荧光增强型有机小分子荧光探针的设计、合成及其性能研究

发布时间：2018-03-22 19:12

本文选题：有机小分子荧光探针　切入点：荧光增强　出处：《新疆大学》2017年硕士论文　论文类型：学位论文

【摘要】：近年来,有机小分子荧光探针以其结构简单、合成方便、选择性高、灵敏度高和抗干扰能力突出等优点,而被广泛应用在检测环境中各种有毒有害的重金属阳离子和阴离子污染物。此外,有机小分子荧光探针还可以在细胞和活体组织中实现荧光成像,对医学领域有着非凡的意义。本论文利用常见检测机理基于常用的荧光基团设计合成了一系列荧光增强型(“turn on”)有机小分子荧光探针,并在水溶液体系下对剧毒阴离子CN~-和有毒有害的重金属阳离子Ag~+、Zn~(2+)以及Hg~(2+)进行了检测。本文将从以下研究内容展开:1.我们用4-(N,N-二苯胺基)苯甲醛、2-苯基-1,2,3-三唑基-4-甲醛、喹喔啉醛和1,2,3,3-四甲基-3-氢-吲哚VA碘化物发生Knoevenagel缩合反应,设计合成了三种简单的小分子M1、M2和M3,并成功的筛选出一种在水溶液中检测CN~-的荧光增强型(“turn on”)有机小分子荧光探针M1。探针M1与CN~-基于亲核加成反应机理阻碍了M1分子的ICT效应进而由无荧光变为很强的蓝色荧光并伴随颜色由紫色变为无色。检测限达到6.1×10-7 M,在混合溶剂为DMSO-H2O(3:2 v/v,Tris-HCl=50 mM,pH=7.0)测试条件下,探针M1对CN~-的识别具有快速响应(1min)、选择性专一、灵敏度高和抗干扰性强且可以裸眼识别等优点。另外,在不同水样中对CN~-的检测中发现,探针M1有应用于真实的水体环境体系检测CN~-的可能性。我们为检测CN~-提供了一种新型高选择性、高灵敏度、强的抗干扰性的荧光探针传感器。2.我们用4-(N,N-二苯胺基)苯甲醛和4-氨基-5-苯基-4-氢-1,2,4-三唑基-3-硫醇进行反应,成功合成了荧光增强型有机小分子荧光探针M4。首先,在DMSO溶液中探针M4对Ag~+进行了检测,表现出非常好的荧光响应行为,M4检测Ag~+具有很高的灵敏性和很好的抗干扰能力,其检测限为2.7×10-7 M。其次,体系在混合溶剂EtOH-H2O(1:1 v/v,HEPES=50 mmol,pH=7.4)中,探针M4对Ag~+也表现出非常好的荧光响应行为,且具有很高的灵敏性和很好的抗干扰能,检测限为7.5×10-7 M。最后,体系在混合溶剂EtOH-H2O(1:1 v/v,Tris-HCl=50 mM,pH=7.0)中探针M4对Zn~(2+)的检测表现出非常好的荧光响应行为,检测限为2.35×10-7 M。另外,探针M4在Hela细胞中实现了对Ag~+及Zn~(2+)的识别。3.基于罗丹明结构设计合成了一种比色荧光双通道检测Hg~(2+)的荧光增强型有机小分子荧光探针M5。体系在混合溶剂EtOH-H2O(1:1 v/v,HEPES=50 mM,pH=7.0)中,探针M5对Hg~(2+)的检测具有高的灵敏性和很好的抗干扰能力,检测限为1.73×10-8 M。另外,在不同水样中对Hg~(2+)的检测中发现,探针M5有应用于真实的水体环境体系检测Hg~(2+)的可能性。我们为检测Hg~(2+)提供了一种新型高选择性、高灵敏度、强的抗干扰性的荧光增强型有机小分子荧光探针。
[Abstract]:In recent years, organic small molecule fluorescence probe has the advantages of simple structure, convenient synthesis, high selectivity, high sensitivity and outstanding anti-interference ability. It has been widely used to detect various toxic and harmful heavy metal cations and anionic pollutants in the environment. In addition, fluorescence probes of small organic molecules can also be used for fluorescence imaging in cells and living tissues. In this paper, a series of fluorescence probes of "turn on" organic molecules were designed and synthesized based on common fluorescent groups. The highly toxic anions CN- and the toxic and harmful heavy metal cations Ag2 and Hg~(2) were determined in aqueous solution system. In this paper, the following research contents were carried out: 1. We use 4-N- N- (N-diphenylamino) benzaldehyde, 2-phenyl-1-triazol-2-triazol-4-formaldehyde. The Knoevenagel condensation reaction between quinoxaldehydes and 3-tetramethyl-3-hydro-indole VA iodides was observed. Three simple small molecules M _ 1M _ 2 and M _ 3 were designed and synthesized, and a fluorescence enhanced organic fluorescence probe ("turn on") was successfully selected for the detection of CNN- in aqueous solution. The reaction mechanism of probe M1 and CN-based on