．用此方法对5种具有代表性的水处理剂即羟基乙叉二膦酸,氨基三甲叉膦酸,聚丙烯酸,水解聚马来酸酐及绿色阻垢剂聚环氧琥珀酸进行了评价．实验结果表明,浊度法通过比较不同阻垢剂作用于水体中的成核抑制时间,能迅速、高效地评定阻垢性能的差别,所需实验时间不超过100min,所需实验设备简单．对晶体X-射线衍射结果与浊度法结果进行比较,证明羟基乙叉二膦酸与氨基三甲叉膦酸在实验水中对碳酸钙结晶的影响是相似的．     

新型水处理剂EDDAP阻垢性能的研究(Ⅱ)

本文对合成产物———新型水处理剂乙二胺 -N,N'-二乙酸 -二甲叉膦酸 (EDDAP)阻磷酸钙垢的性能进行了研究。结果表明 ,EDDAP具有优异的阻磷酸钙垢性能 ,且明显优于羟基乙叉二膦酸(HEDP)。     

新型水处理剂EDDAP的合成

本文成功地合成了乙二胺—N,N′—二乙酸—二甲叉膦酸(EDDAP),详细研究了合成EDDAP适宜的反应条件和精制条件。EDDAP的精制产物经红外光谱分析、1H核磁共振谱的分析表征其结构     

α—三甲硅氧基烃基膦酸二烷基酯的合成

磷硅试剂与羰基化合物反应是制备α-三甲硅氧基烃基膦酸二烷基酯的简单而有效的方法。本文报导了用此法合成十二个α-三甲硅氧基烷基膦酸二乙酯的反应条件以及产物的IR和H~1-NMR数据,初步探讨了影响反应的有关因素。     

合成δ—甲氧羰基—β—羰基戊酸乙酯

本文介绍了δ－甲氧碳基－β－羰基戊酸乙酯（Ⅴ）的合成方法，使二乙氧基镁和丙二酸乙脂叔丁酯（Ⅰ）的衍生物（Ⅱ）与β－甲氢羰基丙酰氯（Ⅲ）缩合生成三酯（Ⅳ），使三酯Ⅳ在酸存在下减压回流分解，然后分馏可得纯度高的Ⅴ。     

全乙酰化环丙烷甲酸糖酯类化合物的合成及结构确证

以环丙烷甲酸及2,2-二甲基环丙烷类化合物甲酸为先导化合物,合成了8个新的（呋喃、吡喃）糖基环丙烷甲酸及2,2-二甲基环丙烷甲酸酯类化合物,所有新化合物都经元素分析、^1H NMR得到确证,合成产率为40．5％～59．7％。     

不同羧酸配体对铽三元配合物发光性能的影响

采用传统的共沉淀法,以Tb³⁺为中心离子,选择5种不同的羧酸:甲基丙烯酸（MAA）、丙烯酸（AA）、笨甲酸（BA）、丁二酸（SA）和己二酸（HDA）分别作为第一配体,以1,10-邻菲罗啉（phen）为第二配体合成一系列稀土羧酸配合物。对配合物进行红外光谱（IR）、热分析（TG-DSC）、紫外光谱（UV）和荧光光谱（PL）的测定。结果表明:各稀土配合物均能够发出Tb³⁺的特征荧光,提高配体的共轭性和刚性均有利于荧光强度的增加;二元酸的传能效率强于一元酸;第一配体与第二配体间的位阻效应越小、能级匹配程度越高,配合物的荧光强度越大。     

Convergence of 9-cis retinoic acid and peroxisome proliferator signalling pathways through heterodimer formation of their receptors.

Peroxisomes are cytoplasmic organelles which are important in mammals in modulation of lipid homeostasis, including the metabolism of long-chain fatty acids and conversion of cholesterol to bile salts (reviewed in refs 1 and 2). Amphipathic carboxylates such as clofibric acid have been used in man as hypolipidaemic agents and in rodents they stimulate the proliferation of peroxisomes. These agents, termed peroxisome proliferators, and all-trans retinoic acid activate genes involved in peroxisomal-mediated beta-oxidation of fatty acids. Here we show that the receptor activated by peroxisome proliferators and the retinoid X receptor-alpha (ref. 6) form a heterodimer that activates acyl-CoA oxidase gene expression in response to either clofibric acid or the retinoid X receptor-alpha ligand, 9-cis retinoic acid, an all-trans retinoic acid metabolite; simultaneous exposure to both activators results in a synergistic induction of gene expression. These data demonstrate the coupling of the peroxisome proliferator and retinoid signalling pathways and provide evidence for a physiological role for 9-cis retinoic acid in modulating lipid metabolism.     

