杯芳烃配位性质的研究进展

杯芳烃由于其结构的特殊性,几乎可以与大部分的金属离子形成配合物。文章综述了杯芳烃对碱金属、碱土金属、过渡金属及镧系锕系金属的配合作用,并对其应用前景进行了展望。     

我国杯芳烃化学的研究进展

简述了杯芳烃的结构特征、特性及应用,较为详细地综述了2010年以来杯芳烃研究的新进展.即:①多种新型杯芳烃的合成;②新型杯芳烃金属配合物的合成;③新型杯芳烃的自组装.     

硫杂杯芳烃类衍生物络合能力的探究

通过金属离子的萃取试验和氨基酸的萃取试验研究了五种硫杂杯芳烃类化合物的络合性能,结果显示硫杂杯芳烃类化合物对软金属和脂肪族氨基酸萃取能力较好。分析其配合能力主要与空腔的匹配程度以及上下缘的取代基有关,其次,当能够形成分子间氢键时,其配合能力也较强。     

杯芳烃配位性质的研究进展

杯芳烃及其衍生物由于其结构的特殊性,几乎可以与所有的金属离子形成配合物。本文主要综述了其对碱金属及碱土金属、过渡金属及镧系锕系金属的配合作用,并对其应用前景进行了展望。     

杯芳烃合成研究进展

杯芳烃是一类超分子主体化合物,主要有杯[4]、杯[6]和杯[8]芳烃的杯芳烃衍生物、杯芳烃聚合物及杯芳烃配合物等。介绍了不同杯芳烃及其衍生物的合成工艺的研究进展。     

杯芳烃在染料中的应用

综述了近年来杯芳烃在染料方面的研究进展,重点介绍了偶氮类杯芳烃、杯芳烃与金属络合的显色作用和对染料包合后染料性能的改进作用,并对其应用前景进行了展望。     

对叔丁基杯[6]芳烃与黑索金的配合研究

对叔丁基苯酚和甲醛在KOH催化下制备对叔丁基杯[6]芳烃。用荧光光谱法研究了对叔丁基杯[6]芳烃与黑索金(RDX)在溶液中的相互作用,结果表明对叔丁基杯[6]芳烃与RDX在溶液中存在较强的配合作用,RDX的激发峰发生明显红移,荧光强度增强,主客体间发生了包合作用。通过对叔丁基杯[6]芳烃-RDX配合物的发射光谱与紫外光谱分析,确定了在DMF溶液中对叔丁基杯[6]-RDX配合物的化学计量比为1∶1,稳定常数为325.70。     

醛肟基杯[4]芳烃衍生物的合成及性能研究

利用盐酸羟胺与杯[4]芳烃二醛衍生物的亲核加成反应,设计并合成了下沿含醛肟基团的新型杯[4]芳烃衍生物,经1HNMR、MS和元素分析等表征确证其结构,测定了醛肟基杯[4]芳烃衍生物对系列金属阳离子的液液两相萃取性能,实验结果表明醛肟基杯[4]芳烃衍生物对软酸类金属阳离子具有较好的配位性能,特别是对Hg2+和Ag+的萃取率分别达到39.2%和35.6%。     

全羟基杯[4]芳烃对Pb~(2+)、Hg~(2+)和Cd~(2+)配位结合模拟预测

采用Gaussian 09软件对全羟基杯[4]芳烃与Pb2+、Hg2+、Cd2+直接配位形成的配合物进行模拟预测,对全羟基杯[4]芳烃及其与Pb2+、Hg2+、Cd2+形成的配合物分子的构型进行对比分析,并对杯[4]芳烃与Pb2+、Hg2+、Cd2结合能力进行对比研究。结果表明,配合物中全羟基杯[4]芳烃对Cd2+的结合力度明显高于Hg2+和Cd2+。     

氮杂杯[6]芳烃及其叠氮衍生物与RDX、HMX的配合研究

研究了氮原子桥连杯[3]芳烃[3]三嗪化合物(简称氮杂杯[6]芳烃)与黑索今、奥克托今的配合能力。通过紫外光谱和X射线衍射(XRD)对氮杂杯[6]芳烃及其叠氮衍生物与黑索今、奥克托今的配合性能进行了表征分析。结果表明主客体之间发生了相互作用,为超分子炸药的制备提供了理论支持。     

蓬勃发展的杯芳烃化学

简要介绍了杯芳烃的结构特征、产生、发展及应用,详细介绍了:①新型杯芳烃的点击合成及应用;②多种系列新型杯芳烃的合成及应用;③新型杯芳烃的合成及其对金属离子的选择性络合作用。并对杯芳烃的发展进行了展望。     

基于杯芳烃识别金属离子的荧光化学传感器研究进展

杯芳烃荧光传感器以杯芳烃衍生物为识别主体,以荧光为信号传感手段,通过主体和客体间的选择性结合,实现对客体分子的定性和定量检测。由于荧光传感器具有高度灵敏性、良好选择性和易于操作等优点,研究能选择性识别金属离子的荧光化学传感器对生命化学和环境化学都具有非常重要的意义。文章就基于杯芳烃识别金属离子（碱金属离子、碱土金属离子、重金属离子、过渡金属离子）的荧光化学传感器研究进展进行了综述。     

Silver electrowinning from silver(I)–calixarene complexes by two-phase electrolysis

Results are reported, providing the basis for an elegant new process for metal recovery from acidic solutions, by integrating solvent extraction (SX) and electrowinning (EW) in a single process, rather than operating them separately, as in conventional SX–EW processes. Calixarene-tetramide and its thio-analogue were used for the extraction of silver(I) ions from aqueous phases into dichloromethane, both compounds achieving extraction efficiencies >90%. The effects were determined of extractant and silver(I) concentrations, aqueous phase pH, and the presence of sodium ions, on the distribution of Ag(I) between aqueous and organic phases. Due to the impossibility of stripping the extracted metal conventionally, electro-reductive stripping of silver(I) from the loaded organic phase was carried out in the calixarene/nitric acid two-phase system. The effects were also investigated of current density or electrode potential on silver deposition current efficiencies and cell voltages. Based on experimental data, a new process for silver(I) removal from very dilute solutions was proposed that showed high percentage extractions of silver(I) from the aqueous phase, coupled to direct EW of silver from the calixarene complex in the loaded organic phase, regenerating the extractant for recycle. Current efficiencies in the range from 60% to 90% and cell voltages <3.5 V were achieved simultaneously in this process.     

