新型水溶性共轭材料的制备、表征及其应用研究
发布时间:2018-05-25 04:12
本文选题:水溶性共轭材料 + 多支化结构 ; 参考:《南京邮电大学》2016年硕士论文
【摘要】:水溶性共轭材料因其优异的光电性能和水溶性的特点,被广泛应用于生物传感、细胞成像、疾病诊疗、药物释放、光动力治疗、器件制备和超分子自组装研究等各个方面。本论文针对水溶性共轭材料在生物成像和超分子自组装方面的应用需求做了以下研究:1.针对水溶性共轭材料在生物成像应用方面的一些不足,如聚集荧光猝灭、吸收/发射波长偏短等缺陷,设计了基于四苯甲烷、芴、双键、对二甲苯二聚体的多支化结构水溶性共轭材料,引入窄带隙基团苯并噻二唑使光谱红移,并做了初步的合成,为后续的实验奠定了基础。2.通过引入间位取代的苯环结构,合成折线形水溶性共轭聚苯撑乙炔M1’和M2’,研究溶剂效应和分子结构对其自组装构象的影响。M1’和M2’都表现出溶剂效应导致的螺旋构象变化。在M1’中引入窄带隙的苯并噻二唑基团得到M2’,虽然苯并噻二唑体积比苯环大,刚性更强,但对螺旋构象影响很小,导致聚苯撑乙炔单元和苯并噻二唑单元之间发生更高效的分子内荧光共振能量转移过程,M1’的发射光谱从蓝光变为黄光。同时,用M2’和多壁碳纳米管制备复合物,在良性溶剂甲醇中,聚合物单层螺旋包覆在碳纳米管上,复合物分散性较好。这可能是由于间位取代的苯环结构和碳碳三键的旋转导致主链构象自由度增大,并且共轭主链和碳纳米管之间的π-π作用,使聚合物容易缠绕在碳纳米管表面;此外,阳离子基团除了可以增加水溶性外,由于电荷排斥作用,更利于碳纳米管在溶剂中分散。
[Abstract]:Water soluble conjugate materials have been widely used in biosensor, cell imaging, disease diagnosis and treatment, drug release, photodynamic therapy, device fabrication and supramolecular self-assembly for their excellent photoelectric properties and water-soluble properties. In this thesis, the following research work has been done on the application of water-soluble conjugate materials in biomedical imaging and supramolecular self assembly. In view of the shortcomings of water-soluble conjugate materials in the application of biological imaging, such as fluorescence quenching of aggregation, short absorption / emission wavelength, etc., based on tetraphenylmethane, fluorene, double bonds, etc. Water-soluble conjugated materials with multi-branched structure of p-xylene dimer were introduced into narrow band gap group benzothiadiazole to make spectral red shift, and the preliminary synthesis was carried out, which laid a foundation for further experiments. Water soluble conjugated poly (phenylene acetylene) M1 'and M2' were synthesized by introducing the meso-substituted benzene ring structure. The effects of solvent effect and molecular structure on the self-assembly conformation. Both M1 'and M2' showed the helical conformation change induced by solvent effect. A narrow band gap benzothiadiazole group was introduced into M 1'to obtain M 2 O. Although the volume of benzothiadiazole is larger than that of benzene ring and its rigidity is stronger, it has little effect on the helical conformation. A more efficient intramolecular fluorescence resonance energy transfer process occurs between the polyphenylene acetylene unit and the benzthiadiazole unit. The emission spectrum of M 1 'changes from blue to yellow light. At the same time, the composite was prepared by using M2 'and multi-walled carbon nanotubes. In the benign solvent methanol, the polymer monolayer was coated on the carbon nanotubes, and the dispersion of the composite was better. This may be due to the increase of the conformational degree of freedom of the main chain due to the interposition substituted benzene ring structure and the rotation of the carbon-carbon triple bond, and the 蟺-蟺 interaction between the conjugated main chain and the carbon nanotubes, which makes the polymer easily wound around the surface of the carbon nanotube. In addition to increasing water solubility, cationic groups are more favorable for the dispersion of carbon nanotubes in solvents due to charge repulsion.
【学位授予单位】:南京邮电大学
【学位级别】:硕士
【学位授予年份】:2016
【分类号】:O621.1;O631.1
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