本文關(guān)鍵詞： 石墨烯量子點(diǎn) 檸檬黃 抗壞血酸 谷胱甘肽 熒光傳感　出處：《鄭州大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

【摘要】：石墨烯量子點(diǎn)(Graphene quantum dot,GQDs)是石墨烯家族中的最新成員,也是近三年來發(fā)展起來的一種準(zhǔn)零維的納米熒光材料。和傳統(tǒng)的半導(dǎo)體量子點(diǎn)相比,GQDs具有生物相容性好,毒性低,光學(xué)性質(zhì)穩(wěn)定等優(yōu)異的性能,在熒光傳感、細(xì)胞標(biāo)記以及生物成像等方面具有廣闊的應(yīng)用前景。然而,目前基于GQDs的熒光傳感分析仍處于初級階段,在報(bào)道的文獻(xiàn)中存在熒光量子產(chǎn)率低,熒光傳感敏感度低,選擇性差等問題。因此,改進(jìn)合成條件和傳感體系的設(shè)計(jì),以及構(gòu)建高靈敏度和高選擇性的GQDs傳感器是非常重要的。本研究合成了GQDs和氮摻雜的石墨烯量子點(diǎn)(N-GQDs),基于內(nèi)濾光效應(yīng),以及熒光共振能量轉(zhuǎn)移兩種熒光猝滅方式,分別構(gòu)建了基于GQDs的檸檬黃熒光傳感體系和基于N-GQDs的抗壞血酸(Ascorbic Acid,AA)和谷胱甘肽(Glutathion,GSH)的熒光傳感體系,所獲結(jié)果對于GQDS在熒光傳感體系的應(yīng)用和三種目標(biāo)物的分析提供了方法學(xué)的參考和依據(jù)。具體內(nèi)容如下:1.基于GQDs熒光傳感法測定檸檬黃(tartrazine)利用Hummer法,通過濃硫酸和高錳酸鉀對石墨在高溫條件下的氧化剝離,合成GO;采用TOP-down的合成策略,以獲得的GO為碳源,濃氨水(濃NH3·H2O)為堿性介質(zhì),在高溫高壓條件下(200℃反應(yīng)5 h),使GO去氧化并斷裂成尺寸較小的GQDs,利用紅外光譜(IR)和透射電鏡(TEM)等對獲得的GQDs進(jìn)行了表征。該GQDs在440 nm具有較強(qiáng)的熒光,與檸檬黃的吸收光譜具有較大程度的重疊,基于二者之間的內(nèi)濾光效應(yīng),建立了檸檬黃的熒光傳感分析新方法。在最優(yōu)的實(shí)驗(yàn)條件下,檸檬黃的加入量與體系熒光的猝滅在0.008μmol/L~4μmol/L呈線性關(guān)系,檢出限為0.0035μmol/L,相對于報(bào)道的方法,該方法具有更靈敏的檢測限和更高的選擇性。常見的金屬離子和色素不干擾體系的測定,該方法可成功用于飲料中檸檬黃的測定。2.基于N-GQDs-MnO_2熒光off-on法測定抗壞血酸(AA)采用Down-TOP的合成策略以檸檬酸為碳源,氨水為氮源,水熱法200℃反應(yīng)3 h,合成了N-GQDs,通過IR,X射線電子能譜(XPS),TEM等對合成的N-GQDs進(jìn)行了表征;通過Na2SO_3還原KMnO_4合成了MnO_2納米片,MnO_2納米片在N-GQDs發(fā)射峰處具有較寬范圍的光吸收,并且和N-GQDs之間具有較強(qiáng)的π-π堆積作用,二者之間發(fā)生共振能量轉(zhuǎn)移,從而猝滅N-GQDs的熒光;AA具有較強(qiáng)的還原性,可以將MnO_2納米片還原為Mn2+,從而使得體系的熒光恢復(fù),基于此,建立了檢測AA的熒光傳感新方法,AA的加入量在0.02μmol/L~8μmol/L范圍內(nèi)與體系熒光的恢復(fù)呈線性關(guān)系,檢測限5.6 nmol/L。相對于報(bào)道的方法,該方法不僅具有最高的檢測靈敏度,而且可以消除生物血樣中常見干擾物尿酸(UA)、多巴胺(DA)、谷胱甘肽(GSH)的干擾,該方法成功用于血樣中AA的檢測,加標(biāo)回收率在96.5-102.7%之間。3.基于N-GQDs-MnO_2熒光off-on法測定谷胱甘肽(GSH)在上一章合成的N-GQDs的基礎(chǔ)上,以2-(N-嗎啡啉)乙磺酸為還原劑合成MnO_2納米片,MnO_2納米片通過π-π堆積,與N-GQDs發(fā)生共振能量轉(zhuǎn)移,N-GQDs熒光猝滅,還原型的GSH能夠?qū)nO_2還原成Mn2+,從而使得體系的熒光恢復(fù)�；诖�,建立了檢測GSH的熒光傳感新方法,相對于Na2SO_3還原合成的MnO_2納米片來說,該熒光能量轉(zhuǎn)移體系對GSH具有更高的選擇性。在0.02~8μmol/L濃度范圍內(nèi),GSH的加入量與體系的熒光恢復(fù)成線性關(guān)系,檢測限為16 nmol/L,常見的金屬離子、氨基酸,UA和DA不干擾GSH的測定,該方法成功的用于血樣中GSH的檢測,回收率在95.2-103.8%之間。
[Abstract]:Graphene quantum dots (Graphene quantum, dot, GQDs) is the newest member of the family of graphene, a quasi zero dimensional nano fluorescent material is developed in three years. Compared with traditional semiconductor quantum dots, GQDs has good biocompatibility, low toxicity, stable optical properties and excellent performance in fluorescence sensing, and has wide application prospect cell markers and biological imaging. However, the fluorescence sensing analysis based on GQDs is still in the primary stage, reported in the literature have low fluorescence quantum yield and fluorescence sensing sensitivity is low, the problem of poor selectivity. Therefore, the improved design of synthesis conditions and sensing system, and the construction of high sensitivity and high selectivity of GQDs sensor is very important. The graphene quantum dots GQDs and nitrogen doped were synthesized in this study (N-GQDs), based on the inner filter effect, and fluorescence resonance energy transfer Two fluorescence quenching method, were constructed based on Huang Yingguang lemon sensing system based on N-GQDs GQDs and ascorbic acid (Ascorbic Acid AA) and glutathione (Glutathion, GSH) the fluorescence sensing system, the analysis of the results for the application of GQDS in fluorescence sensing system and three kinds of objects provide methodological reference and the specific contents are as follows: 1.. Based on the determination of lemon yellow fluorescence sensing method based on GQDs (tartrazine) by using Hummer method, by