新型正丁醛杯[4]芳烃醚衍生物的合成

以正丁醛间苯二酚杯[4]芳烃为原料,经酯化、水解、酰氯化后再与9-蒽甲醇反应,合成了蒽单取代的正丁醛间苯二酚型杯[4]芳烃醚衍生物。其结构经1H NMR和IR表征。     

四烷基间苯二酚杯芳烃八[N-(2-吡啶甲基)乙酰胺]的合成和分子结构

为深入开展杯芳烃为骨架的超分子拓扑结构的组装和性能,开展了间苯二酚杯芳烃八取代吡啶酰胺的合成和分子结构的研究。 以四丙基、四己基和四庚基间苯二酚杯芳烃为原料,使用α-氯乙酸甲酯实现O-烃基化,后者在无溶剂条件下与2-氨甲基吡啶反应实现酰胺化,制备了烷基间苯二酚杯芳烃八[N-(2-吡啶甲基)乙酰胺]衍生物。 用X衍射方法测定了四丙基间苯二酚杯芳烃八乙酸甲酯、四丙基以及四己基间苯二酚杯芳烃八[N-(2-吡啶甲基)乙酰胺]的单晶分子结构。 在晶体中,间苯二酚杯芳烃都以全顺式构型存在,在成环的四个间苯二酚单元中,1,3-位的两个间苯二酚单元处于近直立构象,2,4-位的另两个间苯二酚单元处于近平伏构象,而4个烷基皆处于分子的下缘,8个乙酰胺支链伸向分子的外围。     

两亲型杯芳烃诱导ZnO微纳结构的合成及光催化性能

回流条件下将两亲型杯芳烃,即丙基间苯二酚杯[4]芳烃(PRCA)、己基间苯二酚杯[4]芳烃(HRCA)和壬基间苯二酚杯[4]芳烃(NRCA),应用于诱导制备ZnO微纳结构,采用X射线衍射、扫描电镜、紫外可见漫反射光谱、红外光谱、X射线光电子能谱等分析了所制备ZnO样品的组成、形貌与微观结构,并以罗丹明B为模型污染物考察了所制备杯芳烃保护的ZnO样品的光催化性能。表征结果显示当杯芳环下缘所连直链烷基中含较多碳原子个数时(HRCA和NRCA),可调控ZnO粒子的尺寸和形貌;而无保护剂和下缘连接较短直链烷基的间苯二酚杯[4]芳烃(PRCA)调控ZnO形貌的能力较弱。模拟太阳光照射下,HRCA-ZnO和NRCA-ZnO的光催化效率相近且均高于无保护剂制备的ZnO和PRCA-ZnO。     

丙醛间苯二酚杯[4]芳烃烷基化衍生物的合成

以间苯二酚和丙醛为原料合成了丙醛杯[4]芳烃(1),1经不同的烷基化反应合成了新的丙醛杯[4]芳烃烷基化衍生物,其结构经1H NMR和IR表征。     

以含氨基酸1,3-桥联杯[4]芳烃为涂层的压电石英传感器对有机胺和有机醇的选择性识别研究

分别以三种新型含氨基酸1,3-桥联杯[4]芳烃衍生物作为压电石英传感器的敏感涂层,测定了一系列相同浓度的有机胺和有机醇蒸气．三种敏感涂层均对正构胺和正构醇表现出明显高的响应值．烷烃基支链越多,相应的频率变化就越小,说明涂层膜对气体分子的选择性识别主要是分析物的位阻效应、氢键及空腔疏水力共同作用的结果．含胱氨酸的1,3-桥联杯[4]芳烃衍生物涂层对各种蒸气的响应值均高于另外两种涂层,桥联杯芳烃的构象和衍生桥环的大小及构成均对涂层识别胺和醇的异构体有重要影响．本文也研究了实验条件的优化．     

