基于三芳基硼衍生物的双功能化荧光探针的研究

发布时间：2018-01-21 05:35

本文关键词： 三芳基硼双功能荧光探针汞离子氟离子 pH　出处：《山东大学》2016年硕士论文　论文类型：学位论文

【摘要】：Hg2+作为毒性最大的重金属离子之一,对环境以及人体健康造成了极大的危害；F-以氟化物的形式广泛分布在自然界中,对生态环境以及人体健康起着重要的作用；此外,pH作为人体健康的重要指标之一,在细胞的各种代谢过程中起着重要的作用。为此,建立有效的检测Hg2+、F-以及pH的方法具有重要的意义。相比于传统的分析方法,如原子吸收光谱法、高效液相色谱法、电化学分析法等,荧光检测具有高灵敏度、高选择性和简单方便等优点,受到越来越多的关注。虽然目前已报道了很多检测Hg2+、F-和pH的荧光探针分子,但能够同时检测两种物质的双功能化荧光探针还非常有限。在最近的研究中,我们课题组设计合成了一种基于三芳基硼的F-比率荧光探针BN,2-二米基硼基-2'-(N,N-二甲氨基)联苯,三芳基硼中心和F-的络合可以引起荧光大幅度的蓝移(165 nnm),进而可以实现对F-的比率荧光检测。值得注意的是,BN的氨基对位亲电取代活性较高,为此我们希望通过在此位置引入可以检测其他离子的官能团以实现对氟离子和其他离子的同时检测。基于这一设计思想,我们开展了一下两方面的工作：首先,我们通过甲酰化引入醛基,再与硫醇缩合,在BN氨基的对位引入了对Hg2+有响应的硫缩醛,合成了化合物BN-S,作为同时检测Hg2+和F-的双功能化比率荧光探针。BN-S中存在着分子内电荷转移,不仅在有机相中会发射强的荧光,而且即使在水相中形成纳米聚集体的状态下荧光也很强。Hg2+的加入可以诱导硫缩醛发生脱保护反应生成醛基,使体系的最大发射波长发生蓝移,颜色由黄绿色变为绿色。而氟离子的加入,打断了体系中的pπ-π*共轭,可以使体系荧光发生大幅度的蓝移,荧光颜色由黄色变为蓝色。因此BN-S可以作为同时检测Hg2+和F-的双功能化比率荧光探针,此外,BN-S对Hg2+的检测可以以纳米聚集体形式在水相中进行。其次,我们又通过溴代反应及Suzuki偶联反应,在BN的氨基对位引入了对H+有响应的吡啶环,合成了荧光分子1,2,3,以实现同时对氟离子和pH的荧光检测。这些研究结果为深入研究BN的光学性质,以它为基本单元进行官能团修饰设计合成各种不同的双功能化荧光探针提供了一定的理论依据。
[Abstract]:One of the most toxic heavy metal ions as Hg2+, caused great harm to the environment and human health; F- in the form of fluoride is widely distributed in nature, on the ecological environment and human health plays an important role; in addition, pH as important health indicator, it plays an important role in various metabolic processes cells. Therefore, the establishment of effective detection of Hg2+, the significance of F- and pH analysis method. Compared with traditional methods, such as atomic absorption spectrometry, high performance liquid chromatography, electrochemical analysis, fluorescence detection with high sensitivity, high selectivity and advantages such as simple and convenient, more and more concern. Although there has been reported a lot of detection of Hg2+, F- and pH fluorescent probe molecules, but also can detect double function of two kinds of material of the fluorescent probe is very limited. In a recent study In our group, we designed and synthesized a three arylboron F- ratio fluorescent probe based on BN, 2- two -2'- (N, Mickey boron based N- two dimethylamino biphenyl), complex three arylboron center and F- can cause large amplitude fluorescence blue shift (165 NNM), which can be achieved on the the F- ratio of fluorescence detection. It is worth noting that the amino BN para electrophilic substitution of higher activity, so we hope that through the introduction of functional groups in this position can detect other ions to achieve the detection of fluoride ion and other ions at the same time. This design based on the idea, we carried out two aspects: first of all, we introduce the formyl aldehyde with thiol condensation in Para BN amino thioacetals are introduced on the responses of Hg2+, compound BN-S, at the same time as the dual function of detection of Hg2+ and F- ratio of fluorescence probe.BN-S exists in intramolecular charge transfer Shift, not only in the organic phase will emit strong fluorescence, and the formation of nano aggregates even in aqueous solution under the condition of fluorescence is also very strong with the addition of.Hg2+ can occur deprotection reaction of aldehyde acetal induced by sulfur, the maximum emission wavelength of the blue shift system, color from yellow green color is green. The fluoride added P, interrupted pi conjugation in the system, can make the fluorescence system has the large scale blue shift, fluorescent color from yellow to blue. So BN-S can be used as a dual function of detection of Hg2+ and F- at the same time, the ratio of fluorescence probe, in addition, the detection of Hg2+ BN-S can be carried out in the form of nano aggregates in aqueous phase. Secondly, we through bromination reaction and Suzuki coupling reaction, the amino para BN introduced a pyridine ring on the response of the H+, the synthesis of fluorescent molecules 1,2,3, to achieve simultaneous fluorescent detection of fluoride ion and pH test. These research The results provide a theoretical basis for in-depth study of the optical properties of BN and the design and synthesis of various bifunctional fluorescent probes based on its basic unit functionalization.

【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O657.3

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