【作者】 任爱民；

【导师】 宋志光；

【作者基本信息】 吉林大学 ， 有机化学， 2021， 硕士

【摘要】 近几十年来,对环境中的离子进行检测变得愈发重要,利用有机小分子对环境和生物体中离子进行检测的方法受到了广泛的关注。香豆素是一类广泛存在于植物界的杂环化合物,具有重要的生物活性和用途。香豆素类衍生物由于其独特的分子结构,优良的光物理活性等优点,在离子检测领域得到了广泛应用。香豆素结构中含有多个可以修饰的位置,本论文工作主要是通过对香豆素3号位和7号位进行修饰,合成了两种新型荧光探针,并对探针的荧光性质及应用进行了进一步研究。主要的研究内容如下:（1）、以4-二乙氨基水杨醛、芳香醛为原料,合成了16个含有不同芳香团取代基的新型香豆素衍生物,并对化合物的结构、光学性质及对金属离子的选择性进行了研究。其中钯离子对含有吡啶基的化合物具有较强的荧光猝灭效果。对三种含有吡啶基的化合物进行研究发现,化合物（E）-N′-（（4-氯吡啶-2-基）亚甲基）-7-（二乙氨基）-2-氧代-2H-色烯-3-碳酰肼（CMD₁）具有较强的专一选择性。我们以化合物CMD₁作为代表性荧光探针,优化了检测钯离子的条件。在最佳测试条件下,探针CMD₁响应时间短（3min）,p H测试范围宽（2.0-10.0）,检测限低(4.45×10^-8mol/L),实现了对钯离子高效、快速的检测。（2）、设计合成了三个以三氮唑-香豆素为骨架的化合物。在香豆素3号位引入N2取代的三氮唑,不仅增加了3号位的拉电子能力,同时增加了化合物的共轭结构。在7号位羟基上引入保护基,降低了7号位的给电子能力。由于氟离子切断硅氧键后,形成氧负离子,增大了香豆素7号位的给电子能力,同时也增大了分子的共轭结构,因此探针在加入氟离子后,荧光发生较大的红移。由于探针加入氟离子前后荧光红移较大,相互之间没有影响,因此可作为“Off-On”型探针。同时,化合物CTA₃不仅可以用于有机相中氟离子检测,还可以作为比率型探针对水相中的氟离子进行检测。更多还原

【Abstract】 In recent decades,the detection of ions in the environment has become particularly important.The method of using small organic molecules to detect ions in the environment and organisms has attracted widespread attention.Coumarins are a kind of heterocyclic compounds widely found in the plant and have important biological activities and uses.Coumarin derivatives have been widely used in the field of organic fluorescent small molecules due to their unique molecular structures and excellent optical activities.The structure of coumarin contains many positions that can be modified.The main work of this thesis is to synthesize two new fluorescent probes by modifying positions 3 and 7 of coumarin,and further investigating the fluorescent properties and applications of the probes.The main research contents are shown as following:（1）Using 4-ethylenediaminosalicylic aldehyde and aromatic aldehyde as the starting materials,16 novel coumarin derivatives with variant aromatic substituents were synthesized,and the relationship between their structures,optical properties and the selectivity of metals has been studied.Palladium has a strong quenching effect on the compounds with pyridyl groups.Three compounds containing pyridyl groups were analyzed,among which the compound（E）-N′-(（（4-chloropyridin-2-yl）methylene）-7-（diethylamino）-2-oxo-2H-chromene-3-carbohydrazide（CMD₁）has unique specific selectivity.We used compound CMD₁ as a representative fluorescent probe to screen the optimal detection conditions of palladium.Under the best test condition,the probe CMD₁ has a short response time（3min）,a wide p H test range（2.0-10.0）,and a low detection limit(4.45×10^-8mol/L),which achieves efficient and rapid detection of palladium.（2）Three compounds using triazole-coumarin as the skeleton has been designed and synthesized.The N2-substituted triazole in the position 3 of coumarin increases not only the electron withdrawing ability of the third position,but also the conjugate structure of the compound.The protecting group on the hydroxyl group at the position7 reduces its electron donating ability.After the cleavage of Si-O bond,an oxygen anion is formed,increasing its electron-donating ability and the conjugate structure as well.Therefore,after the fluoride ion is added to the probe,the fluorescence shows significant redshift.Because the redshift is large enough,there is no other influence,so it can be used as an"Off-On"probe.At the same time,compound CTA₃ can be used to detect fluoride in the organic phase,and also as a ratio probe to detect fluoride in the water phase.更多还原