吡唑啉类荧光探针的合成及对金属离子的检测研究

发布时间：2018-06-11 16:39

本文选题：吡唑啉 + 荧光探针　；参考：《兰州理工大学》2017年硕士论文

【摘要】：荧光分子探针结构中应具备多共轭体系,或者在共轭体系上增加强的供电子基团、以及分子刚性,使得合成的探针在紫外-可见-近红外区产生强的荧光效应。而在所有的荧光分子探针体系中,吡唑啉类探针化合物具有刚性平面结构、高荧光量子产率、高效率空穴传输、强烈蓝色荧光的优点,基于此,本文就以吡唑啉结构为基础设计合成了用于检测金属阳离子的新型荧光分子探针,主要内容如下:设计合成了荧光性能优异的吡唑啉探针D/L/M,分别在吡唑啉环上引入不同的取代基,并在不同的溶剂条件下通过紫外吸收光谱和荧光发射光谱测试其光学性能和探针对金属离子的识别效果,并探讨其络合机理。检测发现,探针D实现了在水溶液中对特定金属离子Cu~(2+)的选择性识别。探针D与Cu~(2+)之间以1:1的形式络合,从而产生探针D本身荧光的淬灭效应。探针D与Cu~(2+)浓度滴定呈现出良好的线性关系,最低检测线为1.16×10-7 M。探针D与Cu~(2+)络合过程的可逆性,以及探针D的低毒性可在细胞中成像应用,表明了探针D用于快速和及时识别Cu~(2+)有潜在的实际应用价值。探针L对目标离子Cu~(2+)的识别性能虽然没有发生改变,但可在复杂性、干扰性更多的环境下识别Cu~(2+),同时发现Cu~(2+)对探针L的淬灭效果更好,并由核磁滴定可知探针L除通过识别基团上与Cu~(2+)发生络合以外,蒽基和萘基也能起到协助作用,增强探针的识别能力。随之发现,在吡唑啉环1-位苯并噻唑的引入使探针M对不同的目标离子Zn~(2+)/Cd~(2+)显示出了高效灵敏的选择。而且在与目标离子Zn~(2+)/Cd~(2+)络合时产生了不同与以往的荧光增强现象,探针M与Zn~(2+)络合产生的吸收峰也发生了相对移动。这表明与吡唑啉环1-位相连的苯并噻唑基团影响着探针M对Zn~(2+)/Cd~(2+)的识别。总之,通过在吡唑啉环上引入不同的取代基合成了3种不同的探针D/L/M,并分别对其光学特性进行探究,可以得出这3种吡唑啉型荧光探针在识别目标离子上显示了其优良的选择识别性、络合能力,以及络合体系的可逆性。为今后荧光探针检测金属阳离子的进一步探讨提供了依据。
[Abstract]:The structure of fluorescent molecular probes should have multiple conjugated systems, or increase strong electron donor groups in conjugated system, as well as molecular rigidity, so that the synthesized probes have strong fluorescence effect in the UV-Vis near infrared region. In all fluorescent molecular probe systems, pyrazoline probe compounds have the advantages of rigid planar structure, high fluorescence quantum yield, high efficiency hole transport and strong blue fluorescence. A novel fluorescent molecular probe for the detection of metal cations was designed and synthesized based on the structure of pyrazoline. The main contents are as follows: a pyrazoline probe D / L / M with excellent fluorescence performance was designed and synthesized, and different substituents were introduced into the pyrazoline ring, respectively. The optical properties and the effect of the probe on the recognition of metal ions were measured by UV absorption and fluorescence emission spectra under different solvent conditions, and the complexation mechanism was discussed. It was found that the probe D could selectively recognize the specific metal ions in aqueous solution. The fluorescence quenching effect of probe D is produced by chelating the probe D with Cuanz2 in the form of 1:1. A good linear relationship was found between the titration of probe D and the concentration of Cuan2. The lowest detection line was 1.16 脳 10 ~ (-7) M. The reversibility of the complex process of probe D and the low toxicity of probe D can be used in cell imaging, which indicates that probe D has potential practical application value for rapid and timely identification of Cuanzao 2. Although the recognition performance of the probe L to the target ion Cuanz2) has not changed, it can be recognized in the environment of complexity and more interference. At the same time, it is found that Cuanz2) has a better quenching effect on the probe L. In addition to the complexation of the probe L with Cuan2 on the recognition group, the anthracene group and naphthyl group can also play a assisting role and enhance the recognition ability of the probe. Then it was found that the introduction of 1-position benzothiazole in pyrazoline ring made probe M highly sensitive to different target ions ZnN ~ (2 +) / CD ~ (2 +). In addition, the fluorescence enhancement phenomenon is different from that of the past in the complexation with the target ion Zn ~ (2 +) / CD ~ (2 +), and the absorption peak of the probe M / Zn ~ (2 +) is also shifted. It is suggested that the benzothiazole group linked to the 1-position of pyrazoline ring has an effect on the recognition of Zn ~ (2 +) / CD ~ (2 +) by probe M. In a word, three different probes D / L / M were synthesized by introducing different substituents into the pyrazoline ring, and their optical properties were investigated. It can be concluded that these three kinds of pyrazoline fluorescent probes show their excellent selectivity, complexing ability and reversibility in the recognition of target ions. The results provide a basis for further study on the detection of metal cations by fluorescent probes in the future.
【学位授予单位】：兰州理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

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