Sorption of Cu(II) onto silica gel immobilized calix[4]arene derivative with tripodal structure

This study contains the synthesis of silica gel-immobilized calix[4]arene derivative (TR-CL[4]P) as a new sorbent and its sorption studies towards Cu (II) ion in aqueous solution. The aldehyde pointed calix[4]arene derivative 5 was synthesized and then it was immobilized onto 3-aminopropilsilica gel (APS). In batch sorption experiments, the experimental results showed that TR-CL[4]P is effective sorbent towards Cu (II) ion. Therefore, the effect of solution pH, sorption time, temperature and initial metal ion concentration onto Cu (II) sorption was investigated. Maximum Cu(II) removal was obtained at 30?°C, 30?min and pH 6.0 for TR-CL[4]P and the batch sorption capacity was found as 17.8?mg/g. The characteristics of the sorption process for Cu (II) ion were evaluated by using the Langmuir, Freundlich and Dubinin–Radushkevich (D–R) adsorption isotherms. Also, thermodynamic parameters, i.e., ΔG, ΔS, and ΔH were calculated for the system.     

Synthesis and characterization of novel calix[4]arene piperazine derivative for the extraction of transition metals and dichromate ions

This article displays the synthesis of N-(2-tosylato)ethylpiperazine (ii) and 5,11,17,23-tetra-tert-butyl-25,27-bis-(2-piprazinoethyl)-26,28-dihydroxycalix[4]arene (3). Compounds (ii) and 3 were characterized through elemental analysis, FT-IR, ¹H NMR and/or ¹³C NMR studies. The transition metal cations (Hg²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Cd²⁺) and dichromate anion were studied by liquid–liquid extraction experiment. The results showed that compound 3 has moderate but selective extraction ability for Hg²⁺ and dichromate anion. Comparison between extraction properties of compound 3 with previously reported 5,11,17,23-tetra-tert-butyl-25,27-bis(isoniazidylcarbonylmethoxy)-26,28-dihydroxy-calix[4]arene (4) and protonated pyridinium form of 4 (5) is also described.     

杯[4]芳烃单取代1,3-二酮衍生物的合成及生物活性研究

以杯[4]芳烃为原料经醚化和克莱森缩合两步反应首次合成杯[4]芳烃单取代1,3-二酮衍生物,其结构经1H NMR、13C NMR及MS表征。初步的HIV-1整合酶链转移反应活性测试结果表明,该杯[4]芳烃单取代1,3-二酮衍生物在测试浓度为25μM时其抑制率为12.67%。     

一种新型杯[4]芳烃的合成

本文通过对特丁基杯[4]芳烃的酚羟基烷基化和苯环特丁基位上的IPSO-硝化制备了一系列对硝基杯[4]芳烃烷基醚,烷基分别是n-C~4H~9(3a)、n-C~8H~1~7(3b)、n-C~1~2H~2~5(3c)和n-C~1~6H~3~3(3d)。^1HNMR表明所有新的杯[4]芳烃都具有锥形(cone)构象。     

Synthesis and Conformational Properties of Bis（calix [4] arene）

The bis(calix [4] arene)3 was synthesized in moderate yield by the reaction of p-tert-butylcalix [4] arene (1) with 1,4-bis(chloromethyl) benzene (2). The conformation of all alkylated product 4 was investigated by the variable-temperature ^1H-NMR.     

Synthesis of novel biscalixarene-tube containing two kinds of calix[4]arene derivative units

A novel biscalixarene with two kinds of calix[4]arene derivative units connected by four bridging chains, was facilely＇ synthesized by ＂1 ＋ 1＂ condensation mode in high yield. The element analyses, ESI-MS, ^1H NMR and ^1H-^1H COSY spectrum showed that the calix[4]arene units of compound 4 were in cone conformations and compound 4 possessed biscalixarene-tube structure. 2007 Fa Fu Yang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.     

