双套索硫杂冠醚及主链含硫杂冠醚聚酯的合成

从３，１６－二羟基－１－硫杂－５，３，１１，１４－四氧杂环十七烷（二羟基硫杂－１７冠－５）出发，通过醚化反应，合成了双（己氧基），双（十二烷氧基）、双（十六烷氧基），双（苄氧基）和双（烯丙氧基）硫杂－１７－冠－５。单己氧基、单十二烷氧基，单十六烷氧基和单苄氧基硫杂－１７－冠－５作为副产物分离得到。通过二羟基硫杂－１７－冠－５与丁二酰氯缩聚，合成了主链含硫杂冠醚的聚酯。     

硫杂杯芳烃-金属离子的新型配位化合物

选择性分离贵金属、放射金属、碱金属等金属离子是重要研究方向之一。硫杂杯芳烃是一类由硫原子桥链苯酚单元构成的大环化合物。作为第三代超分子材料,硫杂杯芳烃反应位点丰富,上边缘、下边缘以及桥链的硫原子上都有进行功能化的可能性,而功能化后硫杂杯芳烃能够表现出与金属离子优异的配位性能,从而达到选择性分离金属离子的目的。本文介绍了硫杂杯芳烃的合成历史、自身结构特点以及配位机理。在此基础上分析了在硫杂杯芳烃的上缘、下缘引入酯基、酰胺、亚胺/胺等官能团后与碱金属、碱土金属、放射金属、贵金属离子等的配位情况,总结了硫杂杯芳烃自身构型、杯环的大小、溶剂类型等对其配位性能的影响,并深入分析了与金属离子的不同配位机理。本文可以为开发高效选择性分离提取各种金属离子的技术提供理论依据。     

二氰基取代的四硫富瓦烯硫杂冠醚衍生物的合成及性质研究

在甲苯溶液中,在亚磷酸三乙酯存在下,采取高度稀释的方法,使4,5-二氰基-1,3-二硫杂环戊二烯-2-酮分别和多缩硫杂冠醚进行交叉偶联反应,成功地得到了不对称的2,3-二氰基四硫富瓦烯衍生物。用1HNMR、MSI、R和EA表征了其结构,并用循环伏安法研究了它们的电化学性质,用1HNMR初步评价了衍生物对钠离子的配合性能。     

新型冠醚化合物的合成及选择性识别作用

介绍了新型冠醚化合物的合成、特殊结构冠醚的合成及选择性识别作用、冠醚对金属离子的选择性络合作用,并对冠醚化学的发展进行了展望。     

氮杂冠醚壳聚糖研究(Ⅲ)--双羟基中环二胺交联壳聚糖的制备

以壳聚糖为原料,与经环氧活化的双羟基中环二胺反应,制备了一种新型的氮杂冠醚交联壳聚糖。主要中间体及产物经红外光谱、X-射线粉末衍射等进行了确证。     

氮杂冠醚壳聚糖研究(Ⅲ)——双羟基中环二胺交联壳聚糖的制备

以壳聚糖为原料,与经环氧活化的双羟基中环二胺反应,制备了一种新型的氮杂冠醚交联壳聚糖。主要中间体及产物经红外光谱、X-射线粉末衍射等进行了确证。     

硅杂原子提升冠醚对锂离子络合能力的机理理论研究

将Si引入冠醚有希望大幅度提升其对阳离子的络合能力,但其中的调控机理尚不清晰。基于量子化学密度泛函理论计算,以12-冠-4、1,1-2甲基-1-硅杂12-冠-4、1,1,2,2-4甲基-1,2-2硅杂12-冠-4、1,1,2,2,4,4,5,5-8甲基-1,2,4,5-4硅杂12-冠-4和1,1,2,2,7,7,8,8-8甲基-1,2,7,8-4硅杂12-冠-4络合Li⁺为计算模型,探究了冠醚与Li⁺之间的相互作用机理。结果表明,由于O—Li⁺配位键的键长增加,掺杂Si的数量为2和4的Si杂12-冠-4对Li⁺的共价相互作用略弱,但静电相互作用和色散相互作用更强、Pauli排斥作用更小,最终导致所有Si杂12-冠-4对Li⁺的络合能力都比12-冠-4更强。上述有利因素源于Si—O键中Si的电子显著向O极化,同时,Si杂12-冠-4中—SiMe₂—SiMe₂—和—CH₂—SiMe₂—单元远离Li⁺,有效避免了Si—Li⁺之间的静电排斥。揭示的冠醚-Li⁺相互作用机理将为未来设计与合成杂原子冠醚提供理论指导。     

