臺灣博碩士論文加值系統

本研究主要探討中碳鏈脂肪酸之雙甘油酯製備方法，以液液萃取及矽膠管柱進行純化得到高純度的 1,3-DAG，並測定其理化性質及加速儲存試驗。以含有辛酸及癸酸之中碳鏈三甘油酯 (Medium Chain Triglyceride, MCT) 為原料，利用低溫化學合成法 (low temperature chemical synthesis, LTCS) 與酵素甘油解法 (enzyme glycerol, EG) 製備雙甘油酯 (diacylglycerol, DAG)。 LTCS 的最適製備條件是將 MCT 加入 2 莫耳比 (油/甘油) 之甘油於 50°C 下反應 6 小時，並以丙酮作為溶劑。DAG 的產量可達 49.99%。EG 的最適條件是將 MCT 加入 10% 之脂肪酶，並加入 2 莫耳比 (油/甘油) 之甘油，於 50 °C 下反應 8 小時，DAG 的產量可達 44.14%。粗 DAG 經純化之後，LTCS (丙酮) 製備之 1,3-DAG 含量為 24.62%，此結果表示約有 50% 的 DAG 是 1,3-DAG。 LTCS (乙醇) 製備之 1,3-DAG 含量為 12.96%，此結果表示約有 41% 的 DAG 是 1,3-DAG。 EG 製備之 1,3-DAG 含量則為 19.38%，此結果表示約有 44% 之 DAG為 1,3-DAG。 LTCS 或 EG 製備之 1,3-DAG 其物理特性，包含熔點、黏度及折射率皆比 MCT 來的高，但發煙點比 MCT 低。另一方面，化學特性包含酸價、過氧化價、茴香胺價及 TBA 價皆很低。因此， LTCS 或 EG 皆可製得品質良好的中碳鏈 1,3-DAG。在加速儲存試驗中， LTCS 製備之 1,3-DAG 的酸價、過氧化價、茴香胺價以及 TBA 價均高於 EG。然而， LTCS (乙醇) 製備之 1,3-DAG 的總脂肪酸含量低於其他樣品。LTCS 製備之 1,3-DAG的折射率以及油脂色澤高於 EG。此表示 EG 製備之 1,3-DAG 的氧化安定性較佳。

This study was to investigate a diglyceride containing a medium-chain fatty acid, which was purified by liquid-liquid extraction and column fractionation to obtain high-purity 1,3-DAG, and determined its physicochemical properties and accelerated storage test. Diacylglycerol (DAG) was prepared from MCT (mediun chain triglyceride) contained octanoic acid and decanoic acid by low temperature chemical synthesis (LTCS) and enzyme glycerolysis (EG). The optimal condition of LTCS was: MCT/glycerol ratio of 2 mol, reaction temperature of 50°C, reaction time of 6 hrs and acetone as solvent. The yield of DAG could reach up to 49.99% by using this reaction condition. In addition, the optimal condition of EG was: MCT/glycerol ratio of 2 mol, reaction temperature of 50°C and reaction time of 8 hrs. As the DAG was prepared by this condition, the yield of DAG was maximized to 44.14%. After column purification, the 1,3-DAG content of the crude DAG prepared by LTCS (acetone) was 24.62%. This result indicated that the content of 1,3-DAG was about 50% in purified DAG. The 1,3-DAG content of the crude DAG prepared by LTCS (ethanol) was 12.96%. This result indicated that the content of 1,3-DAG was about 41% in purified DAG. On the other hand, the 1,3-DAG content of the crude DAG prepared by EG was 19.38%. This result indicated that the content of 1,3-DAG was around 44% in purified DAG. The physical properties (including melting point, viscosity and refractive index) of 1,3-DAG prepared by LTCS or EG were all higher than that of MCT while the smoke point was slightly lower. On the other hand, the chemical properties (including acid value, peroxide value, p-anisidine value and TBA value) of 1,3-DAG prepared by LTCS and EG were all very low. Therefore, medium-chain 1,3-DAG prepared by LTCS or EG had a good quality. In the accelerated storage test, the acid value, peroxide value, p-anisidine value, and TBA value of 1,3-DAG prepared by LTCS were slightly higher than that of EG. However, the total fatty acid content of 1,3-DAG prepared by LTCS (ethanol) was the lowest among samples. Refractive index and oil color of 1,3-DAG prepared by LTCS was higher than that of EG. This indicates that the 1,3-DAG prepared by EG was a best oxidation stability.

