Arsenate and Dichromate Removal Efficiency of a New Calix[4]arene Impregnated Resin

This article highlights a newly synthesized 5,11,17,23-tetra-tert.butyl-25,26,27,28-tetrakis(hydrazidecarbonylmethoxy)-calix[4]arene (3) impregnated resin 4 and it's sorption ability for the removal of selected oxoanions, i.e., (arsenate and dichromate) from aqueous environment. Resin 4 was characterized by using FT-IR spectroscopy, scanning electron microscope (SEM), elemental, and thermogravimetic (TGA) analyses techniques. Sorption study was carried out through static and dynamic methods with continuous flow operation to evaluate the potency of resin 4 under various conditions. Several parameters, such as effect of sorbent dosage, contact time, pH, and initial concentration were optimized through batch experiments. Results justify that % sorption of these oxoanions is highly dependent on pH of the solution. Equilibrium was achieved in 45 min, while sorption efficiency of resin 4 can be better explained by Langmuir and Temkin isotherm models. Furthermore, kinetically both oxoanions follow pseudo second order model. Additionally, sorption of arsenate more appropriately could be explained by Moris-Weber diffusion kinetic model. For the dynamic method, Thomas model was used to calculate the kinetic coefficient (k_TH) and maximum sorption capacity (q_o) of resin 4 which are 3.84 and 5.94 ml mg^?1 min^?1 and 0.185, 0.160 mg g^?1 for As (V) and Cr (VI) respectively. Furthermore, resin 4 has been found as potential sorbent for removal of these oxoanions from contaminated surface water samples.     

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.     

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。     

杯[4]芳烃偶氮衍生物的合成及其金属离子萃取性能

杯芳烃作为超分子化学的重要组成部分,近年来得到了快速发展并成为化学家的研究热点。以脱叔丁基-杯[4]芳烃为原料合成了杯[4]芳烃偶氮衍生物,其结构经IR和1H NMR所表征。研究了该主体分子对金属离子的萃取性能,实验结果表明,该主体分子对Mg2＋具有较高的萃取作用。讨论了主客体间配位作用的机制。     

Calix[4]arene Resin,An Efficient Adsorbent for Azo Dyes

Dyes are a potential menace and are considered major contributors to environmental pollution. However, the cleanliness of the environment from colored toxicants is a challenging task of the contemporary era. In this regard, this approach is based on the confiscation of hazardous dyes. The main features of this work are the synthesis and the application of newly synthesized calix[4]arene grafted Amberlite XAD-4 (resin 5) for the selected methyl orange (MO) and methyl red (MR) azo dyes removal from aqueous environment. The adsorption ability of resin 5 for the selected azo dyes was evaluated through optimizing various parameters. Moreover, treatment with real water samples reveal that newly synthesized resin is an extremely effective adsorbent for the removal of the selected azo dyes from aqueous media.     

含氮杯[4]芳烃的合成

以对叔丁基苯酚为起始原料,经过3步反应,在母体杯芳烃的下沿引入3种不同的含氮基团,得到5种含氮杯[4]芳烃,并通过1HNMR和熔点测定确定了产物结构.实验中发现,当母体杯芳烃下沿引入的溴代烷基变长时,进一步引入含氮基团,只能得到1,3位环化的含氮杯[4]芳烃.     

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％.     

对叔丁基杯[4]芳烃巯基吡啶衍生物的合成

以对叔丁基苯酚为起始原料,通过缩合得到对叔丁基杯[4]芳烃,再对其下沿酚羟基进行化学改性,得到具有化学活性的杯[4]衍生物中间体,该中间体与具有活泼氢的2-巯基吡啶反应制得新的含N、S杯芳烃衍生物,总收率14.4%。     

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％。     

新型杯[4]芳烃衍生物对Pb~(2+),Cd~(2+)的萃取性质

研究了新型杯[4]芳烃D对Pb2+,Cd2+离子的液-液萃取性质,并将其与自制的杯[4]芳烃A及其衍生物B、C对Pb2+,Cd2+离子的液-液萃取性质进行了比较。结果表明,与化合物A~C相比,D对Pb2+萃取率最高,在实验条件下,可达到42.8%;测试的四种化合物对Cd2+离子的萃取效率均不佳,未经任何修饰的杯[4]芳烃A的萃取效率最高,仅8.5%。推测对Cd2+的萃取为阳离子交换机理。     

