摘要
有机磷化学武器的使用以及有机磷农药滥用给社会安全以及人类健康造成了极大危害.因此,发展能够高效检测有机磷化合物的方法对于防范和治理有机磷化合物污染至关重要.本工作中合成了以1,4,7-三氮杂环壬烷衍生物为配体的Tb(III)配合物——TbL^(3+),该配合物的分子结构中不含芳环结构,故其发光效率很低.当有机磷化合物杀螟腈和TbL^(3+)络合后,由于杀螟腈的T1能级与Tb(III)的5D4能级高度匹配,前者作为能量给体可大幅敏化TbL^(3+)的荧光,且最大敏化效率为I/I0=55,对杀螟腈的检出限可达59 nmol/L.高分辨质谱、荧光滴定实验和荧光寿命测试表明,TbL^(3+)可络合2个杀螟腈分子和1个甲醇分子.丙溴磷、毒死蜱、乐果、二嗪农、辛硫磷、倍硫磷、甲基对硫磷和敌敌畏8种有机磷化合物几乎不对TbL^(3+)的荧光产生影响,据此实现了对有机磷化合物杀螟腈的特异传感识别.
The abuse of organophosphate pesticides and chemical-warfare agents has made severe effects on human and animal health. Consequently, it is vital to develop sensitive and selective strategies for the detection of organophosphates. In this work, the Tb（Ⅲ） complex--TbL3＋, consisting of a 1,4,7-triazacyclononane derivative as ligand was synthesized. As TbLa＋ contains no aromatic groups （function as an antenna）, its intrinsic luminescence is thus minimized. The coordination of cyanophos to TbLa3＋ could largely sensitize its luminescence （I/I0=55）because the energy of the triplet state of benzene is slightly higher in energy than the 5D4 of Tb（Ⅲ）. The detection limit for cyanophos was determined as 59 nmol/L. High resolution mass spectrum measurements, luminescence titration experiment and luminescence lifetime measurements reveal that TbLa~ is bound with two cyanophos molecules and one methanol molecule. However, other organophosphates such as profenofos, chlopyrifos, dimethoate, diazinon, phoxim, fenthion, methyl parathion and dichlorvos almost did not induce any changes on luminescence intensity under the same conditions. By this work, we prepared a new luminescence probe for cyanophos with good selectivity and sensitivity.
作者
全静苗
雷海瑞
刘峰毅
严军林
刘静
房喻
Jingmiao Quan＊ Hairui Lei Fengyi Liu Junlin Yan Jing Liu Yu Fang(Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry ＆ Chemical Engineering, Shaanxi Normal University, Xi＇an 710119, China)
出处
《中国科学：化学》
CAS
CSCD
北大核心
2017年第7期876-881,共6页
SCIENTIA SINICA Chimica
基金
国家自然科学基金(编号:21273143
21573141)
教育部新世纪优秀人才支持计划(编号:NCET-13-0887)
全国优秀博士学位论文作者专项资金(编号:201223)资助项目
