固体基质室温磷光新基质的研究与应用

【作者】 徐文婷；

【导师】 朱若华；

【作者基本信息】 首都师范大学 ， 化学， 2008， 硕士

【摘要】 固体基质室温磷光分析法(SS-RTP)具有灵敏度高、线性范围宽、选择性好、操作简便快速、投资少等特点,近年来在生命科学、环境科学、医学临床、法检、工业卫生和能源等领域应用广泛,特别是对环境中农药残余、多环芳烃、氮杂环类污染物的检测以及药物分析表现出明显优势。本文主要从新型固体基质材料的制备和同步扫描技术在室温磷光分析中的应用两个方面,对固体基质室温磷光分析方法进行了研究:第一章综述了固体基质室温磷光分析方法的原理,应用和展望。详述了室温磷光的发光机理,影响因素,环糊精在室温磷光分析中的应用,以及固相萃取技术和同步扫描技术与固体基质室温磷光方法的联用和发展前景。第二章研究并建立了Pullulan膜的合成方法。优化了合成条件(包括合成方法,β-环糊精和2-溴乙醇的用量,超声振荡时间和干燥条件等),考察了15种有机物质在Pullulan膜上的室温磷光(RTP)行为,结果表明含有β-环糊精和2-溴乙醇的Pullulan膜能选择性地增强一些多环芳烃和含氮杂环类物质的室温磷光强度,大大提高它们检测的灵敏度。第三章研究并建立了β-环糊精修饰有机聚合整体材料的合成方法,并将其用作固相萃取-固体基质室温磷光分析方法(SPE-SS-RTP)的固体基质。考察了β-环糊精修饰有机聚合整体材料的合成方法,物理性质,化学性质以及14种有机化合物经固相萃取(SPE)后在其上的室温磷光行为,发现合成材料磷光背景低,选择性好且富集能力较β-环糊精修饰滤纸高出100倍。该方法用于环境水样和生物样品中的芴和菲的测定,回收率分别达到76.7%~101.7%和83.3%~92.0%,相对标准偏差(RSD)不超过8.06%(n=3)。第四章研究并建立了恒波长同步扫描固体基质室温磷光法对咔唑的分析测定方法。以β-环糊精修饰滤纸为固体基质,KI为重原子,考查了咔唑在芴,7,8-苯并喹啉,苊,蒽等多环芳烃存在下同步扫描的最优条件。该方法用于环境水样中咔唑的测定,检出限达到6.30ng·mL-1,相对标准偏差为3.67%,回收率为94%~109%。第五章研究了植物激素α-萘乙酸(α-NAA)和6-苄氨基嘌呤(BAP)混合物体系的导数-同步固体基质室温磷光光谱。结果表明,选择△λ=180nm时二者的同步磷光光谱得到了较好的分离,同步磷光峰分别位于257nm和305nm,可同时分别对其进行定量分析。α-NAA和BAP的绝对检出限分别为14.90 ng·spot-1和6.76 ng·spot-1,方法用于蔬菜和水样中α-NAA和BAP的测定,回收率分别为95.0%~102%和92.7%~97.7%。更多还原

【Abstract】 Solid substrate-room temperature phosphorescence (SS-RTP) has advantages of high sensitivity, wide linear range, less sample usage, rapid and simple. In recent years, this analytical method has been widely used in the life sciences, environmental sciences, clinical medicine, law seized, industrial hygiene and the energy field, especially in the analysis of pesticide residues, polycyclic aromatic hydrocarbons (PAHs), nitrogen heterocyclic compounds (NHCs) and medicines in biological or environmental samples. However, the preparation of the solid substrate which can induce strong RTP and have low background and the application of synchronous scanning technology in SS-RTP are still important study topics, in this thesis:Chapter one: the mechanism, application and prospect of SS-RTP were introduced in detail. The luminescence mechanism and impact factors of RTP, the application ofβ-cyclodextrin (β-CD) in RTP, the principle of solid phase extraction technology and synchronous scanning technology were described completely.Chapter two: the experimental method of Pullulan substrate was developed. Experimental conditions of the preparation of Pullulan substrate was optimized, including the amount ofβ-CD and 2-bromoethanol, the stir time and drier conditions, and RTP behavior of 15 organics on the Pullulan substrate were studied. The results indicated that the intensities of RTP of several PAHs and NHCs were selectively intensified on the Pullulan substrate, and the sensitivities of determination of them were enhanced.Chapter three: an organic polymeric monolithic substrate was prepared by situ polymerization and modified by a reaction withβ-CD. Theβ-CD modified substrate can be used as solid substrate and solid phase extraction (SPE) membrane for solid phase extraction-room temperature phosphorescence (SPE-RTP). The synthesis conditions, physical properties and chemical properties ofβ-CD modified substrate were studied, and theβ-CD modified substrate shows low RTP background, high selectivity and extraction ability. After SPE, the limits of detection (LODs) of organics with two or three rings were decreased to sub ug/mL level. The developed method was applied to the determination of fluorene and phenanthrene in water samples and biosamples, and the recoveries for fluorene and phenanthrene in samples mentioned above were 76.7%~101.7% and 83.3%~92.0% respectively. For 3 measurements, RSDs were below 8.06%.Chapter four: carbazole was determined by synchronous scanning with solid substrates-room temperature phosphorescence. Some experimental conditions were examined, including drying time, heavy atom and the constant wavelength interval. This method was applied to the determination of carbazole in environmental water samples, and the limit of detection (LOD) was 6.30ng·mL-1, the RSD was 3.67% and the recovery was 94%~109%.Chapter five: a method for the determination ofα-Naphthylacetic Acid (α-NAA) and 6-Benzylaminopurine (BAP) simultaneously by synchronous - derivative solid substrate-room temperature phosphorimetry was described. With pH9.5, 1.5mol·L-1KI-CH3COOLi as heavy atom salt, andΔλ=180nm, the overlapped phosphorescence spectrums ofα-NAA and BAP were well separated, the two synchronous derivation phosphorescence peaks are located at 305nm and 257nm. Forα-NAA and BAP, the absolute detection limit is 14.88ng·spot-1 and 6.75ng·spot-1 respectively. The method was applied to the determination ofα-NAA and BAP in vegetable samples, and the recoveries were 95.0%~102% and 92.7%~97.7%.更多还原