摘要 I
Abstract II
謝誌 IV
目錄 V
圖目錄 X
表目錄 XII
壹、前言 1
貳、文獻整理 3
一、中碳鏈三甘油酯 3
(一) 簡介 3
(二) 理化特性 3
(三) MCT 之合成方法 5
(四) 安全性 5
(五) MCT 代謝特色 6
(六) MCT 對體重和體脂的影響 8
1. MCT 對體重的影響 8
2. MCT 對血脂的影響 9
(七) MCT 的應用 10
1. 嬰幼兒食品之應用 10
2. 運動食品中之應用 10
3. 醫藥及病患食品之應用 10
4. 減肥產品之應用 11
5. 化妝品之應用 11
6. 其他食品工業之應用 11
二、 雙甘油酯 12
(一) 簡介 12
(二) 理化特性 12
(三) DAG 之合成方法 14
1. 甘油解法 14
2. 甘油與脂肪酸直接酯化法 16
3. 酯交換法 16
4. 水解法 16
5. 先水解後酯化法 17
(四) 安全性 17
1. 膳食毒性 17
2. 致癌性 17
(五) DAG代謝特色 18
(七) DAG 的應用 18
1. 烘焙產品的應用 18
2. 即溶飲品之應用 19
3. 食品保鮮之應用 19
4. 低熱量產品之應用 20
5. 醫藥產品之應用 20
6. 工業上之應用 20
三、油脂替代物 (fat replacer) 20
(一) 蛋白質基質合成之油脂替代物 21
(二) 油脂基質合成之油脂替代物 23
(三) 碳水化合物基質合成之油脂替代物 25
四、脂肪酶 26
(一) 簡介 26
(二) 特異性 26
(三) 應用 27
五、油脂之氧化反應 27
六、溶劑之特性 29
七、DAG 之分析方法 32
(一) 高效液相層析法 32
(二) 氣相層析法 34
(三) 薄層層析法 34
八、DAG 之純化方法 35
(一) 分子蒸餾法 35
(二) 管柱層析法 35
(三) 溶劑結晶法 36
(四) 液液萃取法 36
(五) 超臨界二氧化碳萃取法 36
參、材料與方法 38
一、實驗架構 38
(一) 1,3-雙甘油酯製備 38
(二) 1,3-雙甘油酯理化特性探討 39
(三) 加速儲存試驗 40
(一) 實驗樣品 41
(二) 實驗藥品與儀器 41
1. 實驗藥品 41
2. 實驗儀器 42
(三) 實驗方法 43
1. 1,3-雙甘油酯製備 43
(1) 低溫化學合成法 43
(2) 酵素甘油解法 43
2. 雙甘油酯之純化方法 43
(1) 液液萃取 43
(2) 管柱層析 44
3. 甘油酯組成分析 44
4. 1,3-雙甘油酯之理化特性探討 45
(1) 1,3-雙甘油酯之物理特性之探討 45
(2) 1,3-雙甘油酯的化學特性之探討 46
5. 加速儲存試驗 50
6. 統計分析 50
肆、結果與討論 51
一、低溫化學法合成雙甘油酯最適條件之探討 51
(一) MCT/甘油莫耳比 51
(二) 溫度 54
(三) 溶劑 56
(四) 時間 58
二、酵素甘油解法合成雙甘油酯最適條件之探討 60
(一) MCT/甘油莫耳比 60
(二) 溫度 62
(三) 酵素添加量 62
(四) 時間 65
三、低溫化學法合成與酵素甘油解法製備雙甘油酯之比較 68
四、純化中碳鏈 1,3-雙甘油酯含量之探討 70
五、中碳鏈 1,3-雙甘油酯之理化特性 73
(一) 物理特性 73
1. 熔點 73
2. 折射率 73
3. 黏度 75
4. 發煙點 75
5. 色澤 76
(二) 化學特性 76
1. 酸價 76
2. 過氧化價 79
3. 硫巴比妥酸價 79
4. 茴香胺價 80
5. 脂肪酸組成 80
六、中碳鏈1,3-雙甘油酯之加速儲藏試驗 82
(一) 物理方法測定 82
1. 折射率 82
2. 色澤 82
(二) 化學方法測定 85
1. 酸價 85
2. 過氧化價 87
3. 硫巴比妥酸價 87
4. 茴香胺價 90
5. 脂肪酸組成 92
伍、結論 94
陸、參考文獻 96

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