1,3-交替香豆素-硫杂杯[4]荧光探针对Fe^3＋和牛血红蛋白的光谱识别  

The Thiacalix[4]arene-Coumarin Fluorescence Probe Recognition for Fe^(3+) and Bovine Hemoglobin

作　　者：李燕琴[1] 牟兰[1] 曾晞[1] 李俊[1] 大和武彦 

机构地区：[1]贵州省大环化学及超分子化学实验室,贵州大学化学与化工学院,贵州贵阳550025 [2]Department of Applied Chemistry, Faculty of Science and Engineering, Saga University, Honjo-machi 1, Saga 840-8502, Japan

出　　处：《光谱学与光谱分析》2015年第11期3111-3116,共6页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(21165006);教育部“春晖计划”项目(Z2011033,Z2012053);贵州省国际合作项目(20137002)资助

摘　　要：以1,3-交替二乙酯硫杂杯[4]芳烃和7-羟基香豆素为原料,分步取代杯芳烃下沿,合成得到1,3-交替香豆素-硫杂杯[4]芳烃荧光探针1。在DMSO/H2O(φ,3/7,pH 7)溶液中,探针1发射的强荧光被Fe3+选择性猝灭;Fe3+使探针1的紫外吸收显著增强。相同条件下其他常见金属离子的加入对探针1的荧光及吸收光谱无影响,探针在水溶液介质中仅对Fe3+高选择性识别,荧光和吸收光谱法的检测限均达10-8 mol·L-1。光谱滴定、等温滴定量热及质谱法均测出探针1与Fe3+形成1∶1配合物,作用常数达105 L·mol-1。从摩尔结合自由能和结合熵分别表明配合作用为自发过程。同时,在DMSO/H2O(φ,1/9,Tris-HCl,pH7,0.1mol·L-1 NaCl)介质中,探针1能选择性猝灭识别牛血红蛋白(BHb),线性范围在0.2~3.0μg·mL-1,检测限达0.12μg·mL-1。为一种选择性识别Fe3+和BHb的杯芳烃荧光探针。1,3-alternate coumarin substituted thiacalix[4]arene fluorescent probe 1 was synthesised from 1,3-alternate diethyl thiacalix[4]arene and 7-hydroxycoumarin by-step reactions.In DMSO/H2O（φ,3/7,pH 7）solution,the strong fluorescence emission and UV absorption of probe 1 can be selectively quenched or significantly enhanced by Fe3＋ion.The probe 1 showed high Fe3＋selective fluorescence quenching or absorption enhancement over commonly coexistent metal ions in neutral aqueous media,and the limit of detections were obtained as low as 10-8 mol·L-1 of Fe3＋by fluorescence and absorption spectrometry.Spectral titration,isothermal titration calorimetry and mass spectrometry were showed that probe and Fe3＋form 1∶1complexes,the constant up to 105 L·mol-1 and coordinate process was spontaneous by the mole binding free energy and entropy of probe with Fe3＋.In addition,the probe can identification bovine hemoglobin（BHb）over other proteins through quenched its fluorescence in DMSO/H2O（φ,1/9,Tris-HCl,pH 7,0.1mol·L-1 NaCl）media.The limit of detection was obtained as 0.12μg·mL-1 of BHb,as well as a linearity of 0.2~3.0μg·mL-1,indicating the probe of high sensitivity and quantitation range.It can be used as a selective recognition Fe3＋and BHb of thiacalix[4]arene fluorescent probe.

关 键 词：香豆素 1 芳烃 FE3+ 牛血红蛋白 

分 类 号：O657[理学—分析化学]