Fundamental Study on Development of Anion Adsorbent of Anti-Hofmeister Type

抗霍夫迈斯特型阴离子吸附剂研制的基础研究

基本信息

批准号：
03650607
负责人：
JYO Akinori
金额：
$ 1.15万
依托单位：
KUMAMOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

项目摘要

Adsorbents for anions with anti-Hofmeister anion-selectivity sequences were developed based on cobalt(III) complex of the dioxocyclam (1,4,8,11-tetraazacyclotetradecane-5,7-dione) moiety. Significant results of this work can be summarized as follows:(1) The cobalt(III) complex of dioxocyclam moiety selectively recognizes nitrite or thiocyanate in the presence of excess nitrate or perchlorate in weakly acidic aqueous solutions.(2) The cobalt(III) complex of alkylated dioxocyclam (6-octadecyl-1,4,8,11-tetraazacyclotetradecane-5,7-dione) in chloroform extracts thiocyanate in preference to perchlorate from weakly acidic solutions, indicating an anti-Hofmeister anion selectivity.(3) The hydrophobic cobalt(III) complex adsorbed on Amberlite XAD-7 also shows the anti-Hofmeister anion selectivity; the Amberlite XAD-7 modified with the complex mentioned above (2) takes up nitrite in the presence of nitrate in large excess. However, this approach is not promising, since the loading of the complex larger than ca. 0.3 mmol/g is difficult to achieve.(4) The chelating resin (RGD), which was obtained by the reaction of dioxocyclam with macroreticular glycidyl methacrylate-divinylbenzene copolymer beads, adsorbs cobalt(III) up to 0.6 - 0.7 mmol/g. The cobalt(III) loaded RGD acts as an anion-exchanger with the anti-Hofmeister anion selectivity. For example, this newly developed anion-adsorbent takes up thiocyanate under conditions that molar ratio of thiocyanate to perchlorate is 1:10, while a conventional anion exchange resin adsorbs little thiocyanate under the same conditions. The adsorbed anions were easily and rapidly eluted with aqueous alkaline solutions, and columnar approach has clarified that repeated use of the adsorbent is also possible.

基于二氧化碳（III）复合物的二氧化碳（1,4,4,8,11-tetraazacyCloteTrateTradecane-5,7-7-二酮）部分的钴（III）复合物，开发了具有抗Hofmeister阴离子选择性序列的阴离子的吸附剂。这项工作的重大结果可以概括如下：（1）在弱酸性水溶液中存在过量的硝酸盐或高氯酸盐的情况下，二氧化碳囊肿部分的钴（III）复合物选择性地识别亚硝酸盐或硫氰酸盐。（6-二十烷基-1,4,4,8,11-tetraazacyCloteTradecane-5,7-二酮）在氯仿提取物中提取硫氰酸硫氰酸硫氰酸硫氰酸酯，而不是弱酸性溶液中的多氯酸盐，表明抗hofmementer andion的选择性。阴离子的选择性；在大量过量的硝酸盐存在下，在上面提到的复合物（2）中修饰的琥珀酸盐XAD-7会占用亚硝酸盐。但是，这种方法并不是有希望的，因为复合物的负载大于Ca。（4）螯合树脂（RGD）是通过二氧化碳与大甲基乙二醇甲基丙烯酸二烯基苯基苯基共聚物珠的反应而获得的，螯合树脂（RGD）是通过反应，adsorbs钴（III），最高0.6--0.7 -0.7 mmol/g。钴（III）加载的RGD充当具有抗Hofmeister阴离子选择性的阴离子交换器。例如，这种新开发的阴离子吸附剂在硫氰酸酯与高氯酸盐的摩尔比为1:10的条件下会占据硫氰酸酯，而常规的阴离子交换树脂在相同的条件下却很小的硫氰酸酯。吸附的阴离子很容易迅速用碱性溶液洗脱，并且柱状方法澄清说，反复使用吸附剂也是可能的。