Synthesis and fluorescence sensing properties of a new naphthalimide derivative of calix[4]arene

A new naphthalimide derivative of calix[4]arene was synthesized as a highly selective fluorescent compound for Cu²⁺ among the selected metal ions. This compound was examined for its fluorescent properties toward different metal ions (Na⁺, Li⁺, Mg²⁺, Ni²⁺, Ba²⁺, Ca²⁺, Cu²⁺, Pb²⁺, Zn²⁺) and anions (F^?, Cl^?, Br^?, ${\text{H}}_2{\text{PO}}_4^{-}$, ${\text{NO}}_3^{-}$, I^?, ${\text{HSO}}_4^{-}$, CH₃COO^?) by UV, NMR and fluorescence spectroscopy.     

Potentiometric sensors based on poly(3,4-ethylenedioxythiophene) (PEDOT) doped with sulfonated calix[4]arene and calix[4]resorcarenes

Potentiometric ion sensors have been prepared by galvanostatic electrosynthesis of the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with p-sulfonated calix[4]arene (C[4]S) and p-methylsulfonated calix[4]resorcarenes (R_n[4]S) with alkyl substituents of different chain length (R₁=CH₃; R₂=C₂H₅; R₃=C₆H₁₃). The bowl-shape of these doping ions makes them suitable as ionic recognition sites, and their bulky character is expected to prevent them from leaching out of the conducting polymer membrane. For comparison, sensors based on PEDOT doped with poly(styrene sulfonate) (PSS) and poly(vinyl sulfonate) (PVS) were also constructed. The resulting GC/PEDOT electrodes were conditioned in 0.01 mol L^–1 AgNO₃ and their performance as Ag⁺ ion-selective electrodes (ISEs) studied. Results reveal that selectivity and lifetime of the electrodes is affected by the doping anion structure, although all electrodes show selectivity towards Ag⁺ ions. Interaction of Ag⁺ with sulfur atoms present in the conducting polymer backbone is considered to be the main reason for this behavior. A second set of electrodes was constructed and conditioned in 0.1 mol L^–1 KCl. These electrodes were tested in chloride solutions of quaternary ammonium cations, showing that C[4]S and R₂[4]S exhibit significant sensitivity towards pyridinium.Dedicated to Professor György Horányi on the occasion of his 70th birthday in recognition of his outstanding contributions to electrochemistry     

新型杯[4]芳烃氨基苯酚类衍生物的合成及对La3 的选择性识别

设计合成了下缘连有氨基苯氧基结构的杯[4]芳烃衍生物:5,11,17,23-四叔丁基-25-[2-(2-氨基苯氧基)乙氧基]-27-(2-羟基乙氧基)-26,28-二羟基杯[4]芳烃(化合物C),增加了与阳离子的结合位点,有利于通过配位作用对金属离子进行识别。化合物C的结构通过红外光谱、1H NMR、13C NMR和质谱进行了表征。通过紫外可见光谱和荧光发射光谱对化合物C与24种金属阳离子的络合作用进行了研究,结果发现,其对La3+有特殊的识别作用,化合物C与La3+的络合比为1∶1。     

Synthesis of calix[4]arene(amido)monocrowns and their photoresponsive derivatives

A series of new calix[4]arene(amido)mono-crown compounds have been synthesized through aminolysis of calix[4]arene esters and intramolecular cyclization of the intermediates. The title compounds were converted into their nitro and azo substituted derivatives to provide novel photoresponsive molecular receptors for transition metal ions. Single crystal X-ray analysis of calix[4]arene(ethyleneamido)mono-crown (2a) revealed that the compound is present in a cone conformation with an amido loop that caps the lower rim of calix[4]arene cavity to result in stacking along axis a and axis c to provide supramolecular aggregates in the solid state. Evaluation of synthesized macrocycles in the solution phase for recognition of transition metal cations (Cr³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Ag⁺, Cd²⁺, Pb²⁺, Hg⁺, Hg²⁺, Pd²⁺, and Pt²⁺) by UV-visible spectroscopy revealed that p-tert-butyl-calix[4]arene mono-(amidocrown) 1c selectively shows a blue shift at 38 nm on interaction with Hg⁺ ions.     

