基于聚集诱导发光性质席夫碱类衍生物的合成及离子识别

发布时间：2018-04-13 10:08

本文选题：水杨醛类席夫碱 + 分子内氢键　；参考：《渤海大学》2017年硕士论文

【摘要】：近年来出现了一种新型的分子,在高浓度状态下能够发出强的荧光,这类分子统称为聚集诱导发光(AIE)分子,其具有很好的聚集态荧光效率,因此在新型的发光材料和生物传感器等领域有着非常广阔的应用前景。Tong课题组发现具有AIE性质的水杨醛类席夫碱化合物,可以形成分子内氢键组成六元环结构。我们以此为出发点设计合成了水杨醛类与邻羟基胺类席夫碱衍生物,其同样具有良好的聚集诱导发光的性质,并且能够对CN-,Al~(3+),Zn~(2+),Mg~(2+),Fe~(3+),Cr~(3+),Cu~(2+)离子具有很好的识别能力,因此获取了一些有意义的实验结果:1、以1-萘甲醛和邻氨基苯硫酚为底物制备了席夫碱L1。通过荧光信号的改变发现探针分子L1在二甲基亚砜(DMSO)溶剂中对铁离子具有很好的选择性,同时还具有良好的抗干扰能力。2、以9-蒽甲醛和2-氨基4-硝基苯酚为原料合成了席夫碱L2。通过调控溶剂体系中水的含量检测L2的荧光信号变化,结果证明分子L2具有很好的聚集荧光增强的性质(AIE),同时在乙醇和水混合体系中(3:7)能够高效选择性识别CN-,表现出荧光增强。检测限为1.02×10-4 M,并且不受其它离子的干扰,具有很好的选择性。3、用邻氨基苯酚分别与5-氯水杨醛与5-溴水杨醛反应合成了席夫碱L3和L4。改变溶剂体系中水的含量,比较荧光信号的改变,结果表明L3和L4都具有AIE性质。在纯水体系中L3对Zn~(2+)具有很好的识别能力,表现为荧光信号增强,通过1:1结合方式,检测限为4.51×10-5 M。同时在纯水体系中L4对Al~(3+)具有较好的选择性,表现为荧光增强现象,结合模式为1:1,其它离子对L4识别Al~(3+)没有干扰,检测限为5.21×10-5 M。4、以2-氨基苯并咪唑分别与5-甲基水杨醛和5-溴水杨醛反应制备了席夫碱L5和L6,实验结果证明L5和L6均具有聚集荧光增强的性质,而且在乙醇溶剂中L5对锌离子具有良好的识别能力并发出强的荧光;而在DMSO中L6能够选择性识别Mg~(2+),通过1:1的方式结合,检测限达到了3.49×10-5 M。5、利用2-羟基-1-萘甲醛分别和2-(4-氨基苯基)苯并噻唑,2-(2-羟基-4-氨基苯基)苯并噻唑反应合成了席夫碱L7和L8,研究在不同水含量体系中L7和L8的荧光变化,发现L7和L8都具有AIE性质。在DMSO中,L7可以高效识别三价离子(Al~(3+),Fe~(3+),Cr~(3+)),以1:1模式结合,且识别三价离子不受其他离子干扰,检测限分别达到了1.49×10-5 M(Al~(3+)),2.88×10-5 M(Cr~(3+)),2.12×10-5 M(Fe~(3+))。在DMSO与水的混合体系中(1:1),L8通过1:1结合有效的识别Cu~(2+),且其不受其它离子的干扰影响,具有很好的抗干扰能力,检测限达到了1.48×10~(-6) M。
[Abstract]:In recent years, a new type of molecule has emerged, which can emit strong fluorescence at high concentration. This kind of molecule is called agglomeration induced luminescence (AIEs) molecule, and it has good fluorescence efficiency of aggregation state.Therefore, the new luminescent materials and biosensors have a very broad application prospect. Tong team found that salicylaldehyde Schiff base compounds with AIE properties can form intramolecular hydrogen bonds to form six-member ring structures.Therefore, some significant experimental results were obtained, and Schiff base L1 was prepared by using 1-naphthalene formaldehyde and o-aminophenol as substrates.By changing the fluorescence signal, it was found that the probe molecule L1 had a good selectivity for iron ion in the solvent of dimethyl sulfoxide (DMSO), and also had good anti-interference ability .2.Schiff base L _ 2 was synthesized from 9-anthracene formaldehyde and 2-amino-4-nitrophenol.By adjusting the water content in solvent system to detect the change of fluorescence signal of L2, the results show that L2 has the property of agglomeration and fluorescence enhancement. At the same time, the molecular L2 can selectively recognize CN-in ethanol and water mixture system with 3: 7) and exhibit fluorescence enhancement.The detection limit is 1.02 脳 10 ~ (-4) M, and it has good selectivity. The Schiff base L _ 3 and L _ 4 were synthesized by the reaction of o-aminophenol with 5-chlorosalicylaldehyde and 5-bromosalicylaldehyde, respectively.By changing the content of water in the solvent system and comparing the changes of fluorescence signals, the results show that both L _ 3 and L _ 4 have AIE properties.In pure water system, L3 has a good ability to recognize Zn~(2. The fluorescence signal is enhanced. The detection limit is 4.51 脳 10 ~ (-5) M by 1:1 combination.At the same time, L4 has a good selectivity for Al~(3 in pure water system, which shows fluorescence enhancement. The binding mode is 1: 1, and the other ions have no interference with L4 to recognize Al~(3.The detection limit was 5.21 脳 10 ~ (-5) M.4.Schiff base L _ 5 and L _ 6 were prepared by the reaction of 2-aminobenzimidazole with 5-methylsalicylaldehyde and 5-bromosalicylaldehyde, respectively.Moreover, L5 has good ability to recognize zinc ion and emit strong fluorescence in ethanol solvent, while L6 can selectively recognize Mg~(2 ion in DMSO and bind it by 1:1.The detection limit was 3.49 脳 10 ~ (-5) M. 5. Schiff base L _ 7 and L _ 8 were synthesized by the reaction of 2-hydroxy-1-naphthalene formaldehyde and 2-oxo-4-aminophenyl) benzothiazole, respectively. The fluorescence changes of L7 and L8 in different water content systems were studied.It is found that both L7 and L8 have AIE properties.In DMSO, L7 can efficiently identify the trivalent ions, which can be combined in 1:1 mode, and the detection limit is 1.49 脳 10 ~ (-5) M(Al~(3 / L ~ (2.88 脳 10 ~ (-5)) M(Cr~(3 ~ (2. 12) 脳 10 ~ (-5) M(Fe~(3, and the detection limit is 1.49 脳 10 ~ (-5) M(Al~(3 / L ~ (-1) and 2.88 脳 10 ~ (-5) M(Cr~(3 / L ~ (-1) respectively.In the mixed system of DMSO and water, 1: 1 / L ~ (8) can effectively identify Cu~(2 ~ (2 +) by 1:1, and it is not affected by other ions, so it has good anti-interference ability, and the detection limit is 1.48 脳 10 ~ (-1) ~ (-6) M, and the detection limit is 1.48 脳 10 ~ (-1) ~ (-1) 路m ~ (-1) ~ (-1).
【学位授予单位】：渤海大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

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