新型水溶性共軛材料的制備、表征及其應(yīng)用研究
發(fā)布時(shí)間:2018-05-25 04:12
本文選題:水溶性共軛材料 + 多支化結(jié)構(gòu)。 參考:《南京郵電大學(xué)》2016年碩士論文
【摘要】:水溶性共軛材料因其優(yōu)異的光電性能和水溶性的特點(diǎn),被廣泛應(yīng)用于生物傳感、細(xì)胞成像、疾病診療、藥物釋放、光動(dòng)力治療、器件制備和超分子自組裝研究等各個(gè)方面。本論文針對(duì)水溶性共軛材料在生物成像和超分子自組裝方面的應(yīng)用需求做了以下研究:1.針對(duì)水溶性共軛材料在生物成像應(yīng)用方面的一些不足,如聚集熒光猝滅、吸收/發(fā)射波長偏短等缺陷,設(shè)計(jì)了基于四苯甲烷、芴、雙鍵、對(duì)二甲苯二聚體的多支化結(jié)構(gòu)水溶性共軛材料,引入窄帶隙基團(tuán)苯并噻二唑使光譜紅移,并做了初步的合成,為后續(xù)的實(shí)驗(yàn)奠定了基礎(chǔ)。2.通過引入間位取代的苯環(huán)結(jié)構(gòu),合成折線形水溶性共軛聚苯撐乙炔M1’和M2’,研究溶劑效應(yīng)和分子結(jié)構(gòu)對(duì)其自組裝構(gòu)象的影響。M1’和M2’都表現(xiàn)出溶劑效應(yīng)導(dǎo)致的螺旋構(gòu)象變化。在M1’中引入窄帶隙的苯并噻二唑基團(tuán)得到M2’,雖然苯并噻二唑體積比苯環(huán)大,剛性更強(qiáng),但對(duì)螺旋構(gòu)象影響很小,導(dǎo)致聚苯撐乙炔單元和苯并噻二唑單元之間發(fā)生更高效的分子內(nèi)熒光共振能量轉(zhuǎn)移過程,M1’的發(fā)射光譜從藍(lán)光變?yōu)辄S光。同時(shí),用M2’和多壁碳納米管制備復(fù)合物,在良性溶劑甲醇中,聚合物單層螺旋包覆在碳納米管上,復(fù)合物分散性較好。這可能是由于間位取代的苯環(huán)結(jié)構(gòu)和碳碳三鍵的旋轉(zhuǎn)導(dǎo)致主鏈構(gòu)象自由度增大,并且共軛主鏈和碳納米管之間的π-π作用,使聚合物容易纏繞在碳納米管表面;此外,陽離子基團(tuán)除了可以增加水溶性外,由于電荷排斥作用,更利于碳納米管在溶劑中分散。
[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.
【學(xué)位授予單位】:南京郵電大學(xué)
【學(xué)位級(jí)別】:碩士
【學(xué)位授予年份】:2016
【分類號(hào)】:O621.1;O631.1
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