摘要
本研究中主要以低能量、環保和高效率之光聚合反應探討雙離子型高分子合成和提升水凝膠強度。凝膠含有兩種雙離子型高分子，2-甲基丙烯酰氧基乙基磷酰膽鹼（poly-MPC）和[2-（甲基丙烯酰氧基）乙基]二甲基 - （3-磺丙基）氫氧化銨（poly-DMAPS）分別具有不同的雙離子之電荷作用性。其中poly-DMAPS具有高分子鏈段與鏈段之間以及高分子鏈段之內的交互作用力，此作用力導致poly-DMAPS最高臨界溶解溫度upper critical solution temperature(UCST) ，即低溫時分子鏈聚集而升高溫度時此鏈聚集因熱能而解開，而溫度範圍取決於高分子之分子量及水溶液中高分子之濃度。對於低分子量的聚DMAPS高分子(63kDa)，調控溶液中濃度，1wt%, 5wt%和10wt%，其最高臨界溶解溫度(UCST)為出37°C, 42°C和49°C，對於高分子量的DMAPS高分子(92kDa)，溶液濃度1wt%, 5wt%和10wt%，其最高臨界溶解溫度(UCST)51°C, 57°C 和69°C，高分子量及高濃度水溶液需要更高熱能才能解開此聚集。為了進一步製備高強度的含雙離子型高分子之水凝膠，我們探討了互相穿透的雙離子型高分子雙網絡水凝膠，設計方法是將一雙離子型高分子均勻分散及交聯於另一雙離子型高分子水凝膠中。第一種水凝膠將poly-MPC混合在poly-DMAPS交聯的網絡中，命名為MD膠，其網絡中，物理和化學的交聯位於同一高分子鏈上；第二種水凝膠將poly-DMAPS混合在poly-MPC交聯的網絡中，命名為DM膠，其網絡中物理交聯的部分位於poly-DMAPS鏈段，化學交聯的部分位於poly-MPC鏈段。和DM膠與無序排列的交相比，MD膠擁有最強的黏度值，結果驗證了在水凝膠若於相同鏈段上若含軟(物理交聯)及硬(化學交聯) ，能夠得到較高強度的雙離子型高分子水凝膠。MD膠表現出高的黏度值(1.4MPa•s)和更密集的結構(孔徑約4微米)。此外，我們進一步測試了設計的水凝膠對細胞沾黏實驗和動物模型的抗沾黏測試。結果表示高強度的水凝膠在體內植入中的潛在之應用性。

Abstract
In this study, zwitterionic polymers and hydrogels were synthesized under low energy, eco-friendly, and high efficiency photo-polymerization. Two zwitterionic polymers, 2-Methacryloyloxyethyl phosphorylcholine (poly-MPC) and [2-(Methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (poly-DMAPS) exhibited different electrostatic charge interaction. The inter and intrapolymer interaction in poly-DMAPS resulted upper critical solution temperature (UCST) property. In addition, the UCST of poly-DMAPS can be tuned with concentration of polymer solution and molecular weight. For low molecular weight of poly-DMAPS (21kDa), the UCST presented at 37°C, 42°C and 49°C for the concentration range from 1wt%, 5wt% to 10wt%, respectively. For high molecular weight of poly-DMAPS (46kDa), the UCST presenting 51°C, 57°C and 69°C for the polymer concentration range from 1wt%, 5wt% to 10wt%, respectively. To further preparation of tough hydrogel, we consider to prepare zwitterionic hydrogel with interpenetrating double network. The designed system was that, one of the zwitterionic polymer was homogenously dispersed inside another zwitterionic polymeric hydrogel. In the first gel, the synthesized poly-MPC was blended in poly-DMAPS hydrogel, called MD gel. In the MD gel, this gel involved chemical crosslinking and physical crosslinking (electrostatic interaction chain) at the same chain. In the second gel, the synthesized poly-DMAPS was blende in poly-MPC hydrogel, called DM gel. In the DM gel, the physical crosslinking moiety was at poly-DMAPS and chemical crosslinking moiety was at poly-MPC, separately. The highest viscosity was founded in MD hydrogel when compare with DM and random gels. This result suggests that the tough zwitterionic hydrogel can be obtained by designing the rigid and soft crosslink moiety at same network. In addition, the MD hydrogel also exhibited a higher compressive strength of 1.4 MPa•s and a denser packed structure (pore size = 4μm) than that of DM and random gels. We have further tested the design hydrogel on cell adhesion experiment and anti-adhesion of surgical animal model. Those result indicated the further potential application of tough hydrogel in bio-implanted application.

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