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.     

几种新型杯[4]芳烃衍生物的合成

以对叔丁基苯酚为起始原料,通过缩合、一步取代反应合成了对叔丁基杯[4]芳烃的衍生物,两步取代反应合成了对叔丁基杯[4]芳烃的衍生物。用FT-IR,^1HNMR,FAB-MS对产物的结构进行了表征。     

第三代超分子主体化合物杯芳烃的研究新进展

简要介绍了杯芳烃的结构特征．综述了杯芳烃超分子化合物的组装与聚集、新型杯芳烃大环分子的合成及结构性能、新型杯芳烃的合成组装及选择性识剐作用等方面的研究新进展。     

基于杯[4]芳烃的选择性识别二酸的化学传感器

设计、合成了以杯[4]芳烃为平台,以氨基吡啶基团为双识别位点的新型化学传感器,并用红外光谱、质谱、核磁共振和元素分析方法对其进行了表征。紫外和荧光光谱研究结果表明,该受体分子在二氯甲烷溶液中能选择性识别脂肪二酸,络合常数可达103~104L/mol,络合能力大小顺序为:丙二酸>草酸>丁二酸>戊二酸>已二酸。     

超分子杯芳烃修饰Fe3O4磁性纳米粒子

对超分子杯芳烃和磁性纳米粒子的基本性质和应用进行了综述。     

氨基苯甲酸酯杯[4]芳烃衍生物的合成及性能研究

以对叔丁基杯[4]芳烃为原料,与1,2-二溴乙烷反应得到25,27-二(2-溴乙氧基)-26,28-二羟基-5,11,17,23-四叔丁基杯[4]芳烃,分别与苯佐卡因、三卡因、盐酸普鲁卡因在K2CO3、Na I/DMF体系中反应,以48%~63%的产率合成了3种新型含氨基苯甲酸酯结构的杯[4]芳烃衍生物——25,27-二(2-(对乙氧羰基苯基)氨基)乙氧基-26,28-二羟基-5,11,17,23-四叔丁基杯[4]芳烃、25,27-二(2-(3-乙氧羰基苯基)氨基)乙氧基-26,28-二羟基-5,11,17,23-四叔丁基杯[4]芳烃和25,27-二(2-(4-(2-(二乙基氨基))乙氧羰基苯基)氨基)乙氧基-26,28-二羟基-5,11,17,23-四叔丁基杯[4]芳烃。新化合物的结构与构象经元素分析、IR、1HNMR表征证实。研究它们对K+、Pb2+等9种金属离子的萃取性能以及对氨基酸的分子识别作用。结果表明,新型杯[4]芳烃衍生物对过渡金属离子具有良好的萃取效果,对Fe2+、Cu2+、Pb2+、Zn2+、Ag+的萃取率高达90%以上;同时与氨基酸也能发生很好的配合作用,能有效地识别氨基酸,对带芳环的氨基酸比脂肪氨基酸的识别效果更好。     

杯芳烃对中性分子识别的最新研究进展

简要综述了近年来杯芳烃识别中性分子的研究进展，主要涉及以π相互作用、氢键力、静电引力和疏水相互作用等发生的包结作用及作用方式。     

杯芳烃的合成及性能研究的新进展

简要介绍了杯芳烃的结构、性能及应用,重点综述了：（1）新型杂原子杯芳烃的合成及超分子自组装;（2）杯芳烃衍生物的合成及对金属离子的识别;（3）杯[4]吡咯席夫碱衍生物的合成。     

杯[4]芳烃巯基吡啶衍生物的合成

以对叔丁基苯酚为起始原料,通过缩合得到对叔丁基杯[4]芳烃,再对其下沿酚羟基进行化学修饰,得到具有化学活性的杯[4]衍生物,该化合物与具有活泼氢的4巯基吡啶反应制得新的含N、S杯芳烃衍生物,总收率15.3%。     

官能团化杯芳烃的超分子化学

杯芳烃被认为是继冠醚和环糊精之后的第三代超分子主体化合物。近年来有关杯芳烃的研究论文快速增多,本文从不同的方面回顾了杯芳烃的研究进展,包括杯芳烃的结构修饰,杯芳烃对分子和离子的识别和杯芳烃的生物学活性。     

含氮杯[4]芳烃的合成

以对叔丁基苯酚为起始原料,经过3步反应,在母体杯芳烃的下沿引入3种不同的含氮基团,得到5种含氮杯[4]芳烃,并通过1HNMR和熔点测定确定了产物结构.实验中发现,当母体杯芳烃下沿引入的溴代烷基变长时,进一步引入含氮基团,只能得到1,3位环化的含氮杯[4]芳烃.     

