冠醚存在下稀土络合物荧光体系的荧光增强效应

本详细研究了冠醚对Ｅｕ－ＴＴＡ荧光体系的增敏作用和稀土离子Ｄｙ＾３＾＋或Ｈｏ＾３＾＋对Ｅｕ－ＴＴＡ－冠醚体系的荧光强增效应。对Ｅｕ－ＴＴＡ－冠醚和Ｅｕ－Ｄｙ（或Ｈｏ）－ＴＴＡ－冠醚体系，Ｅｕ的浓度分别在１．０×１０＾－＾８－４．０×１０＾－＾６ｍｏｌ／Ｌ，１．０×１０＾－＾９－１．０×１０＾－＾７ｍｏｌ／Ｌ和１．０×１０＾－＾８－９．０×１０＾－＾６ｍｏｌ／Ｌ范围内与体系的荧光强度呈线性关系，检     

5—羟色胺敏感膜电极的研究：Ⅱ.中性载体5—羟色胺膜电极的研制和应用

通过比较６种冠醚组成的２种不同配比的１１个配方，研制出了对５－羟色胺有较好的灵敏性和较高的选择性的涂碳膜电极。电极敏感膜的活性成分是１８－冠－６，增塑剂为磷酸三（２－乙基乙基）酯。电极的线性是１．００×１０＾－２～１．７８×１０＾－５ｍｏｌ／Ｌ，斜率为５８．４ｍＶ／Ｐ＾５－ＨＴ，检测下限为５．０１×１０＾－６ｍｏｌ／Ｌ，电极寿命超过９５天。用该电极测定了１９５名健康人血小板中的５－羟色胺浓度，算术     

冠醚增敏稀土配合物荧光增强效应的研究及其应用

本文详细研究了二苯并－１８冠－６对Ｓｍ－ＴＴＡ荧光体系的增敏作用和稀土离子Ｄｙ＾３＋对Ｓｍ－ＴＴＡ－冠醚体系的荧光增强效应，在冠醚存在下，Ｓｍ－ＴＴＡ二元配合物荧光体系的荧光强度增加了２８０倍，Ｓｍ－ＴＴＡ－二苯并－１８－冠－６体系中引入适量的Ｄｙ＾３＋后，使体系的荧光强度提高２６倍，对Ｓｍ－ＴＴＡ－冠醚和Ｓｍ－Ｄｙ－ＴＴＡ－冠醚体系，Ｓｍ的浓度分别在２．０×１０＾－７～１．０×１０＾－５ｍｏｌ／     

基于荧光熄灭的硫阴离子选择性光化学敏感膜

基于Ｓ＾２－对固定于增塑的聚氯乙烯膜上的荧光素汞的荧光熄灭，研制了Ｓ＾２－选择性光化学敏感膜。该膜测定Ｓ＾２－的浓度范围为１０＾－９ｍｏｌ／Ｌ～１０＾－６ｍｏｌ／Ｌ，其荧光信号具有选择性强、重现性高且可逆的特点，适用于水相中硫化物的测定。     

簇合物膜亚硫酸根离子选择性电极的研制

报道了复ＭｏＳ６２－４在铜表面形成不溶性族合物膜的性质，研制了一种簇合物膜亚硫酸根离子选择电极。电极对ＨＳＯ＾－３的线性响应范围为１×１０＾－４－１×１０＾－１ｍｏｌ／Ｌ；检测限为８×１０＾－５ｍｏｌ／Ｌ；响应斜度为５８．５ｍＶ／ｄｅｃ；适宜的ｐＨ范围为９－１０。     

洛美沙星离子选择电极的研制及应用

用正交设计法研究了离子缔合物的种类,膜相中活性物浓度和增塑剂３个因素对电极性能的影响,以四苯硼－洛美沙星形成的缔合物为电活性物质研制了涂碳ＰＶＣ膜洛美沙星电极。其能斯特响应范围为２．０×１０＾－３－１．０×１０＾－５ｍｏｌ／Ｌ;检测限为４．０×１０＾－６ｍｏｌ／Ｌ,级差为２８．９ｍＶ／ｐＣ。     

