小分子荧光探针的合成及其在羟基自由基和汞离子检测中的应用

发布时间：2018-01-16 13:39

本文关键词：小分子荧光探针的合成及其在羟基自由基和汞离子检测中的应用　出处：《山东农业大学》2012年硕士论文　论文类型：学位论文

【摘要】：活性氧粒子（ROS）不断产生于有机体的氧化代谢过程，它是诱发细胞损伤和老化重要的因素。过量活性氧和其衍生物的存在，可诱发许多疾病的产生。因此，ROS的检测得到了极大关注。羟基自由基（·OH）是最具有代表性的自由基。迄今为止,检测和清除羟基自由基方法已有许多，其中荧光分析由于具有灵敏度高、选择性好、操作简单等优势受到人们的青睐。但由于用于检测·OH的荧光探针比较少见，因此开发,对·OH专一识别、快速响应的荧光探针已成为研究的热点。汞是一种毒性较强的金属元素且严重危害人类的健康，因此开发具有选择性、灵敏度高、选择性强、水溶性好的探针，已成为荧光法测定Hg~(2+)的焦点。罗丹明类荧光染料由于具有摩尔消光系数高、光稳定性好、荧光量子产率高、有较长的激发波长和发射波长等优异的光物理和光化学性能，因此拓展罗丹明类染料作为荧光探针在Hg~(2+)荧光测定中的应用十分必要。本文合成了三种新型荧光探针，，利用探针对·OH和Hg~(2+)进行了检测，提出了新的检测方法，主要研究工作： (1)合成了荧光探针香草醛缩苯胺，利用红外光谱、元素分析、核磁等方法对探针结构进行了表征；该探针的荧光可被·OH猝灭，藕合Fenton反应，建立了一种荧光猝灭法测定·OH的新方法，该方法的检测线性范围为2×10~(-6)-2×10~(-5)mol·L~(-1)，检出限为8×10~(-7)mol·L~(-1)。利用该方法测定了几种大豆提取液对·OH清除作用，结果满意。 (2)合成了一种新的RBHT（罗丹明B酰肼-肉桂酸硫脲)荧光探针，利用红外光谱、元素分析、核磁等方法对探针结构进行了表征；该探针与Hg~(2+)结合后产生较强荧光，由此建立了一种测定汞的荧光法分析方法。Hg~(2+)测定的线性范围为8.0×10~(-7)~(-6).0×10~(-6)mol·L~(-1)，检出限为7.0×10~(-8)mol·L~(-1)。该方法具有操作简单、灵敏度高和选择性好等特点。方法试用于自来水、河水中痕量汞的测定，结果满意。 (3)根据Hg~(2+)具有很强的嗜硫性特点，设计并合成了探针硫代罗丹明B-水杨醛酰腙。利用红外光谱、元素分析、核磁等方法对探针结构进行了表征；该化合物可以有效地与Hg~(2+)络合，使罗丹明的环状结构被破坏，生成开环化合物。Hg~(2+)与探针分子相结合，溶液由无色、无荧光，到溶液变为紫红色，产生强烈的荧光。该化合物在Hg~(2+)浓度为1.0×10~(-8)~(-1).0×10~(-6)mol·L~(-1)范围内，有很好的线性。检出限为5.4×10~(-9)mol·L~(-1)。方法成功用于自来水、河水中Hg~(2+)的检测，结果满意。
[Abstract]:Reactive oxygen species (Ros) are produced by the oxidative metabolism of organisms, which are important factors in inducing cell damage and aging, and the presence of excess reactive oxygen species and its derivatives. It can induce many diseases. Therefore, the detection of Ros has attracted much attention. Hydroxyl radical (路OH) is the most representative free radical. So far. There are many methods for detecting and scavenging hydroxyl radicals, among which fluorescence analysis has high sensitivity and selectivity. The advantages of simple operation are favored by people, but the fluorescence probe used for the detection of 路OH is rare, so it has become a hot research topic to develop a fluorescence probe that specifically recognizes 路OH and responds quickly. Mercury is a highly toxic metal element and seriously endangers human health. Therefore, it has high selectivity, high sensitivity, high selectivity and good water solubility. Rhodamine fluorescent dyes have high molar extinction coefficient, good light stability and high fluorescence quantum yield. It is necessary to expand the application of Rhodamine dyes as a fluorescent probe in the determination of Hg~(2 fluorescence because of their excellent photophysical and photochemical properties such as long excitation wavelength and emission wavelength. In this paper, three new fluorescent probes were synthesized, and the 路OH and Hg~(2 were detected by the probes. A new detection method was proposed, and the main research work was as follows: The fluorescence probe vanillin aniline was synthesized. The structure of the probe was characterized by IR, elemental analysis and NMR. The fluorescence of the probe can be quenched by 路OH and coupled with Fenton reaction. A new method for the determination of 路OH by fluorescence quenching method has been established. The linear range of this method is 2 脳 10 ~ (-6) ~ (-2) 脳 10 ~ (10) ~ (-5) mol 路L ~ (-1). The detection limit was 8 脳 10 ~ (10) ~ (-7) mol 路L ~ (-1) 路L ~ (-1). The method was used to determine the scavenging effect of several soybean extracts on 路OH with satisfactory results. A novel RBHT (Rhodamine B hydrazide-thiourea cinnamate) fluorescence probe was synthesized and characterized by IR, elemental analysis and NMR. The probe combines with Hg~(2 to produce strong fluorescence. A fluorescence method for the determination of mercury was established. The linear range of determination was 8.0 脳 10 ~ (10) ~ (-7) ~ (?) ~ (6). 0 脳 10 ~ (10) ~ (-6) mol 路L ~ (-1). . The detection limit is 7.0 脳 10 ~ (10) ~ (-8) mol 路L ~ (-1) 路L ~ (-1). The method has the advantages of simple operation, high sensitivity and good selectivity. The method has been applied to the determination of trace mercury in tap water and river water. The result is satisfactory. (3) according to the characteristic of Hg~(2, the probe thiorhodamine B- salicylaldehyde-acyl Hydrazone was designed and synthesized. Infrared spectrum and elemental analysis were used. The structure of the probe was characterized by NMR. The compound can be efficiently complexed with Hg~(2), resulting in the destruction of the ring structure of Rhodamine and the formation of ring-opening compound. Until the solution turns purple. Strong fluorescence was produced. The concentration of the compound was 1.0 脳 10 ~ (10) ~ (-8) ~ (-1) ~ (-1). 0 脳 10 ~ (10) ~ (-1) mol 路L ~ (-1). The detection limit is 5.4 脳 10 ~ (-9) mol 路L ~ (-1). The method has been successfully applied to the determination of Hg~(2 in tap water and river water with satisfactory results.
【学位授予单位】：山东农业大学
【学位级别】：硕士
【学位授予年份】：2012
【分类号】：R115;O657.3

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