固体表面发光技术及其在环境分析中的应用

【作者】 苏文斌；

【导师】 谷学新；

【作者基本信息】 首都师范大学 ， 分析化学， 2003， 硕士

【摘要】 固体表面发光技术是一种灵敏的分析技术，对于环境样品中痕量有毒有机污染物的分析十分有用。本论文分别采用固体表面的荧光（薄层色谱法-荧光检测法）和固体表面磷光分析法（固体基质-室温磷光法）对环境样品中有机污染物的分析方法进行了研究，测定了钩藤、野菊花、生蒲黄、地骨皮四种中药材中西维因的残留量，并研究了不同固体表面的苯并喹啉、芴、荧葸的荧光和磷光行为。 薄层色谱法的测定是在硅胶G板上以环己烷：丙酮：氯仿=5∶1∶1作为展开剂，以313nm的紫外光作为照射光，直接进行荧光测量，检测波长为347nm。结果表明，西维因浓度在0.004mg/ml～0.10mg/ml范围内线性良好，绝对检测限达到10ng，但只有生蒲黄、地骨皮两种中药材的加标回收率满意。 固体基质-室温磷光法是在国产定性滤纸上使用2mol/L的KI溶液作为重原子溶液，在烘干温度为80℃、烘干时间为5min的条件下直接测量其磷光发射。结果表明，西维因的最大激发波长为284nm，最大发射波长为520nm。在520nm处测定其磷光强度，西维因浓度在4×10^-6～2×10^-4mol/L范围内与磷光强度成良好线性，绝对检测限为0.89 ng，只有钩藤的加标回收率变化较大，其他三种样品的加标回收率和样品测定满意。 研究比较了7，8-苯并喹啉、芴、荧蒽三种有机污染物的滤纸表面磷光、滤纸表面荧光、聚醚砜膜表面荧光性质。研究结果表明，不同重原子溶液可以选择性的增强三种物质的纸上磷光，且灵敏度高，绝对检出限分别为1.25ng，0.87ng，0.83 ng。7，8-苯并喹啉、荧蒽的滤纸表面荧光强度均低于聚醚砜膜表面荧光强度，但滤纸具有较低的荧光背景。研究表明荧蒽在滤纸表面的绝对检出限低于在聚醚砜膜表面的检出限，而7，8-苯并喹啉却在聚醚砜膜表面具有较低检出限。芴的固体表面荧光未曾观测到，原因有待于进一步研究。 研究了洋金花中三种莨菪生物碱的薄层扫描法测定。具体方法是在硅胶G薄层板上，以甲苯：丙酮：无水乙醇：氨水=15∶10∶7∶2（v/v）为展开剂，用改良碘化铋钾与KI-I₂混合液作为显色剂，采用双波长薄层扫描法实现了中药材洋金花中三种莨菪生物碱（山莨菪碱、阿托品、东莨菪碱）的同时分离和测定。分离效果良好，平均加标回收率在105％～107％之间。更多还原

【Abstract】 Solid surface luminescence is a sensitive analytical technique which is very useful for the analysis of trace poisonous organic pollutants in environmental samples. In this thesis, solid surface fluorescence (SSF) and solid surface phosphorescence(SSP) were investigated for the determination of some organic pollutants in four Chinese herbs. Also the fluorescence and phosphorescence on filter paper and fluorescence on polyether sulfone membrane of 7, 8-benzoquinoline, fluorene, fluoranthene were studied.Thin layer chromatography-fluorimetry for the determination of carbaryl in Chinese herbs was established. The separation was carried out on the silica gel G plate. Cyclohexane:actone:chloroform=5:1:1(V/V) was selected as the developing reagent and the determination of carbaryl was directly measured by fluorescence emission at 347nm. The result showed that the concentration of carbaryl in the range of 0. 004 mg/ml~0.10 mg/ml had fine linearity with its fluorescence intensity and the absolute detection limit was 10 ng. The recoveries were satisfactory for Digupi and Crude Pollen Typhae(ShengPuHuang) samples.Determination of carbaryl in Chinese herbs by Solid Substrate Room Temperature Phosphorescence(SS-RTP) was developed. The Chinese qualitative filter paper was selected as the solid substrate. 2 mol/L KI solution was selected as the heavy atom solution and the dry temperature was 80 for 5 minutes. The maximum excitation and emission wavelength of carbaryl were 284 nm and 520 nm respectively. The concentration of carbaryl in the range of 4 10-6~2 10~4 mol/L had fine linearity with its phosphorescence intensity and the absolute detection limit was 0.89 ng per spot. The recoveries were satisfactory for three samples except Uncaria(GouTeng).The phosphorescence and fluorescence on the surface of different solid substrates of three compounds including 7, 8-benzoquinoline, fluorene, fluoranthenewere studied and compared. The results showed that different heavy atom solution could strengthen the phosphorescence intensity of above-mentioned three substances selectively and the absolute detection limits of 7, 8-benzoquinoline, fluorene, fluoranthene were 1.25 ng,0.87 ng,0.83 ng per spot respectively. The fluorescence intensity of 7, 8-benzoquinoline and fluoranthene on the surface of polyether sulfone membrane was higher than on the surface of filter paper while the filter paper had the lower background fluorescence emission. The results showed that the absolute detection limit of fluoranthene on the surface of filter paper was lower than on the surface of polyether sulfone membrane while the case of 7, 8-benzoquinoline was just the opposite. The fluorescence of fluorene on both the solid surface were not observed which should need the further investigation.Besides, the separation and analysis of three hyoscyamines including anisodamine, atropine and scopolamine in Flos Daturae by Scanning TLC was studied. The separation was carried out on the silica-gel G plate using C6H5CH3-CH3COCH3-C2H5OH-NH3H2O=15:10:7:2(V/V) as developing solvent and the mixture of modified Bismuth Potassium Iodide and KI-I2 as the color agent. The separation and the determination of the three hyoscyamines were satisfactory. The average recovery was between 105-107%.更多还原