氟哌酸离子选择电极的研制及应用

本采用正交设计法，研究了离子缔合物种类，活性物在膜相中的浓度及增塑剂三因素对电极性能的影响，研制了稳定性和重现性良好的氟哌酸石墨内导ＰＶＣ膜电极。电极的线性响应范围为１０＾－２－１０＾－５ｍｏｌ／Ｌ；检测下限可达２．５×１０＾－６ｍｏｌ／Ｌ。电极直接用于胶囊含量测定，平均回收率９９．３６％；相对标准偏差０．８５％。与药典法比较，结果基本一致。     

葡萄糖脱氢酶微型生物传感器的研制及应用

以甲苯胺兰（ＴＢ）修饰碳糊微电极为基体，将葡萄糖脱氢酶（ＧＤＨ）用丝素蛋白膜固定于修饰微电极表面制成了生物传感器，在ｐＨ７．０的ＮａＯＨ－ＮａＨ２ＰＯ４缓冲溶液中，烟酰胺腺嘌呤二核苷酸（ＮＡＤ）的浓度为１．０４×１０＾－３ｍｏｌ／Ｌ的条件下，其响应电流与葡萄糖浓度在１．０×１０＾－４～３．２×１０＾－３ｍｏｌ／Ｌ范围内有良好线性关系，响应时间为２０ｓ；检测限为４．０×１０＾－５ｍｏｌ／Ｌ。该传感器     

头孢噻肟钠的降解及其产物伏安行为的研究

头孢噻肟钠在ＮａＯＨ溶液中降解后，于０．１ｍｏｌ／ＬＮａＯＨ中得一灵敏的吸附伏安原峰，Ｅｐ＝－０．７８Ｖ（νｓＡｇ／ＡｇＣｌ），ｉｐ与头孢噻肟钠浓度在１．０×１０＾－＾９－１．０×１０＾－＾８，１．０×１０＾－＾８－１．０×１０＾－＾７，１．０×１０＾－＾７－１．０×１０＾－＾６ｍｏｌ／Ｌ范围内呈线性关系，检出限为５．０×１０＾－＾１＾０ｍｏｌ／Ｌ。用多种电化学手段研究其降解产物的伏安行为，测定了     

以双核有机锡化合物为载体的PVC膜磷酸根离子敏感电极

以双（三苄基锡）氧化物为载体制备了一种对磷酸氢根离子具有良好电位响应性能的溶剂聚合膜离子敏感电极。在ｐＨ为７．２０±０．０２的测试液中，电极的线性响应范围为５ ×１０＾－６￣１０＾－１ｍｏｌ／Ｌ，斜率为－３０．１ｍＶ／ｄｅｃ．．用分别溶液法测得其对于各种阴离子的选择性次序：ＨＰＯ４＾２－￣Ｉ＾－〉Ｂｒ＾－〉Ｃｌ＾－〉Ａｃ〉ＳＯ４＾２－。膜相中荷电离子添加实验的结果表明，电极响应系中性载体作用机制。     

含噁二唑大环冠醚的合成、 结构及金属离子识别性能

合成了含有1,3,4-噁二唑基团的大环冠醚: 2,3,11,12-二苯并-4,7,10,16-四氧-14,15-二氮杂双环[11.2.1]-十六烷-13,15-二烯(2)、 2,3,14,15-二苯并-4,7,10,13,19-五氧-17,18-二氮杂双环[14.2.1]-十九烷-16,18-二烯(3)和2,3,17,18-二苯并-4,7,10,13,16,22-六氧-20,21-二氮杂双环[17.2.1]-二十二烷-19,21-二烯(4), 并培养得到其单晶; 通过核磁共振波谱、 高分辨质谱及X射线单晶衍射对其结构进行了表征. 结果表明, 冠醚2属正交晶系, Pna2₁空间群; 冠醚3属于单斜晶系, C2/c空间群; 冠醚4属正交晶系, Pbca空间群. 在3个主体化合物中均存在分子间氢键和π-π相互作用将分子连接成三维空间结构. 采用荧光光谱测定了开链冠醚2,5-二[2-(2-甲氧乙氧基)苯基]-1,3,4-噁二唑(1)和不同环空腔大小的噁二唑冠醚(2~4)对金属离子Li ⁺, Na ⁺, K ⁺, Rb ⁺, Mg ²⁺和Ca ²⁺的键合行为. 研究结果表明, 开链冠醚1和冠醚4对碱土金属Mg ²⁺和Ca ²⁺表现出荧光猝灭行为, 且对Ca ²⁺表现出良好的键合能力和选择性; 而冠醚2对Na ⁺和K ⁺表现出良好的键合能力, 但其Na ⁺/K ⁺的选择性较差.     