Exploring the Assembly of Resorc[4]arenes for the Construction of Supramolecular Nano-Aggregates

Many biologically active compounds feature low solubility in aqueous media and, thus, poor bioavailability. The formation of the host-guest complex by using calixarene-based macrocycles (i.e., resorcinol-derived cyclic oligomers) with a good solubility profile can improve solubilization of hydrophobic drugs. Herein, we explore the ability of resorc[4]arenes to self-assemble in polar solutions, to form supramolecular aggregates, and to promote water-solubility of an isoflavone endowed with anti-cancer activity, namely Glabrescione B (GlaB). Accordingly, we synthesized several architectures featuring a different pattern of substitution on the upper rim including functional groups able to undergo acid dissociation (i.e., carboxyl and hydroxyl groups). The aggregation phenomenon of the amphiphilic resorc[4]arenes has been investigated in a THF/water solution by UV–visible spectroscopy, at different pH values. Based on their ionization properties, we demonstrated that the supramolecular assembly of resorc[4]arene-based systems can be modulated at given pH values, and thus promoting the solubility of GlaB.     

Pillar[n]arenes at the Chemistry-Biology Interface

Macrocyclic chemistry has provided chemists with a wealth of molecular ‘hosts’. Ever since resurgence in the field during the 1970s and 1980s these hosts’ similarities to natural structures, such the active sites of enzymes, have been noted. Latterly there has been great interest in the recently reported pillar[n]arenes. As if to underline the importance of these compounds, exciting applications are starting to emerge, from electrochemical sensors to antimicrobial agents. Novel uses appear destined to have an impact on clinical conditions from Alzheimer's disease to cancer treatment. In order to demonstrate the impact of pillar[n]arenes across the chemistry-biology interface this review will cover the current state of the art from biomimicry and analyte-specific detection to emerging clinical applications. Examples include pillar[n]arene-based ion channels, enzyme-responsive compounds, imaging agents, biofilm inhibiting derivatives, drug complexing and drug releasing systems.     

两种杯[6]芳烃的红外光谱和拉曼光谱研究

研究了两种对－叔丁基杯〔６〕芳烃的红外和拉曼光谱。对－叔丁基杯〔６〕芳烃Ｉ的环状的分子内缔合氢键和部分甲基化的（１,３,５－三甲基）－对－叔丁基杯（６）芳烃Ⅱ的三中心氢键在红外光谱中有明显反映杯（６）芳烃的ｐｉｎｃｈｅｄ ｃｏｎｅ（紧锥型）构象也得到了证明,而两种杯（６）芳烃氢键构象和强度的不同导致了二者的拉曼谱图也存在较大的差异。     

Solid Lipid Nanoparticle-Based Calix[n]arenes and Calix-Resorcinarenes as Building Blocks: Synthesis,Formulation and Characterization

Solid lipid nanoparticles (SLNs) have attracted increasing attention during recent years. This paper presents an overview about the use of calix[n]arenes and calix-resorcinarenes in the formulation of SLNs. Because of their specific inclusion capability both in the intraparticle spaces and in the host cavities as well as their capacity for functionalization, these colloidal nanostructures represent excellent tools for the encapsulation of different active pharmaceutical ingredients (APIs) in the area of drug targeting, cosmetic additives, contrast agents, etc. Various synthetic routes to the supramolecular structures will be given. These various routes lead to the formulation of the corresponding SLNs. Characterization, properties, toxicological considerations as well as numerous corresponding experimental studies and analytical methods will be also exposed and discussed.     

