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基于微流控技術(shù)的熒光微膠囊制備以及梯度共聚物自組裝

發(fā)布時間:2018-09-01 05:42
【摘要】:微流控技術(shù)是處理或操控微量流體的一種新型技術(shù),它在化學(xué)、生物、醫(yī)學(xué)等領(lǐng)域已經(jīng)有廣泛的應(yīng)用。近年來,制作工藝簡單、成本低的毛細(xì)管微流控裝置在微膠囊的制備、微凝膠的構(gòu)筑、聚合物自組裝等領(lǐng)域具有越來越重要的應(yīng)用價值。本論文通過設(shè)計具有特定結(jié)構(gòu)的毛細(xì)管微流控裝置,利用微流控技術(shù)重點開展了以下兩方面的研究工作。一方面,設(shè)計了一種可實現(xiàn)氣-液剪切的毛細(xì)管微流控裝置,并通過氣-液微流控技術(shù)制備了CdS量子點/殼聚糖復(fù)合微膠囊。量子點被包覆在微膠囊的液體腔中,并保持其良好的熒光特性。通過三維顯微鏡分析微流控參數(shù)對微膠囊粒徑及分布的影響,采用顯微鏡研究了熒光微膠囊對不同環(huán)糊精(CD)溶液的響應(yīng)性,并結(jié)合掃描電鏡對微膠囊囊壁分析,分析了響應(yīng)性產(chǎn)生的原因。研究結(jié)果表明,微膠囊的粒徑隨著氣體流速的增大而變小但仍保持單分散性,液體流速對微膠囊的粒徑影響不大。α-CD會使Cd S量子點/殼聚糖復(fù)合微膠囊表面變的粗糙、出現(xiàn)裂縫、甚至塌陷。更有趣的是,熒光微膠囊在α-CD溶液中會出現(xiàn)熒光的衰減,且α-CD溶液濃度越大熒光衰減的越明顯。而β-CD卻不會引起微膠囊表面形態(tài)和熒光強度發(fā)生變化。另一方面,設(shè)計了一種可實現(xiàn)同軸流體模型的毛細(xì)管微流控裝置,并采用液-液微流方法進(jìn)行梯度共聚物自組裝的研究。先通過RAFT無皂乳液聚合的方法合成丙烯酸/甲基丙烯酸三氟乙酯(AA-TFEMA)梯度共聚物,利用核磁、DSC等表征了共聚物鏈的梯度結(jié)構(gòu)。在微流控裝置中對AA-TFEMA梯度共聚物進(jìn)行自組裝,詳細(xì)探究了外相流速、內(nèi)外相總流速、外相溶液、聚合物濃度對自組裝聚集體形態(tài)的影響。結(jié)果表明,在微流控裝置中,共聚物容易形成具有多種形態(tài)的聚集體,如球形和非球形的膠束。增大外相流速,非球形膠束的比例會增加?偭魉贉p小后,微流控自組裝不易進(jìn)行。隨著外相溶液中水含量減小,非球形膠束逐漸消失,而形成單一的球形膠束。共聚物濃度增大,會使自組裝結(jié)構(gòu)出現(xiàn)由球形向棒狀向囊泡的轉(zhuǎn)變。
[Abstract]:Microfluidic technology is a new technology for handling or manipulating trace fluids. It has been widely used in chemical, biological, medical and other fields. In recent years, capillary microfluidic devices with simple fabrication process and low cost have become more and more important in the preparation of microcapsules, the construction of microgels and the self-assembly of polymers. In this paper, a capillary microfluidic device with a specific structure is designed, and the following two aspects of research work are focused on by using the microfluidic technique. On the one hand, a capillary microfluidic device was designed to realize gas-liquid shear, and CdS quantum dot / chitosan composite microcapsules were prepared by gas-liquid microfluidic technique. Quantum dots are encapsulated in the liquid cavity of microcapsules and have good fluorescence properties. The effects of microfluidic parameters on the particle size and distribution of microcapsules were analyzed by three dimensional microscope. The response of fluorescent microcapsules to different cyclodextrin (CD) solutions was studied by microscope, and the wall of microcapsules was analyzed by scanning electron microscope (SEM). The causes of responsivity are analyzed. The results showed that the particle size of microcapsules decreased with the increase of gas flow rate, but remained monodispersity, and the flow rate of liquid had little effect on the particle size of microcapsules. 偽 -CD would make the surface of Cd S quantum dots / chitosan composite microcapsules rougher. Cracks appear, even collapse. What is more interesting is that fluorescent microcapsules show fluorescence decay in 偽 -CD solution, and the larger the concentration of 偽 -CD solution is, the more obvious the fluorescence decay is. However, 尾-CD did not change the surface morphology and fluorescence intensity of microcapsules. On the other hand, a capillary microfluidic device which can realize the coaxial fluid model is designed, and the self-assembly of gradient copolymers is studied by liquid-liquid microflow method. The gradient copolymer of acrylic acid / trifluoroethyl methacrylate (AA-TFEMA) was synthesized by RAFT soap-free emulsion polymerization. The gradient structure of the copolymer chain was characterized by NMR. The AA-TFEMA gradient copolymers were self-assembled in a microfluidic device. The effects of the flow rate of external phase, the total flow rate of internal and external phase, the solution of external phase and the concentration of polymer on the morphology of self-assembled aggregates were investigated in detail. The results show that the copolymers are easy to form aggregates with many forms, such as spherical and non-spherical micelles in microfluidic devices. The ratio of the non-spherical micelles will increase with the increase of the flow velocity of the external phase. The microfluidic self-assembly is not easy to carry out when the total flow velocity decreases. With the decrease of water content in the external phase solution, the non-spherical micelles gradually disappeared and formed a single spherical micelle. When the concentration of copolymer increases, the self-assembled structure changes from sphere to rod to vesicle.
【學(xué)位授予單位】:武漢理工大學(xué)
【學(xué)位級別】:碩士
【學(xué)位授予年份】:2015
【分類號】:TB33;O631.1

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