本文選題：碳量子點 + 石墨烯量子點　； 參考：《鄭州大學(xué)》2017年碩士論文

【摘要】：熒光碳基量子點作為新興的有機碳材料,因其具有特異的熒光性能、穩(wěn)定的物理化學(xué)性質(zhì)、高的生物相容性等優(yōu)異性能而躋身于材料界的“翹楚”。近年來,碳基量子點的廣泛研究越來越貼近生物和環(huán)境等相關(guān)領(lǐng)域,使得我們在材料制備和應(yīng)用的過程中,都更加關(guān)心其生物相容性和毒理風(fēng)險性的探索。本論文以兩種生物質(zhì)(頭發(fā)和豬皮)以及一種低毒無害的物質(zhì)檸檬酸為原料制備了三種綠色低毒、高生物相容性的碳量子點,并將其應(yīng)用于斑馬魚熒光成像的研究。另外,我們從現(xiàn)在研究很熱門的石墨烯材料出發(fā),制備了一種熒光性能優(yōu)越的還原性氧化石墨烯量子點,將其應(yīng)用于斑馬魚熒光成像和相關(guān)毒理學(xué)的研究。首先,以兩種生物質(zhì)頭發(fā)和豬皮為原料,采用微波輔助碳化的方法高效合成了基于頭發(fā)和豬皮這兩種富含蛋白的生物質(zhì)的熒光碳量子點。既沒有外加摻雜劑,也沒有使用任何有毒試劑,直接將生物質(zhì)原材料通過微波輔助碳化的方法快速制備了頭發(fā)量子點(HCDs)和豬皮量子點(SCDs)。同時,我們也通過化學(xué)水熱合成法以檸檬酸和尿素作為原材料合成了檸檬酸碳量子點,并與前兩種以生物質(zhì)為原料的量子點做對照,探索三種不同碳量子點的熒光性能及其他各項性質(zhì)的差異。三種碳量子點都是在10 nm以內(nèi)的納米顆粒,原材料的不同導(dǎo)致了其化學(xué)組成和熒光性能的不同,HCDs和SCDs在紫外光范圍內(nèi)主要為藍色熒光而CCDs主要為綠色熒光,且三種量子點的量子產(chǎn)率QY也有較大差異,分別為86.06%(HCDs),51.35%(SCDs)和19.73%(CCDs)。三種碳量子點都具有激發(fā)依賴性的寬光譜熒光,能夠被用作熒光標記物。其次,采用改進的Hummer的方法將石墨粉在高比例的氧化劑(KMnO4)下氧化成氧化石墨烯(GO),并通過后續(xù)DMF熱處理的方法獲得氮摻雜的高效熒光的還原性氧化石墨烯量子點(rGOQDs)。以GO為前體,通過DMF水熱修飾的方法制備了還原性氧化石墨烯量子點rGOQDs,其中DMF被用作氮源和還原劑來提高rGOQDs的光致發(fā)光性能。經(jīng)過DMF水熱修飾后,GO被還原和氮摻雜而成為rGOQDs,該rGOQDs被環(huán)氧基團,羰基,羥基和C-N等功能化基團修飾,大大改善了其熒光性能,使得其量子產(chǎn)率由6.53%上升至24.62%,最終所得的rGOQDs擁有激發(fā)依賴性的寬波長熒光性能。然后,成功將HCDs,SCDs和CCDs三種碳量子點應(yīng)用于斑馬魚活體熒光成像,使用一系列不同的濃度來測試不同量子點在斑馬魚體內(nèi)的熒光成像效果,比較不同量子點熒光成像效果的差異,并分析碳量子點在斑馬魚體內(nèi)的吸收、分布、代謝和排泄(ADME)的影響。通過對斑馬魚活體內(nèi)長達15天的熒光效果研究,結(jié)果表明,在量子點溶液浸泡的48小時內(nèi),胚胎的成像效果良好。而隨著時間的延長,碳量子點的熒光效果越來越差,直至最終完全觀測不到熒光。通過向碳量子點溶液中加入生物體內(nèi)含有的物質(zhì)ATP,NADH和Fe3+離子,進行一系列濃度的猝滅測試以模擬生物活體內(nèi)碳量子點的衰敗過程,結(jié)果表明三種物質(zhì)均能不同程度地猝滅碳量子點。最后,對于rGOQDs,主要研究了其在斑馬魚活體動物模型上的熒光成像,以及其相應(yīng)的發(fā)育毒理學(xué),基因毒理學(xué)研究。從其孵化率、死亡率、心率、體長和畸形等指標上反應(yīng)其發(fā)育毒性,各指標都有一定的減弱,表明rGOQDs對斑馬魚有一定的發(fā)育毒性。為了研究rGOQDs對斑馬魚基因表達量擾動性,我們選擇斑馬魚的芳香烴受體相關(guān)的基因cyp1a,cyp1c和cyp7a1以及對外界壓力敏感的基因hsp70四個基因來進行研究。實時熒光定量PCR的結(jié)果表明,四種基因cyp1a,cyp1c,cyp7a1和hsp70分別明顯上調(diào)了8.49,4.65,5.93和3.63倍,表明rGOQDs確實對斑馬魚的芳香烴受體(AhR)信號傳導(dǎo)通路有一定的擾動性。同時,運用Tg(cyp1a:gfp)斑馬魚對rGOQDs進行研究,研究結(jié)果表明rGOQDs暴露后的Tg(cyp1a:gfp)斑馬魚熒光強度顯著增加。此外,Western Blot的結(jié)果進一步證明了綠色熒光蛋白隨著暴露濃度增加而高表達的狀況,與熒光成像及實時熒光定量PCR的結(jié)果相符。這些關(guān)于石墨烯材料風(fēng)險性的研究,將對石墨烯類材料的后續(xù)生物學(xué)應(yīng)用具有重要的借鑒意義和參考價值。
[Abstract]:As a new organic carbon material, fluorescent carbon based quantum dots have become the "top" of the material industry because of their specific fluorescence properties, stable physical and chemical properties, high biocompatibility and other excellent properties. In recent years, the extensive research of carbon based quantum dots is becoming more and more close to the related fields of raw materials and environment. In this paper, two kinds of biomass (hair and pigskin) and a kind of low toxic and harmless citric acid are used as raw materials to prepare three kinds of carbon quantum dots with low toxicity and high biocompatibility, and apply them to the study of zebrafish fluorescence imaging. We have prepared a highly fluorescent reductive graphene oxide quantum dot from the very popular graphene material, and applied it to the study of fluorescence imaging and related toxicology of zebrafish. First, two kinds of biomass hair and pigskin were used as raw materials and microwave assisted carbonization was used to efficiently synthesize the hair based on hair. The fluorocarbon quantum dots (CDS) of two protein rich biomass, such as pigskin and pigskin, have been prepared by microwave assisted carbonization of biomass (HCDs) and quantum dots (SCDs) by microwave assisted carbonization, and we also use the chemical hydrothermal synthesis of citric acid by chemical hydrothermal synthesis. The carbon quantum dots of citrate were synthesized with urea as raw materials, and compared with the first two quantum dots with biomass as raw materials, the difference between the fluorescence and other properties of the three different carbon quantum dots was explored. The three carbon quantum dots were within 10 nm. The difference in the raw material resulted in the chemical composition