Development of Anion Receptors Utilizing Hydrophobic Space Formed by Dendrimer Structures

利用树枝状聚合物结构形成的疏水空间开发阴离子受体

基本信息

批准号：
14550825
负责人：
TOBE Yoshito
金额：
$ 2.24万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2003
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14550825/
关键词：
Dendrimers Receptors Anions Ion-selective Electrodes Hydrogen Bonds Hydrophobic Interactions 疏水相互作用

项目摘要

There have been strong demands from the fields of environmental and clinical analyses to analyze conveniently trace anions dissolved in aqueous media. In this respect, we designed molecules having hydrophobic space formed by the benzyl type dendrimer structure, which may capable of binding anions at the water-membrane interface, producing sufficient electrical response as ion-selective electrodes. From the same points of view, preparation of highly dense dendrimers of phenylacetylene type, which may be used as fluorescence sensors for anions, was also carried out.The benzylic dentrimers of 1st to 4th generations having a thiourea binding site wee prepared. By the NMR dilution experiments, it was clarified that their aggregation in nonpolar solvents was not significant enough to disturb binding with anions. On the basis of the titration experiments with dihydrogenphosphate anion using UV-vis spectroscopy, the binding constants in chloroform were determined to be in the order of 10^3 M^<-1> and the values were not much dependent on the generation. Though none of the dentrimers responded toward dihydrogenphosphate anion as ion-selective electrodes using a PVC membrane containing them, they exhibited sufficient response toward hydrogensulfate anion, which is also known to be strongly hydrated.Dense phenylacetylene type dendrimers of 2nd generation was successfully prepared by using the protocol developed in our laboratory. The fluorescence efficiency of the dendrimer was slightly reduced compared with the 1st generation hexaethynylbenzene. Since the preparation of a dendron unit was also developed, the stage is set for preparation of larger dendrimers of this type.

环境和临床分析领域强烈要求能够方便地分析溶解在水介质中的痕量阴离子。在这方面，我们设计了具有由苄基型树枝状聚合物结构形成的疏水空间的分子，其能够在水膜界面处结合阴离子，产生作为离子选择性电极的足够的电响应。从相同的观点出发，还进行了可用作阴离子荧光传感器的高密度苯乙炔型树枝状聚合物的制备。制备了具有硫脲结合位点的第一代至第四代苯甲基树枝状聚合物。通过核磁共振稀释实验，表明它们在非极性溶剂中的聚集不足以干扰与阴离子的结合。基于使用UV-vis光谱法用磷酸二氢阴离子进行的滴定实验，确定氯仿中的结合常数为10 ^ 3 M ^ -1 量级，并且该值不太依赖于代数。虽然使用含有它们的 PVC 膜作为离子选择性电极时，没有一种树枝状聚合物对磷酸二氢阴离子有响应，但它们对硫酸氢根阴离子表现出足够的响应，而硫酸氢根阴离子也被认为是强水合的。第二代致密苯乙炔型树枝状聚合物成功地制备我们实验室开发的协议。与第一代六乙炔基苯相比，树枝状聚合物的荧光效率略有降低。由于还开发了树枝状单元的制备方法，因此为制备此类更大的树枝状聚合物奠定了基础。