杯芳烃在液相色谱固定相领域的应用及进展

杯芳烃是一类由苯酚单元通过亚甲基桥连的超分子化合物,具有独特的主客体识别性能,是继冠醚和环糊精之后第三代超分子化合物的主要代表。其被广泛应用于离子通道、有机催化反应、跨膜转运、纯化、色谱分离等方面。基于杯芳烃易于修饰的特点,选取不同性质的化合物进行衍生化,可以制备出具有不同识别能力和高选择性的杯芳烃衍生物,进而应用于不同色谱分离模式,可实现复杂样品的分离分析。该文从杯芳烃、杯芳烃衍生物和杯杂芳烃3个方面综述了近年来杯芳烃在液相色谱固定相方面的研究应用及进展,并对杯芳烃在色谱分离领域的发展提出了展望。     

Inherently chiral calixarenes: a decade��s review

Inherently chiral calixarenes are receiving increasing attention due to their intriguing structures and potential applications in chemical, analytical, biological and material fields. This review mainly covers the advances in syntheses, structures, and applications of inherently chiral calixarenes which emerged later than 2000. Outlook on the development orientation of inherently chiral calixarenes is tentatively provided.     

固有手性杯芳烃的研究

固有手性杯芳烃是指在杯芳烃三维骨架上引入数个非手性基团使之不再具有对称面或反转中心而呈现出整体手性。本文综述了固有手性杯芳烃的合成、光学拆分及其在手性识别和不对称催化领域的应用。     

固有手性杯芳烃的研究

固有手性杯芳烃是指在杯芳烃三维骨架上引入数个非手性基团使之不再具有对称面或反转中心而呈现出整体手性。本文综述了固有手性杯芳烃的合成、光学拆分及其在手性识别和不对称催化领域的应用。     

Effect of covalent functionalization of C60 fullerene on its encapsulation by water soluble calixarenes

The molecular encapsulation of functionalized fullerenes (substituted fulleropyrrolidines) with water-soluble calixarenes was studied by photoluminescence and quantum-chemical methods. The results show that both the thiacalix[4]arene-tetrasulfonate and calix[6]arene-hexasulfonate are able to overcome the natural water-repulsive character of fullerenes. However, the functionalization of calixarenes and fullerenes induces significant changes in the molecular encapsulation processes, and the obtained thermodynamic behavior of the complex formation highlights the importance of the entropy. Our results can contribute to the development of the synthesis and design of functionalized calixarenes supporting their application in pharmaceutical and food chemistry.     

Spectroscopic studies of water-soluble sulfonated calix[6]arene

Fluorescence and absorption studies of water-soluble sulfonated calix[6]arene (SCX6) are reported. Water-soluble calixarenes are potentially useful as host molecules for luminophores, and studies of their spectroscopic characteristics are therefore crucial. The absorption and fluorescence spectra of these molecules in aqueous solution were collected, analyzed, and compared with 4-hydroxybenzene sulfonate at different pHs. A red shift in the absorption spectrum and a change in the fluorescence spectrum of the calixarenes are observed upon an increase in pH from 2.0 to 13.0. Some of these spectroscopic changes are attributed to intramolecular hydrogen bonding between adjacent hydroxyl groups of SCX6 after proton disassociation. The formation of excimers between phenolic groups in the calixarene molecule is proposed. In addition, inner-filter effects of SCX6 are discussed. These inner-filter effects prove to be a disadvantage for the use of SCX6 as a host molecule for complexation studies by use of fluorescence probes whose absorption spectra overlap with those of calixarenes.     

Functionalization of Calix[4]resorcinolarenes with Trimethylsilyl Isocyanate

Calix[4]resorcinolarenes and their dialkylaminomethylated derivatives react with trimethylsilyl isocyanate to form addition products containing four silylcarbamate groups. These compounds are unstable and, depending on the nature of alkyl groups at the lower rim of the macrocycle, undergo two types of transformations. Intramolecular silylation yields calixarenes containing four carbamate and four trimethylsilyloxy groups at the upper rim. In the case of dialkylaminomethylated calixarenes, the initially formed addition products can undergo intramolecular cyclization to form a cavitand with four six-membered fragments at the upper rim.     

