本文選題：聚乙烯亞胺 + pH敏感型碳點(diǎn)��； 參考：《東北大學(xué)》2015年博士論文

【摘要】：碳點(diǎn)(CDs)不僅具備碳納米材料的共同特性,如對(duì)環(huán)境和生物體無(wú)毒,合成方法多種多樣,表面官能團(tuán)豐富等,而且作為新型的發(fā)光碳納米材料,其量子產(chǎn)率最高可達(dá)80%,與半導(dǎo)體量子點(diǎn)(QDs)相當(dāng)。因而,碳點(diǎn)成為近年來(lái)碳納米材料的研究熱點(diǎn)。用不同方法和原料制備的CDs可在多個(gè)領(lǐng)域獲得廣泛應(yīng)用,因此,合成碳點(diǎn)的新方法仍是目前亟待探索的領(lǐng)域。碳點(diǎn)的量子產(chǎn)率高,發(fā)射光譜可調(diào),然而,迄今為止,其發(fā)光機(jī)理尚無(wú)定論。CDs表面官能團(tuán)豐富,多被用于表面改性和偶聯(lián)生物分子,實(shí)現(xiàn)特異性傳感和靶向成像、治療等目標(biāo)。另一方面,表面官能團(tuán)的氧化還原性質(zhì)尚未得到深入研究。在傳感應(yīng)用領(lǐng)域,以CDs熒光信號(hào)的猝滅或增強(qiáng)構(gòu)建的傳感器是目前的研究熱點(diǎn),而基于CDs其他物理化學(xué)性質(zhì),如氧化還原性的探針的研究還未見(jiàn)報(bào)道。本文旨在拓展CDs合成方法和原料,研究表面官能團(tuán)對(duì)其發(fā)光性能的影響,探討表面官能團(tuán)的還原性,并利用CDs的還原性構(gòu)建新型傳感器。論文的第一章詳細(xì)介紹了CDs的合成方法,物理化學(xué)性質(zhì)及其在光學(xué)成像、載藥治療、光學(xué)傳感和光催化等領(lǐng)域的應(yīng)用。論文的第二章以陽(yáng)離子型聚電解質(zhì)聚乙烯亞胺(PEI)同時(shí)作為碳源和表面鈍化劑,化學(xué)氧化法一步制備PEI-CDs。PEI被HNO3分解,部分PEI片段被碳化并氧化,得含氧碳核；未反應(yīng)的PEI片段通過(guò)酰胺化與碳核表面的羧基反應(yīng),得到表面同時(shí)富含氨基和羧基的PEI-CDs。該碳點(diǎn)在酸性條件下帶正電,堿性條件下帶負(fù)電。表面氨基和羧基在酸性和堿性介質(zhì)中質(zhì)子化和去質(zhì)子化,使得PEI-CDs的熒光對(duì)溶液pH變化表現(xiàn)靈敏響應(yīng),即隨著pH的升高,熒光強(qiáng)度顯著下降。PEI-CDs的熒光對(duì)pH變化的響應(yīng)可逆：將pH從2增加到12,再?gòu)?2降低到2,10次循環(huán)變化后,碳點(diǎn)熒光依然恢復(fù)初始值。PEI-CDs的熒光不受鹽濃度和光輻照的影響,鹽濃度高達(dá)1 mol L-1,或150 W氙燈連續(xù)激發(fā)3h,其發(fā)光強(qiáng)度無(wú)改變。HeLa細(xì)胞同PEI-CDs孵育24 h,未見(jiàn)明顯細(xì)胞毒性。PEI-CDs穿透細(xì)胞膜,進(jìn)入到細(xì)胞質(zhì)。進(jìn)入細(xì)胞的PEI-CDs在340 nm和495 nm光源激發(fā)下,分別發(fā)射藍(lán)色和綠色熒光。在合成CDs的研究中,其表面豐富的官能團(tuán)吸引了我們的注意,因此第三章主要研究表面官能團(tuán)的氧化還原性。無(wú)須光輻照和外加還原劑,Ag+同CDs的水溶液在50℃下水浴5 min, Ag+被還原為Ago,隨后Ago自發(fā)團(tuán)聚成核,生成平均粒徑為3.1±1.5nm的Ag-NPs。CDs表面的酚羥基和氨基還原Ag+后分別轉(zhuǎn)換成苯醌和偶氮。生成的Ag-NPs吸附在CDs表面,形成Ag-NPs/CDs復(fù)合物。其中CDs充當(dāng)保護(hù)劑,使Ag-NPs在水溶液中穩(wěn)定分散至少45天,而未見(jiàn)團(tuán)聚。CDs催化還原生成的Ag-NPs有強(qiáng)共振光散射(RLS),而且RLS的信號(hào)強(qiáng)度與Ag+的濃度線性相關(guān),基于此,我們建立了環(huán)境水樣中Ag+含量的分析方法。對(duì)兩種河水樣的加標(biāo)回收率分別為103%和106%,測(cè)定結(jié)果滿(mǎn)意。CDs還可還原HAuCl4并生成粒徑為3.0±0.7m的Au-NPs。制備Ag-NPs和Au-NPs的最優(yōu)條件分別是弱堿性和弱酸性介質(zhì),這是因?yàn)镃Ds在堿性條件下帶負(fù)電,而在酸性條件下帶正電,分別適宜結(jié)合Ag+和AuCl4-。在研究Ag-NPs生成的最優(yōu)條件時(shí),發(fā)現(xiàn)過(guò)量的CDs顯著抑制Ag-NPs的生長(zhǎng),我們?cè)诘谒恼轮袑?duì)這一有趣的實(shí)驗(yàn)現(xiàn)象進(jìn)行了深入探索。研究發(fā)現(xiàn),體系中CDs過(guò)量,Ag+迅速吸附到CDs表面,溶液中自由的Ag+數(shù)量少,不能源源不斷地供應(yīng)Ag+到CDs表面,Ag-NPs的生長(zhǎng)被阻斷,因而生成量減少。加入生物硫醇后,巰基同Ag++結(jié)合,二者迅速形成絡(luò)合物。由于生物硫醇的還原能力比CDs弱,絡(luò)合物逐步釋放Ag+,供應(yīng)Ag+給CDs表面官能團(tuán)還原,因而體系中Ag-NPs生成量增多。以增強(qiáng)的Ag-NPs表面等離子體共振吸收峰強(qiáng)度為信號(hào),定量檢測(cè)生物硫醇。當(dāng)Ag+加入量為0.2 mM時(shí),半胱氨酸(cys)的檢測(cè)范圍是20-400 nM。減少體系中的Ag+,可以進(jìn)一步增強(qiáng)生物硫醇傳感的靈敏度。即當(dāng)Ag+加入量為0.1 mM時(shí),體系對(duì)Cys,高半胱氨酸(Hcy)和谷胱甘肽(GSH)三種生物硫醇的傳感范圍分別是2.5-30 nM、5-40 nM和2.5-30 nM。實(shí)際樣品中常見(jiàn)的共存組分,如19種氨基酸,Ca2+, Mg2+,葡萄糖,抗壞血酸和人血清白蛋白對(duì)生物硫醇的檢測(cè)無(wú)干擾。將該體系用于人血樣中生物硫醇的定量檢測(cè),加標(biāo)回收率為94-108%。