Preparation of calix[4]arene-based sporopollenin and examination of its dichromate sorption ability

The present study describes the preparation of a new calix[4]arene-based sporopollenin material and its application for the removal of Na₂Cr₂O₇ from aqueous solution. The novel calix[4]arene-based sporopollenin material was prepared via the immobilization of dihydrazine amide derivative of p-tert-butylcalix[4]arene (3) onto the modified sporopollenin. The newly prepared calix[4]arene-based sporopollenin is characterized by using different analytical techniques such as FT-IR spectroscopy, scanning electron microscope and Elemental analysis. The batch wise sorption study was carried out to optimize various experimental parameters such as the effect of sorbent dosage, pH, temperature and Cr(VI) anion concentration. It has been found that the sorption of Cr(VI) anion on calix[4]arene-based sporopollenin was highly pH dependent and maximum sorption was achieved at pH 1.5. The sorption behavior was also evaluated by Langmuir, Freundlich and Dubinin Radushkevich isotherms. The value of correlation coefficient (R ²) showed a good agreement with Freundlich isotherm model. Result of study demonstrated that calix[4]arene-based sporopollenin proved to be highly effective for the removal of Cr(VI).     

Synthesis of upper rim calix[4]arene carcerands

The synthesis of novel tetra-olefinic calix[4]arene carcerands is described using a synthetic strategy involving palladium catalysed Heck coupling followed by imine formation.     

Synthesis and binding properties of calix[4]arene telomers

Two calix[4]arene derivatives (5 and 8) and their telomers are synthesized to estimate selective extraction of alkali and transition metal cations from the aqueous to the organic phase (chloroform). Compound 5 shows selectivity toward Hg²⁺. Compound 8 and telomers 6 and 9 are not selective but are good extractants for all used transition metal ions. The observations suggest that ethylene glycol bridges are efficient for carrying transition metal cations in a two-phase solvent system. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4351–4355, 1999     

四乙氧羰基甲氧基杯[4]芳烃的合成与性质

配位作用;液膜传递;四乙氧羰基甲氧基杯[4]芳烃的合成与性质     

Evaluation of perchlorate sorption behavior of calix[4]arene appended resin

In the present work, perchlorate sorption ability of calix[4]arene appended resin was investigated to develop a new efficient method for the removal of perchlorate from aqueous media. The column sorption process was performed at a wide range of pH (1–7) and perchlorate content in the effluent was determined through ion chromatography. From the results, it has been concluded that maximum sorption (97 %) of perchlorate is taking place at pH 3. The breakthrough curves were obtained as a function of time to get clear picture of sorption process and the data obtained was tested by applying two kinetic sorption models, i.e. Yoon-Nelson and BDST. The data obtained through experiments were compared with the theoretically calculated values and it has been found that both have close agreement with each other.     

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。     

Synthesis of molybdenocene(IV) and tungstenocene(IV) tropolonato complexes: Its derivative containing calix[4]arene moiety

The cationic di-μ-hydroxo dinuclear complexes of molybdenocene and tungstenocene [Cp₂M(μ-OH)₂MCp₂]⁺ (Cp = η-C₅H₅; M = Mo or W) react with tropolone to afford corresponding tropolonato complexes [Cp₂M(trop)]⁺ (trop = C₇H₅O₂). The products were investigated by IR, ¹H NMR, and ¹³C NMR spectroscopy as well as by X-ray crystallography (M = W). The structure shows that the central metal is surrounded by a distorted tetrahedral array of the two centers of cyclopentadienyl ligands and the two oxygen atoms of tropolonato ligand. The reaction has been extended to the synthesis of calix[4]arene receptor functionalized at the 1,3-positions of the upper rim with two tropolonato-molybdenocene centers.