含杂原子杯芳烃的合成研究进展

综述了含杂原子杯芳烃的结构、命名方法、合成方法等方面的研究进展.指出在超分子化学领域,杯芳烃骨架结构的改变是杯芳烃研究的热点之一;与传统杯芳烃相比,在杯芳烃分子骨架中引入桥联杂原子或芳杂环后,不仅使得其在结构和分子识别方面产生新颖变化,而且使得其合成方法也发生巨大改变.     

CZE Determination of Calixarenes and Related Derivatives Using Acetonitrile as a Modifier

The applications of third-generation host compound calixarenes have been restricted due to their high price and shortage of supply. To obtain high pure calixarenes with high yield, synthesis strategy and analytical method investigations are necessary. The present work describes capillary zone electrophoresis (CZE) for the separation and determination of calixarene derivatives under the optimized CZE conditions within 20 min. The CZE method was evaluated with linear ranges, detection limits, recoveries and repeatability. The results indicated that the method was accurate and reproducible. As expected, it could be utilized to separate and evaluate calixarene derivatives during their synthesis and purification.     

Supramolecular surfactants derived from calixarenes

Supramolecular surfactants self-aggregate via noncovalent interactions. The process is rapid and reversible which makes them potentially useful for the design of stimuli-responsive systems. Here we focus on host:guest interactions using calixarenes as molecular receptors. Calixarenes are an important family of molecular receptors because of their ease of preparation and post-modification. The calixarenes discussed here cannot self-aggregate, but when combined with an appropriate guest molecule readily self-associate. Different types of aggregates are obtained, e.g., micelles or vesicles, depending upon the structures of the calixarene and guest.     

几种磺酸酯桥联杯芳烃的一锅法合成及对金属离子的萃取性能

用一锅法合成了4种磺酸酯桥联杯芳烃化合物,用它们作萃取剂,以氯仿为溶剂,用原子吸收的方法测定了它们对水溶性的Ca2+、Pb2+及部分过渡金属10种金属盐的萃取作用。 结果表明,此类杯芳烃对Cr3+、Cd2+和Co2+等几种有毒有害的离子有良好的选择性识别作用,其中化合物2a对Cr3+、化合物2b对Cd2+的萃取率分别达到了50.15%和46.48%。     

Virus-sized DNA nanoparticles for gene delivery based on micelles of cationic calixarenes

Macrocyclic amphiphilic molecules based on calix[4]arenes are highly attractive for controlled supramolecular assembly of DNA into small nanoparticles, since they present a unique conical architecture and can bear multiple charged groups. In the present work, we synthesized new amphiphilic calixarenes bearing cationic groups at the upper rim and alkyl chains at the lower rim. Their self-assembly in aqueous solution was characterized by fluorescent probes, fluorescence correlation spectroscopy, dynamic light scattering, gel electrophoresis and atomic force microscopy. We found that calixarenes bearing long alkyl chains (octyl) self-assemble into micelles of 6 nm diameter at low critical micellar concentration and present the unique ability to condense DNA into small nanoparticles of about 50 nm diameter. In contrast, the short-chain (propyl) analogues that cannot form micelles at low concentrations failed to condense DNA, giving large polydisperse DNA complexes. Thus, formation of small DNA nanoparticles is hierarchical, requiring assembly of calixarenes into micellar building blocks that further co-assemble with DNA into small virus-sized particles. The latter showed much better gene transfection efficiency in cell cultures relative to the large DNA complexes with the short-chain analogues, which indicates that gene delivery of calixarene/DNA complexes depends strongly on their structure. Moreover, all cationic calixarenes studied showed low cytotoxicity. Thus, this work presents a two-step hierarchical assembly of small DNA nanoparticles for gene delivery based on amphiphilic cone-shaped cationic calixarenes.     