杯[4]芳烃巯基吡啶衍生物的合成

以对叔丁基苯酚为起始原料,通过缩合得到对叔丁基杯[4]芳烃,再对其下沿酚羟基进行化学修饰,得到具有化学活性的杯[4]衍生物,该化合物与具有活泼氢的4巯基吡啶反应制得新的含N、S杯芳烃衍生物,总收率15.3%。     

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。     

氨基硫脲基新型杯[4]芳烃衍生物的合成

通过1,3-环氧丙基杯[4]烃与硫代氨基脲开环反应,合成硫代氨基脲基杯[4]芳烃衍生物,研究了其对阳离子的吸附性能后发现,与其他氨基杯芳烃相比,该衍生物对铜离子的吸附性能较好,并且有很好的选择性。     

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⁺.     

羧基苯偶氮基杯[4]芳烃衍生物的合成、表征及光谱特性

以邻、间、对氨基苯甲酸和杯 [4]芳烃为原料 ,经重氮化 -偶联反应合成了发色邻、间、对羧基苯偶氮基杯 [4]芳烃 ,产物的结构经 IR,1H NMR和元素分析表征 ;研究了它们的生色原理和光谱性能。结果表明它们是一类新型指示剂和具有新型配位空腔的主体分子。     

氮杂杯[6]芳烃的合成与表征

以三聚氯氰和对苯二胺为原料,碳酸钾或氢氧化钾作为缚酸剂,合成氮杂杯[6]芳烃第一步中间体N,N’-二(4,6-二氯-1,3,5-均三嗪-2-基)-1,4-苯二胺(Ⅰ)和第二步中间体2,4-二(4-胺基苯胺基)-6-氯-1,3,5-均三嗪(Ⅱ),再由(Ⅰ)和(Ⅱ)合成最终产物氮杂杯[6]芳烃。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。     

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。     

Selective online solid-phase extraction of copper using p-morpholino-methylcalix[4]arene appended silica-based column

ABSTRACT

This study deals with investigation of selectivity of p-morpholino-methylcalix[4]arene appended silica from a group of metal ions having similar charge and radii. The values of distribution ratio revealed that modified silica possess higher selectivity for Cu²⁺. In addition, relative selectivity coefficients of modified silica were found to be 24.1, 13.8, 8.6 and 4.01 for Cu²⁺/Ni²⁺, Cu²⁺/Co²⁺, Cu²⁺/Cd²⁺, Cu²⁺/Pb²⁺, respectively. The maximum adsorption capacity was 1.5 mmolg^?1. The reusability data suggested no any loss of adsorption capacity of this material up to 10 cycles. The developed material was also applied for determination of copper in lake water samples with satisfactory results.     

杯[4]芳烃醚类衍生物的合成(Ⅱ)

以对叔丁基苯酚和甲醛为起始原料，通过选用不同的催化剂，合成了一系列新的杯[4]芳烃的四醚化衍生物，并对其结构用IR、^1HNMR、^13CNMR、MR进行了表征。     

Synthesis of novel silica gel immobilized‐calix[4]arene amide ionophores and their anion binding abilities toward phosphate and chromate anions

This article describes the synthesis and characterization of four new calix[4]arene ionophores 5–7 and 9 and corresponding two new silica gel‐immobilized calix[4]arene ionophores containing pyridine 10 and 11 via modification of calix[4]arene monoamide derivatives 5 and 6 with aminopropyl silica gel, respectively. The extraction studies have been performed using liquid–liquid extraction for receptors 5–7 and 9 and solid–liquid batchwise sorption procedures for receptors 10 and 11 . Obtained extraction results showed that the immobilized‐calix[4] arene ionophores 10 and 11 have high extraction ability toward chromate and phosphate anions as compared to their corresponding monomeric precursors 5 and 6 . © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012