发光高分子复合薄膜的制备及其传感性能研究
发布时间：2019-02-23 14:34
【摘要】：随着工业化进程的加剧,人们向环境中排放的有毒、有害物质逐年增多,随之而来的大气、水体和土壤污染等问题也日益严重。这些问题不但会对生态环境造成不利影响,而且威胁着人类的生存。因此,针对有毒有害物质研究的传感材料就显得尤为重要。光致发光复合薄膜材料,由于其在薄膜材料的内部或表面引入了发光物种(无机荧光材料或有机荧光材料),故具有一定的光学性能,且薄膜易加工、透明度高、发光稳定性好、发光效率高,目前该类新的复合薄膜材料已成为一类很有发展前景的功能材料。论文分别以铝酸锶、7-硝基苯并呋喃修饰的胆固醇(NBD-chol)为发光物质,易成膜高分子为基质,设计并制备一系列发光高分子复合薄膜材料,并系统研究了这些薄膜对气相和液相中有害物质的传感性能。1.采用本体聚合法合成的聚甲基丙烯酸甲酯(PMMA)为成膜高分子基质,引入发光材料铝酸锶(SrAl2O4),制备得到SrAl2O4/PMMA复合薄膜材料。采用SEM、荧光显微镜等手段对薄膜进行表征;利用静态荧光光谱、荧光寿命、荧光猝灭等光物理手段对其传感性能进行研究;并分析了薄膜干燥方式、铸膜液制备方法对薄膜传感性能的影响。发现该薄膜对气相中醇类化合物表现出灵敏的选择性传感,且传感可逆性良好;荧光寿命测试结果表明,猝灭过程为静态猝灭。2.为了检测水溶液中的有害物质,考虑到其在复合薄膜中快速的扩散,采用亲水性更强的聚甲基丙烯酸羟乙酯(PHEMA)为成膜基质,以具有自组装能力的荧光物质NBD-chol为发光物种,制备得到一系列荧光复合传感薄膜。采用SEM、荧光显微镜等手段对薄膜进行表征;传感性能实验表明,液相中的胺类化合物对该薄膜的荧光发射具有明显的猝灭作用,可以实现高灵敏度的检测,而且传感过程可逆;通过荧光寿命的变化情况,证实了薄膜对胺类化合物的猝灭过程为静态猝灭,并对猝灭机理进行了研究。3.结合上述的研究结果,首先制备得到NBD-chol/PMMA发光薄膜,考虑到用于液相中有害物质的检测,将NBD-chol/PMMA薄膜经浓硫酸水解处理,制备得到NBD-chol/PMAA复合薄膜。采用红外光谱对薄膜组分进行表征;薄膜传感特性的研究结果表明,液相中乙醚对该薄膜的荧光发射具有较为明显的猝灭作用,且传感可逆性良好。荧光寿命测试结果显示,猝灭过程为静态猝灭。
[Abstract]:With the aggravation of industrialization, the poisonous and harmful substances discharged into the environment are increasing year by year, and the following problems such as air, water and soil pollution are becoming more and more serious. These problems will not only adversely affect the ecological environment, but also threaten the survival of mankind. Therefore, the sensing materials for the study of toxic and harmful substances are particularly important. Photoluminescence composite thin film materials, because of the introduction of luminescent species (inorganic fluorescent materials or organic fluorescent materials) into the inner or surface of thin film materials, have certain optical properties, and the films are easy to process and transparent. With good luminescence stability and high luminescence efficiency, this kind of new composite thin films has become a kind of functional materials with good development prospects. In this paper, a series of luminescent polymer composite film materials were designed and prepared by using strontium aluminate, cholesterol modified by 7-nitrobenzofuran (NBD-chol) as luminescent material and easy film forming polymer as substrate. The sensing properties of these films to harmful substances in gas phase and liquid phase were studied systematically. 1. SrAl2O4/PMMA composite films were prepared by bulk polymerization of poly (methyl methacrylate) (PMMA) as film forming polymer matrix and luminescent material strontium aluminate (SrAl2O4). The thin films were characterized by SEM, fluorescence microscope, and their sensing properties were studied by means of static fluorescence spectrum, fluorescence lifetime, fluorescence quenching and other photophysical methods. The effects of the drying method and the preparation method of casting solution on the sensing properties of the film were analyzed. It is found that the film is sensitive to the selective sensing of alcohols in the gas phase, and the sensing reversibility is good, and the fluorescence lifetime measurement shows that the quenching process is static quenching. 2. In order to detect the harmful substances in aqueous solution and to consider the rapid diffusion in the composite film, the hydrophilic polyhydroxyethyl methacrylate (PHEMA) was used as the film substrate. A series of fluorescent composite sensing films were prepared by using NBD-chol, a fluorescent substance with self-assembly ability, as a luminescent species. The films were characterized by SEM, fluorescence microscope. The sensing performance experiments show that the amine compounds in the liquid phase have obvious quenching effect on the fluorescence emission of the film, which can achieve high sensitivity detection, and the sensing process is reversible. The quenching process of amine compounds was confirmed by the change of fluorescence lifetime, and the quenching mechanism was studied. Based on the above results, the NBD-chol/PMMA thin films were prepared. Considering the detection of harmful substances in liquid phase, the NBD-chol/PMMA films were hydrolyzed with concentrated sulfuric acid to prepare NBD-chol/PMAA composite films. The infrared spectra were used to characterize the composition of the thin films, and the results showed that the fluorescence emission of the films was quenched by ether in liquid phase, and the sensing reversibility was good. The fluorescence lifetime test shows that the quenching process is static quenching.
