基于香豆素骨架的熒光探針的構(gòu)筑及其性能研究
發(fā)布時間：2019-02-22 09:24
【摘要】：近些年來,香豆素母體被廣泛應(yīng)用于生物、醫(yī)藥、香料、化妝品及熒光染料等領(lǐng)域。由于其具有熒光量子產(chǎn)率高、Stokes位移大、光物理和光化學(xué)性質(zhì)可調(diào)以及光穩(wěn)定性好等優(yōu)點,香豆素類化合物已成為熒光傳感器分子設(shè)計中的優(yōu)秀候選熒光團。本文成功制備了一系列基于香豆素骨架的熒光探針,這幾種化合物都是很好的熒光傳感器,它們可以高選擇性識別水溶液中的Pd~(2+)或Hg~(2+)。通過改良的Knoevenagel反應(yīng),將2,4-二羥基苯甲醛、氰乙酸乙酯分別與鄰苯二胺、鄰氨基苯酚、鄰氨基硫酚反應(yīng),合成了三種剛性含氮雜環(huán)的單齒香豆素衍生物,并利用紅外、核磁等方法對目標(biāo)化合物進行了結(jié)構(gòu)表征鑒定�？疾炝怂鼈儗ΤＲ婈栯x子的響應(yīng),發(fā)現(xiàn)探針對Pd~(2+)具有良好的選擇性。另外,我們研究了這三種配體和Pd~(2+)的自組裝行為,成功制備了一種新型金屬-有機凝膠材料�；贖g~(2+)誘導(dǎo)脫硫反應(yīng)機理,設(shè)計合成了一種具有柔性硫脲基的香豆素?zé)晒夥肿犹结?并利用紅外、核磁等方法對目標(biāo)化合物結(jié)構(gòu)進行了表征。在HEPES中性緩沖溶液中,該探針在常見金屬離子Ni~(2+),Zn~(2+),Cu~(2+),Cd~(2+),Mn~(2+),Pd~(2+)中能夠?qū)Ｒ恍缘淖R別Hg~(2+)。研究發(fā)現(xiàn)探針和Hg~(2+)配位后Hg~(2+)促使其脫硫,形成電子轉(zhuǎn)移,-NH-呈現(xiàn)出更加扭曲的結(jié)構(gòu),最終導(dǎo)致體系熒光淬滅。除此之外,以2,4-二羥基苯甲醛為母體,通過對香豆素進行功能化修飾,特別是在7位引入給電子基團(-OCH_3),在3位引入吸電子基團(-Br),形成“推-拉”電子體系,獲得了一種具有較好熒光特性的新型胺基香豆素衍生物。通過紫外吸收光譜和熒光光譜研究了其光學(xué)性能,發(fā)現(xiàn)化合物表現(xiàn)出熒光發(fā)射帶高度依賴于溶劑的特性。
[Abstract]:In recent years, coumarin matrix has been widely used in biology, medicine, spices, cosmetics and fluorescent dyes. Because of the advantages of high fluorescence quantum yield, large Stokes shift, adjustable photophysical and photochemical properties and good photostability, coumarins have become excellent candidate fluorescent groups in the molecular design of fluorescence sensors. In this paper, a series of fluorescent probes based on coumarin skeleton have been successfully prepared. These compounds are very good fluorescent sensors. They can selectively identify Pd~ (2) or Hg~ (2) in aqueous solution. Three monodentate coumarin derivatives with rigid nitrogen heterocyclic compounds were synthesized by the modified Knoevenagel reaction and the reaction of 2o 4-dihydroxybenzaldehyde and ethyl cyanoacetate with o-phenylenediamine, o-aminophenol and o-aminothiophenol, respectively. The target compounds were characterized by NMR and other methods. Their responses to common cations were investigated. It was found that the probe had a good selectivity for Pd~ (2). In addition, we studied the self-assembly behavior of the three ligands and Pd~ (2), and successfully prepared a new metal-organic gel material. Based on the mechanism of Hg~ (2) induced desulfurization, a coumarin fluorescent molecular probe with flexible thiourea was designed and synthesized. The structure of the target compound was characterized by IR and NMR. In HEPES neutral buffer solution, the probe can specifically recognize Hg~ (2) in common metal ions Ni~ (2), Zn~ (2), Cu~ (2), Cd~ (2), Mn~ (2), Pd~ (2). It was found that Hg~ (2) promoted the desulfurization of Hg~ (2) and formed electron transfer after the coordination of the probe and Hg~ (2). The structure of-NH- showed a more distorted structure, which led to fluorescence quenching of the system. In addition, the functional modification of coumarin was carried out with 2O4-dihydroxybenzaldehyde as the parent, especially at the 7 position (- OCH_3) and at the 3 position (- Br),). A new kind of aminocoumarin derivative with good fluorescence properties was obtained by forming the "push-pull" electronic system. The optical properties of the compounds were studied by UV absorption and fluorescence spectra. It was found that the compounds exhibited the characteristics of highly solvent dependent fluorescence emission band.
【學(xué)位授予單位】：西南科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O657.3
[Abstract]:In recent years, coumarin matrix has been widely used in biology, medicine, spices, cosmetics and fluorescent dyes. Because of the advantages of high fluorescence quantum yield, large Stokes shift, adjustable photophysical and photochemical properties and good photostability, coumarins have become excellent candidate fluorescent groups in the molecular design of fluorescence sensors. In this paper, a series of fluorescent probes based on coumarin skeleton have been successfully prepared. These compounds are very good fluorescent sensors. They can selectively identify Pd~ (2) or Hg~ (2) in aqueous solution. Three monodentate coumarin derivatives with rigid nitrogen heterocyclic compounds were synthesized by the modified Knoevenagel reaction and the reaction of 2o 4-dihydroxybenzaldehyde and ethyl cyanoacetate with o-phenylenediamine, o-aminophenol and o-aminothiophenol, respectively. The target compounds were characterized by NMR and other methods. Their responses to common cations were investigated. It was found that the probe had a good selectivity for Pd~ (2). In addition, we studied the self-assembly behavior of the three ligands and Pd~ (2), and successfully prepared a new metal-organic gel material. Based on the mechanism of Hg~ (2) induced desulfurization, a coumarin fluorescent molecular probe with flexible thiourea was designed and synthesized. The structure of the target compound was characterized by IR and NMR. In HEPES neutral buffer solution, the probe can specifically recognize Hg~ (2) in common metal ions Ni~ (2), Zn~ (2), Cu~ (2), Cd~ (2), Mn~ (2), Pd~ (2). It was found that Hg~ (2) promoted the desulfurization of Hg~ (2) and formed electron transfer after the coordination of the probe and Hg~ (2). The structure of-NH- showed a more distorted structure, which led to fluorescence quenching of the system. In addition, the functional modification of coumarin was carried out with 2O4-dihydroxybenzaldehyde as the parent, especially at the 7 position (- OCH_3) and at the 3 position (- Br),). A new kind of aminocoumarin derivative with good fluorescence properties was obtained by forming the "push-pull" electronic system. The optical properties of the compounds were studied by UV absorption and fluorescence spectra. It was found that the compounds exhibited the characteristics of highly solvent dependent fluorescence emission band.
【學(xué)位授予單位】：西南科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O657.3
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