冠醚载体离子电极的选择特性研究

阴离子选择电极选择性系数随干扰离子r_j/z_j的变化规律已有报道,但冠醚为中性载体的金属离子电极的选择性系数规律未见报道。本文采用不同桥间结构的11种苯并双冠醚作为中性载体,从钾电极出发探讨了不同冠醚电极选择性系数与干扰离子r_j/z_j间的关系;并以4种烃型双冠醚为中性载体,分别考察了它们对Li~+、Rb~+、Cs~+、Ag~+、Ba~(2+)离子的响应规律。 1 实验部分     

查尔酮冠醚PVC膜钾离子选择性电极的初步研究

查尔酮冠醚ＰＶＣ膜钾离子选择性电极的初步研究李廷盛，蔡汉临，王传林，张建明，魏旭东，胡宏纹（华中师范大学化学系武汉４３００７０））（南京大学化学系南京）关键词查尔酮冠醚ＰＶＣ膜，钾离子电极，性能钾离子在生物细胞膜内外的浓度梯度对生物膜的能量传输等起着...     

冠醚化合物的合成——ⅩⅣ.二茂铁硫冠醚的合成及其银离子选择电极的研究

本文合成了两种类型6个二茂铁硫冠醚1—6,其中4—6是一类新型缩醛硫冠醚。将冠醚2—6作为传感活性物质研制成PVC膜银离子选择电报,其中以用冠醚4的电极性能最佳,对一价和二价干扰离子的选择性,远优于文献[1]结果。     

新型吡啶基冠醚液膜离子选择电极的制备及其性能研究

离子选择电极是分析测试中有用的电化学传感器。它在分析化学中很多领域都有重要用途,尤其是对低浓度离子的测定,具有灵敏、快速简便的优点。本文将自己合成的新型吡啶基冠醚(Ⅰ)作为中性载体,制成PVC液膜钾离子选择电极,并研究了它的响应性能。     

新型冠醚作中性载体的伯胺药物选择性电极研究

本文合成了对伯胺响应性能好的联萘-20-冠-6和N,N′,N″-三甲基-1,7,13-三氮杂-4,10,16-三氧杂环十八烷等6种离子选择性载体。对应用这些载体研制伯胺药物选择性电极进行了系统的研究,研制成了美西律、多巴胺、间羟胺、色胺和脂肪族伯胺等多种伯胺选择性电极,并用于这些药物的分析测定。为解决缔合物型胺(铵)类电极对伯胺的响应性能差和常用冠醚作载体的伯胺电极受K~+,Na~+,NH_1~+离子和仲、叔胺及季铵严重干扰等问题,探索了新的途径。并用计算机数字模拟对电极的电位响应过程进行了研究。     

饱和漆酚冠醚铊(Ⅰ)离子选择电极—冠醚结构与电极性能的关系

本文以8个不同结构的饱和漆酚冠醚(1～8)为传感活性物质,研制了10种铊(Ⅰ)离子选择电极,综合性能最好的为1号和4号两个电极。它们的线性响应范围分别为4×10^-7～5×10^-1和8×10^-7～1×10^-1mol/L TINO₃,检测下限分别为1×10^-7和6.5×10^-7mol/L TINO₃,对钾离子的选择优于文献报道的其它冠醚铊(Ⅰ)离子电极。     

聚冠醚的合成和性质——Ⅵ.聚冠醚为载体的碱金属离子选择性电极

本文报道以含有12-冠-4、15-冠-5和18-冠-6结构单元的双酚A型聚冠醚为载体的钠、钾和铯离子选择性电极的制备及电极响应特性的研究。结果表明三种电极都有较好的Nernstian响应特性和对碱金属及碱土金属的良好选择性。     

冠醚化合物的合成(ⅩⅪ)——开链酰胺型冠醚的合成及其钙离子选择电极的性能

本文以多甘醇为原料,经氧化、取代反应制备了多甘酰氯,再与仲胺反应,合成了7个开链酰胺型冠醚化合物和1个酰胺型大环化合物,除冠醚(Ⅰ)外,其余均未见文献报道。它们的结构经红外、核磁、质谱和元素分析数据确认,并用四圆单晶X射线衍射仪测定了冠醚(Ⅱ)单晶的晶体结构,进一步从理论上说明了它是优良的钙离子选择电极的中性载体。     

Surfactant Ion Selective Membrane Electrodes

Abstract

Calix[8]arene ethers, carboxylic esters having various p-substituents and acid are synthesized and studied. In a bulk membrane transport of dodecylpyridinium the better carrier is the simplest host, calix[8]arene octamethyl ether. Inversely, it is the worst carrier for dodecyltrimethylammonium; the better here is carboxy ester with adamantyl p-substituents. Various calixarenes are successfully used in plasticized membrane ion-selective electrodes (ISE) for both above ammonium and pyridinium surfactants. Operational characteristics, potentiometric selectivity and optimal membrane compositions are reported. Typical limit of detection is at the level of nx10^?6 - 1x10^?5 M, response time 5-10 s, and lifetime is at least 6 months. ISE's selectivity is significantly better than that of ion-association and crown-ether based electrodes.     

