基于苯并噻唑衍生物的反应型荧光探针的合成及离子识别
发布时间：2018-10-07 20:33
【摘要】：苯并噻唑类衍生物是常见的含氮杂环化合物,在生物学和医学领域有着广泛的应用。由于苯并噻唑类化合物大多具有优良的荧光性能。鉴于此,近年来被广泛应用于荧光探针中。本文基于苯并噻唑设计合成了一系列反应型荧光探针,研究了其识别行为和光谱性质,得到了一些有意义的结果。具体内容如下:1.以5-甲基-3-(2-苯并噻唑基)-2-羟基苯甲醛为底物,合成了一种基于苯并噻唑类衍生物的荧光探针2-(4-叠氮苄氧基)-3-(2-苯并[d]噻唑基)-5-甲基苯甲醛(HBTA),表征了其结构,研究了HBTA对H_2S的识别性质。实验结果表明,HBTA在水溶液中(Tris-HCl 10 m M,pH=7.4,含5 m M CTAB)对H_2S具有良好的选择性和灵敏度,且响应快速,抗干扰能力强,并且在较宽的pH范围内有较好的荧光响应,其检测限为9.09×10~(-7) M。细胞成像实验表明,HBTA可用于检测细胞内的H_2S。2.以5-甲基-3-(2-苯并噻唑基)-2-羟基苯甲醛为底物,溴丙炔为羟基保护基团,合成了一种基于苯并噻唑类衍生物的荧光探针2-(2-丙炔-1-氧基)-3-(2-苯并[d]噻唑基)-5-甲基苯甲醛(BBT),表征了其结构,研究了BBT对Pd~(2+)的识别性质。实验结果表明,BBT在CH3CN/H_2O(1/1,v/v,Tris-HCl 10 m M,pH=7.4)的溶液中选择性识别Pd~(2+)。该探针具有合成简单,高选择性,较强的抗干扰能力以及较高的灵敏度等优点。其检测限为1.41×10~(-4) M。此外,试纸实验表明,该探针在各种水体样品中有潜在的应用价值。3.以1-(2-苯并[d]噻唑基)-2-萘酚为底物,吡啶-2-甲酸为羟基保护基团,设计合成了一种反应型荧光探针吡啶-2-甲酸1-(2-苯并[d]噻唑基)-2-萘酚酯(BTNP),该探针能在DMSO/H_2O(7/3,v/v,Tris-HCl 10 m M,pH=7.4)的缓冲溶液中实现对Cu~(2+)的选择性识别。通过利用铜离子促进BTNP中吡啶甲酸酯部分的水解反应,产生了具有激发态分子内质子转移(ESIPT)效应的产物,显示出特有的双波长发射峰。该探针具有合成简单,反应速度快,灵敏度高等优点。经计算准一级速率常数为0.205 min-1,检测限为1.34×10~(-6) M。此外,还考察了BTNP在活体细胞中的荧光成像及实际水样中对铜离子的检测。4.以5-甲基-3-(2-苯并噻唑基)-2-羟基苯甲醛为底物,通过用2,3-二甲基苯并噻唑摀盐来延长共轭体系,设计合成了一种具有近红外发射的比率型荧光探针(E)-2-(3-(2-苯并[d]噻唑基)-2-羟基-5-甲基苯乙烯基)-3-甲基苯并[d]噻唑碘摀盐(DBT),表征了其结构,并研究了其光谱性质。实验结果表明,该探针可以在CH3CN/H_2O(1/1,v/v,HEPES 10 m M,pH=7.4)的溶液中通过比色及比率荧光变化的双重响应机制来识别二氧化硫衍生物(HSO_3~-/SO32-),并且具有良好的选择性和灵敏度。其对HSO_3~-的检测限为3.50×10~(-7 M。该探针识别机理通过1H NMR和HRMS进行了分析,证实了HSO_3~-与DBT进行了迈克尔加成。此外,该荧光探针DBT在活体细胞内进行了成像实验,并且还在线粒体内进行了共定位实验。以上结果表明,荧光探针DBT在生物体内检测二氧化硫衍生物具有潜在的应用价值。
[Abstract]:Benzene is a common nitrogen-containing heterocyclic compound and has wide application in the fields of biology and medicine. Most of these compounds have excellent fluorescence properties due to benzene. In view of this, recent years have been widely used in fluorescent probes. In this paper, a series of reaction-type fluorescent probes are synthesized based on the design of benzene and benzene, and their identification behavior and spectral properties are studied, and some meaningful results are obtained. The specific content is as follows: 1. A fluorescent probe 2-(4-azido) -3-(2-phenoxy) -3-(2-benzene and[d] propynyl) -5-methylbenzaldehyde (HBTA) based on benzoprene derivative was synthesized with 5-methyl-3-(2-benzene and propynyl) -2-hydroxybenzaldehyde as a substrate, and its structure was characterized. The recognition properties of HBTA on H _ 2S were studied. The results show that HBTA has good selectivity and sensitivity to H _ 2S in aqueous solution (Tris-HCl 10m M, pH = 7.4, with 5 m M CTAB), and has good response and strong anti-interference ability, and has better fluorescence response in wider pH range. The detection limit is 9. 