基于久洛尼定的新型希夫碱比色荧光探针对离子的识别检测研究

发布时间：2018-11-23 16:31

【摘要】：第一章:主要介绍了荧光分析法的基本原理,荧光探针的结构及其响应机理,并且对久洛尼定荧光探针的研究进展做了简要概述。第二章:以8-羟基久洛尼定-9-甲醛和氨基脲为原料合成了一种新型的可逆性比色荧光希夫碱探针(L),该探针可检测缓冲水体系中的Al~(3+)离子。加入Al~(3+)后,L的荧光增强,伴随着溶液颜色由无色变成黄色,基于此可识别检测溶液中的Al~(3+)。等摩尔连续变化法和高分辨质谱实验结果表明,L与Al~(3+)以1:1结合形成新的络合物。实验测得Al~(3+)的检测限为4.67nM,远低于WHO规定的饮用水中Al~(3+)最大含量(7.41μM)。此外,L还可通过荧光共聚焦成像用于活体细胞中Al~(3+)离子的识别检测。第三章:设计合成了一种以8-羟基久洛尼定-9-甲醛与4-苯基氨基脲为原料的希夫碱荧光探针L,并对其光学特性进行了研究。在甲醇-水(4:1,v/v,HEPES,pH=7.4)缓冲溶液中,L以1:1与Cu~(2+)特异性结合,540nm处的荧光猝灭,同时溶液从绿色变为黄色。另外,形成的L-Cu~(2+)络合物可以通过金属置换法,进一步用于氰离子的检测。向L-Cu~(2+)中加入CN-,L荧光恢复,且络合物对CN-有较高的选择性。探针对Cu~(2+)和CN-的检测限分别为2.28×10-7M和1.33×10-8M。该传感器已应用于实际水样中CN-的检测,性能优良。此外,L还进行了活细胞中的荧光成像实验,表明其可用来检测活细胞中的Cu~(2+)和CN-。第四章:设计并合成了一种以8-羟基久洛尼定-9-甲醛和4-苯基氨基硫脲为原料的新型希夫碱荧光探针。该探针可以作为一个多功能荧光探针同时检测Al~(3+)和Cu~(2+)。在甲醇溶剂中,向L中加入Al~(3+)后,溶液颜色从黄色变为橙色,并且荧光发射波长发生红移,从540nm移至570nm,荧光颜色由黄绿色变为粉色。通过等摩尔连续变化法测得L与Al~(3+)按1:1结合,计算得L对Al~(3+)的检测限为6.38×10-8M,远低于WHO规定的饮用水中Al~(3+)最高含量(7.41μM);另外,在乙腈-水(1:1,v/v,HEPES,pH7.4)缓冲溶液中,L可以选择性地检测Cu~(2+)。加入Cu~(2+)之后,L溶液的颜色由黄色变为棕褐色,同时荧光猝灭,由实验测得L对Cu~(2+)的检测限为6.7×10-8M,远低于USEPA对饮用水中Cu~(2+)含量的规定。此外,L也可成功地检测实际水样中的Cu~(2+)。
[Abstract]:Chapter 1: the basic principle of fluorescence analysis, the structure of fluorescent probe and its response mechanism are introduced, and the research progress of the fluorescent probe is briefly summarized. Chapter 2: a novel reversibility colorimetric fluorescence Schiff base probe (L), was synthesized from 8-hydroxy-goulonidine-9-formaldehyde and semicarbazone. The probe can be used to detect Al~ (3) ions in buffer water system. After the addition of Al~ (3), the fluorescence of L was enhanced, and the color of the solution changed from colorless to yellow. Based on this, the Al~ (3) in the solution could be identified and detected. The results of constant molar variation method and high resolution mass spectrometry show that L combines with Al~ (3) at 1:1 to form a new complex. The detection limit of Al~ (3) was 4.67 nm, which was far lower than the maximum content of Al~ (3) in drinking water specified by WHO (7.41 渭 M). In addition, L can be used to detect Al~ (3) ions in living cells by fluorescence confocal imaging. In chapter 3, a Schiff base fluorescence probe L- (Schiff base) was designed and synthesized using 8-hydroxy-goulonidine-9-formaldehyde and 4-phenylsemicarbazone as raw materials, and its optical properties were studied. In methanol-water (4: 1 v / v) buffer solution, L binds to Cu~ (2) at 1:1, quenching the fluorescence at 540nm, and the solution changes from green to yellow. In addition, the formed L-Cu2 complex can be further used for the detection of cyanide ions by metal replacement method. CN-,L was added to L-Cu2 to restore fluorescence, and the complex was highly selective to CN-. The detection limits of Cu~ (2) and CN- were 2.28 脳 10 ~ (-7) M and 1.33 脳 10 ~ (-8) M, respectively. The sensor has been applied to the detection of CN- in real water samples and has good performance. In addition, L has carried out fluorescence imaging experiments in living cells, indicating that it can be used to detect Cu~ (2) and CN-. in living cells. In chapter 4, a novel Schiff base fluorescence probe was designed and synthesized from 8-hydroxy iuronidine-9-formaldehyde and 4-phenylthiosemicarbazone. The probe can be used as a multifunctional fluorescent probe for simultaneous detection of Al~ (3) and Cu~ (2). When Al~ (3) was added to L in methanol solvent, the color of the solution changed from yellow to orange, and the fluorescence emission wavelength shifted red from 540nm to 570 nm, and the fluorescence color changed from yellow green to pink. The detection limit of L for Al~ (3) is 6.38 脳 10 ~ (-8) M, which is far lower than the maximum Al~ (3) content (7.41 渭 M);) in drinking water specified by WHO. The combination of L and Al~ (3) is determined by the method of constant molar continuous variation at 1:1, and the detection limit of L for Al~ (3) is 6.38 脳 10 ~ (-8) m. In addition, in acetonitrile-water (1: 1 v / v) buffer solution, L can selectively detect Cu~ (2) in pH 7.4. After the addition of Cu~ (2), the color of L solution changed from yellow to brown, and the fluorescence quenching. The detection limit of L for Cu~ (2) was 6.7 脳 10 ~ (-8) m, which was much lower than that stipulated by USEPA for Cu~ (2) in drinking water. In addition, L can also be successfully used to detect Cu~ (2) in real water samples.
【学位授予单位】：山西大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

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