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標題: Stimulus-Responsive Polymeric Particles Supramolecularly Assembled from Poly(N-isopropylacrylamide) Graft Copolymers: From Micelles to Crosslinked Nanogels
作者: 許源宏
Hsu, Yuan Hung
關鍵字: Temperature/pH responsive;溫度/酸鹼應答;graft copolymer;micelles;nanogels;接枝高分子;微胞;奈米膠粒
出版社: 化學工程學系
In this thesis, graft copolymers comprising poly(acrylic acid) (PAAc) as the backbone and poly(N-isopropylacrylamide) (PNIPAAm) and monomethoxy poly(ethylene glycol) (mPEG) as the grafts were prepared and characterized. These copolymers with the AAc residues in the negatively charged state underwent self-assembling into large polymeric aggregates in water in the range of 32~35 oC due to the formation of the multi-core structure (comprising several solid-like hydrophobic PNIPAAm cores surrounded by the liquid-like interfacial layers) and the inter-core PEG connections. These rather labile inter-core PEG connections were partially destroyed due to the continual dehydration and solidification of the liquid-like interfacial layers with increasing temperature, thereby leading to fragmentation of the original aggregates into smaller particles with the more distinct core/shell structure. The final particle size was virtually governed by the structure of the hydrophobic PNIPAAm microdomains in response to the effects of the PNIPAAm concentration and temperature on the inter-core PEG connections.
The effect of SDS on the hydrodynamic size and structure of these thermally induced polymeric micelles and/or particles was also investigated. Fluorescence study of the polymer solutions in H2O at the ambient temperature using pyrene as a probe indicates that the SDS micelles were induced by the presence of the graft copolymer at its concentration significantly lower than its CMC. Further fluorescence study showed that the SDS micelles occurred by its extensive binding with PNIPAAm grafts. Following the temperature increases of the polymer solutions to 60 oC by the fast heating approach, the copolymer underwent phase transition and, in the presence of polymer-bound SDS micelles, the thermally induced polymeric micelles showed smaller in their size and more hydrophobic in the interior cores, as compared to those in the absence of polymer-induced SDS micelles. It was found that the particle size was reduced by reducing the interactions between PNIPAAm and PEG grafts due to the presence of polymer-bound SDS micelles at low temperatures. After formation of polymeric micelles with increasing temperature, the polymer-bound SDS micelles were destroyed and the dissociated SDS molecules migrated to the core/shell interface within micelles. The stabilization of SDS at the interface and reduction in interactions of PEG with PNIPAAm grafts within micelles rendered the core regions of micelles more hydrophobic. The proposed hypothesis in the effect of polymer-bound micelles on polymeric particles was further confirmed by showing the changes in the particle size in response to the change in the CACSDS.
pH/Temperature responsive crosslinked nanogels were prepared based on vinyl group-bearing PNIPAAm graft copolymers, poly(AAc-co-MEA)/PNIPAAm/mPEG. The structure of the graft copolymers was established by 1H NMR spectroscopy. The graft copolymers underwent self-aggregation into micelle structure with increasing temperature above their critical micelle temperatures (CMTs) in aqueous phase. Strong dependence of the micelle size and structure on pH was observed. Evaluation of the micelle structure by the variable temperature 1H NMR measurements in D2O shows the presences of both the liquid-like interfacial layers and solid-like inner cores in the hydrophobic PNIPAAm microdomains. Nanogels were obtained by radical polymerization of the MEA moieties at 60 oC and pH 5.0 under stirring. The nanogels exhibited capability of undergoing volume changes in response to changes in environmental pH and temperature.

本論文所製備之接枝型雙性高分子,主鏈為親水性的poly(acrylic acid) (PAAc) 鏈段,側鏈則包含親水性的PEG以及能夠隨溫度變換親疏水性質之PNIPAAm鏈段。將此類型高分子水溶液緩慢升溫至32~35 oC時,由於PNIPAAm的相轉換造成此高分子自發排列形成微胞結構。研究中發現,在此溫度範圍下,由於微胞會形成多核結構而造成較大的粒徑。此多核結構主要是在微胞化的過程中,PEG與PNIPAAm鏈段之間的相互作用而形成,核與核之間的連結方式包含較穩固的PNIPAAm連結以及較脆弱的PEG連結。隨著溫度繼續升高,PNIPAAm核心疏水程度漸增而造成脆弱之PEG連結斷裂,進而使得微胞裂解而形成較小且殼-核界面更分明的微胞結構。此微胞之最終粒徑主要取決於PNIPAAm核心的疏水程度。
本論文亦探討加入陰離子型界面活性劑SDS對此高分子微胞結構的影響。實驗結果顯示,在室溫的條件下,SDS分子會在遠低於其CMC的條件下聚集在PNIPAAm鏈段上而形成所謂的高分子誘導型微胞。當溫度升高至60 oC時,此誘導型SDS微胞的存在會使得高分子鏈在聚集的過程中減少PNIPAAm與PEG的交互作用,進而避免多核結構的形成,而形成粒徑較小之高分子微胞。在微胞化的過程中,SDS微胞會被破壞且最終會鑲嵌在高分子微胞的殼-核界面,而形成較穩定且核心疏水程度較高的微胞結構。
此外,本論文亦利用帶有vinyl groups的接枝型高分子poly(AAc-co-MEA)/PNIPAAm/mPEG以製備溫度/酸鹼應答型奈米膠粒。由NMR實驗得知,此高分子在高溫水相中會形成微胞結構,且vinyl group 位於殼層部分。此高分子微胞的粒徑與外界pH值有相當大的關係,實驗結果發現在60 oC下,pH 5的條件下進行殼層vinyl groups的自由基聚合反應可得到粒徑較小(<100 nm)且其結構具有隨溫度及酸鹼變化的特性。
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