硫杂杯芳烃的应用研究进展

硫杂杯芳烃是一类以硫原子取代桥联亚甲基的新型杯芳烃,作为新一代超分子砌块,在分子识别、超分子自组装、晶体工程和纳米材料等方面都获得了广泛的应用,己成为当今超分子化学研究的新热点.     

新型硫氮杂冠醚化合物的合成与表征

经取代、氯乙酰化、成环3步反应合成两种新的硫氮杂冠醚化合物,产率>90%。该合成方法具有反应条件温和,容易提纯等优点。化合物结构经IR、NMR、MS以及元素分析确定。     

脱除萘中硫杂茚的方法(综述)

萘是煤焦油的主要组分之一,其含量波动不大,在１０％～１１．９％（质量,下同）之间,萘含量多少首先取决于烟煤的炼焦制度。商品萘（精萘或工业萘）的制取主要是萘与杂质的分离,萘中的主要杂质含量如下,％：中性烃２．０其中不饱和烃１．４α－甲基萘４．６β－甲基萘７．０其它萘的衍生物２．５氮含量苯甲腈０．１５吲哚０．４硫含量硫杂茚５．０甲基硫杂茚５．０酚类酚０．５邻、间、对甲酚５．４二甲酚２．５盐基吡啶衍生物０．６喹琳及其衍生物１．３高沸点盐基０．２在焦油加工时萘中杂质在某种程度上转入萘馏分,萘的进一步加工…     

Synthesis,complexation and biological effects studies of new thiacrown ethers derived quinoline: part I

A series of new thiacrown ethers derived quinoline 7–9 were synthesized in good yield and in a simple way. Their transition metal ions complexation was studied using a conductometric method in acetonitrile at 25°C. Crowns 7 and 8 showed a continuous decrease in the molar conductances in their complexation with Ag⁺, Cu²⁺, Hg²⁺ and Zn²⁺ which begins to level off at a molar ratio of 1:1 crown to metal, indicating the formation of 1 stable 1:1 complex. On the other hand, crown 9 showed the formation of 1:1 complexes only with Ag⁺, Cu²⁺, Hg²⁺. The in vitro, a preliminary antimicrobial, antioxidant and cytotoxic effects on breast tumor cells were also reported. Five bacterial test strains were included in the present study. Antioxidant activity was measured in terms of the radical scavenging ability and decolorization of 1,1-Diphenyl-2-picrylhydrazyl (DPPH) radicals. Cytotoxic effect of thiacrown was evaluated using MDA MB-231 cell line (human breast adenocarcinoma, ATCC HTB-26).     

Upper Rim Thioether Derivatives of Calix[4,6]Arenes: Extraction of Fission Pd(II) and Ag(I)

Abstract

We report studies on the Pd(II) and Ag(I) complexation and extraction by tetraalkyl(tolyl)thiomethylcalix[4]arenes (1a–c) stabilized in the cone conformation, and by the stereochemically mobile tetraalkyl(tolyl)thiomethylcalix[6]arenes (2a, b). These are found to be 100–1000 times more efficient as extractants of nitric and nitrous forms of Pd(II) and Ag(I) than their ungrafted monodentate analogues. Extraction experiments performed on real HLW show that tetrabutylthiomethylcalix[4]arene 1b is able to concentrate and separate Pd from main fission products. The extraction constants for mono‐ and binuclear Ag complexes have been determined. The stoichiometry and structural features of the complexes of Pd and Ag have been studied experimentally by extraction, IR‐ and mass‐spectroscopy methods as well as in quantum‐mechanical calculations.     

