苯并咪唑并苯并异喹啉酮衍生物的合成及性质
发布时间：2019-01-04 17:29
【摘要】：本论文以苯并咪唑并苯并异喹啉酮为荧光核,在12位羧基上引入四种不同的识别基团,合成了四种荧光探针:苯并咪唑并苯并异喹啉酮-12-羧酸(L1),N-(4-(2-肟基-2-乙酸乙酯)噻唑-2)苯并咪唑并苯并异喹啉酮-12-羧酸酰胺(L2),N-(戊二酸-2)-苯并咪唑并苯并异喹啉酮-12-羧酸酰胺(L3)和N-(丁二酸-2)-苯并咪唑并苯并异喹啉酮-12-羧酸酰胺(L4)。以上四种苯并咪唑并苯并异喹啉酮衍生物以及它们的中间体的化学结构均通过了1H NMR(氢谱)、13C NMR(碳谱)、MS(质谱)以及FTIR(红外)等表征手段的验证,并且用紫外分光光度仪和荧光分光光度仪对其光学性质进行了更深入的研究。研究发现,以上四种以苯并咪唑并苯并异喹啉酮为荧光核的探针对不同的金属离子表现出了不同的响应特性:探针L1在乙腈/水(v/v=1:1,pH=7.2)的缓冲体系中对Hg2+表现出高度的选择性,是“打开”型荧光探针。通过Hg2+与阴离子PPi的多次相互滴加,获知L1对Hg2+的检测是可逆的。而且在不同pH的溶液中,L1的荧光强度有很大的变化。根据荧光测试结果,提出在酸性、中性及碱性溶液中L1分子以两种不同的形式存在,分别为L1和L1-。L1状态时形成一个分子内氢键抑制了PET过程的进行,从而显示强荧光。去质子化发生后,L1-中的PET过程恢复,荧光淬灭。并得到了DFT/TDDFT理论计算的验证。工作曲线显示探针L1与Hg2+之间的络合比为1:1。探针L2分子中去甲基氨噻肟酸乙酯基团的存在使其在乙腈/水(v/v=9:1,pH=7.4)的缓冲体系中,对Fe~(3+)表现出高选择性与高灵敏度,不受其他金属离子的干扰,体现为荧光增强的响应。检测极限为9×10-8 M。在一定波长的激发下,L2的荧光颜色由浅绿色变成亮绿色。质谱滴定证明L2与Fe~(3+)之间以1:1络合。探针L3在纯水(pH=7.4)缓冲体系中,对Fe~(3+)与Al~(3+)表现出不同程度的荧光淬灭。L3分子中两个羧基的存在使其在酸性、中性及弱碱性、强碱性溶液中,荧光强度差别很大,而且在弱碱性溶液中荧光最强。通过理论计算,L3对pH的荧光响应机理也得到了验证。工作曲线显示,L3与Fe~(3+)或Al~(3+)之间均为1:1络合。探针L4与L3在结构上很相似,因此,对Fe~(3+)和Al~(3+)的响应结果也极为相似。不同之处在于,L4的荧光强度弱于L3的荧光强度。
[Abstract]:In this paper, four fluorescent probes, benzimidazole-benzisoquinolinone (L1), were synthesized by introducing four different recognition groups into 12 carboxyl groups, using benzimidazole benzo isoquinolinone as fluorescence nucleus. N- (4- (2-oximo-2-ethyl acetate) thiazole-2) benzimidazole benzisoquinolone-12-carboxylic acid amide (L2), N- (glutaric acid-2) -benzimidazolidazolone-12-carboxylic acid amide (L3) and N- (succinate-2) -benzimidazolinone benzisoquinolone-12-carboxylic acid amide (L4). The chemical structures of the four benzimidazole-benzo-isoquinolinone derivatives and their intermediates were confirmed by 1H NMR, 13C NMR (carbon spectrum), MS (mass spectrometry) and FTIR (infrared). The optical properties were studied by ultraviolet spectrophotometer and fluorescence spectrophotometer. It was found that the four probes with benzimidazolazole-benzo-isoquinolinone as fluorescence nuclei showed different response characteristics to different metal ions: the probe L1 was found to be in acetonitrile / water (v / v = 1: 1). PH=7.2) has a high selectivity for Hg2 in the buffer system and is a "open" fluorescent probe. By adding Hg2 and anionic PPi to each other for several times, it was found that the detection of L1 for Hg2 was reversible. Moreover, the fluorescence intensity of L1 varies greatly in different pH solutions. According to the results of fluorescence measurement, it is suggested that L1 molecules exist in two different forms in acidic, neutral and alkaline solutions. The formation of an intramolecular hydrogen bond in the states of L1 and L1-.L1 respectively inhibits the progress of the PET process, thus showing strong fluorescence. After deprotonation, the PET process in L 1-recovered and fluorescence quenching occurred. The calculation of DFT/TDDFT theory is verified. The working curve shows that the complexation ratio between probe L1 and Hg2 is 1: 1. The presence of ethyl demethylaminotaxime group in the probe L2 makes it exhibit high selectivity and high sensitivity to Fe~ (3) in the buffer system of acetonitrile / water (v / v 9: 1), and is not interfered with by other metal ions. Reflected in the fluorescence enhancement of the response. The detection limit is 9 脳 10 ~ (-8) M. Under the excitation of a certain wavelength, the fluorescence color of L 2 changed from light green to bright green. Mass spectrometric titration showed that L _ 2 complexed with Fe~ (3) at 1:1. The fluorescence quenching of Fe~ (3) and Al~ (3) in the buffer system of pure water (pH=7.4) showed that the probe L3 had two carboxyl groups in the solution of acid, neutral and weak alkalinity and strong alkalinity. The fluorescence intensity varies greatly, and the fluorescence is strongest in weak alkaline solution. The fluorescence response mechanism of L 3 to pH was also verified by theoretical calculation. The working curve showed that the complex between L 3 and Fe~ (3) or Al~ (3) was 1:1. The structure of probe L4 is similar to that of L3, so the response to Fe~ (3) and Al~ (3) is very similar. The difference is that the fluorescence intensity of L 4 is weaker than that of L 3.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626;O657.3
