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系統識別號 U0026-1008201817544700
論文名稱(中文) 不同官能基改質之星狀聚賴胺酸成膠性質探討
論文名稱(英文) Hydrogelation of Star-shaped Poly(L-lysine) Polypeptides Modified with Different Functional Groups
校院名稱 成功大學
系所名稱(中) 化學工程學系
系所名稱(英) Department of Chemical Engineering
學年度 106
學期 2
出版年 107
研究生(中文) 沈烜右
研究生(英文) Xuan-You Shen
學號 N36054364
學位類別 碩士
語文別 中文
論文頁數 96頁
口試委員 指導教授-詹正雄
口試委員-林睿哲
口試委員-侯聖澍
口試委員-吳文中
口試委員-林宏殷
中文關鍵字 水膠  聚胺基酸  星狀高分子  分子間作用力 
英文關鍵字 hydrogel  polypeptide  star polymer  intermolecular interaction 
學科別分類
中文摘要 本研究以1,1,3,3-四甲基胍作為促進劑,使多元醇進行-胺基酸 N-羧酸酐開環聚合,成功地合成一系列三臂、四臂、六臂星狀聚胺基酸,去除保護基後加以改質,得到星狀聚賴胺酸-接枝-吲哚(PLL-g-Indo)、聚賴胺酸-接枝-苯環 (PLL-g-Phenyl)與聚穀胺酸-接枝-吲哚(PLG-g-Indo),並將其製備成水膠。利用不同臂數目、聚合度及改質之疏水基團種類,探討不同分子型態與各種分子間作用力對水膠形成之影響,並以各種儀器分析水膠之微觀結構與機械性質。以各個接枝聚胺基酸進行成膠濃度測試,可以得知水合能力、靜電排斥力、π-π堆疊、氫鍵作用力、陽離子-π作用力對於水膠之形成扮演相當重要的角色,並且發現星狀結構可以明顯地增強分子間作用力,而同時增加臂的數目與聚合度可以有效地降低成膠濃度,其中六臂聚賴胺酸31-接枝-吲哚0.27(6-armed PLL31-g-Indo0.27)具有本研究中最低的臨界成膠濃度(0.75 wt%)。X光繞射圖譜證明PLL-g-Indo與PLL-g-Phenyl的疏水基團堆疊是形成水膠的原因之一,另外,由掃描式電子顯微鏡與小角度X光散射實驗發現星狀PLL-g-Indo水膠中,高分子堆疊成膜狀與部分纖維結構,並且可以得知臂數目的增加會使相關長度(mesh size)變小、聚合度的增加會使相關長度變大。進一步利用流變儀分析水膠的強度與回復情形,發現星狀PLL-g-Indo水膠之黏彈性質與臂的數目有關,並且回復能力極佳。由本研究的結果說明了星狀接枝聚賴胺酸水膠性質的可調控性,可以藉由改變臂數目、聚合度與改質之疏水基團種類控制水膠之微觀結構與機械性質。
英文摘要 In this study, we reported the synthesis and hydrogelation of linear and star-shaped graft poly(L-lysine) and poly(L-glutamic acid) (PLL-g-Indo, PLL-g-Phenyl and PLG-g-Indo). Star-shaped polypeptides were synthesized by N-carboxyanhydrides (NCAs) ring opening polymerization (ROP) using polyols as the initiators with the aid of 1,1,3,3-tetramethylguanidine (TMG), followed by deprotection and partial side chain modification. Successful synthesis of these polypeptides was confirmed by 1H NMR and GPC analyses. Investigation of circular dichroism (CD) spectroscopy suggested that PLL-g-Indo and PLL-g-Phenyl mainly adopted random coil conformation. PLL-g-Indo exhibited better gelation ability than PLL-g-Phenyl and PLG-g-Indo, which indicated that the balance between hydration, charge repulsion, π-π stacking, cation-π interaction and hydrogen bonding dictated the physically entangled gelation of polypeptides. In addition, compared to linear ones, the star-shaped architecture could efficiently promote intermolecular interactions between polypeptide chains. CGC decreased as arm number and arm length increased simultaneously, and 6-armed PLL31-g-Indo0.27 exhibited the lowest CGC of 0.75 wt%. XRD profiles showed that π-π stacking was one of the reasons to form hydrogel, while SAXS patterns could be described by the Ornstein-Zernike equation. Besides, SEM images revealed that polypeptide chains formed continuous, membranous hydrogel networks. Furthermore, rheological properties and mesh sizes of these star-shaped graft polypeptide hydrogels were found to depend on arm number, arm length and composition.
