【作者】 李仁军；

【导师】 冯锋；

【作者基本信息】 南昌大学 ， 分析化学， 2008， 硕士

【摘要】 室温磷光法（Room Temperature phosphorescence，RTP）是一种微量技术与痕量分析相结合的测试手段，具有灵敏度高、分析曲线线性范围宽、检出限低、选择性好等特点，而且操作简便快速，投资少，适用于常规痕量分析。液滴光化学传感器是光化学传感器研究领域中的一个新兴领域，这类光化学传感器是将小液滴的独特物理性能融入到光化学传感探头的设计思想中，构建可更新的光池、无光窗污染的具有自聚焦功能的新型液滴光化学传感器，因而避免了德统的光化学测量试剂和样品对比色池的污染以及因反应池池壁对光的吸收、散射或过程中产生的吸附物质等所引起的对测量信号的干扰，可提高传感器检测的灵敏度和准确性。本论文旨在将动态液滴光化学传感技术应用于室温磷光测量体系中，利用液滴作为无光窗光池进行室温磷光测量，研制了以可更新动态液滴光化学技术为基础的磷光化学传感器，拓展了液滴光化学传感技术的应用领域和范围。本文具体内容如下：利用以LS55型荧光／磷光／发光光度计为基础的液滴磷光化学传感装置，对流体室温磷光体系下的多种物质如邻菲罗啉、Fe³⁺、苏丹Ⅲ等进行检测；1．溴代菲-脱氧胆酸钠体系能在非除氧条件下产生出强室温磷光，邻菲罗啉可显著猝灭此体系的室温磷光。利用自制的可更新液滴磷光化学传感装置，实施检测邻菲罗啉的含量。在优化条件下，体系的相对磷光强度与邻菲罗啉的浓度在4．0×10^-7 mol·L^-1～4．0×10^-5 mol·L^-1范围内呈良好的线性关系，线性回归方程为：I₀／I-1=53086C+0．017（R=0．997），检出限为0．031μg／mL。将该法用于样品中微量邻菲罗啉的测定，结果满意。2．在非除氧和常温条件下，环糊精能诱导卤代菲（XP）发射较强的室温磷光。金属离子选择实验结臬表明，Fe³⁺能选择性猝灭卤代菲的磷光发射，利用可更新动态液滴技术对体系的磷光强度变化进行了测定，实验结果显示：优化条件下，氯代菲．环糊精体系中，Fe³⁺在4．0×10^-7mol·L^-1～6．0×10^-4mol·L^-1的浓度范围内呈良好的线性关系，线性回归方程为I₀／I-1=0：027+0．67×10⁴C。在溴代菲-环糊精体系中，在4．0×10^-7mol·L^-1～6．0×10^-4 mol·L^-1的浓度范围内，Fe³⁺浓度和体系的磷光强度呈良好的线性关系，线性回归方程为I₀/I-1=0．39+1．34×10⁴C。在碘代菲-环糊精体系中，Fe³⁺浓度在1．0×10^-6 mol·L^-1～1．0×10^-4mol·L^-1的浓度范围内呈良好的线性关系，线性回归方程为I₀／I-1=0．42+1．47×10⁴C。将该液滴磷光传感器用于实际样品中Fe³⁺含量的检测，结果满意。3．在室温下，利用微量的苏丹Ⅲ能显著猝灭溴代菲（BrP）在β-环糊精体系中的的室温磷光发射（RTP），而苏丹其它系列无影响的现象，使用液滴磷光传感技术对体系磷光强度进行测量，并对实验条件进行了优化，建立了可更新动态液滴磷光传感技术测量微量苏丹Ⅲ的方法。实验结果显示苏丹Ⅲ的浓度在2．0×10^-7mol／L至6．0×10^-5mol/L的范围内，苏丹Ⅲ的浓度与体系的Stern-Volmer猝灭曲线呈现良好的线性关系，线性相关系数为0．998，苏丹Ⅲ的检出限为0．1μg/mL。并对实际样品进行检测，结果良好。更多还原

【Abstract】 The Room Temperature phosphorescence is a analyze method with wide linear range and higher precision, lower limit of detection, higher selection. The method is operated much fast, more simply and fewer investment for general analyze.As a new focus in the field of optical chemical sensors, The original idea of liquid-drop chemical optrode is constructive in exploiting some unique features of liquid drop, namely, reproducibility, renewability, the lack of containment wall and lens like optical cell. The infection of optical signal caused by the absorption and scattering of cell surface or the contaminations of reagents and samples to cells in conventional photometric analysis can be avoided. The unique features of a liquid drop can be characterized in its reproducibility, renewability, defined volume, and lack of containment walls. The features individually or in combination, may result in high sensitivity and accuracy for analyses.In this paper, the technique of droplet optical chemical sensor has been applied in room temperature phosphorescence. A novel method of drop-based analysis, which regarding LS55 luminescence spectrometers as its experiment window, has been developed, many new phosphorescence chemical sensors combined with flow-injection analysis and the technique of dynamical drop-based sensing are developed. The apply domain and area of droplet optical chemical sensor has been extended.The contents of this thesis include as following:1. A room temperature phosphorescence based on renewable optical chemical biosensor combined with flow injection technique has been developed for the determination of o-phenanthroline.The RTP of 9-bromophenanthrene can be induced by sodium deoxycholate （NaDC） in the presence of oxygen, but it is obviously quenched by trace o-phenanthroline. A method of flow injection renewable drop （FIRD） phosphorescence for monitoring o-phenanthroline was established. The experimental conditions was investigated and discussed. Under the optimum conditions, the linear range was 4.0×10^-7 mol·L^-1to 4.0×10^-5mol·L^-1, and the limit of detection was 0.031μg/mL. This method has been applied to the determination of o-phenanthroline with satisfactory results.2. Iron ion can quench 9-chlorophenanthrene, 9-bromophenanthrene, 9-Iodophenanthrene RTP of reducing byβ-CD. Based on this reaction, the content of iron ion was determined utilizing renewable droplet optical- chemical phosphorescence sensor. Under the optimum conditions, the sensor shows linear response in the range from 4.0×10^-7 mol·L^-1-6.0×10^-4 mol·L^-1 in 9-chlorophenanthrene solution. The regression equation is I₀/I-1=0.027+0.67×10⁴C. The sensor shows linear response in the range from 4.0×10^-7 mol·L^-1-6.0×10^-4 mol·L^-1 in 9-bromophenanthrene solution. The regression equation is I₀/I-1= I₀/I-1=0.39+1.34×10⁴C. The sensor shows linear response in the range from 1.0×10^-6 mol·L^-1-1.0×10^-4mol·L^-1 in 9-iorophenanthrene solution. The regression equation is I₀/I-1 =0.42+1.47×10⁴C. This method has been applied to the determination of Fe³⁺ with satisfactory results. Thetechnique provides a simple, effective and sensitive method to assay the Fe³⁺.3. The room temperature phosphorescence （RTP） of 9-bromophenanthrene （BrP） can beinduced byβ-cyclodextrin （β-CD） and micro cyclohexane （CH） in the presence of oxygen, but it is quenched obviously by trace SudanⅢ. A novel optical phosphorescence chemical sensor based on the flow injection renewable drop was established for monitoring SudanⅢ. The experimental conditions were investigated. Under the optimum conditions, the linear range of was SudanⅢ2.0×10^-7mol/L to 6.0×10^-5 mol/L, and the limit of detection was 0.1μg/ml. This method has been applied to the determination of SudanⅢwith satisfactory results. The technique provides a simple, effective and sensitive method to assay the SudanⅢ.更多还原