基于分子内电荷转移的新型Cr(Ⅲ)比率荧光探针  

A Novel Ratio Fluorescent Probe for Cr(Ⅲ)Based on Intramolecular Charge Transfer

作　　者：冯宁坤 双少敏 董川 宋胜梅 FENG Ningkun;SHUANG Shaomin;DONG Chuan;SONG Shengmei(College of Chemistry and Chemical Engineering,Institute of Environmental Science,Shanxi University,Taiyuan 030006,China)

机构地区：[1]山西大学环境科学研究所,化学化工学院,山西太原030006

出　　处：《山西大学学报（自然科学版）》2023年第4期879-887,共9页Journal of Shanxi University(Natural Science Edition)

基　　金：国家自然科学基金(21575084);山西省应用基础研究基金(201901D111038)。

摘　　要：三价铬(Cr^(3+))不仅会造成环境污染,还会在人体摄入Cr^(3+)过多或不足时导致多种疾病。因此,Cr^(3+)含量的测定是必要的。文章通过1,2-二氨基蒽醌与N-乙基咔唑-3-甲醛缩合反应合成了荧光探针1-氨基-2-(N-乙基咔唑-3-亚甲基氨基)-蒽醌(R)。R对Cr^(3+)具有良好的选择性和抗干扰能力,并利用HRMS和Job’s plot方法讨论了合理的反应机理。探针R的荧光通过Cr^(3+)与R之间分子内电荷转移(ICT)的静态猝灭方法猝灭,R的比荧光强度(F_(452 nm)/F_(600 nm))与Cr^(3+)浓度的关系符合Perrin方程。此外,新的分析方法显示出低检测限(2 nmol·L^(-1))、宽定量范围(14μmol·L^(-1)~288μmol·L^(-1))和大结合常数(9.688×10^(6)L/mol)。最后,使用探针R测定自来水中的Cr^(3+)。计算实际样品的加标回收率为99.5%~101.7%。因此所建立的分析方法在环境、食品、药品等中Cr^(3+)的测定中具有潜在的应用价值。Trivalent chromium(Cr^(3+))is not only an environmental pollutant,but also an important ion for human health that excessive or insufficient intake of Cr^(3+)could cause a variety of human diseases.Therefore,it is necessary to determine the Cr^(3+)content.In this study,the fluorescent probe 1-amino-2-(N-ethylcarbazole-3-methyleneamino)-anthraquinone(R)was synthesized by the condensation between 1,2-diaminoanthraquinone and N-ethylcarbazole-3-carbaldehyde.The R has good selectivity and anti-interference ability in probing Cr^(3+).The rational reaction mechanism was discussed by HRMS and Job's plot.The fluorescence of R was quenched by the static quenching method of intramolecular charge transfer(ICT)between Cr^(3+)and R,and the relationship of the fluorescence intensity(F_(452 nm)/F_(600 nm))of R and the concentration of Cr^(3+)conforms to the Perrin equation.Moreover,the novel analytical method showed a low detection limit(2μmol·L^(-1)),wide quantification range(14-288μmol·L^(-1))and large binding constant(9.688×10^(6) L/mol).Finally,the probe R was applied to determine Cr^(3+)in the tap water and lake water.And the spike recovery for the actual samples is excellent to be 99.5%-101.7%.Thus,the analytical method established has potential applications in the measurement of Cr^(3+)in the environment,food and drugs and so on.

关 键 词：Perrin方程 席夫碱 结合常数 Cr(Ⅲ) 

分 类 号：O657.33[理学—分析化学]