摘要
以4-二乙氨基水杨醛和丙二酸二乙酯为原料,通过Knoevenagel缩合关环(中间体Ⅰ)、水解脱羧(中间体Ⅱ)、Vilsmeier反应(中间体Ⅲ)、亲核加成反应,合成了目标化合物7-二乙氨基-3-甲酰基香豆素(2′-噻吩甲酰)腙(L),通过核磁共振谱(^(1)HNMR、^(13)CNMR)进行结构表征。在研究其紫外光谱、荧光光谱和聚集诱导发光基础上,探索了其离子识别应用。结果表明:在四氢呋喃溶液中,探针L对Cu^(2+)呈选择性荧光淬灭识别,而对Zn^(2+)呈比率型荧光识别,具有精准的离子识别能力和较好的检测灵敏度,受到其他离子的干扰较小,并且反应前后伴有明显的颜色变化(在365 nm紫外灯照射下,加入铜离子后,荧光淬灭;加入锌离子后,由绿色变为黄色)。Job′s曲线显示,探针L与Cu^(2+)、Zn^(2+)的物质的量之比为1∶1和2∶1,缔合常数K b分别为5.18×10^(5)、1.51×10^(6) L/mol,检出限分别为5.52×10^(-7)、1.13×10^(-6) mol/L,均低于世界卫生组织对饮用水中Cu^(2+)和Zn^(2+)所允许的最高浓度。实验结果表明,该荧光探针在环境监测领域具有潜在应用价值,有望用于食品和水环境中Cu^(2+)和Zn^(2+)的检测。
Target compound 7-diethylamino-3-formylcoumarin(2′-thienoyl)hydrazone(L)was synthesized from 4-diethylaminosalicylaldehyde and diethyl malonate through Knoevenagel condensation cyclization(intermediateⅠ),hydrolytic decarboxylation(intermediateⅡ),Vilsmeier reaction(intermediateⅢ),and nucleophilic addition reaction.The structure was characterized by nuclear magnetic resonance spectroscopy(^(1)HNMR,^(13)CNMR).Based on the study of its UV spectrum,fluorescence spectrum,and aggregation induced emission(AIE),its ion recognition applications were explored.The results showed that in tetrahydrofuran solution,probe L selectively quenched fluorescence for Cu^(2+) and displayed a ratio type fluorescence recognition for Zn^(2+),demonstrating precise ion recognition ability and good detection sensitivity.It was less affected by interference from other ions,with significant color changes before and after the reaction(fluorescence quenching occurred upon adding copper ions under 365 nm UV light;the color changed from green to yellow upon adding zinc ions).The Job′s curve showed that the stoichiometric ratios of probe L to Cu^(2+) and Zn^(2+) were 1∶1 and 2∶1,respectively,with binding constants K_(b) of 5.18×10^(5) and 1.51×10^(6) L/mol.The detection limits were 5.52×10^(-7) and 1.13×10^(-6) mol/L,respectively,which are both lower than the maximum allowable concentrations of Cu^(2+) and Zn^(2+) in drinking water as per the World Health Organization.The experimental results indicate that the fluorescent probe has potential application in environmental monitoring and is expected to be used for the detection of Cu^(2+) and Zn^(2+) in food and water environments.
作者
刘杰
田文慧
朱雪宇
李慧
李子康
刘喜
张凤祥
LIU Jie;TIAN Wen-hui;ZHU Xue-yu;LI Hui;LI Zi-kang;LIU Xi;ZHANG Feng-xiang(School of Chemistry and Materials Engineering,Fuyang Normal University,Fuyang 236037,China)
出处
《化学试剂》
2025年第8期23-31,共9页
Chemical Reagents
基金
教育部产学合作协同育人项目(231006655114826)
省教育厅重点项目(2024AH051450)
省工程研究中心重点项目(FYKFKT24093)
国家级大学生创新创业项目(202410371011)
省级大学生创新创业项目(S202410371081、S202310371096、S202310371109)
校级科研资助项目(XSXM24-064)。
关键词
席夫碱
聚集诱导发光
光学性质
比率型荧光探针
铜离子和锌离子识别
schiff base
aggregation induced emission
optical properties
ratiometric fluorescent probe
identification of copper and zinc ions