Adsorption of amino acid derivatives on calixarene carboxylic acid impregnated resins

Macrocyclic host molecules calixarene carboxylic acid derivatives are found to act as powerful extractants for biologically important amino compounds. A series of adsorbents were prepared from a methacrylate-based polymer Amberlite XAD-7 by impregnation with various calixarene derivatives, for adsorptive recovery of amino acid derivatives. The larger macrocycles calix[6]arene and calix[8]arene carboxylic acid derivatives were more effective for adsorption of amino acid derivatives on the impregnated resin than the calix[4]arene derivative. Since adsorption proceeds mainly via electrostatic interaction, the carboxylic acid groups introduced into the calixarene platform were important for adsorption of cationic amino acid derivatives. The adsorption selectivity for amino compounds using adsorbent impregnated with the calix[6]arene carboxylic acid derivative depends simply on the hydrophobicity of the adsorbates.     

杯芳烃及其衍生物在生命科学中的研究进展

通过查阅近五年来的文献,对被称为第三代主体超分子化合物的杯芳烃及其衍生物在生命科学领域中的研究进展进行了综述。主要阐述了杯芳烃对生物分子的识别作用、生物分子在杯芳烃化合物功能修饰中的应用及杯芳烃与生物分子相互作用的应用研究,同时还对杯芳烃及其衍生物在生命科学领域中的应用前景进行了展望。     

胆红素金属配合物的合成与表征

本文报导了从猪胆中提取的胆红素与锰、钴、铜、锌的醋酸直力氯化亚锡、二氯二甲基锡等分别在不同条件下，在ＣＨＣｌ３或ＤＭＦ溶剂中合成的一系列金属配合物固体。对它们进行了元素分析、红外、紫外、差热、质谱等表征。着重讨论了它们的分子组成和配位结构。研究发现：胆红素对金属离子的配位表现出多样性，由于胆红素分子本身结构的异构化和金属离子性质的不同，它们的结构随金属离子不同而异，既可以形成１：１（摩尔比）的类卟     

Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces

Understanding the interaction of ions with organic receptors in confined space is of fundamental importance and could advance nanoelectronics and sensor design. In this work, metal ion complexation of conformationally varied thiacalix[4]monocrowns bearing lower-rim hydroxy (type I), dodecyloxy (type II), or methoxy (type III) fragments was evaluated. At the liquid–liquid interface, alkylated thiacalixcrowns-5(6) selectively extract alkali metal ions according to the induced-fit concept, whereas crown-4 receptors were ineffective due to distortion of the crown-ether cavity, as predicted by quantum-chemical calculations. In type-I ligands, alkali-metal ion extraction by the solvent-accessible crown-ether cavity was prevented, which resulted in competitive Ag⁺ extraction by sulfide bridges. Surprisingly, amphiphilic type-I/II conjugates moderately extracted other metal ions, which was attributed to calixarene aggregation in salt aqueous phase and supported by dynamic light scattering measurements. Cation–monolayer interactions at the air–water interface were monitored by surface pressure/potential measurements and UV/visible reflection–absorption spectroscopy. Topology-varied selectivity was evidenced, towards Sr²⁺ (crown-4), K⁺ (crown-5), and Ag⁺ (crown-6) in type-I receptors and Na⁺ (crown-4), Ca²⁺ (crown-5), and Cs⁺ (crown-6) in type-II receptors. Nuclear magnetic resonance and electronic absorption spectroscopy revealed exocyclic coordination in type-I ligands and cation–π interactions in type-II ligands.     

杯[4]芳烃偶氮衍生物的合成及其金属离子萃取性能

杯芳烃作为超分子化学的重要组成部分,近年来得到了快速发展并成为化学家的研究热点。以脱叔丁基-杯[4]芳烃为原料合成了杯[4]芳烃偶氮衍生物,其结构经IR和1H NMR所表征。研究了该主体分子对金属离子的萃取性能,实验结果表明,该主体分子对Mg2＋具有较高的萃取作用。讨论了主客体间配位作用的机制。     

新型杯芳烃化合物的合成自组装键合及应用

简要介绍了杯芳烃的结构特点及应用,详细综述了:①杯芳烃衍生物的合成组装键合及应用;②新型杯芳烃的合成及络合作用;③新型杯芳烃的合成及在医药学方面的应用。     

Novel Bifunctional Resins in Metal Ion Separations: Ion Exchange/Coordination Resins and Ion Exchange/Precipitation Resins

Abstract

Dual mechanism bifunctional polymers (DMBP's) as metal ion extractants are described within the context of two new examples. The carboxylic acid/pseudocrown resin is a new example of the DMBP class of resins described as ion exchange/ coordination resins. The polyethylene glycol ligand within the resin functions as a coordinating site for metal ions which are brought into the resin via ion exchange with the acid ligand. Initial studies with alkali metal ions are presented. The third general class of DMBP's is also presented. In this case, precipitation is the reaction occurring along with ion exchange thus yielding the ion exchange/precipitation resins. Barium recovery from aqueous solution via barium sulfate precipitation is described.