臺灣博碩士論文加值系統

寬度與長度分別為5~20nm與100~500nm之短桿狀結構纖維素奈米結晶(Cellulose Nanocrystals, CNCs)，其表面帶有大量SO3-基團，而能容易地在水中形成穩定的膠體懸浮液，當其溶液乾燥後便能得到透明的纖維素薄膜，然而此薄膜與水接觸後便會溶解而分散懸浮，且乾燥之薄膜彎曲時也易斷裂。因此為了解決這些問題，我們將纖維素結合蛋白(CBD)融合上彈性蛋白resilin 1成為CBD-resilin 1，此外也在彈性蛋白兩端分別融合上CBD成為CBD-resilin 1-CBD，此兩種融合蛋白分別與含有1%甘油之CNCs混合可製備出仿生之纖維素複合薄膜，由於彈性蛋白resilin 1的存在，此兩種生物複合膜的應變量(strain-at-break)可分別提升42%與85%。此外，將CNCs分別與幾丁質奈米纖維素(CNF)與疏水性穀聚醣(HMCS)混和可製備出透明且耐水的CNCs@CNF與CNCs@HMCS複合薄膜，耐水性改善的原因在於CNF與HMCS結構上皆帶有正電荷胺基，與CNCs接觸後能中和掉CNCs上之負電荷，此外HMCS上的疏水性C12烴鏈，亦會賦予CNCs@HMCS複合薄膜疏水性，其接觸角由53.27提升為84.96。CNCs@HMCS複合薄膜仍然保有HMCS本身對染劑之吸附性與抗菌活性，不僅能達到70%以上的大腸桿菌殺菌效果；且1克重之複合薄膜也能吸附181.95 1.14毫克的甲基橙。也由於CNCs與HMCS能在薄膜內形成穩定的氫鍵網絡，因此能提升複合薄膜的熱穩定度，使熱降解起始溫度與最大質量損失率的溫度點分別比CNCs薄膜高34 oC與50 oC；而楊氏模數(Modulus)、拉伸強度(Tensile Strength)、應變量與CNCs薄膜相比下，也分別提升了95%、66%與93%。

Cellulose Nanocrystals (CNCs) are highly crystalline rod-like nanomaterials can readily form stable colloidal suspensions in deionized water. However, the transparent dry film obtained via simple evaporation-induced self-assembly of coated CNCs suspension will readily dissolve in water due to the presence of strong anionic SO3- groups on the surface of CNCs. Besides, the dry CNCs film is not tough enough to endure the repeated bending. In order to improve these drawbacks, we created CBD-resilin 1 and CBD-resilin 1-CBD fusion proteins by fusing one or two cellulose binding domain (CBD) with elastic protein resilin 1. The biomimetic composite films could be acquired by drying the mixture consisted of CBD fusions proteins, CNCs solution and 1% of the glycerol. Due to the elasticity of the resilin 1, the strain-at-break of the biocompoiste films increased by 42% and 85% respectively in comparison with the pure CNCs film.
Water durable and transparent CNCs@CNF and CNCs@HMCS composite films can be generated by drying the mixture containing CNCs, chitin nanofiber (CNF), and hydrophobically modified chitosan (HMCS) respectively. The charge neutralization of the biocomposite film caused by the cationic amino groups of CNF and HMCS contributes to the water durability of the composite films. Especially, the presene of hydrophobicity of C12 hydrocarbon tail grafted on HMCS increased the water contact angle of CNCs@HMCS film from 53.27 to 84.96. Additionally, the HMCS doped CNCs film can effectively adsorb methyl orange with capacity of 181.95 1.14 mg /g and kill at least 70% of E-coli. It indicates the composite still maintained the dye adsorption and antimicrobial activity of HMCS. Not only the better thermal stability of the transparent CNCs@HMCS composite film could be achieved, but its mechanical properties were signigicantly impoved with Young’s modulus (GPa), tensile strength (Mpa) and strain-at-break (%) increased 95%, 66% and 93% respectively as compared with CNCs film.

