Langmuir-Schaefer Film Investigation and Density Functional Theory Band Gap Calculations of Calix[n]arene-Para-Aminobenzoic Acid for Drug Nanosensor Application

Calix[n]arenes was utilized to detect PABA,the primary sunscreen component.This study investigates the interaction of calix[4]arene(C4),calix[6]arene(C6),and PABA using the Langmuir method and first-principle density functional theory(DFT).Using the Langmuir-Schaefer(LS)technique,an ultrathin film composed of calix[n]arenes and their complexes with PABA was deposited on various substrates.Based on the Langmuir study,the PABA molecule was bonded to the lower rims of both C4 and C6 with the host-guest ratio of 1:1.All of the LS films formed were then characterized by ultravioletvisible spectroscopy(UV-Vis),Fourier-transform infrared spectroscopy(FTIR)and carbon,hydrogen,nitrogen,sulfur elemental analyzer(CHNS).The band gap reduction obtained in the DFT study denotes the charge transfer interaction with promising reactivity between the calix[n]arenes and PABA.The sensing of PABA by C4 and C6 is successful based on the formation of bonding between them due to the hosts’effective trapping capacity.The outcomes of this study could be applied to drug delivery systems for future pharmaceutical and medical applications.

Preparation and Characterization of Silica Modified with Calix[4]arene Derivatives

Three new silica gel modified with calix[4]arene derivatives （p-tert-butyl-calix[4]arene （PC4）, calix[4]arene （C4） and calix[4]arene sulfonate （C4S）） have been prepared via modification of activated silica gel with toluene 2,4-di-iso-cyanate （TDI） as linker in tow step. The modified silica were characterized by fourier transform infrared spectroscopy （FT1R）, thermal analysis （TGA） and elemental analysis. The FTIR spectra and TGA analysis verified that the calix[4]arene derivates are covalent attached to the silica. Scanning electron microscope SEM and Brunauer-Emmett-Teller BET analysis have been done to get information about the sample＇s surface shape and area. SEM and BET analysis reveal that the modified silica are in the range of microporous adsorbent.

Synthesis and Extraction Studies of Calix[4]-Crown-4 Oxime Derivatives

The article comprises synthesis of calyx[4]-oxa-crown, and calix[4]-thia-crown compounds containing nitrile groups (3a, 3b) and amino groups (4a, 4b) and their corresponding oxime derivatives (5a, 5b) and liquid-liquid extraction studies of these compounds. The oxime derivatives of compounds (5a, 5b) have been synthesized by reacting of di-n-butylamino derivatives of calix[4]-oxa-crown, and calix[4]-thia-crown compounds (4a, 4b) with amphi-chloroglyoxime in methanol-THF. Their cation and anion transfer studies were performed by using liquid-liquid extraction procedure. It has been concluded from the observations that the compound 3a shows a good extraction behavior toward Na+ ion in the presence of other metal cations. Whereas, its oxime derivatives transfers all of the metal cations used in the liquid-liquid extraction studies.

醌类电极材料Calix[4]quinone在二次电池中的应用

随着社会对大型储能设备的环保、充放电性能以及可持续发展的要求越来越高,基于金属氧化物的传统锂/钠离子电极材料受限于比容量,已难以满足未来储能系统的要求。有机材料、锂-硫/氧、液态流体等电池的研发与应用已成为未来能源系统研究的重要内容。其中,有机正极材料中的羰基类化合物Calix[4]quinone(C4Q)是一种很有前途的正极材料。该分子的空间位阻小,8个羰基结构都能发生可逆电极反应,其理论比容量高达446mA·h/g,远超传统无机电极材料。C4Q不仅可以作为储锂材料,也可作为钠、锌、镁等二次电池的电极材料。本文分别介绍了C4Q在锂、钠二次电池和锌水系电池中的应用成果,并对C4Q今后进一步的开发利用做了展望。

Calix[4]arene Polyaza Derivatives: Novel Effective Neutral Receptors for Cations and α-Amino Acids

Introduction Calixarenes are one of the most important supra- molecular building blocks, which can be modified by introducing different functional and/or structural groups to create a specific interaction between the host and the target molecules, such as metal cations and small organic molecules. In particular, the recognition of amino acids is an interesting theme in biomimetic chemistry.

Calix[4]Crowns类化合物在分离铯中的应用

Calix[4]Crowns类化合物作为超分子识别材料能够有效地分离铯,并能很好地应用在溶剂萃取、液膜萃取、色谱分离等领域。介绍了Calix[4]Crowns类化合物及其复合超分子材料对铯离子的识别和分离效果,为寻求对Cs(Ⅰ)有优异配合能力的Calix[4]Crowns类有机配体结构及相应的功能材料提供参考。

A Novel Type of Lower-Rim-Connected Double-Calix[6]arenes Composed of A 1,2,4-Triply Bridged and A Normal Calix[6]arene

The synthesis and characterization of the first example of lower-rim-connected double-calix[6]arene are reported, in which a 1,2,4-triply bridged calix[6]arene subunit is connected to a calix[6]arene subunit via a polyether chain.

