基于香豆素骨架的荧光探针的构筑及其性能研究
发布时间：2019-02-22 09:24
【摘要】：近些年来,香豆素母体被广泛应用于生物、医药、香料、化妆品及荧光染料等领域。由于其具有荧光量子产率高、Stokes位移大、光物理和光化学性质可调以及光稳定性好等优点,香豆素类化合物已成为荧光传感器分子设计中的优秀候选荧光团。本文成功制备了一系列基于香豆素骨架的荧光探针,这几种化合物都是很好的荧光传感器,它们可以高选择性识别水溶液中的Pd~(2+)或Hg~(2+)。通过改良的Knoevenagel反应,将2,4-二羟基苯甲醛、氰乙酸乙酯分别与邻苯二胺、邻氨基苯酚、邻氨基硫酚反应,合成了三种刚性含氮杂环的单齿香豆素衍生物,并利用红外、核磁等方法对目标化合物进行了结构表征鉴定。考察了它们对常见阳离子的响应,发现探针对Pd~(2+)具有良好的选择性。另外,我们研究了这三种配体和Pd~(2+)的自组装行为,成功制备了一种新型金属-有机凝胶材料。基于Hg~(2+)诱导脱硫反应机理,设计合成了一种具有柔性硫脲基的香豆素荧光分子探针,并利用红外、核磁等方法对目标化合物结构进行了表征。在HEPES中性缓冲溶液中,该探针在常见金属离子Ni~(2+),Zn~(2+),Cu~(2+),Cd~(2+),Mn~(2+),Pd~(2+)中能够专一性的识别Hg~(2+)。研究发现探针和Hg~(2+)配位后Hg~(2+)促使其脱硫,形成电子转移,-NH-呈现出更加扭曲的结构,最终导致体系荧光淬灭。除此之外,以2,4-二羟基苯甲醛为母体,通过对香豆素进行功能化修饰,特别是在7位引入给电子基团(-OCH_3),在3位引入吸电子基团(-Br),形成“推-拉”电子体系,获得了一种具有较好荧光特性的新型胺基香豆素衍生物。通过紫外吸收光谱和荧光光谱研究了其光学性能,发现化合物表现出荧光发射带高度依赖于溶剂的特性。
[Abstract]:In recent years, coumarin matrix has been widely used in biology, medicine, spices, cosmetics and fluorescent dyes. Because of the advantages of high fluorescence quantum yield, large Stokes shift, adjustable photophysical and photochemical properties and good photostability, coumarins have become excellent candidate fluorescent groups in the molecular design of fluorescence sensors. In this paper, a series of fluorescent probes based on coumarin skeleton have been successfully prepared. These compounds are very good fluorescent sensors. They can selectively identify Pd~ (2) or Hg~ (2) in aqueous solution. Three monodentate coumarin derivatives with rigid nitrogen heterocyclic compounds were synthesized by the modified Knoevenagel reaction and the reaction of 2o 4-dihydroxybenzaldehyde and ethyl cyanoacetate with o-phenylenediamine, o-aminophenol and o-aminothiophenol, respectively. The target compounds were characterized by NMR and other methods. Their responses to common cations were investigated. It was found that the probe had a good selectivity for Pd~ (2). In addition, we studied the self-assembly behavior of the three ligands and Pd~ (2), and successfully prepared a new metal-organic gel material. Based on the mechanism of Hg~ (2) induced desulfurization, a coumarin fluorescent molecular probe with flexible thiourea was designed and synthesized. The structure of the target compound was characterized by IR and NMR. In HEPES neutral buffer solution, the probe can specifically recognize Hg~ (2) in common metal ions Ni~ (2), Zn~ (2), Cu~ (2), Cd~ (2), Mn~ (2), Pd~ (2). It was found that Hg~ (2) promoted the desulfurization of Hg~ (2) and formed electron transfer after the coordination of the probe and Hg~ (2). The structure of-NH- showed a more distorted structure, which led to fluorescence quenching of the system. In addition, the functional modification of coumarin was carried out with 2O4-dihydroxybenzaldehyde as the parent, especially at the 7 position (- OCH_3) and at the 3 position (- Br),). A new kind of aminocoumarin derivative with good fluorescence properties was obtained by forming the "push-pull" electronic system. The optical properties of the compounds were studied by UV absorption and fluorescence spectra. It was found that the compounds exhibited the characteristics of highly solvent dependent fluorescence emission band.
【学位授予单位】：西南科技大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O657.3
[Abstract]:In recent years, coumarin matrix has been widely used in biology, medicine, spices, cosmetics and fluorescent dyes. Because of the advantages of high fluorescence quantum yield, large Stokes shift, adjustable photophysical and photochemical properties and good photostability, coumarins have become excellent candidate fluorescent groups in the molecular design of fluorescence sensors. In this paper, a series of fluorescent probes based on coumarin skeleton have been successfully prepared. These compounds are very good fluorescent sensors. They can selectively identify Pd~ (2) or Hg~ (2) in aqueous solution. Three monodentate coumarin derivatives with rigid nitrogen heterocyclic compounds were synthesized by the modified Knoevenagel reaction and the reaction of 2o 4-dihydroxybenzaldehyde and ethyl cyanoacetate with o-phenylenediamine, o-aminophenol and o-aminothiophenol, respectively. The target compounds were characterized by NMR and other methods. Their responses to common cations were investigated. It was found that the probe had a good selectivity for Pd~ (2). In addition, we studied the self-assembly behavior of the three ligands and Pd~ (2), and successfully prepared a new metal-organic gel material. Based on the mechanism of Hg~ (2) induced desulfurization, a coumarin fluorescent molecular probe with flexible thiourea was designed and synthesized. The structure of the target compound was characterized by IR and NMR. In HEPES neutral buffer solution, the probe can specifically recognize Hg~ (2) in common metal ions Ni~ (2), Zn~ (2), Cu~ (2), Cd~ (2), Mn~ (2), Pd~ (2). It was found that Hg~ (2) promoted the desulfurization of Hg~ (2) and formed electron transfer after the coordination of the probe and Hg~ (2). The structure of-NH- showed a more distorted structure, which led to fluorescence quenching of the system. In addition, the functional modification of coumarin was carried out with 2O4-dihydroxybenzaldehyde as the parent, especially at the 7 position (- OCH_3) and at the 3 position (- Br),). A new kind of aminocoumarin derivative with good fluorescence properties was obtained by forming the "push-pull" electronic system. The optical properties of the compounds were studied by UV absorption and fluorescence spectra. It was found that the compounds exhibited the characteristics of highly solvent dependent fluorescence emission band.
【学位授予单位】：西南科技大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O657.3
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