含噻吩环的罗丹明类荧光化学传感器的合成及性能的研究

发布时间：2018-05-26 14:13

本文选题：罗丹明B + 罗丹明6G　；参考：《青岛科技大学》2017年硕士论文

【摘要】：铁作为人体含量最多的必需微量元素,对人的生长发育以及维持必要的生理功能起着不可或缺的作用。铁元素主要以结合蛋白质的形式存在于人类体内,若人体缺铁,便会导致血色素降低,引发缺铁性贫血、疲倦无力、手脚冰凉、面色苍白、失眠腹泻等;但若体内含铁量过高,则会造成铁中毒,危害健康。地壳中含量最多的金属元素铝,是酸性土壤污染的重要成因。人体内的铝元素积累过多,会引发众多疾病,比如脑病、软骨症、贫血和阿尔茨海默病等。因此,研究一类能对Fe~(3+)和Al~(3+)实现有效识别的化学传感器显得尤为重要。由于荧光分析法具有操作方法简单、反应灵敏、选择性优异等特点,被广泛运用于离子的研究检测中。罗丹明衍生物作为荧光探针的一种,具有特殊的内酰胺结构和优良的荧光性能,成为了理想的荧光探针母体。本论文正是基于罗丹明特殊的内酰胺结构,采用罗丹明B和罗丹明6G作为探针母体,通过噻吩甲酸、噻吩乙酸地修饰,合成一系列含噻吩环的罗丹明类荧光传感器B2SY、BYJ、BYY、GYJ、GYY,并通过核磁共振分析、质谱分析、紫外和荧光分析等技术对它们的结构和性能进行了表征与探究。论文主要包括以下3方面:一、通过综述介绍了荧光探针的概念、种类、特点以及罗丹明类化学传感器的原理、发展和成果。二、根据文献设计并合成了以罗丹明B为母体的化合物B2SY、BYJ和BYY。运用核磁、质谱、紫外、荧光等分析手段对三者的结构性能进行探究:化合物B2SY在乙醇-水(1:4,v/v)溶液中作为一个“裸眼”探针对Fe~(3+)表现出了优异的选择性。其与Fe~(3+)以1:1的方式络合,检测限达到1.3′10-7 M,络合稳定常数为2.95′104 M-1。同时,B2SY还能在生理值pH的范围以及活体细胞中有效地检测Fe~(3+)的存在。化合物BYJ和BYY能同时识别Fe~(3+)和Al~(3+),并不受其他金属离子的干扰。其中,BYJ-Fe~(3+)络合比为1:1,BYJ-Al~(3+)、BYY-Fe~(3+)、BYY-Al~(3+)的络合方式均为1:2。三、以罗丹明6G为基本构架,通过噻吩甲酸、噻吩乙酸的修饰合成了化合物GYJ、GYY,并对二者的光学性能开展了研究。化合物GYJ能同时和Al~(3+)、Fe~(3+)作用,并伴随着溶液由无色向粉红色的转变。GYJ-Fe~(3+)、GYJ-Al~(3+)是以1:2完成络合,络合稳定常数分别为3.91×108 M-2、5.26×108M-2。化合物GYJ还能渗透入细胞膜,成为在活体细胞中有效检测Fe~(3+)和Al~(3+)含量的化学传感器。化合物GYY能排除众多金属离子的干扰有效识别Fe~(3+)和Al~(3+),并产生颜色的变化(透明—粉红)。GYY和Fe~(3+)或Al~(3+)都是以1:2的形式络合,络合稳定常数分别为6.64×108 M-2和5.69×108 M-2。
[Abstract]:Iron, as the most essential trace element in human body, plays an indispensable role in the growth and maintenance of the necessary physiological functions. Iron is mainly in the form of protein in human body. If the human body is deficient in iron, it can cause the reduction of hemoglobin, causing iron deficiency anemia, weariness, cold hands and feet, pale face color. But if the iron content is too high in the body, it will cause iron poisoning and harm health. Aluminum, the most abundant metal element in the earth's crust, is an important cause of acid soil pollution. The excessive accumulation of aluminum in the human body causes many diseases, such as encephalopathy, cartilaginous disease, anemia and Alzheimer's disease. Therefore, a class of research can be used for Fe~ (3+). Chemical sensors, which are effectively identified with Al~ (3+), are particularly important. Because of the characteristics of simple operation, sensitive reaction and excellent selectivity, fluorescence analysis is widely used in the research and detection of ions. As one of the fluorescent probes, Luo Danming derivatives have special lactam structure and excellent fluorescence properties. The ideal fluorescent probe matrix is based on Luo Danming's special lactam structure, using Luo Danming B and Luo Danming 6G as the probe matrix, by modifying thiophene formic acid and thiophene acetic acid to synthesize a series of Luo Danming fluorescent sensors, B2SY, BYJ, BYY, GYJ, GYY, and by magnetic resonance analysis, mass spectrometry, and purple. The structure and properties of them are characterized and explored by external and fluorescence techniques. The thesis mainly includes the following 3 aspects: first, the concept, types, characteristics and the principles, development and achievements of the Luo Danming chemical sensors are introduced through a summary. Two, according to the design and synthesis of the compound B with B as the parent body 2SY, BYJ and BYY. explored the structural properties of the three by NMR, MS, UV, and fluorescence analysis. Compound B2SY showed excellent selectivity to Fe~ (3+) as a "naked eye" probe in ethanol water (1:4, v/v) solution. It complex with Fe~ (3+) in a 1:1 way, the detection limit reached 1.3 '10-7 M, and the stability constant was 2. .95 '104 M-1. simultaneously, B2SY can also effectively detect the presence of Fe~ (3+) in the range of physiological value pH and in living cells. Compounds BYJ and BYY can simultaneously identify Fe~ (3+) and Al~ (3+) without interference from other metal ions. 6G is the basic framework for the synthesis of compounds GYJ, GYY by thiophenic acid and thiophene acetic acid, and the optical properties of the two are studied. Compound GYJ can simultaneously interact with Al~ (3+), Fe~ (3+), and with the solution from colorless to pink to.GYJ-Fe~ (3+), GYJ-Al~ (3+) is complex, complex stability constant, respectively. The 3.91 * 108 M-2,5.26 * 108M-2. compound GYJ can penetrate into the cell membrane and become a chemical sensor for the effective detection of the content of Fe~ (3+) and Al~ (3+) in living cells. Compound GYY can exclude the interference of many metal ions and effectively identify Fe~ (3+) and Al~ (3+). The complexation stability constants of 2 were 6.64 x 108 M-2 and 5.69 x 108 M-2. respectively.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

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