【作者】 郭莹；

【导师】 于永丽；

【作者基本信息】 东北大学 ， 化学工程， 2020， 硕士

【摘要】 稀土配合物具有优异的光学特性,如大的Stokes位移,超长的荧光寿命及类线状的发射光谱,已经在化学检测、生物标记以及发光成像等领域中得到应用。克林沙星(CLI)是一种新型的第四代氟喹诺酮类药物,常被用于治疗动物肺部和外科感染。吡罗昔康(PX)是一种长效非甾体抗炎药,可用于治疗类风湿、风湿性关节炎和急性肌肉骨骼疾患等疾病。临床医学中,药物的不当使用会造成药物在生物体内的残留,对人体健康造成危害,因此建立灵敏准确、简便快速的CLI和PX的分析方法十分必要。时间分辨荧光法是一种基于发光物质荧光寿命的不同而进行分析的方法,与普通的荧光法相比,时间分辨荧光分析可以有效地消除背景荧光信号的干扰,因而具有更高的灵敏度和准确度,本实验采用时间分辨荧光法对CLI和PX两种药物分子进行测定。以Eu3+作为中心离子,使其与CLI结合生成二元配合物。加入荧光惰性的La3+和十二烷基苯磺酸钠(SDBS),由于La3+的共发光效应和表面活性剂的增敏效应,配合物的荧光强度增大,据此建立了测定CLI的时间分辨荧光法。对反应的实验条件进行了优化,在最佳实验条件下,当CLI浓度在5.00×10-7～1.40×10-5mol/L之间时,CLI浓度与体系荧光强度具有良好的线性关系,线性方程为ΔI=-6.79+68.04c(c的单位:/10-6 mol/L),相关系数R=0.9989,方法的检出限为6.4×10-8 mol/L。将该方法用于牛奶中CLI的测定,回收率在98.6%～109%之间。论文中对SDBS和La3+对配合物的荧光增敏机理进行了探讨。在适当的反应条件下,Eu3+与PX以及邻菲罗啉(phen)反应,生成三元配合物。以加入表面活性剂吐温-80(TW-80),Eu-PX-phen配合物的荧光强度大大增强,据此建立了时间分辨荧光法测定PX的分析方法。通过单因素试验与正交试验对配合物的反应条件进行优化,确定了最佳测定条件。当PX浓度在1.00×10-7～6.00×10-6 mol/L之间时,PX的浓度与体系的荧光强度具有良好的线性关系,线性方程为ΔI=-0.11+13.68c(c的单位:/10-7 mol/L),线性相关系数R=0.9997,方法的检出限为3.2×10-8 mol/L。用该方法测定了血清中PX的含量,回收率在95%～102%之间,结果令人满意。论文中对phen和TW-80对配合物的荧光增敏机理进行了探讨。更多还原

【Abstract】 Rare earth complexes have excellent optical properties,such as large Stokes shift,long fluorescence lifetime and linear emission spectrum,which have been used in chemical detection,biomarking and luminescence imaging.Clinaofloxacin(CLI)is one of the fourth generation of fluoroquinolones,which is often used to treat lung and surgical infection in animals.Piroxicam(PX)is a long-acting non-steroidal anti-inflammatory drug that can be used to treat diseases such as rheumatoid arthritis,rheumatoid arthritis and acute musculoskeletal disorders.In clinical medicine,the improper use of drugs can cause the residues of drugs in the body,which is harmful to human health.Therefore,it is necessary to establish a sensitive,accurate,simple and rapid analysis method of CLI and PX.Time-resolved fluorescence is an analytical method based on the different fluorescence lifetimes of luminescent materials,compared with common fluorescence methods,time-resolved fluorescence analysis can effectively eliminate the interference of background fluorescent signals,thus providing higher sensitivity and accuracy.This experiment established a time-resolved fluorescence analysis method for the determination of two drug molecules,CLI and PX.Using Eu3+ as a central ion,it combines with the CLI to form a binary complex.Fluorescence-inert La3+ and sodium dodecylbenzenesulfonate(SDBS)were added.Due to the co-luminescence effect of La3+ and the sensitizing effect of the surfactant,the fluorescence intensity of the complex increases,and a time-resolved fluorescence method for determining CLI is established accordingly.According to the co-luminescence effect of La3+ and the sensitizing effect of the surfactant,the fluorescence intensity of the complex is increased to establish a time-resolved fluorescence method for determining CLI.The experimental conditions of the reaction were optimized.Under the optimal experimental conditions,when the CLI concentration was between 5.00×10-7～1.40×10-5 mol/L,the CLI concentration had a good linear relationship with the fluorescence intensity of the system.The linear equation isΔI=-6.79+68.04c(×10-6 mol/L),the correlation coefficient is R=0.9989,and the detection limit of the method is 6.4×10-8 mol/L.The method was applied to the determination of CLI in milk,and the recovery rate was between 98.6%and 109%.The mechanism of fluorescence sensitization of SDBS and La3+ complexes was discussed in the paper.Under the appropriate reaction conditions,Eu3+reacts with PX and phenanthroline(phen)to form a ternary complex.With the addition of the surfactant Tween-80(TW-80),the fluorescence intensity of the Eu-PX-phen complex was greatly enhanced,and a time-resolved fluorescence method for the determination of PX was established.The optimum measurement conditions were determined by optimizing the reaction conditions of the complex by a single factor test and an orthogonal test.When the PX concentration is between 1.00×10-7～6.00×10-6 mol/L,the concentration of PX has a good linear relationship with the fluorescence intensity of the system.The linear equation is ΔI=-0.11+13.68c(×10-7 mol/L),linear correlation coefficient R=0.9997,the detection limit of the method is 3.2×10-8 mol/L.The content of PX in serum was determined by this method,and the recovery rate was between 95%and 102%.The results were satisfactory.The mechanism of fluorescence sensitization of phen and TW-80 complexes was discussed in the paper.更多还原