摘要
本研究之目的在探討幾丁聚醣之分子量、褐藻酸鈉溶液之濃度、幾丁聚醣溶液之pH對製備幾丁聚醣與褐藻酸鈉之聚電解質複合之物物化性質的影響與幾丁聚醣-褐藻酸鈉複合膜在人工腸衣的製備與適用性的探討。物化性質的探討包含了複合膜的復水性、拉張力、拉張變形度、熱性質與水氣透過率與分析複合膜中幾丁聚醣與褐藻酸鈉的組成比。利用大頭紅蝦的加工廢棄物來萃取幾丁質，並以熱鹼的去乙醯作用來製備高去乙醯度的幾丁聚醣，再經鹽酸的降解可以得到相同去乙醯度不同分子量幾丁聚醣，並使用反應曲面法來設計實驗條件，以相同去乙醯度不同分子量幾丁聚醣與褐藻酸鈉製備複合膜，SAS統計分析系統來做回歸分析，以探討幾丁聚醣之分子量、褐藻酸鈉溶液的濃度與幾丁聚醣溶液之pH對於複合膜的物化性質之影響，其結果如下：
高去乙醯度 (DD = 93%) 之幾丁聚醣在8N鹽酸55℃的降解下對其去乙醯度並無顯著 (DD = 93% ± 2) 的影響，但其分子量的降解會隨著時間的增加而有顯著的下降，當分子量變為原本的1/10其降解速率會趨於平緩，主要為N-乙醯葡萄胺醣之醣苷鍵的活化能較低。
綜合DSC與反應面法之結果得知，幾丁聚醣之分子量、褐藻酸鈉溶液的濃度與幾丁聚醣溶液之pH均會影響幾丁聚醣與褐藻酸鈉的交互作用，(1) 當pH越高時，幾丁聚醣與褐藻酸鈉的作用力可能主要為分子鏈間的交纏作用，反之，其作用力則可能主要為離子性鍵結；(2) 當褐藻酸鈉溶液之濃度越高時，幾丁聚醣與褐藻酸鈉的作用力趨向離子性鍵結，反之，其作用力則趨向於分子鏈間的交纏作用；(3) 幾丁聚醣之分子量越低時，幾丁聚醣與褐藻酸鈉的作用力趨向離子性鍵結，當幾丁聚醣之分子量越高時，因為分子鏈的增長會有助於分子間的交纏，但分子鏈的增長時，胺基的數目亦會增加，使得幾丁聚醣與褐藻酸鈉的作用力趨向離子性鍵結，因此高分子量的幾丁聚醣對於交互作用的影響會受到幾丁聚醣溶液之pH與褐藻酸鈉溶液之濃度的影響。由反應曲面法得知，幾丁聚醣與褐藻酸鈉作用最適的分子量為150 kDa ~ 160 kDa，幾丁聚醣溶液之pH與褐藻酸鈉溶液之濃度的影響則依條件而異。
由適用性的實驗得知，幾丁聚醣腸衣較膠原腸衣更耐熱油而不會破裂，可能是其反應為脫水作用結合區較不易被破壞；而在水煮過程中，膠原腸衣可保持原狀，而幾丁聚醣-褐藻酸鈉腸衣則會成潰爛狀，可能是水分子的滲透與熱的作用，使得其結合區與離子性鍵結被破壞，因此，幾丁聚醣-褐藻酸鈉腸衣較可應用在熱油處理上。

Abstract
The aims of the study are to explore the effects of the molecular weight of chitosan, the concentration of sodium alginate solution and the pH of chitosan solution on the physical-chemical properties of the chitosan-sodium alginate polyelectrolyte complex (CS-AL PEC) and to establish the application conditions of the CS-AL PEC casing. The physical-chemical properties studied including the rehydration property, tensile stress, tensile strain and thermal property and the analyzation of the composite ratio of chitosan and sodium alginate in the PEC. Chitin was extracted from red shrimp (Solemocera prominenitis) processed waste, then the high degree of deacetylated chitosan was prepared by hot alkali deacetylation. The HCl degradation on chitosan prepared were used to get the same degree of deacetylation but different molecular weight chitosans. Response surface methodology (RSM) was used to set the experimental design. The same degree of deacetylation but different molecular weight chitosans and sodium alginate were used to prepare the PEC. SAS statistics analysis package was used to regressing the data of the experiments and the results obtained were as following:
During hydrolysis of high degree of deacetylated chitosan (DD = 93%) by HCl (8N) at 55℃, changed in the degree of deacetylation was not significant. However the molecular weight decreased significantly over time. At the time, the molecular weight decreased to 1/10 of the original molecular weight, the rate of degradation became level off. It is because the activity energy of glucosidic bond of N-acetyl-glucosamine was lower.
