【作者】 彭博；

【导师】 牛承岗；

【作者基本信息】 湖南大学 ， 环境科学与工程， 2010， 硕士

【摘要】 荧光分析法具有较高的灵敏度,一般比分光光度法高2-3个数量级,且具有选择性高,方法简便,取样量少等优点,近年来得到迅速发展。卟啉是一类具有刚性的共轭大环类化合物,在光的照射下,易被激发,产生强荧光。卟啉能与周期表中几乎所有的金属离子和大部分非金属离子配合,可用于测定多种金属离子及生化反应和医学研究工作。本论文的主要工作是设计、合成新型的不仅检测简便,而且灵敏度、选择性、稳定性等方面均有突出优点的卟啉类分子荧光探针,研究其用于水中的双氧水和重金属离子的检测并考察其各项性能。又对pH及重金属离子的测定提出了新的思路,制备了相关的荧光传感器。具体包括以下三个方面：(1)根据荧光分子探针设计原理,结合本组的相关研究经验,合成了一种稳定性好、灵敏度高、安全方便的荧光分子探针四(4-氨基苯基)卟啉TAPP,对其在水中的荧光光学性质进行了研究,研究了溶液pH值及表面活性剂对荧光强度的影响,并用于识别水中的钴离子和镍离子。实验发现当离子浓度为2.0×10-7-1.0×10-5 mol/L范围内,Co(Ⅱ)及Ni(Ⅱ)的浓度和荧光强度之间存在着线性关系。Ni(Ⅱ)的检测限为4.0×10-8 mol/L,Co(Ⅱ)的检测限为2.0×10-8 mol/L。这个传感体系具有令人满意的灵敏度,这种方法可以用于自然水体和污水中Co(Ⅱ)和Ni(Ⅱ)的测定。(2)利用卟啉类荧光探针TAPP来检测环境中H202含量。实验发现当H202含量在2.0×10-6-1.0×10-4%范围内,H202的含量和荧光强度存在着线性关系。H202的检测限为6.0×10-7%,这个传感体系具有令人满意的灵敏度,这种方法可以用于自然水体和雨水中H2O2的测定。(3)同时实验还将TAPP制备为荧光传感器,有望用于对pH值和重金属离子的检测。虽然结果不令人满意,但合成产物,及传感器制备方法以后还值得研究与改进,并将其应用于pH值和重金属离子的测定中。更多还原

【Abstract】 Fluorescence analytical method has been rapidly developed for its high selectivity, easy to operate, small sample quantity, and other advantages. It has a higher sensitivity, which is about 2-3 orders of magnitude higher than spectrophotometry. Porphyrins are a class of macrocyclic compounds with rigid conjugate structure, it can easily emit strong fluorescence under irradiation. Porphyrin can chelated with most metal and non-metallic ions in the Periodic Table, and can be used for detections of varieties of metal ions for the research works of biochemical reaction and medical science.In this paper, the main task is to design and synthesize new types of Porphyrin probes, which have the excellent performances of easy to detect, high sensitivity, selectivity, and stability. Study the properties of fluorescent probes and their applications in the detection of heavy metal ions and H2O2 in water. Furthermore, to propose a new thinking of detection of pH and heavy metals using such fluorescent dye based fluorescence sensor. The details including three aspects are as follows:(1) A fluorescent dye,5,10,15,20-tetra(4-aminophenyl)-porphyrin (TAPP) with good stability, high sensitivity was synthesized by simple steps. The fluorescence properties of TAPP, and the effects of pH and surfactant on the fluorescence intensity were investigated. Results showed that it can be used for selectively sensing Ni(Ⅱ) and Co(Ⅱ) through complexation-induced fluorescence quenching. Additionally, the TAPP probe showed linear response toward Ni(Ⅱ) and Co(Ⅱ) in the concentration range of 2.0×10-7-1.0×10-5 mol/L. The prepared sensing system presented satisfactory sensitivity, and the detection limits could be as low as 4.0×10-8 mol/L for Ni(Ⅱ) and 2.0×10-8 mol/L for Co(Ⅱ). The developed method was successfully employed for preliminary application in natural water and domestic sewage.(2) The fluorescence probe of TAPP was used to determine the content of H2O2 in envrionment. In the concentration range of 2.0×10-6-1.0×10-4%, the fluorescence intensity of TAPP changed as linear function of H2O2 content. The prepared sensing system presented satisfactory sensitivity, and the detection limit could be as low as 6.0×10-7% for H2O2. The developed method was successfully employed for preliminary application in natural water and rain water. (3) The author tried to prepare new pH or heavy metal fluorescence sensors based on such fluorescence indicator of TAPP. Although the results are not satisfactory, the synthetic products, and sensors is still worth studying after improvement, and will be applied to the determination of pH and heavy metal ions.更多还原