芳香基官能化聚硅氧烷的设计、合成及其荧光响应研究

发布时间：2018-05-13 19:58

本文选题：荧蒽有机硅聚合物 + 多苯基基苯有机硅聚合物　；参考：《山东大学》2017年硕士论文

【摘要】：荧蒽及其衍生物具有极其优异的荧光性能,基于该类荧光基团的小分子化合物已经得到了广泛应用。本文利用Knoevenagel/Diels-Alder反应,将该类荧光基团引入聚硅氧烷,制备得到以聚硅氧烷为主链,端基连有荧光基团的基于聚硅氧烷的新型荧光聚合物。进一步通过核磁共振谱(H谱等)、元素分析等手段对合成的聚合物进行了结构表征和分析,并且通过热重分析研究了其热力学性质。结果表明,Knoevenagel/Diels-Alder反应成功进行,该荧光聚合物得到成功制备,而且具有良好的热稳定性。通过荧光光谱仪等测试手段研究了荧蒽有机硅聚合物对金属阳离子的荧光响应,结果表明:在加入各种碱金属和过渡金属阳离子后,只有铁离子存在下发生了明显的荧光猝灭现象,而其他金属阳离子对荧光发射基本没有影响。同时,研究了荧蒽有机硅聚合物对铁离子的选择性响应能力,通过在荧蒽有机硅聚合物溶液中加入铁离子与未加入铁离子的荧光强度对比发现,相对于其他金属阳离子,该聚合物对铁离子具有更好的选择性。研究了荧蒽有机硅聚合物在四氢呋喃稀溶液中对铁离子的荧光响应能力,发现随着铁离子浓度的增加,荧光强度逐渐降低,所得的Stern-Volmer(SV)曲线是一条向上弯曲的曲线,这表明随着铁离子浓度的增加,荧蒽有机硅聚合物的检测效率越来越高。另外通过变温荧光测试和荧光寿命测试对其猝灭机理进行了详细分析。进一步设计并合成了多苯基苯有机硅聚合物。多苯基苯衍生物的特殊三维结构,能够有效地抑制各个分子之间的π-π相互作用,而且限制了分子本身各个苯环的共轭度,具有优异的荧光性能。通过荧光测试,研究了多苯基苯有机硅聚合物对铁离子的选择性响应能力。研究发现,在多苯基苯有机硅聚合物的稀溶液中,溶液对铁离子具有良好的选择性响应能力,而且其对铁离子检测的Stern-Volmer(SV)曲线呈向上弯曲。通过紫外吸收光谱和对双分子猝灭过程速率常数的计算,分析了其对铁离子的猝灭机理。
[Abstract]:Fluoranthene and its derivatives have been widely used because of their excellent fluorescence properties. In this paper, a novel polysiloxane based fluorescent polymer based on polysiloxane was prepared by Knoevenagel/Diels-Alder reaction. The polysiloxane was used as the main chain and the end group was connected with the fluorescent group. Furthermore, the structure of the synthesized polymer was characterized and analyzed by means of nuclear magnetic resonance (NMR) spectra and elemental analysis, and its thermodynamic properties were studied by thermogravimetric analysis. The results showed that the Knoevenagel / Diels-Alder reaction was successfully carried out and the fluorescent polymer was successfully prepared and had good thermal stability. The fluorescence response of fluoranthene organosilicon polymer to metal cations was studied by means of fluorescence spectrometer. The results showed that: after adding various alkali and transition metal cations, The fluorescence quenching occurred only in the presence of iron ions, while other metal cations had little effect on the fluorescence emission. At the same time, the selectivity of fluoranthene organosilicon polymer to iron ion was studied. By comparing the fluorescence intensity of fluoranthene organosilicon polymer solution with and without iron ion, it was found that the fluorescence intensity of fluoranthene organosilicon polymer was relative to that of other metal cations. The polymer has better selectivity to iron ions. The fluorescence response of fluoranthene organosilicon polymer to iron ions in dilute tetrahydrofuran solution was studied. It was found that the fluorescence intensity of fluoranthene organosilicon polymer decreased with the increase of iron ion concentration, and the Stern-Volmerian SVV curve was an upward curve. This indicates that the detection efficiency of fluoranthene organosilicon polymer is higher with the increase of iron ion concentration. In addition, the quenching mechanism was analyzed in detail by means of variable temperature fluorescence measurement and fluorescence lifetime test. Polyphenyl benzene organosilicon polymer was further designed and synthesized. The special three-dimensional structure of the polyphenyl benzene derivatives can effectively suppress the 蟺-蟺 interaction among the molecules and limit the conjugation degree of each benzene ring of the molecule itself, so it has excellent fluorescence properties. The selective response of polyphenyl benzene organosilicon polymer to iron ions was studied by fluorescence measurement. It is found that in the dilute solution of polyphenyl benzene organosilicon polymer, the solution has a good selective response to iron ions, and its Stern-Volmerian SVcurve for iron ion detection is bent upward. The quenching mechanism of iron ion was analyzed by UV absorption spectrum and calculation of the rate constant of bimolecular quenching process.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O634.41

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