臺灣博碩士論文加值系統

本研究之主要目的在探討幾丁聚醣 (chitosan) 之分子量、去乙醯度 (degree of deacetylation, DD)、濃度以及凝膠系統中pH影響幾丁聚醣與褐藻酸鈉 (sodium alginate) 所製備的複合水合膠之物化性質，物化性質的探討包括水合膠之動粘彈性、吸水性以及熱性質。從大頭紅蝦 (Solemocera prominenitis) 之加工廢棄物抽取幾丁質 (chitin)，利用熱鹼處理法製備三種不同去乙醯程度之幾丁聚醣；再將這三種不同去乙醯程度之幾丁聚醣以超音波降解，以得到相同去乙醯度不同分子量之幾丁聚醣。利用相同分子量不同去乙醯度或相同去乙醯度不同分子量之幾丁聚醣與褐藻酸鈉製備複合水合膠並探討濃度與pH值對水合膠之物化性質影響結果如下：
幾丁聚醣之濃度、分子量、去乙醯度以及凝膠製備pH均會影響其與褐藻酸鈉之交互作用，隨著這些因子的增加，水合膠之粘彈特性尤其是貯存模數 (storage modulus, G) 隨之提高，其中又以濃度及分子量所造成之交纏結構影響最為顯著。水合膠的吸水性亦受到上述因子所影響，但其呈現出不同的效應，即隨著這些因子的增加，水合膠之吸水性會相對較差，這現象除了與聚合物間之靜電交互作用以外，分子內及分子間之氫鍵結構亦是影響因子。水合膠之最大熔化溫度及熱焓會隨著幾丁聚醣之分子量、去乙醯度、濃度以及凝膠pH增加而提高，顯示上述因子均會增加幾丁聚醣與褐藻酸鈉間之交互作用。由紅外線光譜之分析得知增加幾丁聚醣之濃度會加強與褐藻酸鈉間之靜電交互作用及氫鍵結構，而增加幾丁聚醣之分子量對紅外線光譜之差異不大，表示在相同濃度下，幾丁聚醣之分子量大小對水合膠之機械強度所造成的差異原因主要來自於分子鏈之交纏度所造成。

The aims of this study are to explore the effects of molecular weight, degrees of deaectylation, concentrations of chitosan and gelling pH on physical-chemical properties of complex hydroges prepared from chitosan and alginate. Physical-chemical properties includes dynamic viscoelastic, water absorptivity and thermal properties. Chitin was extracted from red shrimp (Solemocera prominenitis) process waste. Three different degrees of deacetylation chitosans were prepared by hot alkali deacetylation from prepared chitin. The same degrees of deacetylation but different molecular weight chitosans were produced by ultrasonication treatment on three different degrees of deacetylation chitosans. The effect of the same degrees of deacetylation but different molecular weight or the same molecular weight but different degrees of deacetylation, their concentration and gelling pH on physical-chemical properties of complex hydrogels of chitosans and alginate were explored and results obtained are as following:
The viscoelastic properties especially the storage modulus (G) of complex hydrogels of chitosans and alginate increased with increasing concentration, molecular weight, degrees of deacetylation of chitosans and gelling pH. This may be due to the conformation, chain flexibility of the chitosan molecules and entanglement between chitosan and alginate were affected by increasing concentration and molecular weight of the chitosan. The electrostatic interaction between chitosan and alginate and hydrogen bond of intra-molecular and inter-molecular were then play their role to form hydrogels. The absorptivity of these hydrogels were also affected by these factors, but in the opposite trends. Increasing of these factors, the absorptivity of the hydrogels decreased. The maximum melting point and enthalpy also increased with increasing the molecular, degree of deacetylation and concentration as well as the gelling pH. This may be owing to that these factors enhanced the interactions of chitosan and alginate. The infrared spectra data show that increasing the concentration of chitosan would facilitate the electrostatic interactions and hydrogen bond between chitosan and alginate. But increasing the molecular weight of chitosan did not result in significant difference in infrared spectra. These results indicated that the main factor that increased the mechanical strength of the hydrogel of the same concentration were the entanglement of the molecular chains between chitosan and alginate.