The results of differential scanning calorimeter (DSC) and RSM studies show that the properties of the CS-AL PEC affected by the molecular weight of chitosans, the concentration of sodium alginate solution and the pH of chitosan solution. The results show that (1) higher chitosan solution pHs used in the system, the interaction of chitosan and sodium alginate was mainly due to entanglement between chitosan and alginate molecules. On the other hand, lower chitosan solution pH, the interaction of chitosan and sodium alginate mainly via the ionic bond. (2) higher sodium alginate concentration used in the system, the interaction of chitosan and sodium alginate mainly via the ionic bond. On the other hand, lower sodium alginate solution, the interaction of chitosan and sodium alginate tended to be the entanglement of molecular chains. (3) lower molecular weight of chitosan in the system, the interaction of chitosan and sodium alginate tended to be the ionic bond. However, higher molecular weight of chitosans, the interaction of chitosan and sodium alginate tended to be the entanglement of molecular chains. It may be due to that the longer chain molecule facilitate the entanglement. However, the longer the molecular chain of chitosan, the higher the numbers of amino group have. The interaction of chitosan and sodium alginate will tend to be the ionic bond. Therefore, the interaction of the high molecular weight chitosan will be affected by the pH of chitosan solution and the concentration of sodium alginate solution in the system. The results show that the optimal molecular weight of chitosan is 150 ~ 160 kDa and the pH of chitosan solution and the concentration of sodium alginate solution depended on the conditions used.
The CS-AL PEC casing was more endured to be ruptured in deep frying treatment than gelatin casing. It maybe due to the junction zone was resistant to be destroyed in the frying treatment. During boiling, the gelation casing could sustain the original shape, but the CS-AL casing could not. It maybe due to the destruction of the junction zone and ionic bond by the permeation of water molecule and hydrolysis process. Therefore, the CS-AL casing was more suitable to be used in the frying treatment.

目錄
摘要................................................................................................................... Ⅳ
Abstract............................................................................................................. Ⅵ
一. 前言............................................................................................................ 1
二. 文獻整理.................................................................................................... 3
1. 幾丁質與幾丁聚醣的來源、化學結構................................................. 3
2. 幾丁質與幾丁聚醣在食品上的應用.................................................... 4
2.1 抑菌作用.......................................................................................... 4
2.2 食品加工.......................................................................................... 5
2.3 膳食纖維.......................................................................................... 5
2.4 抗氧化作用...................................................................................... 6
2.5 保水與乳化作用.............................................................................. 6
2.6 其他食品應用.................................................................................. 6
2.7 食用幾丁質與幾丁聚醣的安全性及營養評估.............................. 6
3. 幾丁質類物質的凝膠製備…………………………………….…....... 7
4. 褐藻酸鈉的來源、化學結構................................................................. 7
5. 褐藻酸鈉的凝膠機制............................................................................ 8
6. 水合膠 (Hydrogel) 的定義、種類與應用........................................... 9
7. 幾丁聚醣-褐藻酸鈉之離子性水合膠................................................... 10
7.1 聚電解質複合物 (Polyelectrolyte complex, PEC)......................... 10
7.2 幾丁聚醣-褐藻酸鈉之離子性水合膠的應用................................. 11
8. 幾丁聚醣對幾丁聚醣-褐藻酸鹽膠體的影響....................................... 12
8.1 幾丁聚醣之乙醯度與醯基對幾丁聚醣-褐藻酸鹽膠體的影響..... 12
8.2 幾丁聚醣之分子量對幾丁聚醣-褐藻酸鹽膠體的影響................. 12
9. pH與鈣離子對幾丁聚醣-褐藻酸鹽膠體的影響.................................. 13
9.1 pH對幾丁聚醣-褐藻酸鹽膠體的影響............................................ 13
9.2 鈣離子對幾丁聚醣-褐藻酸鹽膠體的影響..................................... 14
10. 不同腸衣對中式香腸品質的影響...................................................... 14
10.1 腸衣之簡介.................................................................................... 14
10.2 腸衣對中式香腸品質的影響........................................................ 15
三. 材料與方法................................................................................................ 18
1. 材料........................................................................................................ 18
2. 方法........................................................................................................ 18
