二氧化硅纳米棒的制备、荧光功能化及其在免疫检测中的应用
发布时间：2018-08-21 13:08
【摘要】：一维二氧化硅纳米材料由于具有各向异性的结构、大的长径比和表面易功能化等优点,使其在生物检测、药物运输和疾病治疗等生物医学领域展现了广阔的应用前景。截止目前,相比于球形纳米材料,一维二氧化硅纳米材料的发展依旧十分缓慢,制备形貌、尺寸和化学组成精确可控的一维二氧化硅纳米材料还存在一定的技术壁垒,限制了一维二氧化硅纳米材料的开发与应用。为此,本论文设计并采用了一种简单、高效的一锅合成法,利用聚乙烯吡咯烷酮、柠檬酸钠、戊醇和水构建反相微乳液体系,以硅酸乙酯(TEOS)作为硅源,在氨水催化下制备了长径比和红外吸收指纹信号精确可调的一维二氧化硅纳米棒,系统研究了其形成机理,实现了基于二氧化硅纳米棒形状信息和红外吸收指纹信号的双模超灵敏免疫检测;并将该方法拓展至荧光二氧化硅纳米棒的制备,实现了超灵敏荧光免疫检测。主要研究内容如下:(1)针对现有合成方法难以精确、便捷调控二氧化硅纳米棒长径比及其相关特性的问题,我们设计并采用了简单的一锅反相微乳液合成法,在4小时、静置条件下成功制备了二氧化硅纳米棒。通过控制反应体系中氨水的浓度,实现了二氧化硅纳米棒长径比1.0到11.6的精确调控。TEOS的消耗速率、反应溶液电导率及红外吸收光谱分析表明,二氧化硅纳米棒的形貌、尺寸、横光学波(TO)和纵光学波(LO)红外光谱指纹信号是由TEOS的水解和缩合反应速率共同决定的。我们构建了三明治型免疫检测器件,开发了基于二氧化硅纳米棒的双模免疫检测:利用二氧化硅纳米棒独特的、在光学显微镜下易识别的形状信息,实现了目标蛋白的快速筛查及半定量检测;利用其TO、LO红外光谱指纹信号,实现了目标蛋白的准确、超灵敏定量检测,检测下限可以达到0.5 pM,线性检测区间为1 pM到10 nM。该研究为推进一维二氧化硅纳米材料的工业化生产,加快其实用化进程开辟了新道路。(2)为了验证一锅反相微乳液合成法的普适性,实现二氧化硅纳米棒的荧光功能化拓展,我们选用了光化学性质相对稳定的傒四羧酸二酐与氨基硅烷反应,制得了傒硅烷衍生物,以其和TEOS为硅源,利用一锅反相微乳液合成法,成功制备了荧光二氧化硅纳米棒。由于傒染料是以共价键的形式连接到二氧化硅纳米棒的结构中,因此有效解决了染料的泄露问题,提高了染料的光稳定性。通过控制反应过程中氨水的浓度、反应时间和反应温度,实现了荧光二氧化硅纳米棒长径比由1.0到13.4的精确调控。我们构建了三明治免疫检测器件,利用荧光二氧化硅纳米棒的荧光信号作为检测信号,实现了目标蛋白高灵敏度、高稳定性和高特异性的检测,检测下限为0.3 pM,线性区间为1 pM到20 nM。这种一锅反相微乳液合成法有望推广用于二氧化硅纳米棒其它相关材料体系的制备。
[Abstract]:Due to its anisotropic structure, large aspect ratio and easy surface functionalization, one-dimensional silica nanomaterials have been widely used in biomedical fields such as biological detection, drug transportation and disease treatment. Up to now, compared with spherical nanomaterials, the development of one-dimensional silica nanomaterials is still very slow, and there are still some technical barriers to the preparation of one-dimensional silica nanomaterials with precise and controllable morphology, size and chemical composition. The development and application of one-dimensional silica nanomaterials are limited. In this paper, a simple and efficient one-pot synthesis method was designed and used to construct reverse microemulsion system using polyvinylpyrrolidone, sodium citrate, pentanol and water. Ethyl silicate (TEOS) was used as silicon source. One-dimensional silica nanorods with precise aspect ratio and infrared absorption fingerprint signal were prepared under the catalysis of ammonia. The formation mechanism of the nanorods was systematically studied. The double mode hypersensitive immunoassay based on the shape information of silica nanorods and infrared fingerprint signal was realized, and the method was extended to the preparation of fluorescent silica nanorods, and the hypersensitive fluorescence immunoassay was realized. The main research contents are as follows: (1) in order to control the aspect ratio of silicon dioxide nanorods and its related characteristics, we designed and adopted a simple one-pot reverse microemulsion synthesis method in 4 hours. Silica nanorods were successfully prepared under static conditions. By controlling the concentration of ammonia in the reaction system, the consumption rate of TEOS was accurately regulated by the aspect ratio between 1.0 and 11.6 of silica nanorods. The conductivity of the reaction solution and the infrared absorption spectrum analysis showed that the morphology and size of SiO2 nanorods were obtained. The infrared fingerprint signals of transverse optical wave (TO) and longitudinal optical wave (LO) are determined by the rate of hydrolysis and condensation of TEOS. We built a sandwich immune detector and developed a dual-mode immunoassay based on silica nanorods: shape information that is unique to silica nanorods and easily recognized under optical microscopy. The fast screening and semi-quantitative detection of target protein were realized, and the accurate and hypersensitive quantitative detection of target protein was realized by using its TOLO IR fingerprint signal. The detection limit could reach 0.5 pm, and the linear detection range was from 1 pm to 10 nm. This research has opened up a new way to promote the industrial production of one-dimensional silica nanomaterials and speed up its practical process. (2) in order to verify the universality of one-pot reverse microemulsion synthesis method, the fluorescent functionalization of silica nanorods can be expanded. The siloxane derivatives were prepared by the reaction of tetracarboxylic anhydride with aminosilane, which has relatively stable photochemical properties. The fluorescent silica nanorods were successfully prepared by one-pot reverse microemulsion synthesis with TEOS as the silicon source. Because the dyes are connected to the structure of silica nanorods in the form of covalent bonds, the problem of dye leakage is effectively solved and the photostability of the dyes is improved. By controlling the concentration of ammonia water, reaction time and reaction temperature, the ratio of length to diameter of fluorescent silica nanorods from 1.0 to 13.4 was achieved. A sandwich immunodetector was constructed, and the fluorescence signal of fluorescent silica nanorods was used as the detection signal. The target protein was detected with high sensitivity, high stability and high specificity. The detection limit is 0.3 pm and the linear range is from 1 pm to 20 nm. The one-pot reverse microemulsion synthesis method is expected to be used in the preparation of silica nanorods.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;O657.3