Seasonal variation and sources of low molecular weight organic acids in precipitation in the rural area of Anshun

Low molecular weight (LMW) organic acids are important and ubiquitous chemical constituents in the atmosphere. A comprehensive study of the chemical composition of precipitation was carried out from June 2007 to June 2008 at a rural site in Anshun, in the west of Guizhou Province, China. During this period, 118 rainwater samples were collected and the main LMW carboxylic acids were determined using ion chromatography. The average pH of rainwater was 4.89 which is a typical acidic value. The most abundant carboxylic acids were formic acid (volume weight mean concentration: 8.77 μmol L⁻¹) and acetic acid (6.90 μmol L⁻¹), followed by oxalic acid (2.05 μmol L⁻¹). The seasonal variation of concentrations and wet deposition fluxes of organic acids indicated that direct vegetation emissions were the main sources of the organic acids. Highest concentrations were observed in winter and were ascribed to the low winter rainfall and the contribution of other air pollution sources northeast of the study area. The ratio of formic and acetic acids in the precipitation ([F/A] _T ) was proposed as an indicator of pollution source. This suggested that the pollution resulted from direct emissions from natural or anthropogenic sources. Comparison with acid precipitation in other urban and rural areas in Guizhou showed that there was a decreasing contribution of LMW organic acids to free acidity and all anions in rainwater from urban to remote rural areas. Consequently, it is necessary to control emissions of organic acids to reduce the frequency of acid rain, especially in rural and remote areas.     

羧酸在油水相中的分布

研究了甲酸和乙酸于水中和不同有机介质中的分配系数,重点研究了含21、24和27碳原子的三烷基叔胺对甲酸和乙酸的成盐萃取作用。同时,在不同稀释剂及其用量、温度以及甲酸和乙酸浓度的条件下,确定了小分子羧酸的分配系数及其变化规律,最后,根据有机羧酸叔胺盐的热分解行为获得了纯度达90％的甲酸和乙酸,从而为重有机工业的酸回收提供了工艺技术设计的依据。     

邻羧基苯甲醛缩邻氨基苯甲酸席夫碱及其配合物的合成和表征

合成了邻羧基苯甲醛缩邻氨基苯甲酸席夫碱及其配合物CoLIm,MnLIm,NiLIm,CuLIm(L=邻羧基苯甲醛缩邻氨基苯甲酸席夫碱负二价阴离子,Im=咪唑）,进行了元素分析,紫外－可见,红外光谱及摩尔电导表征。     

1,3,4-噁二唑类荧光物质的合成及性能研究

以芳香羧酸和单酰肼为原料,通过缩合反应得到芳香双酰肼,三氯氧磷的作用下进行环合,制备得到3个2,5-二芳基-1,3,4-噁二唑类化合物,其结构经IR和1HNMR测试技术加以确证;荧光性能测试结果表明,目标产物具有较高的荧光量子收率和较大的斯托克斯位移.     

L-组氨酸不对称转化的研究

L-组氨酸(L-His)在醛的催化下,在羧酸溶剂中能发生消旋.当反应温度升高时,消旋反应速率加快.L-His用(R)-酒石酸((R)-TA)做拆分试剂,在乙酸溶剂中、水杨醛存在下进行不对称转换,合成了D-组氨酸(D-His)的酒石酸盐,经处理得到D-His.在最佳工艺条件下的收率为95.76%,光学纯度大于99.5%.     

Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite

The origin of the organic matter in carbonaceous meteorites remains controversial despite extensive study over the past 20 yr. Motivated by the expectation that the patterns of isotopic variation with molecular structure among the organic compounds would contain important clues to their origin, we have measured the carbon isotopic compositions for individual hydrocarbons and monocarboxylic acids from Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of 13C to 12C decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar; they also impose constraints on the identity of the reactant species.     

对甲苯磺酸／甲醇试剂用于气相色谱法中羧酸甲酯的衍生化反应

羧酸和甲醇在酸的催化下进行酯化反应,是气相色谱衍生化反应的常见方法。常用方法有CH_3OH～HCl法,CH_3OH_3OH—H_2SO_4法,CH_3OH—BF_3法,这些方法都比较成熟,在实际应用中也各具特点。曾有人用对甲苯磺酸(P—TSA)作为羧酸酯化反应的催化剂,该法对一些复杂的有机酸和醇反应转化率较高,并有不少这方面的合成专利和报导。本文探讨将PTSA—CH_3OH法用于色谱分析的新的甲酯化方法。采用某些有机酸和甲醇反应,考察P—TSA的催化效能,实验结果表明:P—TSA对三类羧酸的甲酯化反应都有较好的催化效果,尤其苯甲酸、水杨酸、邻氯苯甲酸等芳香酸用CH_3OH—PTSA法优于CH_3OH—HCl,CH_3OH—BF_3法。