2.1 幾丁質的製備.................................................................................. 18
2.2 幾丁聚醣的製備.............................................................................. 18
2.3 相同去乙醯度不同分子量之幾丁聚醣的製備.............................. 18
2.4 幾丁聚醣之去乙醯度的測定.......................................................... 18
2.5 幾丁聚醣之分子量的測定.............................................................. 19
2.6 幾丁聚醣之錳含量的測定.............................................................. 19
2.6.1 樣品的分解............................................................................. 19
2.6.2原子吸光分光光譜儀的測定.................................................. 20
2.7 褐藻酸鈉分子量的測定.................................................................. 20
2.7.1. dn / dc 的測定........................................................................ 20
2.7.2 褐藻酸鈉分子量的測定......................................................... 20
2.8 褐藻酸鈉 M / G比的測定.............................................................. 21
2.9 幾丁聚醣-褐藻酸鈉複合膜的製備................................................. 21
2.10 複合膜的物性測定........................................................................ 22
2.10.1 厚度 (mm)............................................................................ 22
2.10.2 吸水膨潤率........................................................................... 22
2.10.3 拉張力 (kg / cm2) 與拉張變形度 (%)............................... 22
2.10.4 水汽透過率 (water vapor transmission rate, WVTR)......... 22
2.10.5 Differential scanning calorimetry (DSC)............................... 23
2.10.6 複合膜中幾丁聚醣與褐藻酸鈉的組成比........................... 23
2.11 香腸的製造.................................................................................... 23
2.12 適用性試驗.................................................................................... 23
2.12.1 煎........................................................................................... 23
2.12.2 炸........................................................................................... 23
2.12.3 煮........................................................................................... 23
四. 結果與討論................................................................................................ 24
1. 酸水解幾丁聚醣的變化........................................................................ 24
2. 錳在幾丁聚醣處理過程中的含量........................................................ 24
3. 幾丁聚醣-褐藻酸鈉複合膜的物理性質............................................... 24
3.1 複合膜的復水率.............................................................................. 24
3.1.1 幾丁聚醣溶液之pH與褐藻酸鈉溶液之濃度對複合膜
之復水率的影響......................................................................
25
3.1.2 幾丁聚醣溶液之pH與幾丁聚醣之分子量對複合膜之
復水率的影響..........................................................................
26
3.1.3 幾丁聚醣之分子量與褐藻酸鈉溶液之濃度對複合膜之
復水率的影響..........................................................................
27
3.2 複合膜的拉張力.............................................................................. 28
3.2.1 幾丁聚醣溶液之pH與褐藻酸鈉溶液之濃度對複合膜
之拉張力的影響.....................................................................
29
3.2.2 幾丁聚醣溶液之pH與幾丁聚醣之分子量對複合膜之
拉張力的影響..........................................................................
29
3.2.3 幾丁聚醣之分子量與褐藻酸鈉溶液之濃度對複合膜之
拉張力的影響…......................................................................
30
3.3 複合膜的拉張變形度..................................................................... 31
3.3.1 幾丁聚醣溶液之pH與褐藻酸鈉溶液之濃度對複合膜
之拉張變形度的影響..............................................................
31
3.3.2 幾丁聚醣溶液之pH與幾丁聚醣之分子量對複合膜之
拉張變形度的影響…..............................................................
32
3.3.3 幾丁聚醣之分子量與褐藻酸鈉溶液之濃度對複合膜之
拉張變形度的影響..................................................................
33
4. 幾丁聚醣-褐藻酸鈉複合膜中幾丁聚醣與褐藻酸鈉之組成比........... 33
5. Differential scanning calorimetry 分析.................................................. 34
5.1 幾丁聚醣溶液之pH的影響........................................................... 34
5.2 褐藻酸鈉溶液之濃度的影響.......................................................... 35
5.3 幾丁聚醣之分子量的影響.............................................................. 35
6. 幾丁聚醣-褐藻酸鈉腸衣的是用性....................................................... 35
五. 結論............................................................................................................ 36
六. 參考文獻.................................................................................................... 37
圖....................................................................................................................... 50
表....................................................................................................................... 73
附表................................................................................................................... i

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