双相（O/W）识别手性萃取分离多巴对映体研究

为了研究多巴在D（L）-2酒石酸异丁酯1,2二氯乙烷有机相和羟丙基-β-环糊精水相萃取体系中的分配行为;运用双相（O/W）识别手性萃取,考察酒石酸构型和浓度、羟丙基-β-环糊精浓度、水相pH值等因素对萃取性能的影响。羟丙基-β-环糊精对S-多巴对映体的识别能力大于对R-多巴对映体的识别能力,而L-酒石酸异丁酯的识别能力刚好相反;在羟丙基-β-环糊精和L-酒石酸异丁酯萃取体系中,多巴外消旋体一次萃取分离后R和S对映体的分配系数（kR和kS）分别为8.92和5.34,分离因子α达1.67;同时pH值和萃取剂浓度对手性分离能力有显著的影响。双相（O/W）识别手性萃取具有较强的手性分离能力,它对外消旋体化合物的制备性分离有着十分重要的意义。     

Structure-Based Inhibitor Discovery of Class I Histone Deacetylases (HDACs)

Class I histone deacetylases (HDACs) are promising targets for epigenetic therapies for a range of diseases such as cancers, inflammations, infections and neurological diseases. Although six HDAC inhibitors are now licensed for clinical treatments, they are all pan-inhibitors with little or no HDAC isoform selectivity, exhibiting undesirable side effects. A major issue with the currently available HDAC inhibitors is that they have limited specificity and target multiple deacetylases. Except for HDAC8, Class I HDACs (1, 2 and 3) are recruited to large multiprotein complexes to function. Therefore, there are rising needs to develop new, hopefully, therapeutically efficacious HDAC inhibitors with isoform or complex selectivity. Here, upon the introduction of the structures of Class I HDACs and their complexes, we provide an up-to-date overview of the structure-based discovery of Class I HDAC inhibitors, including pan-, isoform-selective and complex-specific inhibitors, aiming to provide an insight into the discovery of additional HDAC inhibitors with greater selectivity, specificity and therapeutic utility.     

发射药钝感剂分布的萃取测定

为建立一种测定钝感剂在药粒中渗透深度和浓度分布的方法,在频率为45kHz的超声波清洗器中,将单樟-11A-8/1发射药试样按规定的不同萃取时间在20℃时用二氯甲烷溶剂萃取,用气相色谱测定每次萃取后萃取液中钝感剂浓度,并计算不同时间段参与萃取的发射药体积,换算成萃取深度,绘制出了发射药深度和樟脑浓度关系曲线。结果表明,以发射药由表及里的深度与其对应樟脑含量关系曲线表示钝感剂分布的方法,更合理,但对试验条件和操作要求较高。     

Thiosubstituted Organophosphorus Acids as Selective Extractants for Ag(I) from Acidic Thiourea Solutions

Abstract

This paper deals with the solvent extraction of silver from thiourea leaching Ag ore liquors as an alternative to the traditional process involving cyanide. The investigation of the extraction mechanism of silver from acidic thiourea solution had not been clearly established to date.

The extraction behavior of silver using di(2‐ethylhexyl)dithiophosphoric acid (D2EHDTPA) and di(2,4,4‐trimethylpentyl) thiophosphinic acid (CYANEX 302) was studied. The effect of various parameters such as concentrations of metal, mineral acid, thiourea, and extractant has been investigated. The extracted complexes have been identified through a slope method analysis as AgX(HX)₅ for CYANEX 302 and AgX for D2EHDTPA, where HX denotes the extractant. Moreover, complete stripping was ensured with a mixture of NH₄SCN and H₂SO₄. In addition we showed that a first step of extraction with D2EHPA or CYANEX 272 results in the preferential separation of Fe(III) from the Ag(I) leach solution.     

A Cu(I) ion conductor obtained by replacement of Ag(I) in α-AgI

A solid conductor for Cu(I) was obtained by introducing Cu(I) into the high temperature form of AgI. The cationic transport number is practically one with negligible electronic conduction. The formula of the compound may be expressed by Ag_(1–x)Cu _x I withx varying with the temperature.     

灯盏花素提取技术和结构修饰的研究进展

总结近年来灯盏花素的提取技术和结构修饰的研究进展,为灯盏花素的提取工业化提供依据,并指出灯盏花结构修饰的关键在于提高灯盏乙素的水溶性,为进一步的药代动力学研究奠定了基础。