基于苯并噻唑衍生物的反應(yīng)型熒光探針的合成及離子識(shí)別
發(fā)布時(shí)間：2018-10-07 20:33
【摘要】：苯并噻唑類衍生物是常見的含氮雜環(huán)化合物,在生物學(xué)和醫(yī)學(xué)領(lǐng)域有著廣泛的應(yīng)用。由于苯并噻唑類化合物大多具有優(yōu)良的熒光性能。鑒于此,近年來被廣泛應(yīng)用于熒光探針中。本文基于苯并噻唑設(shè)計(jì)合成了一系列反應(yīng)型熒光探針,研究了其識(shí)別行為和光譜性質(zhì),得到了一些有意義的結(jié)果。具體內(nèi)容如下:1.以5-甲基-3-(2-苯并噻唑基)-2-羥基苯甲醛為底物,合成了一種基于苯并噻唑類衍生物的熒光探針2-(4-疊氮芐氧基)-3-(2-苯并[d]噻唑基)-5-甲基苯甲醛(HBTA),表征了其結(jié)構(gòu),研究了HBTA對(duì)H_2S的識(shí)別性質(zhì)。實(shí)驗(yàn)結(jié)果表明,HBTA在水溶液中(Tris-HCl 10 m M,pH=7.4,含5 m M CTAB)對(duì)H_2S具有良好的選擇性和靈敏度,且響應(yīng)快速,抗干擾能力強(qiáng),并且在較寬的pH范圍內(nèi)有較好的熒光響應(yīng),其檢測(cè)限為9.09×10~(-7) M。細(xì)胞成像實(shí)驗(yàn)表明,HBTA可用于檢測(cè)細(xì)胞內(nèi)的H_2S。2.以5-甲基-3-(2-苯并噻唑基)-2-羥基苯甲醛為底物,溴丙炔為羥基保護(hù)基團(tuán),合成了一種基于苯并噻唑類衍生物的熒光探針2-(2-丙炔-1-氧基)-3-(2-苯并[d]噻唑基)-5-甲基苯甲醛(BBT),表征了其結(jié)構(gòu),研究了BBT對(duì)Pd~(2+)的識(shí)別性質(zhì)。實(shí)驗(yàn)結(jié)果表明,BBT在CH3CN/H_2O(1/1,v/v,Tris-HCl 10 m M,pH=7.4)的溶液中選擇性識(shí)別Pd~(2+)。該探針具有合成簡(jiǎn)單,高選擇性,較強(qiáng)的抗干擾能力以及較高的靈敏度等優(yōu)點(diǎn)。其檢測(cè)限為1.41×10~(-4) M。此外,試紙實(shí)驗(yàn)表明,該探針在各種水體樣品中有潛在的應(yīng)用價(jià)值。3.以1-(2-苯并[d]噻唑基)-2-萘酚為底物,吡啶-2-甲酸為羥基保護(hù)基團(tuán),設(shè)計(jì)合成了一種反應(yīng)型熒光探針吡啶-2-甲酸1-(2-苯并[d]噻唑基)-2-萘酚酯(BTNP),該探針能在DMSO/H_2O(7/3,v/v,Tris-HCl 10 m M,pH=7.4)的緩沖溶液中實(shí)現(xiàn)對(duì)Cu~(2+)的選擇性識(shí)別。通過利用銅離子促進(jìn)BTNP中吡啶甲酸酯部分的水解反應(yīng),產(chǎn)生了具有激發(fā)態(tài)分子內(nèi)質(zhì)子轉(zhuǎn)移(ESIPT)效應(yīng)的產(chǎn)物,顯示出特有的雙波長(zhǎng)發(fā)射峰。該探針具有合成簡(jiǎn)單,反應(yīng)速度快,靈敏度高等優(yōu)點(diǎn)。經(jīng)計(jì)算準(zhǔn)一級(jí)速率常數(shù)為0.205 min-1,檢測(cè)限為1.34×10~(-6) M。此外,還考察了BTNP在活體細(xì)胞中的熒光成像及實(shí)際水樣中對(duì)銅離子的檢測(cè)。4.以5-甲基-3-(2-苯并噻唑基)-2-羥基苯甲醛為底物,通過用2,3-二甲基苯并噻唑摀鹽來延長(zhǎng)共軛體系,設(shè)計(jì)合成了一種具有近紅外發(fā)射的比率型熒光探針(E)-2-(3-(2-苯并[d]噻唑基)-2-羥基-5-甲基苯乙烯基)-3-甲基苯并[d]噻唑碘摀鹽(DBT),表征了其結(jié)構(gòu),并研究了其光譜性質(zhì)。實(shí)驗(yàn)結(jié)果表明,該探針可以在CH3CN/H_2O(1/1,v/v,HEPES 10 m M,pH=7.4)的溶液中通過比色及比率熒光變化的雙重響應(yīng)機(jī)制來識(shí)別二氧化硫衍生物(HSO_3~-/SO32-),并且具有良好的選擇性和靈敏度。其對(duì)HSO_3~-的檢測(cè)限為3.50×10~(-7 M。該探針識(shí)別機(jī)理通過1H NMR和HRMS進(jìn)行了分析,證實(shí)了HSO_3~-與DBT進(jìn)行了邁克爾加成。此外,該熒光探針DBT在活體細(xì)胞內(nèi)進(jìn)行了成像實(shí)驗(yàn),并且還在線粒體內(nèi)進(jìn)行了共定位實(shí)驗(yàn)。以上結(jié)果表明,熒光探針DBT在生物體內(nèi)檢測(cè)二氧化硫衍生物具有潛在的應(yīng)用價(jià)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.
【學(xué)位授予單位】：渤海大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：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.
【學(xué)位授予單位】：渤海大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O657.3
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