09-10 ~ (-7) M. Cell imaging experiments show that HBTA can be used to detect H _ 2S in cells. taking 5-methyl-3-(2-benzene and propynyl) -2-hydroxybenzaldehyde as a substrate, wherein the bromine group is a hydroxyl protecting group, A fluorescent probe 2-(2-oxo-1-oxy) -3-(2-benzene and[d] propynyl) -5-methylbenzaldehyde (BBT) based on benzene-based derivatives was synthesized, and its structure was characterized, and the recognition properties of BBT on Pd ~ (2 +) were studied. The results show that BBT selectively recognizes Pd ~ (2 +) in CH3CN/ H _ 2O (1/ 1, v/ v, Tris-HCl 10 m M, pH = 7.4) solutions. The probe has the advantages of simple synthesis, high selectivity, strong anti-interference capability and higher sensitivity. The detection limit is 1. 41-10 ~ (-4) M. In addition, the test paper shows that the probe has potential application value in various water samples. A reaction-type fluorescent probe is designed and synthesized by using 1-(2-benzene and[d] propynyl) -2-pentanone as a substrate and a hydroxyl protecting group, which can be used in DMSO/ H _ 2O (7/ 3, v/ v). The selective recognition of Cu ~ (2 +) was realized in buffer solution of Tris-HCl (10 m M, pH = 7.4). By using copper ions to promote the hydrolysis reaction of the formate moiety in the BTNP, a product having an electron transfer (ESIPT) effect in the excited state molecule is produced, showing a specific dual wavelength emission peak. The probe has the advantages of simple synthesis, low toxicity, high sensitivity and the like. In addition, the fluorescence imaging of BTNP in living cells and the detection of copper ions in real water samples were also investigated. using 5-methyl-3-(2-benzene and propynyl) -2-hydroxybenzaldehyde as a substrate, A ratio-type fluorescent probe (E) -2-(3-(2-benzene and[d] propynyl) -2-hydroxy-5-methylstyrene-based) -3-methylphenoxy salt (DBT) with near-infrared emission is designed and synthesized, its structure is characterized, and its spectral properties are studied. The experimental results show that the probe can identify sulfur dioxide derivatives (HSO _ 3 ~-/ SO32-) in CH3CN/ H _ 2O (1/ 1, v/ v, HEPES 10 m M, pH = 7. 4) solutions, and has good selectivity and sensitivity. The detection limit of HSO _ 3 ~-was 3. 50 ~ 10 ~ (-7 M). The identification mechanism of HSO _ 3 ~-was analyzed by 1H NMR and HRMS, and the Michael addition of HSO _ 3 ~-and DBT was confirmed. In addition, the fluorescence probe DBT underwent an imaging experiment in a living cell, and a co-localization experiment was performed in the mitochondria. The above results show that the fluorescence probe DBT has potential application value in the detection of sulfur dioxide derivatives in organisms.