論文目次 摘要 I
Extended Abstract II
誌謝 X
目錄 XI
表目錄 XV
圖目錄 XVI
第一章 緒論 1
1.1 前言 1
1.1.1 生醫材料 1
1.1.2 聚胺基酸 1
1.2研究動機 2
第二章 文獻回顧 3
2.1 聚胺基酸 3
2.1.1 胺基酸 3
2.1.2 蛋白質之結構 5
2.2 胺基酸之聚合 7
2.2.1 NCAs之合成 7
2.2.2 以一級胺作為起始劑進行NCAs開環聚合 8
2.2.3 以一級醇作為起始劑進行NCAs開環聚合 9
2.2.4 以鎳金屬錯合物作為起始劑進行NCAs開環聚合 12
2.3 非線性高分子 13
2.3.1 樹枝狀聚合物 13
2.3.2 星狀聚合物 14
2.4 水膠 15
2.4.1 水膠形成機制 16
2.4.2 水膠之種類 17
2.4.3 水膠之微觀結構 19
第三章 實驗方法與步驟 21
3.1 實驗藥品 21
3.2 實驗儀器與原理 23
3.2.1 核磁共振光譜儀(NMR) 23
3.2.2 凝膠滲透層析儀(GPC) 24
3.2.3 圓二色光譜儀(CD) 26
3.2.4 掃描式電子顯微鏡(SEM) 27
3.2.5 X光繞射儀(XRD) 28
3.2.6 小角度X光散射儀(SAXS) 28
3.2.7 流變儀(Rheometer) 30
3.3乾燥溶劑 30
3.4 N-carboxyanhydrides (NCAs)之製備 31
3.4.1 Z-L-lysine NCAs (ZLL NCAs)之製備 31
3.4.2 γ-benzyl-L-glutamic acid NCAs (BLG NCAs)之製備 31
3.5 線性聚胺基酸之合成 32
3.5.1 以一級胺進行NCAs開環聚合 32
3.5.2 以鎳金屬錯合物進行NCAs開環聚合 33
3.6 星狀聚胺基酸(star polypeptides)之合成 33
3.6.1 星狀聚賴胺酸(star PZLL)之合成 34
3.6.2 星狀聚穀胺酸(star PBLG)之合成 35
3.7 移除聚胺基酸之保護基 36
3.7.1 移除聚賴胺酸之Cbz保護基 36
3.7.2 移除聚穀胺酸之benzyl保護基 36
3.8 利用不同羧酸修飾聚賴胺酸側鏈 37
3.8.1 利用3-吲哚乙酸修飾聚賴胺酸側鏈 37
3.8.2 利用苯甲酸修飾聚賴胺酸側鏈 38
3.9 利用L-色胺酸甲酯修飾聚穀胺酸側鏈 39
3.10 水膠性質測試 40
3.10.1 圓二色光譜鑑定聚胺基酸之二級結構 40
3.10.2 以接枝聚胺基酸製備水膠 41
3.10.3 水膠之流變性質 41
3.10.4 接枝聚胺基酸水膠之堆疊 41
3.10.5 接枝聚胺基酸水膠之結晶性質 42
第四章 結果與討論 43
4.1 聚胺基酸之合成分析 43
4.1.1 聚胺基酸之聚合度與分子量 43
4.1.2 接枝聚胺基酸之接枝率 56
4.2 接枝聚胺基酸水膠之形成 68
4.2.1 臨界成膠濃度 68
4.2.2 接枝聚胺基酸成膠機制探討 70
4.3 接枝聚胺基酸水膠之結構 72
4.3.1 接枝聚胺基酸之二級結構 72
4.3.2 接枝聚胺基酸之堆疊 74
4.4 接枝聚賴胺酸水膠之流變性質 78
4.4.1 應變掃描實驗 78
4.4.2 頻率掃描實驗 79
4.4.3 回復實驗 80
第五章 結論 82
第六章 參考文獻 84
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