接力识别Al^(3+)及F^(-)的偶氮类荧光探针合成与应用  

Synthesis and application of azo-based fluorescent probe for sequential recognition of Al^(3+)and F^(-)

作　　者：刘其业 喻艳超 荆军凯 由君[1] 武文菊 LIU Qiye;YU Yanchao;JING Junkai;YOU Jun;WU Wenju(Key Laboratory of Green Chemical Engineering and Technology of College of Heilongjiang Province,College of Materials Science and Chemical Engineering,Harbin University of Science and Technology,Harbin 150080,Heilongjiang,China)

机构地区：[1]哈尔滨理工大学材料科学与化学工程学院绿色化工技术黑龙江省高校重点实验室,黑龙江哈尔滨150080

出　　处：《精细化工》2024年第10期2164-2170,共7页Fine Chemicals

基　　金：黑龙江省自然科学基金项目(LH2021H001)。

摘　　要：以6-氨基间甲酚和1-萘酚为原料,合成了2-(2-羟基-4-甲基苯偶氮)-1-萘酚(探针NA-M),通过^(1)HNMR、^(13)CNMR、FTIR、HRMS表征了其结构。测试了探针NA-M对Al^(3+)的选择性识别性能及其与Al^(3+)形成的络合物(NA-M+Al^(3+))对F^(-)的选择性识别性能,推测了探针NA-M与Al^(3+)和F^(-)间的作用机制。考察了探针NA-M在实际样品中的应用。结果表明,在pH=7.4、V(甲醇)∶V(N-2-羟乙基哌嗪-N'-2-乙磺酸)=9∶1的溶剂中,探针NA-M与Al^(3+)在590 nm处发生显著的荧光增强作用,并对Al^(3+)的识别表现出高选择性、抗金属离子干扰性和良好的灵敏度(检测限为8.4×10^(-7)mol/L),Al^(3+)与探针NA-M形成了配位比为1∶2的NA-M+Al^(3+);NA-M+Al^(3+)在F^(-)加入后发生显著的荧光猝灭现象,F^(-)可以捕获NA-M+Al^(3+)中的Al^(3+),从而引起荧光变化。NA-M+Al^(3+)对F^(-)的识别也显示出高选择性和良好的抗其他阴离子干扰能力和灵敏度(检测限为9.5×10^(-7)mol/L);在体系pH为5~10时,探针NA-M识别Al^(3+)及F^(-)表现出良好的效果,交替加入Al^(3+)和F^(-)可引起其荧光强度的可逆变化,探针NA-M可以通过荧光信号的“关-开-关”转变,用于接力识别Al^(3+)和F^(-)。在实际样品的检测中,Al^(3+)的回收率在98.8%~107.0%之间,相对标准偏差(RSD)为2.6%~4.3%;F^(-)的回收率为97.8%~101.4%,RSD为1.4%~2.3%。2-(2-Hydroxy-4-methylbenzene-azo)-1-naphthol,fluorescent probe(NA-M),was synthesized from 6-amino-m-cresol and 1-naphthol,and characterized by ^(1)HNMR,^(13)CNMR,FTIR,HRMS.The selective recognition of Al^(3+)by the probe NA-M and of F^(-)by the complex formed with Al^(3+)(NA-M+Al^(3+))were analyzed,with the interaction mechanism between the probe NA-M and Al^(3+)and F^(-)speculated.The application of probe NA-M in practical samples was further evaluated.The results showed that in V(methanol)∶V(N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid)=9∶1 solvent with pH=7.4,the fluorescence of the probe NA-M and Al^(3+)was significantly enhanced at 590 nm.The probe exhibited Al^(3+)detection limit of 8.4×10^(-7)mol/L with high selectivity,resistance to metal ion interference and good sensitivity.Furthermore,Al^(3+)and probe NA-M formed NA-M+Al^(3+)with a coordination ratio of 1∶2,which displayed a significant fluorescence quenching phenomenon after addition of F^(-),which was attributed to the capture of Al^(3+)in NA-M+Al^(3+)by F^(-)resulting in fluorescence changes.NA-M+Al^(3+)demonstrated outstanding selectivity and anti-interference capability towards F–by quenching the fluorescence,with a detection limit for F^(-)of 9.5×10^(-7)mol/L.When the pH of the system was 5~10,the probe NA-M exhibited a good effect in recognizing Al^(3+)and F^(-).The addition of Al^(3+)and F^(-)alternately could cause a reversible change in the fluorescence intensity.The probe NA-M could be used for sequential recognition of Al^(3+)and F^(-)through the"off-on-off"transformation of the fluorescent signal.In actual samples,the recoveries of Al^(3+)ranged from 98.8%to 107.0%with relative standard deviations(RSD)of 2.6%~4.3%,while those of F^(-)ranged from 97.8%to 101.4%with RSD of 1.4%~2.3%.

关 键 词：偶氮 荧光探针 Al^(3+) F^(-) 接力识别 功能材料 

分 类 号：TQ422[化学工程] O657.3[理学—分析化学]