【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
[Abstract]:Benzene is a common nitrogen-containing heterocyclic compound and has wide application in the fields of biology and medicine. Most of these compounds have excellent fluorescence properties due to benzene. In view of this, recent years have been widely used in fluorescent probes. In this paper, a series of reaction-type fluorescent probes are synthesized based on the design of benzene and benzene, and their identification behavior and spectral properties are studied, and some meaningful results are obtained. The specific content is as follows: 1. A fluorescent probe 2-(4-azido) -3-(2-phenoxy) -3-(2-benzene and[d] propynyl) -5-methylbenzaldehyde (HBTA) based on benzoprene derivative was synthesized with 5-methyl-3-(2-benzene and propynyl) -2-hydroxybenzaldehyde as a substrate, and its structure was characterized. The recognition properties of HBTA on H _ 2S were studied. The results show that HBTA has good selectivity and sensitivity to H _ 2S in aqueous solution (Tris-HCl 10m M, pH = 7.4, with 5 m M CTAB), and has good response and strong anti-interference ability, and has better fluorescence response in wider pH range. The detection limit is 9. 09-10 ~ (-7) M. Cell imaging experiments show that HBTA can be used to detect H _ 2S in cells. taking 5-methyl-3-(2-benzene and propynyl) -2-hydroxybenzaldehyde as a substrate, wherein the bromine group is a hydroxyl protecting group, A fluorescent probe 2-(2-oxo-1-oxy) -3-(2-benzene and[d] propynyl) -5-methylbenzaldehyde (BBT) based on benzene-based derivatives was synthesized, and its structure was characterized, and the recognition properties of BBT on Pd ~ (2 +) were studied. The results show that BBT selectively recognizes Pd ~ (2 +) in CH3CN/ H _ 2O (1/ 1, v/ v, Tris-HCl 10 m M, pH = 7.4) solutions. The probe has the advantages of simple synthesis, high selectivity, strong anti-interference capability and higher sensitivity. The detection limit is 1. 41-10 ~ (-4) M. In addition, the test paper shows that the probe has potential application value in various water samples. A reaction-type fluorescent probe is designed and synthesized by using 1-(2-benzene and[d] propynyl) -2-pentanone as a substrate and a hydroxyl protecting group, which can be used in DMSO/ H _ 2O (7/ 3, v/ v). The selective recognition of Cu ~ (2 +) was realized in buffer solution of Tris-HCl (10 m M, pH = 7.4). By using copper ions to promote the hydrolysis reaction of the formate moiety in the BTNP, a product having an electron transfer (ESIPT) effect in the excited state molecule is produced, showing a specific dual wavelength emission peak. The probe has the advantages of simple synthesis, low toxicity, high sensitivity and the like. In addition, the fluorescence imaging of BTNP in living cells and the detection of copper ions in real water samples were also investigated. using 5-methyl-3-(2-benzene and propynyl) -2-hydroxybenzaldehyde as a substrate, A ratio-type fluorescent probe (E) -2-(3-(2-benzene and[d] propynyl) -2-hydroxy-5-methylstyrene-based) -3-methylphenoxy salt (DBT) with near-infrared emission is designed and synthesized, its structure is characterized, and its spectral properties are studied. The experimental results show that the probe can identify sulfur dioxide derivatives (HSO _ 3 ~-/ SO32-) in CH3CN/ H _ 2O (1/ 1, v/ v, HEPES 10 m M, pH = 7. 4) solutions, and has good selectivity and sensitivity. The detection limit of HSO _ 3 ~-was 3. 50 ~ 10 ~ (-7 M). The identification mechanism of HSO _ 3 ~-was analyzed by 1H NMR and HRMS, and the Michael addition of HSO _ 3 ~-and DBT was confirmed. In addition, the fluorescence probe DBT underwent an imaging experiment in a living cell, and a co-localization experiment was performed in the mitochondria. The above results show that the fluorescence probe DBT has potential application value in the detection of sulfur dioxide derivatives in organisms.
【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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