杯芳烃衍生物液－液萃取和液膜传输银的对比研究及机理探讨

以4类含硫、硒、氮等杂原子基团二取代的杯[4]芳烃五衍生物（1－14）为中 性载体，在H2O-CHCl3-苦味酸体系萃取银和H2O-CHCl3-H2O液膜体系中传输银进行 了对比研究。萃取和传输结果具有一致性，除了苯并噻唑取代的杯[4]芳烃衍生物 （3－6）外，其它10个含硫、硒、氮的杯[4]芳烃衍生物1－14均对软重金属银和汞 有很高的选择性，而吡啶取代的杯[4]芳烃衍生物7－10对铅有一定的萃取选择性， 其中羟基硫醚取代的杯[4]芳烃衍生物11－14对银的萃取率和传输速率最大。并且 就杯[4]芳烃衍生物对银的传输机理进行了探讨，发现传输速率随源相中金属离子 浓度和有机相中载体浓度的增加而增大，因此推论这是由金属离子浓度梯度推动下 的传输。     

含硫杯[4]芳烃衍生物修饰电极伏安行为的研究

杯芳烃具有与环糊精类似的洞穴结构,且具有可调节大小的洞穴,有卓越的络合识别能力,杯芳烃衍生物的研究引起了国内外众多化学工作者极大的兴趣,在识别-催化、识别-配合、识别-分析等领域取得了可喜的研究成果。Stuart等研究了亚铁氰化钾及铁氰化钾在杯[4]间苯二酚修饰金电极上的电化学行为。Gomez-Kaifer用循环伏安法研究了系列母体醌式功能化杯[4]衍生物的氧化还原特性,发现该特性对Na^＋、Ag^＋有选择性识别响应。     

乙腈溶液中对叔丁基杯[4]芳烃与一些脂肪胺间的相互作用

用紫外可见光谱法和电导法研究了乙腈溶液中一些脂肪胺与对叔丁基杯[4]芳烃间的相互作用。考察了它们之间的反应机理,测定了它们之间各步反应的平衡常数及表观复合常数等。由紫外可见光谱得到的表观复合常数和同一方法得到的文献值数量级相同但数值相差几倍。电导测定表明在乙腈溶液中脂肪胺与对叔丁基杯[4]芳烃间的反应分两步进行:首先胺从杯芳烃得到一个质子生成胺正离子和杯负离子,然后离子再进一步包合。其总复合常数远小于其表观复合常数。且在对叔丁基杯[4]芳烃的饱和溶解度以下,质子转移所生成的离子是反应的主要产物。结果与文献中结论相反。     

对-叔丁基杯［4］芳烃对聚丙烯热氧稳定性的影响及其动力学研究

制备了对叔丁基杯[4]芳烃和聚丙烯共混体系,用热重法研究了对叔丁基杯[4]芳烃对聚丙烯热氧稳定性的影响,用Coats-Redferm方程进行动力学处理,确定对叔丁基杯[4]芳烃和聚丙烯共混体系的热氧降解的表观反应级数为1．413,表观活化能为154．899kJ/mol。     

基于杯[4]芳烃的手性识别*

手性杯芳烃是一类重要的主体化合物,在手性识别、对映体分离和不对称催化等方面有着广泛的用途。[4]芳烃引其稳定的构象和易于修饰的特点,成为研究最为广泛的杯芳烃分子,其中大量的文献报道了能够用于对映体识别和检测的手性[4]芳烃。在手性识别的研究中,荧光、紫外和核磁是3中最常见的研究方法,本文根据这3种方法进行分类,综述了近年来以杯[4]芳烃为分子骨架的手性受体的合成及其在手性识别中的应用。最后对手性[4]芳烃的发展前景作了展望。     

Extraction of Catecholamines by Calixarene Carboxylic Acid Derivatives

Extraction behaviors of catecholamines with a series of calixarene carboxylic acid derivatives were investigated. Relatively large calix[6]arene and calix[8]arene extract catecholamines into the organic solution, while smaller calix[4]arene and the monomer analog do not. The calix[6]arene, which has a cavity that fits a protonated amino group well, selectively extracts a primary amino compound dopamine over other catecholamines. Slope analysis and Job’s method confirmed formation of a 1:1 complex between the calix[6]arene and dopamine. On the other hand, the calix[8]arene extracts both dopamine and adrenaline, due to the large cavity for induced-fit recognition. Dopamine extracted with the calixarene is quantitatively stripped by contacting the organic solution with a fresh acidic solution.     

