基于荧光素分子骨架荧光探针的设计合成与性质研究

发布时间：2018-03-24 00:23

本文选题：荧光素　切入点：荧光探针　出处：《兰州大学》2017年博士论文

【摘要】：荧光素作为一种染料,在水中具有较高的量子产率、高的消光系数以及在可见光区的激发和发射波长等优点,在荧光探针领域中备受科学家们的亲睐。本论文选用荧光素骨架作为荧光团,利用有机合成化学方法,设计合成一系列荧光素衍生物,并对其性质做了详细研究。本文中完成的主要工作如下:(1)利用甘氨酸、苯丙氨酸以及天冬酰胺修饰荧光素设计出一系列荧光探针类L~1、L~2、L~3。该类探针基于荧光“on-off-on”接力策略在100%HEPES(p H=7.0)水溶液中识别Cu~(2+)和硫醇氨基酸分子。实验结果表明,探针与Cu~(2+)之间结合引起体系中探针荧光猝灭,接着加入硫醇氨基酸置换出探针分子,体系荧光恢复。且被成功应用在IMPLICATION逻辑门模拟和细胞成像中。(2)我们在探针结构设计中集成了荧光素和香豆素结构,提出一种双模式荧光探针L~4和L~5,从生物硫醇中选择性识别半胱氨酸,这种荧光探针能在5分钟内与半胱氨酸完成相互作用,在450 nm激发下发生荧光打开模式,有趣的是在短波长332 nm下,该探针对半胱氨酸表现出比率型荧光模式。所有实验结果表明在其他氨基酸、阴离子、阳离子存在的条件下,探针对半胱氨酸具有专一选择性,检测限达0.084μM,远低于细胞间半胱氨酸浓度,并且在Hep G2细胞中选择性检测了半胱氨酸,目前尚无此类荧光素衍生物识别半胱氨酸的报道。(3)利用荧光素单双醛分子与异烟酰肼反应,制备出异烟酰腙类荧光探针L~6和L~7,分别在纯乙醇和HEPES(p H=7.0)缓冲溶液中对苦味酸进行紫外光谱和荧光光谱响应,实验结果表明了苦味酸(TNP)的强吸电子能力诱导探针中电子云发生转移,导致荧光猝灭。最后,我们将探针吸附在试纸上,成功对不同浓度的TNP溶液进行了定量检测。
[Abstract]:As a kind of dye, fluorescein has the advantages of high quantum yield, high extinction coefficient, excitation and emission wavelength in visible region, etc. In this paper, a series of fluorescein derivatives were designed and synthesized by organic synthetic chemistry. The main work done in this paper is as follows: 1) using glycine. Phenylalanine and asparagine modified fluorescein have designed a series of fluorescent probes, such as L _ (1) and L _ (2) O _ (2) L _ (3), which recognize Cu~(2) and mercaptan amino acid molecules in aqueous solution of 100%HEPES(p H _ (7. 0) based on fluorescent "on-off-on" relay strategy. The fluorescence quenching of the probe was induced by the binding between the probe and Cu~(2, and the thiol amino acid was added to replace the probe molecule. We have integrated the fluorescein and coumarin structures in the probe structure design, and have been successfully used in IMPLICATION logic gate simulation and cell imaging. A double mode fluorescence probe, Ln4 and L5, was proposed to selectively recognize cysteine from biological mercaptan. The fluorescence probe could interact with cysteine in 5 minutes and produce fluorescence open mode at 450 nm excitation. Interestingly, the probe exhibited a ratio fluorescence pattern to cysteine at a short wavelength of 332 nm. All the experimental results showed that the probe was specific to cysteine in the presence of other amino acids, anions and cations. The detection limit was 0.084 渭 m, which was much lower than the concentration of cysteine between cells. Cysteine was selectively detected in Hep G2 cells. There was no report of the recognition of cysteine by this kind of fluorescein derivative. Isoniacyl Hydrazone fluorescent probes Ln6 and L7 were prepared, and the UV and fluorescence spectra of picric acid in pure ethanol and HEPES(p H7. 0 buffer solution were investigated. The experimental results show that the strong electron absorption ability of picrate can induce electron cloud transfer in the probe, which leads to fluorescence quenching. Finally, the probe is adsorbed on the test paper and the different concentrations of TNP solution are detected quantitatively.
【学位授予单位】：兰州大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O657.3

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