Synthesis of Calix[4]resorcinarene Core Dendrimers with Peripheral Salicylideneimine Functional Groups

First to third-generation calix[4] resorcinarene core dendrimers, compounds 4a, 4b, 7a, 7b, 10a and 10b, were prepared via the divergent method in seven steps with the corresponding tetraphenyl- and tetra （hydroxyphenyl） calix[4] resorcinarenes （compounds 1a, 1b） as the starting material. The repeat units of the polyamidoamines of these dendrimers were obtained by the ammonolysis of ethyl calixarylacetates 2a and 2b with 1,3-diaminopropane, that is, amide derivatives with terminal amino groups, which in turn reacted with ethyl acrylate to give a higher generation of ester derivatives. The structures of these dendrimers were characterized by IR, ^1H and ^13C NMR spoctrometries. The crystal structure of compound 2b with 12 ethoxycarbonylmethoxy groups was determined by X-ray analysis.

Synthesis and Properties of Double Calix[4]arene Derivatives Linked by Schiff-base in the Lower Rim

25,27-bis-(2-aminoethoxy)-p-tert-butylcalix[4]arene was linked to double calix[4]arene derivatives by the Schiff-base moiety in its lower rim. They behave strong ability to complex with Ph2+, Cu2+ and Co2+.

Synthesis and Crystal Structure of Calix[4]arene Bearing a 1,8-Bis(propoxy)anthracene-9,10-dione

The title complex （C50H44C14O8） was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/n with a = 19.7768（4）, b =10.2085（2）, c = 21.2721（4）A,β= 97.153（1）°, V = 4261.23（14）A^3, Z = 4, Mr = 914.65, F（000） = 1904, Dc = 1.426 g/cm^3,μ = 0.336, the final R = 0.0550 and wR = 0.1647. The compound was structurally characterized by IR and ^1H NMR. The molecules are stacked through C-H...π interactions and intermolecular C-H...O hydrogen bonds.

Separation of Salbutamol by Nano-baskets of Calix[4]arene Bearing Sulfonyl-carboxamides in Partial-cone Conformation

Salbutamol,which increases the muscle mass and decreases the adipose tissue,is misused as nutrient repartitioning agent in the livestock.The novelty of this work is the determination of salbutamol in the livestock meat via new bonded-phases bearing eight derivatives of p-tert-calix[4]arene in partial-cone conformation.The new synthesized bonded-phases were characterized and optimized.The bonding interactions of solute and stationary-phases were examined and the main interactions were reported.The salbutamol levels in six samples of livestock meat were analyzed and the results reveal that for the best bonded-phases,the limit of detection（LOD） and limit of quantitation（LOQ） were 0.02 and 0.06 μg/mL,respectively.

Surface Activities of Calix [4]resorcinarenes Bearing Four Hydrophobic Chains and Its Solubilization for Organic Compounds

Calix resorcinarenes bearing four hydrophobic side chains ( Ar-Rn, Ar-Ph, and Ar-N) orient stably on water oil interface and show high solubilization capacities for organic compounds, such as long chain alcohols, benzene, toluene and dyes. The capacities are high even near the cmc of polyalkylated calix resorcinarenes, but the solubilities of organic compounds(solubilizates) decrease with the increase of the size of the solubilizates. Ar-R 6, with a chain length of six carbons, is the most effective among Ar-R n , Ar-Ph, and Ar-N; 11 fold mol of hexanol is dissolved in 2×10 -3 mol/L Ar-R 6. Moreover, Ar-R n bearing four alkyl side chains solubilizes the chain alcohols of the same chain length mostly. The solubilization capacities are presumably brought by inclusion in a large cavity of the polyalkylated calix resorcinarenes and by an efficient orientation of the solubilizates.

Synthesis and Absorption Properties of Calix[6]amides-based Polymers

Reacting calix[6]arene hexaesters with poly(ethyleneimine), a series of calix [6]amides- based polymers were obtained for the first time. It is found that they show high absorption capacities towards soft cations comparing to hard cations, and the absorption abilities enhanced with the increasing of calixarene content, which may indicates the cavity of calixarene plays crucial role in absorption. Polymer 2c shows good selective absorption capability towards Ag+ among the tested cations.

