富勒烯的杯芳烃包合物的研究现状与展望

介绍了[60/70]富勒烯与杯[8],[6],[5]芳烃、高氧杂杯[3]芳烃及双杯芳烃形成包合物的研究进展和应用前景。     

Complexation and Separation of Amines, Amino Acids, and Peptides by Functionalized Calix[n]arenes

The ability of calix[n]arenes to form complexes, to act as extractants in liquid–liquid extraction, and run as carriers in transport through liquid membranes of different biological amine compounds (e.g., ammonium ion, amines, amino acids, and peptides) has been the central topics of many reports. These features recommend the calix[n]arenes as competitive candidates for studying the interactions involved in host–guest recognition as well as useful receptors in separation processes. Some specific aspects of their applications in binding and separation of various amine compounds by extraction, and in transport through liquid membranes have therefore been considered. The effect of the factors that might influence the separation of above compounds by extraction, and the transport through liquid membranes using the calix [n]arenes has been presented.     

Calix[n]arenes as Synthetic Membrane Transporters: A Minireview

Several potential applications of functionalized calix[n]arenes as carriers in transport through membranes of various biological compounds aiming their separation are reviewed. Specific aspects of membrane transport and the use of calix[n]arenes for building synthetic ion channels are discussed.     

Solution SERS of an insoluble synthetic organic pigment-quinacridone quinone-employing calixarenes as dispersive cavitands

A possibility of getting SERS spectra of insoluble aromatic compounds in colloidal silver solutions is described. The method tested for the organic pigment quinacridone quinone consists of dispersing it in calix[n]arenes. The potentials of such cavitands, both as dispersing and as silver functionalization agents, is reported as a function of the substitution in their lower rim and their cavity size.     

Complexation and Separation of Amines,Amino Acids,and Peptides by Functionalized Calix[<Emphasis Type="Italic">n</Emphasis>]arenes

The ability of calix[n]arenes to form complexes, to act as extractants in liquid–liquid extraction, and run as carriers in transport through liquid membranes of different biological amine compounds (e.g., ammonium ion, amines, amino acids, and peptides) has been the central topics of many reports. These features recommend the calix[n]arenes as competitive candidates for studying the interactions involved in host–guest recognition as well as useful receptors in separation processes. Some specific aspects of their applications in binding and separation of various amine compounds by extraction, and in transport through liquid membranes have therefore been considered. The effect of the factors that might influence the separation of above compounds by extraction, and the transport through liquid membranes using the calix [n]arenes has been presented.This revised version was published online in July 2005 with a corrected issue number.     

The study of spectrosgraphic properties and molecular recognition of cali

The absorption spectrum and fluorescence spectrum of calix[n]arenes are studied systematically. The self-association of calix[n]arenes is proposed and the self-association constant is also obtained. The recognition properties of calix[n]arenes are studied and the inclusion constant is calculated.     

para‐Sulfonated Calixarenes Used as Synthetic Receptors for Complexing Photolabile Cholinergic Ligand

The water‐soluble tetra‐, hexa‐ and octasulfonated calix[4]arenes, calix[6]arenes, and calix[8]arenes 1 – 3 , respectively, were investigated as potential synthetic receptors for photolabile cholinergic ligand A , a photolytic precursor of choline. Ligand A is a bifunctional molecule carrying a photolabile 2‐nitrobenzyl group at one end and a choline moiety at the other end. Results from NMR studies have shown that calixarenes 1 – 3 form stable 1 : 1 complexes with A , having similar binding potential to that observed with the cholinergic enzymes acetylcholinesterase and butyrylcholinesterase. Further studies have suggested that calix[8]arene forms a ditopic complex by binding concomitantly to both the cationic choline moiety and the aromatic photolabile group of A , whereas calix[4]arene and calix[6]arene form monotopic complexes with A . The ditopic complex between calix[8]arene and A results from mutually induced fitting process, while the monotopic complexes between calix[4]arene and A can be regulated by pH: at neutral pH, calix[4]arene specifically binds the cationic choline moiety, while, at acidic pH, it complexes unselectively both the cationic choline moiety and the aromatic group of A . Our results show that para‐sulfonated calixarenes are versatile artificial receptors which bind in various ways to the bifunctional photolabile cholinergic ligand A , depending on their size, geometry, and state of protonation.     