concentrated sulfuric acid and Potassium Permanganate on oxidation stripping, under the condition of high temperature graphite synthesis GO; synthetic strategy of TOP-down, to obtain the GO as carbon source, ammonia (concentrated NH3 - H2O) for in alkaline medium, under high pressure and high temperature (200 DEG C, the reaction of 5 h) to GO oxidation and broken into smaller size GQDs, using infrared spectroscopy (IR) and transmission electron microscopy (TEM) to obtain GQDs were investigated. The GQDs in 440 nm There is a strong fluorescence, with a greater degree of overlap with the absorption spectrum of lemon yellow, the inner filter effect between the two based on the established fluorescence sensing tartrazine analysis methods. Under the optimal conditions, the amount of lemon yellow fluorescence quenching system and a linear relationship in the 0.008 mol/ L~4 mol/L, the detection limit was 0.0035 mol/L, compared with the reported methods, this method has a detection limit of more sensitive and higher selectivity. Common metal ions do not interfere with the determination of pigment and system, this method can be successfully used for the determination of lemon yellow beverage in.2. based on N-GQDs-MnO_2 off-on fluorescence method for the determination of ascorbic acid (AA) synthesis by Down-TOP's strategy of using citric acid as carbon source, ammonia as nitrogen source, hydrothermal reacting at 200 DEG C for 3 h, N-GQDs was synthesized by IR, X ray photoelectron spectroscopy (XPS), on the synthesis of N-GQDs were characterized by the reduction of Na2SO_3 KM TEM; The synthesis of nO_4 nano MnO_2, nano MnO_2 has wide range of N-GQDs emission peak light absorption, strong stacking interaction between and N-GQDs resonance energy transfer occurs between the two, so the fluorescence quenching of N-GQDs; AA has the strong reducibility, the reduction of MnO_2 nanosheets Mn2+, which makes the system of fluorescence recovery, based on this, a new method was established for fluorescence detection of AA, the amount of AA in the 0.02 mol/L~8 mol/L range and the linear relationship between the fluorescence recovery and detection limit of 5.6 nmol/L. compared with the reported methods, this method not only has the highest detection sensitivity, but also can to eliminate the common biological blood uric acid disruptors (UA), dopamine (DA), glutathione (GSH) interference, the method was successfully used for detection of AA in a blood sample, the recovery rate was 96.5-102.7%.3. N-GQDs-MnO_2 off-o based on fluorescence labeled N method for the determination of glutathione (GSH) on the basis of a chapter on the synthesis of N-GQDs, 2- (N- morpholine) ethane sulfonic acid as reducing agent synthesis of nano MnO_2, nano MnO_2 by tt-tt stacking, resonance energy transfer and fluorescence quenching of N-GQDs, N-GQDs, GSH reduced MnO_2 can be reduced to Mn2+ thus, the fluorescence recovery system. Based on this, a new method was established for fluorescence detection of GSH, compared with Na2SO_3 reduction of MnO_2 nanosheets synthesized, the fluorescence energy transfer system has a higher selectivity to GSH. In the 0.02~8 mol/L concentration range, fluorescence amount and the recovery of the GSH system into a linear relationship, the detection limit is 16 nmol/L, metal ions, common amino acids, UA and DA do not interfere with the determination of GSH, this method has been successfully used to detect GSH in a blood sample, the recovery rate was 95.2-103.8%.

【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O657.3;TP212

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