冠醚共缩聚物的合成与性能

双冠醚化合物对某些金属离子比单冠醚具有更好的络合性能和选择性,它们合成、应用研究越来越受到人们的重视,本工作采用2,6-二羟甲基对甲氧基苯酚为缩合剂与芳香族冠醚缩聚,得到一系列具有双冠醚结构特征的新酚醛型聚苯并冠醚(简称聚冠醚),聚冠醚合成容易,并呈现了比相应单冠醚更优越的络合萃取能力和富集效率。     

Novel Cesium‐Selective Electrodes Based on Lipophilic 1,3‐Bisbridged Cofacial‐calix[6]crowns

Five bisbridged calix[6]crowns have been investigated as Cs⁺ ionophore in PVC membrane electrodes. As ionophores, three 1,3‐bisbridged calix[6]crown‐4‐ethers( I–III ), 1,3‐bisbridged calix[6]crown‐5‐ether( IV ), and 1,3‐bisbridged calix[6]crown‐6‐ether( V ) have been evaluated. The membranes all give good Nernstian response in the concentration range from 1×10^?7 to 1×10^?1 M of cesium ion. The best detection limits (?log aequation/tex2gif-inf-1.gif=7.08–7.36) are obtained for electrode membranes containing 1,3‐bisbridged cofacial‐calix[6]crown‐4‐ethers( I‐III ), and the values are the lowest compared with those reported previously. The highest selectivity coefficients [ 3.74(Cs/K), 2.63(Cs/Rb)] are obtained for the membrane of 1,3‐bisbridged calix[6]crown‐4‐ether( II ), and these values are also the highest compared with previous reports for Cs⁺‐ISEs. The highest selectivity towards cesium ion is attributed to the geometrically cofacial positions of two crown‐ethers in calix[6]crowns in order to provide the complex of cesium ion and eight oxygens of cofacial crowns.     

Interplay of p-sulfonatocalix[4]arene and crown ethers en route to molecular capsules and "Russian dolls"

Diffusion-ordered (1)H NMR spectroscopy techniques have been used to determine the binding strength of p-sulfonatocalix[4]arene (SO(3)[4]) towards a number of charged crown ether species in aqueous conditions. For several (doubly) charged (di)azacrown ethers, all were bound by SO(3)[4] either well or very well with binding constants between 5.1 x 10(2)-9.9 x 10(5) M(-1). These results correlate with, and thus explain the phenomenon of rapid capture of azacrown ethers in molecular capsules based on p-sulfonatocalix[4]arene and lanthanide metals. Similarly, the formation of "Russian doll" superanions in the solution phase is also elucidated. These superanions have been shown to selectively crystallise particular polynuclear aquated metal ions from mixtures in the aqueous phase. Neutral [18]crown-6 is not bound by p-sulfonatocalix[4]arene and displays a binding constant of 0 M(-1). When sodium [18]crown-6 is examined in a similar fashion, binding by SO(3)[4] is observed in solution with K(a) approximately 3.1 x 10(3) M(-1).     

Ion selectivity of crown ethers investigated by UV and IR spectroscopy in a cold ion trap

Electronic and vibrational spectra of benzo-15-crown-5 (B15C5) and benzo-18-crown-6 (B18C6) complexes with alkali metal ions, M(+)?B15C5 and M(+)?B18C6 (M = Li, Na, K, Rb, and Cs), are measured using UV photodissociation (UVPD) and IR-UV double resonance spectroscopy in a cold, 22-pole ion trap. We determine the structure of conformers with the aid of density functional theory calculations. In the Na(+)?B15C5 and K(+)?B18C6 complexes, the crown ethers open the most and hold the metal ions at the center of the ether ring, demonstrating an optimum matching in size between the cavity of the crown ethers and the metal ions. For smaller ions, the crown ethers deform the ether ring to decrease the distance and increase the interaction between the metal ions and oxygen atoms; the metal ions are completely surrounded by the ether ring. In the case of larger ions, the metal ions are too large to enter the crown cavity and are positioned on it, leaving one of its sides open for further solvation. Thermochemistry data calculated on the basis of the stable conformers of the complexes suggest that the ion selectivity of crown ethers is controlled primarily by the enthalpy change for the complex formation in solution, which depends strongly on the complex structure.     