杯芳烃和柱芳烃桥梁部位的衍生及其功能化

随着大环化学的快速发展,对杯芳烃、柱芳烃及其他类似化合物的桥梁亚甲基部位进行高效修饰的方法日益引起人们的关注.桥梁部位修饰后的大环衍生物,在不改变其原有属性的基础上增加了新的功能,不仅可以引入更多的功能基团,而且可以通过主客体的自组装行为,进一步拓展杯芳烃和柱芳烃等超分子大环在药物递送、化学传感、荧光体系构建等诸多领域...     

Synthesis,structures, and conformational characteristics of calixarene monoanions and dianions

The synthesis, complete characterization, and solid state structural and solution conformation determination of calix[n]arenes (n = 4, 6, 8) is reported. A complete series of X-ray structures of the alkali metal salts of calix[4]arene (HC4) illustrate the great influence of the alkali metal ion on the solid state structure of calixanions (e.g., the Li salt of monoanionic HC4 is a monomer; the Na salt of monoanionic HC4 forms a dimer; and the K, Rb, and Cs salts exist in polymeric forms). Solution NMR spectra of alkali metal salts of monoanionic calix[4]arenes indicate that they have the cone conformation in solution. Variable-temperature NMR spectra of salts HC4.M (M = Li, Na, K, Rb, Cs) show that they possess similar coalescence temperatures, all higher than that of HC4. Due to steric hindrance from tert-butyl groups in the para position of p-tert-butylcalix[4]arene (Bu(t)C4), the alkali metal salts of monoanionic Bu(t)C4 exist in monomeric or dimeric form in the solid state. Calix[6]arene (HC6) and p-tert-butylcalix[6]arene (Bu(t)C6) were treated with a 2:1 molar ratio of M(2)CO(3) (M = K, Rb, Cs) or a 1:1 molar ratio of MOC(CH(3))(3) (M = Li, Na) to give calix[6]arene monoanions, but calix[6]arenes react in a 1:1 molar ratio with M(2)CO(3) (M = K, Rb, Cs) to afford calix[6]arene dianions. Calix[8]arene (HC8) and p-tert-butylcalix[8]arene (Bu(t)()C8) have similar reactivity. The alkali metal salts of monoanionic calix[6]arenes are more conformationally flexible than the alkali metal salts of dianionic calix[6]arenes, which has been shown by their solution NMR spectra. X-ray crystal structures of HC6.Li and HC6.Cs indicate that the size of the alkali metal has some influence on the conformation of calixanions; for example, HC6.Li has a cone-like conformation, and HC6.Cs has a 1,2,3-alternate conformation. The calix[6]arene dianions show roughly the same structural architecture, and the salts tend to form polymeric chains. For most calixarene salts cation-pi arene interactions were observed.     

Tuning the antioxidant property of potential calixdrug calix[4]tyrosol: role of aza and thia linkages

Structural Chemistry - Calix[4]arenes are the most renowned and widely studied calix[n]arenes, which are established to have quite a few biological (e.g., antibacterial, antifungal, antioxidant,...     

NMR studies of inclusion complexation of the pyrrolizidine alkaloid retronecine and p-sulfonic acid calix[6]arene

Accidental or intentional drug toxicity in humans and animals is a major concern and the search for detoxificant agents is a challenge. Pyrrolizidine-producing forages are a threat not only to livestock, but also to humans as a consequence of food contamination. Supramolecular systems are promising as detoxificant agents by decreasing the bioavailability of toxic compounds in biological environment. Cyclodextrin and calix[n]arenes are well known hosts for a variety of molecules and/or ions. Surprisingly, only few studies describe the potential of calix[n]arenes as host for toxic molecules. This study focused on the use of NMR techniques as tools for the investigation of the interactions between p-sulfonic acid calix[6]arene and retronecine, a toxic pyrrolizidine alkaloid.     

Microwave-assisted synthesis of 1,3-dialkyl ethers of calix[4]arenes: application to the synthesis of cesium selective calix[4]crown-6 ionophores

Partial etherification of phenolic-OH groups of calix[4]arenes with various alkyl halides/tosylates and K₂CO₃ under microwave irradiation afforded 1,3-dialkoxycalix[4]arenes in their cone conformation only as predominant/sole product in good yields (71–85%). The protocol was found to be much superior to conventional heating both in terms of yield and reaction time. Some of the 1,3-dialkoxycalix[4]arenes were elaborated further to the syntheses of cesium selective calix[4]crown-6 ionophores.     