nucleophilic addition hinders M1. The ICT effect of the molecule then changed from non-fluorescence to strong blue fluorescence and accompanied by color change from purple to colorless. The detection limit was 6.1 脳 10 ~ (-7) M, and the pH value of the mixed solvent was DMSO-H2O(3:2 v / v ~ (-1) Tris-HCln ~ (50) Mm ~ (1) (pH = 7.0), and the detection limit was 6.1 脳 10 ~ (-7) M ~ (-1). Probe M1 has the advantages of fast response, selectivity, high sensitivity, strong anti-interference, and can be recognized by naked eyes. In addition, it is found in different water samples. Probe M1 has the potential to be used in real water environmental systems to detect CNN-. We have provided a new type of high selectivity and high sensitivity for the detection of CN-. Fluorescence probe sensor with strong anti-interference. We have successfully synthesized fluorescence probe M4-, a fluorescence enhanced organic small molecule, by the reaction of 4-Amino-5-Phenyl-4-Hydro-1-triazol-3-mercaptan and 4-Amino-N- (N-diphenylaminyl) benzaldehyde. The probe M4 was used to detect Ag~ in DMSO solution. The fluorescence response behavior of M4 was very good. The detection limit of M4 was 2.7 脳 10 ~ (-7) M4. Secondly, in the mixed solvent EtOH-H2O(1:1 v / vvHEPES ~ (50 mmol / L), the pH value of the system was 7.4, and the detection limit was 2.7 脳 10 ~ (-7) M4. The probe M4 also showed a very good fluorescence response to Ag ~, and had high sensitivity and good anti-interference ability. The detection limit was 7.5 脳 10 ~ (-7) M. finally, the detection limit of M4 was 7.5 脳 10 ~ (-7) m, and the detection limit was 7.5 脳 10 ~ (-7) M. The fluorescence response of probe M4 to Zn~(2 was very good in the mixed solvent EtOH-H2O(1:1 v / v / Tris-HCln (50 mMg pH = 7.0), and the detection limit was 2.35 脳 10 ~ (-7) M. in addition, the detection limit was 2.35 脳 10 ~ (-7) M ~ (-1) 路mol ~ (-1) 路L ~ (-1). The probe M4 has realized the recognition of Ag- and Zn~(2 in Hela cells. (3) based on Rhodamine structure, a fluorescence enhanced fluorescence probe M5 for small organic molecules was designed and synthesized based on the structure of Rhodamine. The detection limit of probe M5 for Hg~(2 is 1.73 脳 10 ~ (-8) M.The detection limit of M5 is 1.73 脳 10 ~ (-8) M. in addition, the detection of Hg~(2 in different water samples has been found. The probe M5 has the potential to be applied to the detection of Hg~(2 in real water environment system. We have provided a novel fluorescence enhanced fluorescence probe with high selectivity, high sensitivity and strong anti-interference for detecting Hg~(2.
【学位授予单位】：新疆大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

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