[Abstract]:Carbon point (CDs) not only has the common characteristics of carbon nanomaterials, such as non-toxic to the environment and organism, many kinds of synthetic methods and rich surface functional groups. Moreover, as a new kind of luminescent carbon nanomaterials, the quantum yield is up to 80%, which is equivalent to the semiconductor quantum dots (QDs). Therefore, the carbon point has become the research heat of carbon nanomaterials in recent years. CDs, prepared with different methods and raw materials, can be widely used in many fields. Therefore, the new method of carbon point synthesis is still an urgent field. The quantum yield of carbon point is high and the emission spectrum is adjustable. However, so far, its luminescence mechanism is not conclusive on the rich.CDs surface functional groups, and is used for surface modification and coupling organisms. Molecules, the realization of specific sensing and target imaging, treatment and other targets. On the other hand, the redox properties of surface functional groups have not been deeply studied. In the field of sensing applications, the quenching or strengthening of CDs fluorescence signals is a hot spot of research, based on other physical and chemical properties of CDs, such as redox probes. The purpose of this study is to expand CDs synthesis methods and materials, to study the effect of surface functional groups on their luminescence properties, to explore the reducibility of surface functional groups and to construct new sensors using the reducibility of CDs. The first chapter of the paper describes the synthesis method of CDs, the physical and chemical properties and the treatment of the optical imaging and drug loading. The second chapter of the paper uses cationic polyelectrolyte polyethyleneimine (PEI) as a carbon source and a surface passivating agent. PEI-CDs.PEI is decomposed by HNO3 in one step by chemical oxidation. Some PEI fragments are carbonized and oxidized to obtain oxygen containing carbon nuclei; the unreacted PEI fragments pass amidation and carbon nuclei. The surface of the carboxyl group reacts with the PEI-CDs., which is rich in the amino and carboxyl groups at the same surface. The carbon point is positive under the acidic condition and is negative under the alkaline condition. The surface amino and carboxyl groups are protonated and deprotoned in the acidic and alkaline medium, making the fluorescence of PEI-CDs responsive to the pH change of the solution, that is, with the increase of pH, the fluorescence intensity is increased. The response of the fluorescence of.PEI-CDs to the change of pH is reversible: the increase of pH from 2 to 12, and then from 12 to the 2,10 secondary cycle, the fluorescence of the carbon point is still restored to the initial value.PEI-CDs, without the effect of salt concentration and light irradiation, the concentration of the salt is up to 1 mol L-1, or the 150 W xenon lamp is continuously excited 3h, and the luminescence intensity does not change.HeLa cells and P. EI-CDs incubated 24 h, no obvious cytotoxic.PEI-CDs penetrated the cell membrane and entered the cytoplasm. The PEI-CDs of entering cells fired blue and green fluorescence respectively under the excitation of 340 nm and 495 nm light sources. In the study of the synthesis of CDs, the rich surface of the functional groups attracted our attention, so the third chapter mainly studied the oxygen of surface functional groups. Without