第一章 緒論 1
1.1 前言 1
1.2 研究內容及目的 2
第二章 文獻回顧 4
2.1 奈米結晶纖維素(Cellulose Nanocrystals, CNCs) 4
2.1.1 纖維素的組成與來源 4
2.1.2 CNCs的製備 4
2.1.3 CNCs於複合材料的應用 6
2.2 纖維素結合功能域 (Cellulose Binding Domain,CBD) 7
2.2.1 CBD與CBD融合蛋白 7
2.2.2 CBD融合蛋白於纖維上之應用 8
2.3 節肢彈性蛋白 (Resilin) 8
2.3.1 Resilin特性 8
2.3.2 Resilin 之組成 9
2.3.3 重組resilin之發展 11
2.4 幾丁質奈米纖維素(Chitin Nanofiber,CNF) 13
2.4.1 幾丁質的來源與結構 13
2.4.2 CNF的製備與應用 14
2.5 疏水性殼聚糖(Hydrophobically modified chitosan,HMCS) 15
2.5.1 HMCS的來源與應用 15
2.5.2 HMCS的抗菌功能 16
2.5.3 HMCS的染劑吸附功能 17
第三章 實驗流程、材料與方法 19
3.1 實驗架構 19
3.2 實驗材料 20
3.2.1 菌株 20
3.2.2 質體 20
3.2.3 標準分子量溶液 (marker) 20
3.2.4 實驗藥品 20
3.3 溶液配置 23
3.4 實驗設備 26
3.5 實驗方法 29
3.5.1 CBD-resilin 1、CBD-resilin 1-CBD菌株培養及融合蛋白之生產 29
3.5.2 CBD-Ag菌株培養及融合蛋白之生產 30
3.5.3 融合蛋白之加熱純化 31
3.5.4 蛋白質濃度分析 31
3.5.5 CBD-resilin 1、CBD-resilin 1-CBD、CBD-Ag於CNCs之吸附 33
3.5.6 蛋白質電泳分析 34
3.5.6.1 SDS-PAGE膠片製作 34
3.5.6.2 待測樣品前處理 35
3.5.6.3 電泳分析 35
3.5.7 薄膜材料 36
3.5.7.1 CNC溶液製備 36
3.5.7.2 CNF溶液製備 36
3.5.7.3 CS、HMCS溶液製備 37
3.5.7.4 融合蛋白粉末製備 39
3.5.8 薄膜製備 39
3.5.8.1 生物複合薄膜 39
3.5.8.2 CNCs、CNF、CS、HMCS薄膜 40
3.5.8.3 CNCs@HMCS、CNCs@CNF複合薄膜 40
3.6 薄膜性質分析 42
3.6.1 透明度 42
3.6.2 界面電位(Zeta-potential) 42
3.6.3 黏度(Viscosity) 42
3.6.4 接觸角(Water contact angle)與耐水性(Water durability) 42
3.6.5 官能基分析 43
3.6.6 SEM觀察下之表面、剖面結構與組成元素分析 43
3.6.7 AFM觀察下之表面結構 43
3.6.8 熱穩定性分析 44
3.6.9 抗菌分析 44
3.6.10 染劑吸附 46
3.6.11 拉伸試驗分析 47
第四章 結果與討論 48
4.1 CBD融合Resilin蛋白改質奈米結晶纖維素(CNCs) 48
4.1.1 融合蛋白純化方法與對其在CNCs上吸附之影響 48
4.1.2 CNCs對融合蛋白之吸附 51
4.2 CNCs生物複合薄膜 52
4.2.1 生物複合膜之透明度 54
4.2.2 AFM分析 58
4.2.3 FTIR-ATR分析 59
4.2.4 拉伸試驗 61
4.3 CNCs@HMCS、CNCs@CNF複合薄膜 64
4.3.1 SEM分析 65
4.3.2 複合膜之透明度 66
4.3.3 AFM分析 68
4.3.4 界面電位與移動率 70
4.3.5 溶液黏度 71
4.3.6 接觸角與耐水性分析 72
4.3.7 FTIR-ATR分析 76
4.3.8 SEM-EDS表面元素分析 77
4.3.9 TGA/DTG分析 78
4.3.10 抗菌(E. coli)功能 81
4.3.11 染劑吸附功能 83
4.3.12 拉伸試驗 86
4.3.13 複合薄膜改質濾紙表面 88
第五章 結論 90
參考文獻 94

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