Synthesis of Bis-substituted Calix[4]arenes and Mechanism of Substituents Effect on K^+ and Hg^(2+) Ions Transports through Liquid Membrane

New calix[4]arene derivatives containing nitro,amino and benzoyl in the upper and lower rims of molecule were successfully synthesized.Their effectiveness towards K+ and Hg2+ across bubbling liquid membrane(BLM) was examined.For K+ ion transfer,preserving phenolic hydroxyl in the lower rim of calix[4]arene could enhance its transport ability.When benzoyl replaced phenolic hydroxyl,the transport would fall off,because benzoyl caused steric hindrance on the K+ transfer.The study also revealed that the group having the electron-withdrawing conjugative effect on phenolic hydroxyl,-NO2 in the upper rim of calix[4]arene,made transport ability of calix[4]arene fall off.On the contrary,-NH2 that had electron-repulsive conjugative effect enhanced the transport ability of the compound.For Hg2+ ion,only -NH2 in the upper rim of calix[4]arenes had high affinity for it and contributed to Hg2+ transfer.Transport amount of Hg2+ ion increased with increasing calix[4]arene5 concentration and ΔpH in BLM.

A New Efficient Synthesis of p-Nitrocalix[4]arene

A new efficient synthesis of p-nitrocalix[4]arene from calix[4]arene by using nitrogen dioxide is described. The compound is an useful intermediates for the introduction of other functional groups to obtain N containing substituted calix[4]arene. The reaction mechanism is briefly discussed.

Synthesis of Schiff Base Calix[4]arene Crowns

This letter reports the synthesis of Schiff base calix[4]arene crowns containing m-xylylene phenol subunit, in which calix[4]arene Schiff base crowns 2a, 2b and 2c were formed by 1:1 condensation of calix[4]arene diamine 1 with dialdehydes (2, 6-diformyl-4-chlorophenol 3a, 2, 6-diformyl-4-methylphenol 3b, 2, 6-diformyl-4-tert-butylphenol 3c) under high dilute condition in refluxing anhydrous ethanol in 65-70% yield.

Synthesis of Calix[4] arene Thia Derivative and Extraction Effect of Substituents on Mercury( Ⅱ) and Lead( Ⅱ)

Calix[4]arene derivatives have been reported to possess high selectivity for metal ions.In order to analyze the extraction effect of substituents on Hg^(2+)and Pb^(2+),calix[4]arene derivatives containing hydroxyl,bromoethoxy and 1,11-dioxa-4,8-dithiahendecene were successfully synthesized,with their extraction effectiveness towards Hg^(2+)and Pb^(2+)were evaluated respectively.The results indicated that the phenolic hydroxyl in calix[4]arene improved the extraction ability on Hg^(2+)by promoting the formation of the negative oxygen ions that could bind with Hg^(2+)by coordination and ionic bonds.The extraction ability of 5,17-dinitro-26,28-(1’,11’-dioxa-4’,8’-dithiahendecene)-calix[4]arene(calix[4]arene thia derivative)was improved slightly due to the better coordination capacity for metal ions after introduction of 1,11-dioxa-4,8-dithiahendecene,which was a chelate-binding centre.Regarding to Pb^(2+),only 1,11-dioxa-4,8-dithiahendecene on molecule contributed to extraction due to the coordination bond.Since the metal ion with higher charge-to-radius ratio could coordinate with one ligand more stably,Pb^(2+)with higher charge-to-radius ratio than Hg^(2+)was coordinated and extracted by the calix[4]arene thia derivative more easily.Furthermore,extraction rates of the calix[4]arene thia derivative on both ions(Hg^(2+)and Pb^(2+))increased with the increase of pH value in acidic aqueous system(pH<7).

Synthesis of Calix[4]pyrroles: A Class of New Molecular Receptor

Calix[4]pyrroles, as a class of new molecular receptor in the area of supramolecular chemistry, have displayed interesting anion and neutral substrate binding properties. In this paper, several new calix[4]pyrrole macrocycles were synthesised and characterized.

Syntheses and Binding Properties of Novel Calix[4]arene Derivatives Containing Multiple Azo-groups

Calixarenes are excellent scaffolds that can De modified by introducing various functional groups to create specific interactions between the host and guest molecules. Thus, many calixarene derivatives containing special functional groups, such as ester, amide and thiourea, have been synthesized and their excellent complexing capability for cations have also been studled. Lately, calixarene derivatives containing two or more sorts of functional groups have attracted much attention.

Novel synthesis of N-substituted-calix[4]azacrown derivatives

A novel series of calix[4]azacrown derivatives with the reaction between calix[4]azacrown and the different fluorophore derivatives,which may be useful fluorescent receptors,have been synthesized and structurally characterized by IR,~1H NMR,^（13）C NMR and MS.From their analysis data,it was found those compounds adopted a cone conformation.