發(fā)布時間：2018-04-11 12:02

  本文選題：熒光探針 + 香豆素��； 參考：《西北大學(xué)》2017年碩士論文

【摘要】：谷胱甘肽(GSH)與生物體中的氧化還原平衡狀態(tài)、機體正常的生命活動息息相關(guān);SO_2作為一種大氣污染物,通過影響植物的光合作用進而影響植物的生長發(fā)育,其衍生物也被廣泛的用作食品添加劑,經(jīng)常被人們攝入體內(nèi)。因此構(gòu)建一種可定性定量,且專一性檢測谷胱甘肽(GSH)及S02衍生物的檢測方法是非常重要的。香豆素廣泛存在于高等植物中,不但容易合成而且易于修飾,因具有高的熒光量子產(chǎn)率和穩(wěn)定的光學(xué)性質(zhì)而備受關(guān)注。本文基于熒光分析法,以香豆素為熒光團分別設(shè)計合成了兩種專一性檢測谷胱甘肽(GSH)及SO_2衍生物的熒光探針。主要內(nèi)容如下:(1)以香豆素作為熒光團專一性檢測谷胱甘肽(GSH)的熒光探針的合成及應(yīng)用研究。根據(jù)文獻報道,本文合成了專一性檢測谷胱甘肽(GSH)的熒光探針A。從探針A的分子結(jié)構(gòu)可以看出,其7-位存在推電子的N,N-二乙胺基,苯環(huán)3-位所連接的烯烴鏈上既存在吸電子的醛基又存在活潑的鹵素C1原子,所以整個探針分子結(jié)構(gòu)存在分子內(nèi)電荷轉(zhuǎn)移(intramolecular charge transfer,ICT)和鹵素氯產(chǎn)生的重原子效應(yīng)(the heavy atom effect),使其在550 nm處有較弱的熒光發(fā)射峰,當向探針A的溶液中加入谷胱甘肽(GSH)后,谷胱甘肽(GSH)中親核性的氨基會進攻探針A上的醛基,由于生成的中間產(chǎn)物存在親核性的巰基,巰基就會接著與其臨近的氯原子發(fā)生親核取代反應(yīng)。上述反應(yīng)不但破壞了探針A分子的ICT效應(yīng)同時也打破了氯原子的重原子效應(yīng),故使溶液的熒光發(fā)射波長由550 nm藍移到500 nm,反應(yīng)體系在500 nm處的熒光強度與GSH的濃度在0-10 μM范圍內(nèi)具有良好的線性關(guān)系,該方法對GSH的檢測非常靈敏,檢出限為68.7 nM。(2)以苯并吡喃嗡為識別基團的HSO_3~-熒光探針的設(shè)計及應(yīng)用研究。由于苯并吡喃嗡染料特別容易受到親核試劑的進攻,從而打破了染料原來的π共軛結(jié)構(gòu),使分子內(nèi)電荷重新排布,體系的發(fā)射波長發(fā)生變化。基于苯并吡喃嗡易受到親核試劑進攻這一原理,本文設(shè)計合成了檢測HSO_3~-的熒光探針B。探針B中的苯并吡喃嗡部分與香豆素熒光團之間存在分子內(nèi)的光誘導(dǎo)電子轉(zhuǎn)移過程(photo-induce electron transfer,PET),導(dǎo)致自身熒光很弱,當向探針B的溶液中加入親核性的HSO_3~-時,HSO_3~-與苯并吡喃嗡中C-4原子發(fā)生親核加成反應(yīng),使分子內(nèi)電荷重新排布,PET效應(yīng)消失,因此反應(yīng)體系在510nm處的熒光信號顯著升高。同時,上述反應(yīng)使溶液的顏色也發(fā)生了顯著地變化由藍色變?yōu)辄S色。探針B在30 s內(nèi)就可以完成對HSO_3~-的檢測,反應(yīng)體系在510 nm處的熒光強度與HSO_3~-的濃度在0.2-7.5 μM范圍內(nèi)具有良好的線性關(guān)系,該方法對HSO_3~-的檢出限為42nM,同時也成功的應(yīng)用探針B檢測了糖溶液和細胞中的HSO_3~-。
[Abstract]:Glutathione GSH (GSH) is closely related to the redox equilibrium in organism and the normal life activity of organism. As an atmospheric pollutant, GSH affects the growth and development of plants by affecting the photosynthesis of plants.Its derivatives are also widely used as food additives and are often ingested in the body.Therefore, it is very important to construct a qualitative, quantitative and specific method for the detection of glutathione glutathione (GSH) and S02 derivatives.Coumarin is widely found in higher plants, which is not only easy to synthesize but also easy to modify, and has attracted much attention due to its high fluorescence quantum yield and stable optical properties.Based on fluorescence analysis, two specific fluorescent probes for the detection of glutathione (GSH) and SO_2 derivatives were designed and synthesized using coumarin as fluorescence group.The main contents are as follows: 1) Synthesis and application of coumarin as fluorescent probe for glutathione glutathione glutathione (GSH) detection.A fluorescence probe A was synthesized for the specific detection of glutathione glutathione (GSH).From the molecular structure of probe A, it can be seen that there is a N-N- diethylamine group at the 7- site, and the alkene chain connected by the 3-site benzene ring has both an electron absorbing group and an active halogen C1 atom.So the whole molecular structure of the probe is characterized by intramolecular charge transfer charge transfer (ICTI) and the heavy atom effect produced by halogen chlorine, making it have a weaker fluorescence emission peak at 550nm, when glutathione glutathione is added to the solution of probe A).Nucleophilic amino groups in glutathione glutathione (GSH) attack the aldehyde group on probe A. due to the existence of nucleophilic sulfhydryl group in the generated intermediate product, the thiol group then reacts with its adjacent chlorine atom to produce a nucleophilic substitution reaction.The above reactions not only destroy the ICT effect of probe A, but also break the heavy atom effect of chlorine atom.Therefore, the fluorescence emission wavelength of the solution is shifted from 550 nm blue to 500 nm. The fluorescence intensity of the reaction system at 500nm has a good linear relationship with the concentration of GSH in the range of 0-10 渭 M. the method is very sensitive to the detection of GSH.The detection limit is 68.7 NM. 2) the design and application of HSOSP-fluorescence probe with benzopyran as the recognition group.Because the benzopyran dyes are especially vulnerable to the attack of nucleophilic reagents, the original 蟺 conjugate structure of the dyes is broken, the intramolecular charge is rearranged and the emission wavelength of the system changes.Based on the principle that benzopyran is easily attacked by nucleophilic reagents, a fluorescent probe B for the detection of HSO _ 3H _ 3- is designed and synthesized in this paper.The photo-induced electron transfer process between the benzopyran humming part of probe B and the coumarin fluorescence group leads to a very weak self-fluorescence.At the same time, the color of the solution changed significantly from blue to yellow.Probe B can detect HSO3- within 30 seconds. The fluorescence intensity of the reaction system at 510 nm has a good linear relationship with the concentration of HSO3- in the range of 0.2-7.5 渭 M.The detection limit of HSO3- for HSO3- was 42 nM.The probe B was also successfully used to detect HSOS3- in sugar solution and cells.
【學(xué)位授予單位】：西北大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.3

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本文編號：1735922