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  • 學位論文

新型光反應性明膠與BTDA和HEMA衍生物之合成與性質探討

Synthesis and Properties of a New Photoreactive Gelatin with BTDA and HEMA Derivatives

指導教授 : 江文彥
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摘要


本研究開發出一種具有生物親和性、光反硬性及快速成膜性的新型感光明膠。在醇水的介質中,利用dicyclohexyl- carbodiimide (簡稱DCC)作為在醯胺反應(amide formation)中羧酸基和胺基之結合劑。明膠和glycine是反應中胺基的供應來源。當每一個3,3',4,4'-benzophenone tetra-carboxylic di-anhydride (BTDA) 分子的雙酐基與導入的2-hydroxyethyl methacrylate (HEMA)分子進行開環反應(ring-opening reaction),BTDA將開環產生四個羧酸基,其中兩個與HEMA進行加成反應結合而生成感光性的明膠,稱之為GE-BTHE。 其中BTDA分子中的ketone基成為光反應的主要元件而HEMA本身的雙鍵則成為交聯所必需的雙鍵提供者。這樣的組合使得光反應性的明膠可以藉由高壓水銀燈(high pressure mercury lamp)經六分鐘的照射之後,由原本透明的溶液轉變為膨潤的不透光薄膜。經實驗分析發現,最有效的照射波長為267 nm而成膜的GE-BTHE最高所能達到的膨潤度為5.9。機械性質部份,乾膜仍然可保有延展度達5-10%,這表示GE-BTHE的乾膜也具有些許的彈性。 GE-BTHE合成還經由醯胺反應的分析來計算其膠聯度、膨潤比並監測其光反應的過程。 GE-BTHE膜也利用atomic force microscopy (AFM), scanning electron microscopy (SEM) 和UV-vis spectroscopy等儀器來進行表面、切面及結構的分析。 藉由這些分析,可以得知UV的照射反應使得GE-BTHE膜同時產生了光交聯反應及光裂解的反應。光交聯反應其最大的吸收波長介於267~275 nm之間,表示在此波長範圍交聯程度遠大於裂解程度。而在254 nm波長照射下發生了所謂相轉移的情形,表示裂解程度大於交聯程度。本研究的許多結果相當具有潛力利用於工業或醫學方面的應用。且藉由控制光膠聯與光裂解,更能使GE-BTHE膜應用的更為廣泛,例如:傷口的保護、止血材料的製造更可推廣至先進的微影手術或血管支架等。

並列摘要


A novel bio-affinitive, photocuring and membrane-forming gelatin derivative was synthesized in this study. This process was based on the amide formation between carboxylic acid and the amine in methanol-water media using dicyclohexyl- carbodiimide (DCC) as a condenser. Gelatin and glycine were the sources of amine in the model reaction. Since there were two anhydride groups in each 3,3',4,4'-benzophenone tetra-carboxylic di-anhydride (BTDA) molecule, two 2-hydroxyethyl methacrylate (HEMA) molecules were used to induce the ring-opening reaction of BTDA and release two carboxylic acid groups. The resulting photoreactive gelatin was called GE-BTHE, of which the photoreactive component was the ketone groups of BTDA and HEMA that played the role of double bond supplier. This photoreactive gelatin could be converted from the transparent liquid phase into swollen membrane by a 6-minute irradiation of high pressure mercury lamp. The most efficient irradiation was at 267 nm and the highest degree of swelling of the cured GE-BTHE membrane could reach 5.9. The elongation from the dried gel remained 5-10%, i.e. relatively elastic. The properties of this gelatin derivative were investigated using amide formation analysis, calculation of the gel content and the swelling ratio, and monitoring of the photocuring process. The membranes of GE-BTHE were also examined with atomic force microscopy (AFM), scanning electron microscopy (SEM) and UV-vis spectroscopy. The results revealed that UV irradiation could bring about both photo-crosslinking as well as photo-degradation in the GE-BTHE membrane. The maximum absorbance of UV irradiation occurred in the range of 267 to 275 nm. Once the membrane was further irradiated at 254 nm, phase transformation took place. The GE-BTHE synthesized in this study should be very potential in biomedical and industrial applications. Furthermore, the photo-crosslinking and photo- degradation behavior of GE-BTHE also makes it more useful such as protective wound dressings and hemostatic absorbents for minimally invasive surgery.

參考文獻


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