Highly Selective Determination of Perchlorate by a Calix[4]arene based Polymeric Membrane Electrode

This article describes a versatile application of 25,27-bis-N-(N,N-diethyl-2-aminoethyl)carbonylmethoxy-26,28-dihydroxycalix[4]arene (4) as an ionophore for the preparation of perchlorate ion-selective electrode. The electrode exhibits a Nernstian response over the perchlorate concentration range of 1.0×10^?9 – 1.0×10^?1 M with a slope of 59.24 ± 0.5 mV per decade of the concentration. The limit of detection as determined from the intersection of the extrapolated linear segments of the calibration plot is 3.04×10^?9 M. The electrode shows good selectivity toward perchlorate with respect to many common anions. The response time of the sensor was 5–10 s and it has maximum life time of 2 months in the acidic pH. The electrode was used to determine perchlorate in real water samples. The interaction of the ionophore with perchlorate ions is also demonstrated by UV–vis spectroscopy.     

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％.     

磺化杯[6]芳烃的合成表征及热性能研究

以杯[6]芳烃为原料,在浓硫酸催化作用下,合成了磺化杯[6]芳烃,并通过红外光谱和核磁共振谱对其进行结构表征。热重分析结果表明,在升温速率为5℃/min时,磺化杯[6]芳烃开始降解温度为125.62℃,最快降解温度为269.43℃。经过Kissinger方程计算,磺化杯[6]芳烃的降解活化能为161.45k J/mol。     

Cu2+ Selective Chromogenic Behavior of Calix[4]arene Derivative

This study involves the copper selective chromogenic response of 5, 11, 17, 23-Tetrakis (N-pyrrolidinomethyl)-25, 26, 27, 28-tetrahydroxycalix[4]arene based mannich base (3). Complexation ability of (3) was explored by examining the effect of a series of various metal ions, such as Li⁺, Na⁺, K⁺, Ag⁺, Ba²⁺, Ca²⁺, Mn²⁺, Mg²⁺, Sr²⁺, Ni²⁺, Cd²⁺, Co²⁺, Cu²⁺, Hg²⁺, Pb²⁺, Zn²⁺, Fe²⁺, Fe³⁺, and Al³⁺, by using UV-visible spectroscopy. Ligand (3) exhibited pronounced selectivity toward Cu²⁺ even in the presence of various co-existing ions. The stoichiometric analysis, i.e., Job's plot revealed that (3) form 1:1 complex with Cu²⁺ ion in DMF-H₂O system. The complexation phenomenon was confirmed by FT-IR spectroscopy that favors the selective nature of (3) with Cu²⁺.     

氮杂杯[6]芳烃迭氮化衍生物的合成与表征

本论文主要以自制氮杂杯[6]芳烃和迭氮化钠为原料,合成氮杂杯[6]芳烃迭氮化衍生物。通过红外光谱分析法和核磁共振氢谱法对产物进行了表征,证实其为目标产物,从而验证了合成路线的可行性。     

Kinetic Study of an Effective Pb(II) Transport through a Bulk Liquid Membrane Containing Calix[6]arene Hexaester Derivative as a Carrier

The article describes transport of Pb(II) through bulk liquid membrane (BLM) containing calix[6]arene hexaester derivative (1) as a carrier. The effect of various parameters such as temperature, carrier concentration, stirring speed and type of solvent on the Pb(II) transport efficiency of the carrier through BLM was evaluated. The activation energy values for the extraction and re-extraction were found as 56.33 kJ mol^?1 and 14.79 kJ mol^?1, respectively. These values demonstrate that the process is diffusionally controlled by Pb(II). Observations indicate that the membrane entrance and exit rate constants (k₁, k₂) increase with increasing stirring speed as well as carrier concentration and decrease with increasing temperature. The effect of solvent on k₁ and k₂ was found to be in the order of CH₂Cl₂ > CHCl₃ > CCl₄.     

杯[6]芳烃在毛细管电泳分离硝基苯胺异构体中的作用

本文研究了在杯 [6]芳烃存在下杯 [6]芳烃的浓度、检测波长、有机混合添加剂对o、m、p -硝基苯胺位置异构体毛细管电泳分离的影响。最优化的电泳缓冲液为A B(1∶1 ,v/v) ,A =2 5mmol/LNH4Ac -HAc (pH 6.0 ) - 2mmol/L杯 [6]芳烃 ,B =MeOH -CH3CN(1∶6,v/v) ,检测波长为 372nm ,运行电压为 2 0kV。在此条件下 ,o、m可以与 p -硝基苯胺达到基线分离。     