Calixazacrown ethers for copper(II) ion-selective electrode

Five novel 1,3-alternate calix[4]azacrown ethers having 2-picolyl, 3-picolyl, and benzyl unit on the nitrogen atom were synthesized and used as ionophores for transition metal-selective polymeric membrane electrodes. The electrode based on 2-picolyl armed 1,3-alternate calix [4] azacrown ether exhibited Nernstian response toward copper (II) ion over a concentration range (10(-4.5) M-10(-2.5) M). The detection limit was determined as 10(-5) M in pH 7 and the selectivity coefficients for possible interfering cations were evaluated. Anions in the sample solution strongly affected the electrode response.     

冠醚聚合物的研究 Ⅱ.以聚硫醚为主链的硫杂冠醚聚合物的合成及其络合性能

本文报道了一种合成硫杂冠醚聚合物的新方法。以聚(2′-氯乙基-2,3-环硫丙基醚)为预聚物与二巯基化合物通过大分子反应直接环化,一步法合成了四种以聚硫醚为主链的新型硫杂冠醚聚合物(PD1-PD4)。并测定了它们对Ag~+、Au~(3+)、Pd~(2+)、Pt~(4+)、Cu~(2+)、Hg~(2+)、Zn~(2+)、Cd~(2+)、Pb~(2+)、Mg~(2+)、K~+、Ns~+等金属离子的络合性能。结果表明:它们除不络合K~+、Na~+、Mg~(2+)、Pb~(2+)外,对其它八种离子有不同程度的络合,其中对Ag~+、Au~(3+)、Pd~(2+)等贵金属离子的络合容量较高。     

多缩乙二醇二苯醚与甲醛缩聚合成酚醛型聚合物假冠醚的研究

本文采用苯酚、多缩乙二醇二氯化物、多缩乙二醇等为起始原料,合成了九个多缩乙二醇二苯醚新单体,经甲醛聚合获得一系列聚合物假冠醚,并对它们的溶解性能、络合性能以及催化作用等进行研究。     

Columnar self-assembled ureido crown ethers: an example of ion-channel organization in lipid bilayers

The self-assembly of ureido crown-ether derivatives has been examined in homogeneous solution, in the solid state, and in planar bilayer membranes. The self-assembly is driven by head-to-tail hydrogen bonding between the urea functional groups. Dimers and higher oligomers are formed in CDCl3 solution as assessed by the change in the ureido NH chemical shift as a function of concentration. Single-crystal X-ray diffraction shows that an antiparallel association of the ureas produces columnar channels composed of face-to-face crown ethers. Powder X-ray diffraction studies also show the presence of a minor phase based upon a parallel urea association leading to an alternative columnar arrangement of the crown ethers. In bilayer membranes at low concentration of ureido crown ether added, membrane disruption is observed together with rare single-channel openings, but at higher concentration, a rich array of interconverting channel conductance states is observed. The channel results are interpreted as arising from discreet stacks of ureido crown ethers where the transport of cations would occur via the macrocycles, admixed with larger pores formed by association of the crown ether headgroups around a central large pore.     

新的酚型开链冠醚及由其衍生的二苯并冠醚的合成

将水杨醛与碱和氯甲基甲基醚反应, 再经过NaBH4还原, 即制得邻(甲氧基甲氧基)苯甲醇, 然后将其在DMF中与NaH和二(或三)甘醇二对甲苯磺酸酯反应, 得开链冠醚1a和1b。1a和1b经稀酸水解, 即脱保护而分别生成新的酚型开链冠醚2a和2b。用2a与二甘醇二对甲苯磺酸酯和NaH在DMF溶液中反应, 合成顺型二苯并-20-冠-6(3); 而2a与环氧氯丙烷在NaOH水溶液中反应, 则合成了17-羟基二苯并-18-冠-5(4)。