【学位授予单位】：长安大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.2
本文编号：2428922
[Abstract]:With the aggravation of industrialization, the poisonous and harmful substances discharged into the environment are increasing year by year, and the following problems such as air, water and soil pollution are becoming more and more serious. These problems will not only adversely affect the ecological environment, but also threaten the survival of mankind. Therefore, the sensing materials for the study of toxic and harmful substances are particularly important. Photoluminescence composite thin film materials, because of the introduction of luminescent species (inorganic fluorescent materials or organic fluorescent materials) into the inner or surface of thin film materials, have certain optical properties, and the films are easy to process and transparent. With good luminescence stability and high luminescence efficiency, this kind of new composite thin films has become a kind of functional materials with good development prospects. In this paper, a series of luminescent polymer composite film materials were designed and prepared by using strontium aluminate, cholesterol modified by 7-nitrobenzofuran (NBD-chol) as luminescent material and easy film forming polymer as substrate. The sensing properties of these films to harmful substances in gas phase and liquid phase were studied systematically. 1. SrAl2O4/PMMA composite films were prepared by bulk polymerization of poly (methyl methacrylate) (PMMA) as film forming polymer matrix and luminescent material strontium aluminate (SrAl2O4). The thin films were characterized by SEM, fluorescence microscope, and their sensing properties were studied by means of static fluorescence spectrum, fluorescence lifetime, fluorescence quenching and other photophysical methods. The effects of the drying method and the preparation method of casting solution on the sensing properties of the film were analyzed. It is found that the film is sensitive to the selective sensing of alcohols in the gas phase, and the sensing reversibility is good, and the fluorescence lifetime measurement shows that the quenching process is static quenching. 2. In order to detect the harmful substances in aqueous solution and to consider the rapid diffusion in the composite film, the hydrophilic polyhydroxyethyl methacrylate (PHEMA) was used as the film substrate. A series of fluorescent composite sensing films were prepared by using NBD-chol, a fluorescent substance with self-assembly ability, as a luminescent species. The films were characterized by SEM, fluorescence microscope. The sensing performance experiments show that the amine compounds in the liquid phase have obvious quenching effect on the fluorescence emission of the film, which can achieve high sensitivity detection, and the sensing process is reversible. The quenching process of amine compounds was confirmed by the change of fluorescence lifetime, and the quenching mechanism was studied. Based on the above results, the NBD-chol/PMMA thin films were prepared. Considering the detection of harmful substances in liquid phase, the NBD-chol/PMMA films were hydrolyzed with concentrated sulfuric acid to prepare NBD-chol/PMAA composite films. The infrared spectra were used to characterize the composition of the thin films, and the results showed that the fluorescence emission of the films was quenched by ether in liquid phase, and the sensing reversibility was good. The fluorescence lifetime test shows that the quenching process is static quenching.
【学位授予单位】：长安大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.2
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