Host-guest sensing by calixarenes on the surfaces

The present critical review reports on recent developments of optical nanoparticles based on the association of gold, silver, silica and quantum dots and calixarenes. These hybrid organic-inorganic compounds characterized by a thick organic layer self-assembled on the surface of a core of mineral surface atoms take advantage of the supramolecular recognition of luminescent calixarenes to fabricate nanodevices of nanoparticle size, capable of detecting metal cations, polyaromatic hydrocarbons and pesticides. Also presented is an explanation of the involvement of such nanoparticles in biochemical systems. This critical review provides an overview of their preparation, the manner in which they are characterized, and their use (108 references).     

用C60键合硅胶固定相液相色谱分离杯芳烃及杯芳冠醚类化合物

以自合成的C60 键合硅胶液相色谱固定相 ,分别选用3种不同选择性的流动相体系 :异丙醇 -环己烷 ,氯仿 -环己烷和二氯甲烷 -环己烷 ,考察了流动相组成对杯芳烃及杯芳冠醚化合物保留行为和分离选择性的影响。在一定的流动相条件下溶质能得到较好分离。     

Heterocalixaromatics, new generation macrocyclic host molecules in supramolecular chemistry

Heterocalixaromatics, the heteroatom bridged calix(hetero)arenes, have been emerging as new generation macrocyclic host molecules in supramolecular chemistry recently. Being different from the conventional calixarenes in which the aromatic rings are linked by methylene units, heterocalixaromatics assemble various aromatic rings by different heteroatoms. Owning to the intrinsic nature of heteroatoms that can adopt different electronic configurations to form various degrees of conjugation with their neighboring aromatic rings, heterocalixaromatics exhibit unique structural features and versatile recognition properties in comparison to conventional calixarenes. This feature article highlights recent advances in the synthesis, functionalization, structure and molecular recognition of nitrogen- and/or oxygen-bridged calixaromatics, with a primary focus on our own work.     

手性杯芳烃的合成及性质

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、不对称催化 等方面有潜在的用途、综述了手性杯芳烃的合成及其在手性识别、对映体分离方面 的性能。     

Inherently chiral calixarenes

Due to the nonplanarity of the basic 1 _n -metacyclophane system, calixarenes and resorcarenes can be transformed into molecules with inherent chirality. Various attempts to achieve this goal are reviewed. Special emphasis is given to derivatives withC _n -symmetry, including derivatives of spherand calixarenes and other calixarene-like macrocycles.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Calixarenes and related macrocycles as gene delivery vehicles

The success of gene therapy depends largely on the development of new efficient gene delivery vehicles. The emerging class of molecules for this application is macrocycles that feature persistent shape, thus ensuring higher level of supramolecular organization of the DNA complexes. The review focuses on recently developed calixarenes and close analogues as gene delivery vectors, their chemistry, ability to compact nucleic acids, transfection ability in vitro and cytotoxicity. Their fixed conformation with the possibility of multiple functional groups at the upper and lower rims allows preparation of cone-shaped macromolecules capable of programmed hierarchical assembly in the presence of DNA. It is shown that specially designed calixarenes, particularly those having amphiphilic structure with clustered DNA binding units, can form small virus-sized DNA nanoparticles with well-defined architecture, high transfection efficiency and low toxicity. The field is still largely underexplored so that there is a lot of room for further improvement of the molecular design of calixarenes. Moreover, their evaluation in vivo on animals will be an important step towards their validation for gene therapy.     

Synthesis of p-Formylphenylazo Calix [ 4 ]arenes

Calixarenes are a versatile class of macrocyclic compounds, which have attracted extensive interest due to their ability to form host-guest complexes and act as enzyme mimic. Moreover, a number of calixarenes with D-π-A units have been synthesized, and their second-order nonlinear optical (NLO) properties investigated.     

Oligodentate glycoconjugates based on calixarenes: methods for the synthesis and biological activity

The review considers principal methods for the preparation of conjugates of carbohydrates with calixarenes and resorcinarenes. The data on the biological activity of glycoconjugates are discussed taking their interaction with the carbohydrate-binding proteins, lectins as an example.