本文選題：熒光探針 + BODIPY�。� 參考：《河南大學(xué)》2016年碩士論文

【摘要】：熒光探針作為一種新型的生物檢測(cè)技術(shù),深受市場(chǎng)和研究者的關(guān)注,相較于傳統(tǒng)的檢測(cè)手段,有以下優(yōu)點(diǎn):操作簡(jiǎn)單、選擇性好、靈敏性高、花費(fèi)低,并且容易應(yīng)用在環(huán)境和生物系統(tǒng)中。1968年,Treibs小組發(fā)現(xiàn)了氟硼二吡咯甲川(BODIPY)類染料,由于其具有眾多優(yōu)點(diǎn),如高摩爾消光系數(shù)、高熒光量子產(chǎn)率、良好的光化學(xué)穩(wěn)定性、分子結(jié)構(gòu)易于修飾、熒光光譜半峰寬窄、對(duì)溶劑極性和p H的耐受性好等被廣泛應(yīng)用在標(biāo)記試劑、熒光開關(guān)、化學(xué)傳感器及激光染料等領(lǐng)域。BODIPY的8位作為敏感的位置,可以通過改變其連接取代基的電子特性,對(duì)探針的最大發(fā)射波長(zhǎng)及熒光量子產(chǎn)率產(chǎn)生很大的影響�；谡n題組以往的研究和文獻(xiàn)調(diào)研,我們將利用O-,N-,S-等基團(tuán)在不對(duì)稱和對(duì)稱BODIPY的8位修飾,以期望改變BODIPY的光物理特性,并研究其在探針方面的應(yīng)用。在第二章中,對(duì)Cl-BODIPY進(jìn)行修飾,合成了3個(gè)meso-Cl的探針,并著重研究了取代基對(duì)探針溶解性、反應(yīng)活性和穩(wěn)定性的影響。從紫外吸收和熒光發(fā)射圖譜可知,當(dāng)BDP2與半胱氨酸(Cys)相遇時(shí),首先Cys的巰基進(jìn)攻正電性較高的BODIPY 8位碳原子,同時(shí)離去一分子氯化氫,生成動(dòng)力學(xué)控制的巰基取代的產(chǎn)物,然后,Cys的氨基環(huán)化連接到BODIPY 8位碳原子上,生成氨基取代的熱力學(xué)控制的產(chǎn)物,釋放藍(lán)色熒光。谷胱甘肽(GSH)由于其分子骨架較大,氨基離巰基較遠(yuǎn),其與BDP2反應(yīng)的產(chǎn)物停留在巰基取代階段。同時(shí),探針的比例式熒光行為大大地增加了熒光測(cè)試的動(dòng)態(tài)范圍,能夠盡可能地減少實(shí)驗(yàn)中的誤差。探針在血漿中對(duì)氨基酸的檢測(cè),更展示了其在生物方面的潛在應(yīng)用。其次,以BODIPY為母體,對(duì)硝基偶氮基團(tuán)為識(shí)別團(tuán),設(shè)計(jì)合成了一個(gè)BODIPY-偶氮共軛的熒光探針。探針利用雙波段對(duì)半胱氨酸/同型半胱氨酸和谷胱甘肽顯示出良好地選擇性,并能區(qū)分檢測(cè)出半胱氨酸/同型半胱氨酸和谷胱甘肽。最后,設(shè)計(jì)合成了以BODIPY為熒光團(tuán),苯硫脲基團(tuán)為官能團(tuán)的熒光增強(qiáng)型探針。首先,我們用乙二胺和苯異硫氰酸酯合成了N-氨基乙基-N'-苯硫脲,在8-Cl-BODIPY的作用下,合成探針。探針對(duì)汞離子顯示了極好地選擇性,據(jù)實(shí)驗(yàn)結(jié)果推斷可能的檢測(cè)機(jī)制是汞離子導(dǎo)致的環(huán)化和相繼的水解作用。另外,探針在人體腫瘤細(xì)胞SMMC-7721內(nèi)實(shí)現(xiàn)了對(duì)汞離子的檢測(cè)。
[Abstract]:As a new biological detection technology, fluorescent probe has attracted much attention from market and researchers. Compared with traditional methods, fluorescent probe has the following advantages: simple operation, good selectivity, high sensitivity and low cost. In 1968, the Treibs group discovered fluoroboron dipyrrolidine-pyrrolidene BODIPY) dyes because of their many advantages, such as high molar extinction coefficient, high fluorescence quantum yield, good photochemical stability, and good photochemical stability, due to their many advantages, such as high molar extinction coefficient, high fluorescence quantum yield, and good photochemical stability. The molecular structure is easy to modify, the half peak of fluorescence spectrum is narrow, the solvent polarity and pH tolerance are good, and so on are widely used in labeling reagent, fluorescent switch, chemical sensor and laser dye. The maximum emission wavelength and fluorescence quantum yield of the probe can be greatly affected by changing the electronic properties of the connected substituents. Based on the previous research and literature investigation, we will use the 8-position modification of O-N- and S- in asymmetric and symmetric BODIPY in order to change the photophysical properties of BODIPY and study its application in probe. In chapter 2, Cl-BODIPY was modified and three meso-Cl probes were synthesized. The effects of substituents on the solubility, reaction activity and stability of the probes were studied. The UV absorption and fluorescence emission spectra show that when BDP2 meets cysteine, the sulfhydryl group of Cys attacks the positively charged 8 carbon atom of BODIPY and leaves a molecule of hydrogen chloride at the same time to form the product of mercapto substitution controlled by kinetics. Then the amino cyclization of Cys is connected to the carbon atom at the BODIPY 8 position to produce a thermodynamically controlled product of amino substitution, which releases blue fluorescence. Glutathione (GSH) has a large molecular skeleton and the amino group is far away from the sulfhydryl group. At the same time, the proportional fluorescence behavior of the probe greatly increases the dynamic range of fluorescence measurement, and can reduce the errors in the experiment as much as possible. The detection of amino acids in plasma by the probe shows its potential biological application. Secondly, using BODIPY as parent and p-nitroazo group as recognition group, a BODIPY- azo conjugated fluorescence probe was designed and synthesized. The probe showed good selectivity for cysteine / homocysteine and glutathione, and could distinguish cysteine / homocysteine and glutathione. Finally, a fluorescence enhanced probe with BODIPY as fluorescence group and benzene thiourea as functional group was designed and synthesized. First, we synthesized N-aminoethyl-N-thiourea with ethylenediamine and phenylisothiocyanate. The probe was synthesized under the action of 8-Cl-BODIPY. The probe showed excellent selectivity for mercury ions. According to the experimental results, the possible detection mechanism is the cyclization and successive hydrolysis induced by mercury ions. In addition, the probe can detect mercury ions in SMMC-7721 of human tumor cells.
【學(xué)位授予單位】：河南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O657.3

【相似文獻(xiàn)】

相關(guān)期刊論文 前10條

1 王姍姍;;小分子熒光探針在硫醇檢測(cè)中的最新研究進(jìn)展[J];科技信息;2010年23期

2 向雨秘;龍少波;朱R，

本文編號(hào)：1904811