本文编号：2400574
[Abstract]:In this paper, four fluorescent probes, benzimidazole-benzisoquinolinone (L1), were synthesized by introducing four different recognition groups into 12 carboxyl groups, using benzimidazole benzo isoquinolinone as fluorescence nucleus. N- (4- (2-oximo-2-ethyl acetate) thiazole-2) benzimidazole benzisoquinolone-12-carboxylic acid amide (L2), N- (glutaric acid-2) -benzimidazolidazolone-12-carboxylic acid amide (L3) and N- (succinate-2) -benzimidazolinone benzisoquinolone-12-carboxylic acid amide (L4). The chemical structures of the four benzimidazole-benzo-isoquinolinone derivatives and their intermediates were confirmed by 1H NMR, 13C NMR (carbon spectrum), MS (mass spectrometry) and FTIR (infrared). The optical properties were studied by ultraviolet spectrophotometer and fluorescence spectrophotometer. It was found that the four probes with benzimidazolazole-benzo-isoquinolinone as fluorescence nuclei showed different response characteristics to different metal ions: the probe L1 was found to be in acetonitrile / water (v / v = 1: 1). PH=7.2) has a high selectivity for Hg2 in the buffer system and is a "open" fluorescent probe. By adding Hg2 and anionic PPi to each other for several times, it was found that the detection of L1 for Hg2 was reversible. Moreover, the fluorescence intensity of L1 varies greatly in different pH solutions. According to the results of fluorescence measurement, it is suggested that L1 molecules exist in two different forms in acidic, neutral and alkaline solutions. The formation of an intramolecular hydrogen bond in the states of L1 and L1-.L1 respectively inhibits the progress of the PET process, thus showing strong fluorescence. After deprotonation, the PET process in L 1-recovered and fluorescence quenching occurred. The calculation of DFT/TDDFT theory is verified. The working curve shows that the complexation ratio between probe L1 and Hg2 is 1: 1. The presence of ethyl demethylaminotaxime group in the probe L2 makes it exhibit high selectivity and high sensitivity to Fe~ (3) in the buffer system of acetonitrile / water (v / v 9: 1), and is not interfered with by other metal ions. Reflected in the fluorescence enhancement of the response. The detection limit is 9 脳 10 ~ (-8) M. Under the excitation of a certain wavelength, the fluorescence color of L 2 changed from light green to bright green. Mass spectrometric titration showed that L _ 2 complexed with Fe~ (3) at 1:1. The fluorescence quenching of Fe~ (3) and Al~ (3) in the buffer system of pure water (pH=7.4) showed that the probe L3 had two carboxyl groups in the solution of acid, neutral and weak alkalinity and strong alkalinity. The fluorescence intensity varies greatly, and the fluorescence is strongest in weak alkaline solution. The fluorescence response mechanism of L 3 to pH was also verified by theoretical calculation. The working curve showed that the complex between L 3 and Fe~ (3) or Al~ (3) was 1:1. The structure of probe L4 is similar to that of L3, so the response to Fe~ (3) and Al~ (3) is very similar. The difference is that the fluorescence intensity of L 4 is weaker than that of L 3.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626;O657.3
【参考文献】
相关期刊论文 前1条
1 李辉;董毅;郝志云;杨新周;朱以常;;萘酰亚胺类荧光分子探针的研究进展[J];化学研究;2014年03期
，本文编号：2400574
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