Dichromate Extraction by Calix[4]arene Appended Amberlite XAD-4 Resin

In the present article a comparative extraction efficiency of dichromate by a calix[4]arene derivative (d) and a newly synthesized calix[4]arene appended Amberlite XAD-4 resin (5) are reported. The liquid and solid phase extraction methods have been applied to ascertain the extraction efficiency of both the calix[4]arene derivative and the resin. Different parameters have been optimized such as pH, dosage, concentration, and temperature. Analysis of experimental data has been carried out by log-log plot analyses and the determination of characteristic parameters of each isotherm model such as Freundlich, Langmuir, and Dubinin-Radushkevich (D-R). The kinetic adsorption experiments show that the adsorption process follows pseudo second order kinetics. The adsorption mechanism has been investigated by Reichenberg (R-B) and Morris-Webster equations. From the thermodynamic parameters it is concluded that the adsorption process is endothermic and spontaneous in nature at higher temperature. The results show that the resin-5 has good capability to efficiently remove dichromate from aqueous media.     

Supramolecular Ligands for Histone Tails by Employing a Multivalent Display of Trisulfonated Calix[4]arenes

Post‐translational modification of histone tails plays critical roles in gene regulation. Thus, molecules recognizing histone tails and controlling their epigenetic modification are desirable as biochemical tools to elucidate regulatory mechanisms. There are, however, only a few synthetic ligands that bind to histone tails with substantial affinity. We report CA2 and CA3, which exhibited sub‐micromolar affinity to histone tails (especially tails with a trimethylated lysine). Multivalent display of trisulfonated calix[4]arene was important for strong binding. CA2 was applicable not only to synthetic tail peptides but also to endogenous histone proteins, and was successfully used to pull‐down endogenous histones from nuclear extract. These findings indicate the utility of these supramolecular ligands as biochemical tools for studying chromatin regulator protein and as a targeting motif in ligand‐directed catalysis to control epigenetic modifications.     

含氨基乙酸酯苯并咪唑杯[4]芳烃荧光分子探针的合成及光谱性能

以4-(N,N-二乙氧酰甲基)氨基苯甲醛和邻苯二胺为原料,首先得到了2-[4-N,N-二(乙氧酰甲基)氨基苯基]-1H-苯并咪唑。再将得到的苯并咪唑与5,11,17,23-四叔丁基-26,28-二羟基-25,27-二丁氧基杯[4]芳烃反应,合成了含氨基乙酸酯苯并咪唑杯[4]芳烃荧光分子探针L,并采用红外和核磁对所合成的化合物进行了结构表征和确认。通过紫外和荧光光谱实验研究表明,探针L在甲醇溶液中对Al3+具有选择性识别性能,且不受其他金属离子的干扰;当Al3+物质的量浓度增加到探针浓度的5倍时,探针L的荧光强度降低到最低值。Job's曲线确定了探针与Al3+之间形成物质的量比为1∶1的金属配合物。     

丙醛杯[4]芳烃母体烷基化衍生物的合成研究

本研究制备了丙醛杯[4]芳烃母体(calix[4]resorcinarenes)化合物,再对母体化合物进行了烷基化反应,得到了新的乙基化衍生物;对新乙基化衍生物2的结构进行了熔点、红外光谱、核磁共振等谱图的表征。     

杯[4]芳烃咪唑盐的微波合成及在氟化反应中的应用

以杯[4]芳烃为起始原料,首先制得中间体杯[4]芳烃双溴代烷基衍生物,然后经微波辐射和阴离子交换,共得9种杯[4]芳烃咪唑盐衍生物,化合物的结构与构象经元素分析、IR、1HNMR、19FNMR、31PNMR表征.研究了它们在对氯硝基苯氟化反应中的催化性能以及对K+的萃取性能.结果表明,这9种化合物在氟化反应中的催化效果良好,对氟硝基苯的收率为80.89％～92.67％;同时化合物对K+具有较好的萃取效果,其中以化合物25,27-二[4-(3-甲基咪唑)乙氧基]-26,28-二羟基-5,11,17,23-四叔丁基杯[4]芳烃六氟磷酸盐的萃取效果最好,萃取率可达75.45％.