本文選題：熒蒽有機硅聚合物 + 多苯基基苯有機硅聚合物　； 參考：《山東大學》2017年碩士論文

【摘要】：熒蒽及其衍生物具有極其優(yōu)異的熒光性能,基于該類熒光基團的小分子化合物已經得到了廣泛應用。本文利用Knoevenagel/Diels-Alder反應,將該類熒光基團引入聚硅氧烷,制備得到以聚硅氧烷為主鏈,端基連有熒光基團的基于聚硅氧烷的新型熒光聚合物。進一步通過核磁共振譜(H譜等)、元素分析等手段對合成的聚合物進行了結構表征和分析,并且通過熱重分析研究了其熱力學性質。結果表明,Knoevenagel/Diels-Alder反應成功進行,該熒光聚合物得到成功制備,而且具有良好的熱穩(wěn)定性。通過熒光光譜儀等測試手段研究了熒蒽有機硅聚合物對金屬陽離子的熒光響應,結果表明:在加入各種堿金屬和過渡金屬陽離子后,只有鐵離子存在下發(fā)生了明顯的熒光猝滅現象,而其他金屬陽離子對熒光發(fā)射基本沒有影響。同時,研究了熒蒽有機硅聚合物對鐵離子的選擇性響應能力,通過在熒蒽有機硅聚合物溶液中加入鐵離子與未加入鐵離子的熒光強度對比發(fā)現,相對于其他金屬陽離子,該聚合物對鐵離子具有更好的選擇性。研究了熒蒽有機硅聚合物在四氫呋喃稀溶液中對鐵離子的熒光響應能力,發(fā)現隨著鐵離子濃度的增加,熒光強度逐漸降低,所得的Stern-Volmer(SV)曲線是一條向上彎曲的曲線,這表明隨著鐵離子濃度的增加,熒蒽有機硅聚合物的檢測效率越來越高。另外通過變溫熒光測試和熒光壽命測試對其猝滅機理進行了詳細分析。進一步設計并合成了多苯基苯有機硅聚合物。多苯基苯衍生物的特殊三維結構,能夠有效地抑制各個分子之間的π-π相互作用,而且限制了分子本身各個苯環(huán)的共軛度,具有優(yōu)異的熒光性能。通過熒光測試,研究了多苯基苯有機硅聚合物對鐵離子的選擇性響應能力。研究發(fā)現,在多苯基苯有機硅聚合物的稀溶液中,溶液對鐵離子具有良好的選擇性響應能力,而且其對鐵離子檢測的Stern-Volmer(SV)曲線呈向上彎曲。通過紫外吸收光譜和對雙分子猝滅過程速率常數的計算,分析了其對鐵離子的猝滅機理。
[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.
【學位授予單位】：山東大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O634.41

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本文編號：1884586