含硫杯芳烃衍生物的合成

杯芳烃是继环糊精、冠醚之后出现的“第三代超分子”．它是由酚类物质与醛或酮借助缩合反应而得到的一类大环化合物．它以良好的化学稳定性、高熔点以及空腔大小可调等独特的物理、化学性能受到众多学者的关注。对杯芳烃下沿酚羟基进行化学改性,可以得到具有化学活性的杯芳烃衍生物．苯酚杯芳烃的酚羟基自身就是一个官能化基团．它的活性比较大．可以与多种试剂反应,能制备各种杯芳烃的衍生物。杯芳烃在一定条件下与卤代烃、卤代冠醚以及其他卤代物等反应可以得到不同类型的酯、醚以及含其他杂原子的化合物和桥连化合物。     

Rate of Adsorption of Uranium from Seawater with a Calix[6]arene Adsorbent

Abstract

The rate of complex formation between calix[6]arene-p-hexasulfonate and uranyl ion is studied over a wide range of carbonate ion concentrations. The presence of carbonate ion decreases the complexation rate. The distribution of various uranyl species is calculated from a set of mass balances of participating ions with their stability constants. UO₂(CO₃)₃ ^4? has the highest concentration, followed by UO₂(OH)₃ ^? and UO₂(CO₃)₂ ^2?. Other uranyl species are negligible. The complexation rate is proportional to the 0.27–1.0 power of the total concentration of uranyl species other than UO₂(CO₃)₃ ^4?. This implies that the rate-determining step of the complexation is the reaction between calix[6]arene-p-hexasulfonate and UO₂(OH)₃ ^? or UO₂(CO₃)₂ ^2?.     

Liquid Membrane Transport of Hg(II) by an Azocalix[4]arene Derivative

Abstract

A kinetic study of Hg(II) transport from an aqueous donor solution into an aqueous acceptor solution through a liquid membrane containing 25,26,27–tribenzoyloxy‐28‐hydroxy‐5,11,17,23‐tetra‐(4‐n‐butylphenylazo)calix[4]arene 1 as a carrier was studied. The kinetic parameters (k ₁, k ₂, R _m ^max, t _max, J _d ^max, J _a ^max) for the transport were investigated in terms of the effect of temperature, the stirring rate, the carrier concentration, and the type of solvent. The kinetics of transport was analyzed in the formalism of two consecutive irreversible first‐order reactions. The membrane entrance rate, and exit rate constants were increased with increasing of temperature stirring rate, and carrier concentration. The membrane entrance rate and exit rate constants depended on the type of solvent and was found to be in order of CH₂Cl₂> CHCl₃> CCl₄. The activation energy values are calculated as 30.67±2.64 and 57.33±4.90 kj mol^?1 for extraction and reextraction, respectively. The values of calculated activation energy indicate that the process is diffusionally controlled by species.     

Transport of Hg2+ Ions across a Supported Liquid Membrane Containing Calix[4]arene Nitrile Derivatives as a Specific Ion Carrrier

Abstract

The transport behavior of Hg²⁺ from aqueous solution through a flat‐sheet‐supported liquid membrane (SLM) has been investigated by using of calix[4]arene derivatives (1 and 2) as carriers and Celgrad 2400 and 2500 as the solid support. The effect of solvent type and anions such as chloride and nitrate ions on the transport of Hg²⁺ was examined. Danesi mass transfer model was used to calculate the permeability coefficients for each parameter studied. The highest values of permeability were obtained with 2‐nitrophenyl ethyl ether (NPOE) solvent and the influence was found to be in the order, NPOE>chloroform>xylene. The transport efficiency on the supported liquid membrane was dependent on the type of carrier, its characteristics, and the type of the solvent.     

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.     

对叔丁基杯[4]及杯[6]芳烃的合成及其对铜离子的萃取研究

以对叔丁基苯酚和甲醛为原料,分别对对叔丁基杯[4]及杯[6]芳烃的合成和萃取性质进行了研究．结果表明,在本研究范围内,以KOH为催化剂,对叔丁基杯[6]芳烃的最高产率为77．8％;以NaOH为催化剂,对叔丁基杯[4]芳烃的最高产率为47．3％。对于对叔丁基杯[4]和杯[6]芳烃,最佳的反应回流温度都为140℃。对叔丁基杯[6]芳烃对模拟废水中的铜离子具有一定的萃取效果,最高萃取率为70．3％。     