light irradiation and external reductant, the water solution of Ag+ and CDs is bathing at 50 C for 5 min, Ag+ is reduced to Ago, then Ago spontaneously agglomerated into nucleation, and the phenolic hydroxyl and amino group of Ag-NPs.CDs surface with an average diameter of 3.1 + 1.5nm are converted into quinone and azo respectively after reducing Ag+, and Ag-NPs is adsorbed on CDs surface to form Ag-NPs. The /CDs complex, in which CDs acts as a protector, makes Ag-NPs stable and dispersed in aqueous solution for at least 45 days, and there is no strong resonance light scattering (RLS) of Ag-NPs generated by the reunion.CDs catalytic reduction, and the signal intensity of RLS is linearly related to the concentration of Ag+. Based on this, we have established an analytical method of Ag+ content in the water samples in the environment. For the two kinds of water samples. The recovery rate of the addition standard is 103% and 106% respectively. The results are satisfied that.CDs can also reduce HAuCl4 and produce Ag-NPs and Au-NPs with a diameter of 3 + 0.7m. The optimum conditions for preparing Ag-NPs and Au-NPs are weakly alkaline and weak acidic medium respectively. This is because CDs is negatively charged under alkaline conditions and is positively charged under acidic conditions, suitable for combining Ag+ and AuCl4-. to study respectively. When investigating the optimal conditions for Ag-NPs generation, we found that excessive CDs significantly inhibited the growth of Ag-NPs. In the fourth chapter, we explored this interesting experimental phenomenon. It was found that CDs overdose, Ag+ quickly adsorbed to the surface of CDs, and the free Ag+ quantity in the solution was less, and could not supply Ag+ to CDs surface, Ag-NPs. After the length was blocked, the amount of raw material decreased. After the addition of bio mercaptan, the sulfhydryl group combined with Ag++, the two quickly formed the complex. Because the reduction ability of the bio mercaptan was weaker than that of CDs, the complex gradually released Ag+ and supplied Ag+ to the CDs surface functional group. Therefore, the formation of Ag-NPs in the system increased much. The enhanced Ag-NPs surface plasmon resonance absorption peak was increased. The intensity is a signal, quantitative detection of bio mercaptan. When Ag+ is added to 0.2 mM, the detection range of cysteine (Cys) is the Ag+ in the 20-400 nM. reduction system. It can further enhance the sensitivity of biothiol sensing. That is, when Ag+ is added to 0.1 mM, the system is sensing of Cys, high cysteinic (Hcy) and glutathione (GSH) three biogenic mercaptan. The range is the common component in the actual samples of 2.5-30 nM, 5-40 nM and 2.5-30 nM., such as 19 kinds of amino acids, Ca2+, Mg2+, glucose, ascorbic acid and human serum albumin have no interference to the detection of biogenic mercaptan. The system is used for quantitative detection of biogenic mercaptan in human blood samples, and the recovery rate is 94-108%.

【學(xué)位授予單位】：東北大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TQ127.11;TP212

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