中文摘要………………………………………………………………... IV
英文摘要………………………………………………………………... V
一. 前言………………………………………………………………… 1
二. 文獻整理…………………………………………………………… 3
1. 水合膠之定義、種類與應用方法………………………………. 3
2. 幾丁質類物質凝膠的製備與應用………………………………. 3
2.1. 幾丁質類物質凝膠的製備………………………………….. 3
2.2. 幾丁質類物質凝膠的應用…………………………………. 4
3. 褐藻酸鈉凝膠的製備與應用……………………………………. 6
3.1. 褐藻酸鈉凝膠的製備………………………………………. 6
3.2. 褐藻酸鈉凝膠的應用………………………………………. 8
4. 幾丁聚醣與褐藻酸鈉之離子鍵水合膠…………………………. 8
4.1. 聚電解質複合物……………………………………………. 8
4.2. 幾丁聚醣與褐藻酸鈉之離子鍵水合膠的應用……………. 9
三. 材料與方法………………………………………………………… 11
1.材料………………………………………………………………... 11
2.方法………………………………………………………………... 11
2.1. 不同去乙醯度幾丁聚醣之製備……………………………. 11
2.2. 相同去乙醯度、不同分子量幾丁聚醣之製備……………. 12
2.3. 幾丁聚醣之去乙醯程度測定………………………………. 12
2.4. 幾丁聚醣分子量之測定……………………………………. 13
2.5. 褐藻酸鈉分子量的測定……………………………………. 13
2.5.1. dn / dc 測定……………………………………………. 13
2.5.2. 褐藻酸鈉分子量的測定………………………………. 14
2.6. 褐藻酸鈉 M / G比的測定………………………………… 15
2.7. 幾丁聚醣-褐藻酸鈉複合水合膠的製備…………………… 16
2.8. 動態粘彈性質之測定………………………………………. 16
2.8.1. 應力掃瞄………………………………………………. 17
2.8.2. 頻率掃瞄………………………………………………. 17
2.9. 複合水合膠吸水膨潤性測定………………………………. 18
2.10. DSC. 分析………………………………………………... 19
2.11. 幾丁聚醣與褐藻酸鈉靜電交互作用系統………………... 19
2.11.1. 傅立葉轉換紅外線光譜分析………………………... 19
四. 結果與討論………………………………………………………… 20
1. 幾丁質/幾丁聚醣的製備………………………………………… 20
2. 褐藻酸鈉性質……………………………………………………. 21
3. 幾丁聚醣與褐藻酸鈉靜電交互作用……………………………. 21
4. 幾丁聚醣與褐藻酸鈉複合水合膠之流變特性…………………. 22
4.1. 幾丁聚醣與褐藻酸鈉複合水合膠之應變掃瞄……………. 22
4.2. 幾丁聚醣與褐藻酸鈉複合水合膠之頻率掃瞄……………. 22
4.2.1. 幾丁聚醣濃度對複合水合膠粘彈性質的影響………. 22
4.2.2. 成膠pH對複合水合膠粘彈性質的影響…………….. 23
4.2.3. 幾丁聚醣分子量對複合水合膠粘彈性質的影響……. 25
4.2.4. 幾丁聚醣去乙醯度對複合水合膠粘彈性質的影響…. 26
5. 幾丁聚醣-褐藻酸鈉複合水合膠之吸水澎潤性………………… 27
5.1. 幾丁聚醣濃度及凝膠pH之影響………………………….. 28
5.2. 幾丁聚醣分子量及去乙醯度之影響………………………. 28
6. DSC分析………………………………………………………… 29
6.1. 幾丁聚醣濃度之影響………………………………………. 29
6.2. 凝膠pH之影響…………………………………………….. 30
6.3. 幾丁聚醣去乙醯度與分子量之影響………………………. 30
7. 傅立葉轉換紅外線光譜分析……………………………………. 31
五. 結論………………………………………………………………… 34
六. 參考文獻…………………………………………………………… 35
圖………………………………………………………………………... 49
表………………………………………………………………………... 73

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