A Convenient Approach Toward Fluoride Sorption by Calix[4]arene Based Sorbent

The present study describes the sorption of fluoride on a potential and newly synthesized p-tetraaminocalix[4]arene based resin (p-TAC4 resin). The p-TAC4 resin was synthesized via immobilization of p-tetranitrocalix[4]arene (p-TNC4) onto the Merrifield resin followed by catalytic reduction with SnCl₂/EtOH/HCl. The p-TNC4 and p-TAC4 resins were characterized using FT-IR, elemental analysis, and scanning electron microscopy (SEM). Fluoride removal capability from the aqueous media of the p-TAC4 resin has been evaluated through batch sorption study. The effect of pH, sorbate concentration, sorbent dosage, and contact time on fluoride removal was evaluated. The Langmuir (L), Freundlich (F), and Dubinin–Radushkevich (D-R) isotherms revealed that the fluoride on p-TAC4 resin follows physiosorption mechanism. All the results support and emphasize that the p-TAC4 resin is an effective sorbent for the removal of fluoride from the aqueous environment at a wide range of pH. The study may confer its impact on human health, reinstate polluted sites and other fields such as analytical, clinical, as well as material sciences.     

对叔丁基杯[6]芳烃合成

以对叔丁基苯酚和甲醛为原料,KOH为催化剂,合成对叔丁基杯[6]芳烃。探讨了催化剂用量、升温速率(从加热到回流所用的时间)、回流温度等因素对叔丁基杯[6]芳烃产率的影响,并从反应机理方面进行了讨论。结果表明,以10 g对叔丁基苯酚为原料,催化剂用量1.6 g,升温速率2 h,回流温度140℃时,产率达到90%。     

Highly Efficient Liquid Membrane Transport of Dyes Using Calix[4]arene-Linked Triphenylene Dimers as Carriers

The extraction of dyes from aqueous phase to organic phase using calix[4]arene-linked triphenylene dimers (1a and 1b) with large π-cavity as extractants were examined. 1a and 1b showed outstanding extraction percentage for four common dyes [Orange G sodium salt (OG), Brilliant ponceau (BP), Methyl Green (MG), and Xylenol Orange disodium salt (XO)]. The highest extraction percentage of 1a was 95% for MG. Moreover, the abilities of liquid membrane transport of 1a and 1b for dyes were studied. The influences of pH value, concentration, solvent, stirring speed, and the temperature on liquid membrane transport was investigated to optimize the transport condition. The results of liquid membrane transport suggested 1a and 1b were excellent carriers for tested dyes with high fluxes. The high concentration in the source phase or membrane phase, CH₂Cl₂, high stirring speed, and low temperature were favorable for the efficiency of liquid membrane transport. The high extraction percentages and outstanding liquid membrane transport abilities indicated that 1a and 1b possessed excellent complexation for dyes based on the π-π stacking action between dyes and triphenylene units.     

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。     

杯[8]芳烃磺酸钠与C60的包合作用研究

制备了杯[8]芳烃磺酸钠与C60的包合物,并利用紫外光谱对合成产物进行了表征.     

Calix[4]arene Polyamine Triazoles: Synthesis,Aggregation and DNA Binding

Artificial gene delivery systems are in great demand from both scientific and practical biomedical points of view. In this paper, we present the synthesis of a new click chemistry calix[4]arene precursor with free lower rim and new water-soluble calixarene triazoles with 12 amino-groups on the upper rim (one with free phenol hydroxyl groups and two another containing four butyl or tetradecyl fragments). Aggregation in the series of amino-triazole calixarenes of different lipophilicity (calixarene with free phenol hydroxyl groups or butyl and tetradecyl fragments on the lower rim) was studied using dynamic light scattering and fluorescent pyrene probe. It was found that calix[4]arene with a free lower rim, like alkyl-substituted butyl calix[4]arene, forms stable submicron aggregates 150–200 nm in size, while the more lipophilic tetradecyl –substituted calix[4]arene forms micellar aggregates19 nm in size. Using UV-Vis spectroscopy, fluorimetry and CD, it was shown that amino-triazole calix[4]arenes bind to calf thymus DNA by classical intercalation. According to DLS and TEM data, all studied macrocycles cause significant DNA compaction, forming stable nanoparticles 50–20 nm in size. Among all studied calix[4]arenes the most lipophilic tetradecyl one proved to be the best for both binding and compaction of DNA.     

对叔丁基杯[6]芳烃合成方法的改进

杯芳烃是一类通常由对叔丁基苯酚和甲醛在碱性条件下缩合而成的环状低聚体.由于杯芳烃易于大量制备、环腔大小可调,可进行多种化学修饰等特点,已引起了许多超分子化学家的极大兴趣,被誉为继冠醚和环糊精之后的第三代主体分子.