[Abstract]:Due to its anisotropic structure, large aspect ratio and easy surface functionalization, one-dimensional silica nanomaterials have been widely used in biomedical fields such as biological detection, drug transportation and disease treatment. Up to now, compared with spherical nanomaterials, the development of one-dimensional silica nanomaterials is still very slow, and there are still some technical barriers to the preparation of one-dimensional silica nanomaterials with precise and controllable morphology, size and chemical composition. The development and application of one-dimensional silica nanomaterials are limited. In this paper, a simple and efficient one-pot synthesis method was designed and used to construct reverse microemulsion system using polyvinylpyrrolidone, sodium citrate, pentanol and water. Ethyl silicate (TEOS) was used as silicon source. One-dimensional silica nanorods with precise aspect ratio and infrared absorption fingerprint signal were prepared under the catalysis of ammonia. The formation mechanism of the nanorods was systematically studied. The double mode hypersensitive immunoassay based on the shape information of silica nanorods and infrared fingerprint signal was realized, and the method was extended to the preparation of fluorescent silica nanorods, and the hypersensitive fluorescence immunoassay was realized. The main research contents are as follows: (1) in order to control the aspect ratio of silicon dioxide nanorods and its related characteristics, we designed and adopted a simple one-pot reverse microemulsion synthesis method in 4 hours. Silica nanorods were successfully prepared under static conditions. By controlling the concentration of ammonia in the reaction system, the consumption rate of TEOS was accurately regulated by the aspect ratio between 1.0 and 11.6 of silica nanorods. The conductivity of the reaction solution and the infrared absorption spectrum analysis showed that the morphology and size of SiO2 nanorods were obtained. The infrared fingerprint signals of transverse optical wave (TO) and longitudinal optical wave (LO) are determined by the rate of hydrolysis and condensation of TEOS. We built a sandwich immune detector and developed a dual-mode immunoassay based on silica nanorods: shape information that is unique to silica nanorods and easily recognized under optical microscopy. The fast screening and semi-quantitative detection of target protein were realized, and the accurate and hypersensitive quantitative detection of target protein was realized by using its TOLO IR fingerprint signal. The detection limit could reach 0.5 pm, and the linear detection range was from 1 pm to 10 nm. This research has opened up a new way to promote the industrial production of one-dimensional silica nanomaterials and speed up its practical process. (2) in order to verify the universality of one-pot reverse microemulsion synthesis method, the fluorescent functionalization of silica nanorods can be expanded. The siloxane derivatives were prepared by the reaction of tetracarboxylic anhydride with aminosilane, which has relatively stable photochemical properties. The fluorescent silica nanorods were successfully prepared by one-pot reverse microemulsion synthesis with TEOS as the silicon source. Because the dyes are connected to the structure of silica nanorods in the form of covalent bonds, the problem of dye leakage is effectively solved and the photostability of the dyes is improved. By controlling the concentration of ammonia water, reaction time and reaction temperature, the ratio of length to diameter of fluorescent silica nanorods from 1.0 to 13.4 was achieved. A sandwich immunodetector was constructed, and the fluorescence signal of fluorescent silica nanorods was used as the detection signal. The target protein was detected with high sensitivity, high stability and high specificity. The detection limit is 0.3 pm and the linear range is from 1 pm to 20 nm. The one-pot reverse microemulsion synthesis method is expected to be used in the preparation of silica nanorods.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;O657.3
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