Electrochemistry of dopamine at the polarised liquid|liquid interface facilitated by an homo-oxo-calix[3]arene ionophore

The homo-oxo-calix[3]arene-facilitated electrochemistry of dopamine at the polarised liquid|liquid interface is presented. Cyclic voltammetry indicated that the dopamine: homo-oxo-calix[3]arene complex formed at the interface between water and 1,2-dichloroethane had a 1:2 stoichiometry, which was confirmed by ¹H NMR titration. The electrochemically-determined association constants for the homo-oxo-calix[3]arene complexes with dopamine (log β 8.3), Na⁺ (8.0) and K⁺ (7.5) showed that the ionophore was more selective for dopamine over the two alkali metal cations than the dibenzo-18-crown-6 ionophore. Square wave voltammetry was employed for assessment of low concentration measurements, with a limit of detection of 3.8 μM dopamine achieved. These results show that oxo-calixarene-based ionophores are useful reagents for the detection of dopamine at the interface between two immiscible electrolyte solutions.     

High-performance Liquid Chromatography Study of the Nitration Course of Tetrabutoxycalix[4]arene at the Upper Rim:Determination of the Optimum Conditions for the Preparation of 5,11,17-Trinitro-25,26,27,28-tetrabutoxycalix[4]arene

A selective nitration of calix[4]arene at the upper rim in one pot process was described by monitoring the time dependence of the distribution of products by high‐performance liquid chromatography (HPLC). The discrimination of five nitrated products was accomplished by molecular symmetry considerations and ¹H NMR analysis. As a result, unusual 5,11,17‐trinitrocalix[4]arene ( 2d ) was obtained in 57% isolated yield. 5,11‐Dinitro‐calix[4]arene ( 2b ) and 5,11,17‐trinitrocalix[4]arene ( 2d ) with tetranitrocalix[4]arene 2e were further characterized by crystal X‐ray diffraction analysis. Furthermore, as an example of potential application, trinitrocalix[4]arene 2d could be converted to triaminocalix[4]arene 3d conveniently.     

Anion influence on extraction and transport of amino acid methyl esters by functionalised calix[4]arene

The liquid–liquid extraction of a series of amino acid methyl esters has been carried out with functionalised calix[4]arene (5,11,17,23-tetrakis(N-methylpiperazino)-25,26,27,28-tetrahydroxycalix[4]arene) from an aqueous phase into a chloroform phase as ion pairs in the presence of picrate ion or tropaeolin 00 as counter ion in order to study the molecular recognition properties of this receptor. The active transport assisted by pH gradient of amino acids as ion pairs through liquid membrane employing the functionalised calix[4]arene as carrier has been investigated. The results showed that the receptor exhibits good extractability towards amino acids and it can also act as carrier through liquid membrane aiming to the separation of amino acids. It was highlighted that the anion nature used as counter ion, the structure of calix[4]arene, and the structure of amino acids are responsible for the experimental results obtained. High yields in both amino acids extraction and transport were obtained for picrate ion used as counter ion.     

Comparative study on the transition metal complexes of a novel thiacalix[4]arene derivative

A comparative study on Zn²⁺ and Cu²⁺ complexes of the novel compound 5,11,17,23-tetra-tert-butyl-25,27-bis{[4-(methoxycarbonyl)phenyl]methoxy}-2,8,14,20-tetrathiacalix[4]arene, that possesses potential as a core unit for the construction of molecular receptors, is presented using semiempirical AM1 calculation. The possible structures of each metal complex and their corresponding energetic data are compared with the parent 5,11,17,23-tetra-tert-butyl-2,8,14,20-tetrathiacalix[4]arene. The complexation ability of both thiacalix[4]arenes towards the two metal ions is discussed on the basis of binding energies. Both thiacalix[4]arene 1:1 complexes show higher complexation ability towards Cu²⁺. However, 5,11,17,23-tetra-tert-butyl-25,27-bis{[4-(methoxycarbonyl)phenyl]methoxy}-2,8,14,20-tetrathiacalix[4]arene presents lower complexation ability when compared with the 5,11,17,23-tetra-tert-butyl-2,8,14,20-tetrathiacalix[4]arene. The results of liquid–liquid extraction experiments of the thiacalix[4]arenes are in good agreement with the theoretical calculations.     