and fluorescein The difference in energy is that HCDs and SCDs are mainly blue fluorescence in the ultraviolet range and CCDs is mainly green fluorescence, and the quantum yield QY of the three quantum dots are also different, 86.06% (HCDs), 51.35% (SCDs) and 19.73% (CCDs), respectively. The three kinds of carbon quantum dots all have wide spectral fluorescence that excite dependence, and can be used as fluorescent labels. Second, Graphite powder was oxidized to graphene oxide (GO) under a high proportion of oxidant (KMnO4) by improved Hummer method, and the reduced graphite oxide quantum dots (rGOQDs) with high efficiency fluorescence of nitrogen doping was obtained by subsequent DMF heat treatment. The amount of reductive graphene oxide was prepared by DMF hydrothermal modification with GO precursor. Subpoint rGOQDs, in which DMF is used as a nitrogen source and reducing agent to improve the photoluminescence properties of rGOQDs. After DMF hydrothermal modification, GO is reduced and nitrogen doped to become rGOQDs. The rGOQDs is modified by functional groups such as epoxy groups, carbonyl, hydroxyl and C-N, greatly improving their fluorescence properties, making the quantum yield rise from 6.53% to 24.62%. The final rGOQDs has excitation dependent wide wavelength fluorescence performance. Then, three carbon quantum dots (HCDs, SCDs and CCDs) are successfully applied to zebrafish living fluorescence imaging, and a series of different concentrations are used to test the fluorescence imaging effects of different quantum dots in zebrafish, and compare the difference of fluorescence imaging effects at different quantum dots. The effects of carbon quantum dots on the absorption, distribution, metabolism and excretion (ADME) in zebrafish were analyzed. The results of 15 days' fluorescence in zebrafish body were studied. The results showed that the imaging effect of the embryos was good within 48 hours of soaking in the quantum dots solution. A series of concentrations of ATP, NADH and Fe3+ ions were added to the carbon quantum dots solution to simulate a series of quenching tests to simulate the decay process of carbon quantum dots in living organisms. The results showed that the three substances could all quenched carbon quantum dots in varying degrees. Finally, for rGOQDs, the main research was The fluorescence imaging of the zebrafish living animal model and its corresponding developmental toxicology and gene toxicology study on the developmental toxicity of its hatchability, mortality, heart rate, body length and malformation have been weakened to a certain extent, indicating that rGOQDs has certain developmental toxicity to zebrafish. In order to study the rGOQDs pair of spots. We chose four genes, CYP1A, cyp1c and CYP7A1, and HSP70 gene HSP70, which were related to the aromatics receptor related genes of zebrafish. The results of real-time quantitative PCR showed that the four genes, CYP1A, cyp1c, CYP7A1, and HSP70, were significantly up to 8.49,4.65,5.93 and 3.63 times higher than that of cyp1c, CYP7A1 and HSP70, respectively. RGOQDs did have a certain disturbance to the signal transduction pathway of the aromatic hydrocarbon receptor (AhR) of zebrafish. At the same time, Tg (cyp1a:gfp) zebrafish was used to study rGOQDs. The results showed that the fluorescence intensity of Tg (cyp1a:gfp) zebrafish after rGOQDs exposure was significantly increased. Moreover, the results of Western Blot further proved that the green fluorescent protein was followed by the results. The high expression of exposure concentration is consistent with the results of fluorescence imaging and real-time fluorescent quantitative PCR. The research on the risk of graphene materials will have important reference and reference value for the follow-up biological application of graphene materials.
【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】：2017
【分類號】：O657.3;TS254.7

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