基于UV光固化聚合膜硫氰酸根离子选择性电极的研究

以二丙烯酸脂肪族尿烷酯低聚物为基本原料 ,碘化十二烷基三庚基铵为电活性物质 ,采用 UV光固化聚合成膜研制硫氰酸根离子电位敏感电极。对膜的成分进行了优化 ,优化后的膜与 PVC膜比较具有较高的机械强度和较强的附着力。电极对硫氰酸根离子响应的线性范围为 4.7× 1 0 - 6 ～ 1 .0× 1 0 - 1mol/L,检测下限为 1 .2×1 0 - 6 mol/L ,电极斜率 5 7.5± 1 .5 m V/decade,对常见阴离子电位选择性系数进行了测试 ,电极具有良好的选择性。将电极用于人体尿样中硫氰酸盐的测定 ,结果令人满意     

A conductance study of the association of alkali cations with 1,13-dibenzo-24-crown-8 in acetonitrile

A conductance study concerning the association of Na⁺, K⁺, Rb⁺, and Cs⁺ with 1,13-dibenzo-24-crown-8 in acetonitrile has been carried out at 35, 30, 25, 20, and 15°C. The observed molar conductivities were found to decrease significantly for mole ratios less than unity. A model involving 11 stoichiometry has been used to analyze the conductivity data. The stability constant, K, and the molar conductivity _C for each 11 complex were determined from the conductivity data by using a nonlinear least squares curve fitting procedure. The binding sequence, based on the value of log K at 25°C, is found to be Rb⁺>Cs⁺>K⁺>Na⁺. Values of H^o and S^o are reported and their significance is discussed.     

Novel Terpyridine-bridged Parallel Dication Metallo-bisviologens and Their Supramolecular Complexes

By utilizing terpyridine-bridged parallel metallo-complexes as dication metallo-bisviologens,herein we present the synthesis and characterization of two novel supramolecular complexes.1-Methylpyridin-1-ium-terpyridine ligands and their metallo-complexes were first designed and synthesized,and the association of methyl-pyridiniums with dibenzo-24-crawn-8 ether(DB24C8)afforded the desired novel complexes through host-guest interactions.The self-assembly behavior of the supramolecular complexes was comprehensively investigated and could be exploited for furtlaer construction of ID to 3D supramolecular infrastructures.     

Bis(benzimidazolium)methane salts: a potential guest for dibenzo-24-crown-8 towards [2]pseudorotaxanes

We investigated the threading of bis(benzimidazolium) methane moieties with DB24C8 at 35 °C (room temperature) and found a high degree of association. The presence of threaded complexes was determined by ¹H NMR and also supported by high resolution mass spectrometry and B3LYP/6-31G**++calculations. A 2D NMR study was done to elucidate the host-guest geometry and the molecular interactions present. The variable temperature NMR experiment was done over a temperature range of 243-323 K. The threading was stable and visible even at 323 K. Acid-base equilibrium established the reversibility of the process. DFT optimized structures establish that two H-bonded links are present between O₁?O_4′ and O₃?O_2′ across the dibenzo axis of the crown.     

Poly (Vinyl Chloride) Matrix Membrane Electrodes Responsive to Thiocyanate,Perchlorate and Periodate

Abstract

Three types of PVC matrix membrane ion-selective electrodes (ISEs) are described. These are based on membranes containing nitron thiocyanate with 2-nitro-phenyl phenyl ether, 2-nitrophenyl phenyl ether alone and tetraphenylarsonium thiocyanate with 2-nitrophenyl octyl ether. Each type is conditioned and stored in 0.1M sodium thiocyanate. The first two electrodes have been evaluated for thiocyanate and perchlorate response and the best linear long range (linear range down to 2.5×10^?5M) response was obtained for perchlorate. The third electrode is suitable as a periodate ISE with linear calibration range down to 2×10^?4M. The plasticized (2-nitrophenyl phenyl ether) PVC electrode for thiocyanate and perchlorate had a much longer pH interference free range (1.5–12.5) than either of the other electrodes.     

Sodium Ion Selective Electrodes Based on Lipophilic 16-Crown-5 Derivatives

Abstract

Six kinds of lipopholic 16-crown-5 derivatives possessing double side-chains were synthesized. The Na⁺-selectivities were examined with poly(vinyl chloride) (PVC) matrix-membrane electrodes using these crown compounds. It is an effective way for obtaining high Na⁺-selectivity by introducing a bulky side-chain such as a benzyloxymethyl group into the 16-crown-5. The electrodes based on 16-crown-5 derivatives having both a methyl or ethyl group and a benzyloxymethyl group at the pivot carbon (C-15) (3 or 4, see Figure 1) exhibited excellent Na⁺-selectivity over K⁺ (log k _Na.x = -2.65 and -2.75 for 3 and 4, respectively).     

五羟色胺分子选择性电极研究

本应用自己合成的联萘２０－冠－６作为活性载体，进行了五羟色胺分子选择性电极研究。电极在１０＾－＾５－１０＾－＾２ｍｏｌ／Ｌ浓度范围内对五羟色胺具有稳定的线性响应，平均斜率为６３ｍＶ／ＰＣ，检测下限为２．７×１０＾－＾６ｍｏｌ／Ｌ。     

双臂套索冠醚PVC膜碘离子选择电极

研究了两种新型双臂套索冠醚1，10－二（5－氯－8－羟基喹啉－7－亚甲基）－1，10－二氮杂－4，7，16－三氧杂－13，19－二硫杂环二十一烷（Ⅰ）和1，13－二（5－甲基－8－羟基喹啉－7－亚甲基）－1，13－二氮杂－4，7，10－三氧杂－16，19－二硫杂环二十一烷（Ⅱ）为载体的PVC膜电极的响应行为；实验结果表明，两电极均显示阴离子响 应，其中对碘离子具有优良的能斯特电位响应性能，线性范围为10^－5－10^-1mol/L，斜率分别为－59．1mV/pcI-和－57．6mV/pcI-；电极具有读数稳定，重复性好，PH值范围宽等优点；将该电极用于药品中碘含量的测定，其结果与药典法一致。