Studies on the Zetapotential of Calcite/p-Sulfonato-calix[4,8]arenes

Zeta potential of calixarenes has been reported for the first time. The water-soluble calixarenes has been used as dispersion media in solid/liquid interface. p-sulfonato-calix[4]arene (PSC4) and p-sulfonato-calix[8]arene (PSC8) were synthesized and characterized by FTIR, NMR, mass spectrometry, and HPLC techniques. It was proved that the zeta potential is a fast and simple measurement to know the adsorption behavior of sufonato calixarnes on calcite. The chemisorption of p-sulfonato-calix[n]arene was confirmed by shift in iso electric point, adsorption studies and FTIR. The calculated free energy of adsorption value and its sign suggests the chemical interaction between the calcite surface and p-sulfonato calix[4]and[8]arene.     

C_(60)键合硅胶液相色谱固定相的合成及其性能评价

 以γ－（乙二胺基）丙基三乙氧基硅烷为偶联剂合成了Ｃ６０键合硅胶固定相；用元素分析法测定得到该固定相的Ｃ６０键合量为５７．５７μｍｏｌ／ｇ。考察了多环芳烃和杯芳烃在Ｃ６０键合硅胶固定相上的分离，多环芳烃在该固定相上的洗脱顺序与ＯＤＳ固定相相似；杯芳烃的洗脱顺序为杯［８］、杯［４］和杯［６］芳烃。     

Synthesis and metal ion complexation studies of proton-ionizable calix

A series of novel N-chromogenic calix[4]arene azacrown ethers were synthesized as selective extractants of potassium ion. 1,3-Alternate calix[4]arene azacrown ethers were prepared by reacting 25,27-dipropyloxy-26,28-bis(5-chloro-3-oxapentyloxy) calix[4]arenes with p-toluenesulfonamide in the presence of potassium carbonate. The coupling reaction of calix[4]arene azacrown ether with 2-hydroxy-5-nitrobenzyl bromide in the presence of triethylamine in THF gave the chromogenic calix[4]arene azacrown ether in moderate yield. These compounds show high potassium selectivity over other metal ions as shown by two-phase extraction, bulk liquid membrane, and 1H NMR studies on a ligand-metal complex. It is assumed that the OH of the chromogenic group attached on nitrogen can assist the complexation by encapsulation of the metal.     

杯芳烃的超分子化学研究（IV）：对-叔丁基杯[4]芳烃对ATP的分子识别及液膜传输作用

采用气泡式准乳化液膜法,研究了对-叔丁基杯[4]芳烃对ATP分子的液膜传输 作用,讨论了源相与吸收相的组成、酸度、源相中的ATP的起始浓度及吸收相中 NH_3·H_2O浓度等因素对传输结果的影响;进而讨论了对-叔丁基杯[4]芳烃对ATP 的分子识别作用和液膜传输机理。     

Structure and conformational equilibrium of thiacalix[4]arene by density functional theory

Density functional theory calculations for the structure and conformational equilibrium of thiacalix[4]arene are reported. The conformational equilibrium of thiacalix[4]arene, a heterocalixarene in which the phenol groups are bridged by sulphur atoms is compared to the conformational equilibrium of calix[4]arene. Thiacalix[4]arene conformational energies relative to the cone conformer (ΔE's) are reduced in comparison with calix[4]arene. This conformational change is in qualitative agreement with recent NMR spectroscopy measurements of the conformational equilibrium for a tetraethylether of thiacalix[4]arene in a CDCl₃ solution which indicates an enhanced chemical exchange of thiacalixarene conformers in comparison with similar methylene bridged structures. Density functional theory results for the structure of thiacalix[4]arene are in good agreement with recent X-ray diffraction measurements. The electrostatic potentials in the cone conformers of thiacalix[4]arene and calix[4]arene suggest that their complexation or recognition abilities can be significantly different. Dipole moments of the four thiacalix[4]arene conformers are in the order: cone>1,2-alternate>partial-cone>1,3-alternate.