Facile synthesis of oligophenylene-substituted calix[4]arenes and their enhanced binding properties

[reaction: see text] A facile and efficient protocol for the synthesis of oligophenylene OPP(n)-substituted calix[4]arenes (with n up to 4) via iodo-substituted oligoarylcalix[4]arenes has been developed. The cooperation effect of the proximate fluoroionophores in hexylsulfanyl end-capped OPP(n)-substituted calix[4]arene assemblies leads to metal ion binding enhancement.     

Salt-Bridge Supported Bilayer Lipid Membrane Modified with Calix[n]arenes as Alkali Cation Sensors

ABSTRACT

Potentiometric behaviors of a salt-bridge supported bilayer lipid membrane (Sb-BLM) modified with Calix[n]arene (n=4, 6, 8) derivatives are described for some alkali metal ions. The modified Sb-BLM was used as an alkali cation sensor. The membrane potentials were observed to generate Nernstian responses to the concentration of alkali metal ions in electrolyte. The Sb-BLM modified with the calix[n]arenes show high selectivity for individual alkali metal ions: Calix[8]arenes for K⁺, calix[6]arenes for Cs⁺ Calix[4]arenes show no selectivity for any alkali ions. The interacting mechanism is also discussed.     

Bridge-disubstituted calix[4]arenes obtained via a new preparative route. Synthesis and structural study

A series of calix[4]arenes bearing various substituents including alkyl, p-bromobenzyl, carboxy and allyl at opposite methylene bridges has been synthesized via successive metallation followed by nucleophilic substitution. In a first step, mono-lithiated calix[4]arenes react with terminal bromoalkanes to give 2-alkylated calix[4]arenes or with CO₂ the respective calixarene-2-carboxylic acid in good yields. A second lithiation step of the monosubstituted products with subsequent attachment of both polar and non-polar substituents yields several new diametrally bridge-disubstituted calix[4]arenes. 2D-NMR measurements establish the disubstituted calixarenes to predominantly adopt the 1,2-alternate conformation in solution. First examples of X-ray crystal structures of the new type of disubstituted calix[4]arenes are described featuring the calix[4]arene also in the rare 1,2-alternate conformation.     

Preparation and Evaluation of Calix[8]arene Bonded Silica Stationary Phase for High Performance Liquid Chromatography

In recent years, calix[n]arenes (n=4,5,6,7,8) as stationary phase have been introduced into the field of chromatography. In our previous works, we have synthesized, characterized and evaluated two different silica-bonded calix[n]arenes (n=4,6) stationary phase, on which the chromatographic behavior of PAHs, positional isomers,nucleosides and bases was investigated. In this paper we report the preparation of calix[8]arene bonded silica stationary phase, and characterization of its structure and chromatographic behavior.     

Halo-derivatised calix[4]tubes

Halo functionalisation of calix[4]tubes has been investigated through both derivatisation of individual calix[4]arenes and calix[4]tubes, using classical synthetic methods, to allow preparation of a series of novel derivatives. The solution and solid state properties are in accordance with the constituent[4]arenes adopting flattened cone arrangements which on complexation with potassium simplify to a regular cone. Electrospray and 1H NMR studies, combined with molecular modelling have been used to ascertain the metal binding of this new series of cryptand like ionophores, demonstrating their retained selectivity for binding potassium over other Group 1 metals and the dependence on counter anion in the weak binding of silver.     

Complexation of fullerenes by calix[n]arenes: molecular dynamic simulations and benesi-hildebrandequilibrium constants

MD simulations using a combination of AMI and AMBER are performed to elucidate the origin of complexation between fullerenes and calix[n]arenes (n = 4,6,8). Only calix[6]arenes and calix[8]arenes are suitable for complex formation. By introducing benzyl substitutents on the upper rim of the calixarenes the interaction energy between host and guest is even improved. Analysis of the data also reveals a strong stabilization by t-butyl or benzyl substitutents beside π-π interactions between the arene units of the calixarene and fullerenes. The calculated data perfectly correlate with the experimentally observed equilibrium constants.     

Calix-arene silver nanoparticles interactions with surfactants are charge, size and critical micellar concentration dependent

The interactions of silver nanoparticles capped by various calix[n]arenes bearing sulphonate groups at the para and/or phenolic faces with cationic, neutral and anionic surfactants have been studied. Changes in the plasmonic absorption show that only the calix[4]arene derivatives sulphonated at the para-position interact and then only with cationic surfactants. The interactions follow the CMC values of the surfactants either as simple molecules or mixed micelles.