輔仁大學
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狀態NC094FJU00255010
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學校名稱輔仁大學
系所名稱食品營養學系
舊系所名稱
學號492446048
研究生(中)沈佳僡
研究生(英)chia-hui shen
論文名稱(中)包覆阿斯巴甜超微膠囊之安定性及其控制釋出動力學研究
論文名稱(英)Stability of aspartame-encapsulated submicron particles and the kinetic studies of its controlled release
其他題名
指導教授(中)陳烱堂
指導教授(英)John Tung Chien Ph. D.
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國圖全文開放日期.2007.06.01
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學位類別碩士
畢業學年度94
出版年
語文別中文
關鍵字(中)交互作用 刺槐豆膠 水溶液 穩定性 高效率
關鍵字(英)aspartame microcapsulation
摘要(中)阿斯巴甜甜味劑在水溶液中加工或貯存時不安定,容易受水活性、pH值、溫度及光照的影響,尤其在受熱時會裂解而失去甜味。故研究目的在於製備熱穩定膠囊化阿斯巴甜,以減緩高溫烤焙時的熱破壞。而高度熱穩定之膠囊,其包覆壁材質對熱穩定性之要求甚高,且需仰賴其分子間具有強的交互作用。由相分離研究κ-紅藻膠與動物膠分子之交互作用發現,在pH 3.6、25℃及κ-紅藻膠固定在0.5% 時,動物膠 (type B) 濃度在2.5-4.0% 或是鹼處理動物膠濃度2.0-4.0%,兩分子呈現強的交互作用。另以物性分析κ-紅藻膠及刺槐豆膠之混合膠體發現,在固定1.5% (w/v) 動物膠及pH 3.5條件下,κ-紅藻膠及刺槐豆膠濃度分別為1.6% (w/v) 及1.2-1.6% (w/v) 時,有最高的膠體硬度。在此條件下,混合膠體的膠性及咀嚼性也最好。另以流變性分析發現,當固定動物膠濃度為1.5% (w/v) 且κ-紅藻膠和刺槐豆膠的比例為1.48% : 1.4% 時,有較強的交互作用。以上述最適條件製備超微膠囊,再以示差掃描熱分析發現,其熱穩定性可達到120℃,而所配製超微膠囊的平均粒徑為197 nm。超微膠囊化阿斯巴甜於pH 3.5經冷凍解凍循環之熱安定性高,然而在鹼性環境 (pH 7.4) 很不安定。以高效率液相層析定量阿斯巴甜及其裂解產物也發現,在pH 7.4比在pH 3.5 的安定性差。在pH 7.4、70℃時阿斯巴甜由超微膠囊中釋出之速率常數為1.17±0.08 h-1,釋出之阿斯巴甜會裂解,而總裂解速率常數為6.24±0.26 h-1,這比在pH 3.5、70℃的總裂解速率常數(0.011±0.001 h-1) 高567倍。進一步分析釋出後阿斯巴甜遇到鹼及熱的各別裂解反應,阿斯巴甜 (A) 降解成3,6-dioxo-5-phenylmethyl-2-peperazineacetic acid (DKP) 的反應速率常數為5.94±0.48 h-1,而反應A? N-L-α-aspartyl-L-phenyalanine (AP) 的速率常數為0.3 h-1,比較兩反應速率常數可了解阿斯巴甜在pH 7.4、70℃加熱之主要降解途徑為A?DKP。此外於70℃阿斯巴甜在pH 3.5裂解成DKP的反應速率常數 (0.0072±0.0015 h-1) 比在pH 7.4者下降825倍。由此可知阿斯巴甜在微鹼性溶液中加熱的裂解速率非常的快,因此超微膠囊之所以可以減緩阿斯巴甜在pH 7.4及70℃環境中裂解,主要靠緩慢的釋出控制。
摘要(英)Aspartame, a dipeptide sweetener, is unstable during storage or heating in an aqueous solution. Its instability can be affected by water activity, pH, temperature and illumination. For instance, aspartame may decompose under heating and lose its sweetness. Therefore, it is our purpose to develop heat-stable encapsulated aspartame strongly depends on the heat stability of coating materials, which was governed by the interaction formed during preparation. Studies of phase separation indicated that strong intermolecular interaction between κ-carrageenan and gelatin was observed at pH 3.6 and 25℃ when 2.5-4.0%gelatin (type B) or 2.0-4.0% alkali-treated gelatin was added into 0.5% κ-carrageenan. Furthermore, rheometric results showed that maximum hardness of the mixed gel were obtained by mixing 1.6% (w/v) κ-carrageenan with 1.2-1.6% (w/v) locust bean gum in presence of 1.5% (w/v) gelatin at pH 3.6. Gumminess and chewiness of the mixed gel also reached the highest value at the same condition. Based on the finding of rheological analysis, strong interaction was also found for the mixed gel at concentration of 1.48% κ-carrageenan, 1.4% locust bean gum and 1.5% gelatin. Heat-stable submicron particles were prepared based on the above optimal conditions. Differential Scanning Calorimetry revealed that the micron particles with particle size of 197 nm had heat stability up to 120℃. At pH 3.5, the aspartame-encapsulated submicron particles were very stable upon freeze-thawing as compared to its instability at pH 7.4. Quantitative analysis of high performance liquid chromatography also showed that aspartame was more stable at pH 3.5 than pH 7.4. When encapsulated release from submicron particles was 1.17±0.08 h-1. The released aspartame was instantaneously degraded with the overall reaction rate constant of 6.24±0.26 h-1, which was 567 times higher than the heating of aspartame at pH 7.4 and 70℃. Further studies on the degradation reaction of aspartame in an aqueous solution indicated that the rate constant for degradation of aspartame (A) to 3,6-dioxo-5-phenylmethyl-2-peperazineacetic acid (DKP) was 5.94±0.48 h-1, whereas the rate constant for reaction A? N-L-α-aspartyl-L-phenyalanine (AP) was estimated to be 0.3 h-1. As we carefully examined the above two heating reactions, it was noted that the major reaction route for aspartame degradation at pH 7.4 and 70℃ was A?DKP. Besides, the reaction rate constant (0.0072±0.0015 h-1) for aspartame degradation at pH 3.5 was 825-folds lower than that at pH 7.4. Thus, aspartame degraded rapidly at a slight alkaline solution. Reduction on aspartame loss during heating can only be achieved by lowering the controlled release rate of submicron particles at pH 7.4 and 70℃.
論文目次目 錄 第一章 前言………..…………………………………………………………4 第二章 文獻回顧……………………………………………………..………6 一、阿斯巴甜………………………………………………………………….6 (一) 阿斯巴甜簡介………………………………………………………6 (二) 阿斯巴甜安定性……………………………………………………6 (1) 加熱溫度………………………………………………………..6 (2) 貯存時間………………………………………………………..6 (3) 水分含量………………………………………………………..7 (4) pH 值……………………………………………………………7 (5) 其他成分作用…………………………………………………..8 (三) 分析方法……………………………………………………………8 (四) 食品上之應用………………………………………………………8 二、微膠囊…………………………………………………………….………9 (一) 微膠囊及其功用…………………………………………….……....9 (二) 微膠囊製備方法…………………………………………………...10 (1) 噴霧乾燥……………………………………………………….10 (2) 相分離法……………………………………………………….11 (三) 微膠囊的控制釋放作用…………………………………………...11 (1) 侵蝕或化學反應控制系統…………………………………….12 (2) 擴散控制系統………………………………………………….12 (3) 膨潤控制釋放系統…………………………………………….13 (4) 滲透泵浦系統……………………………………………….…13 (四) 影響微膠囊控制釋放的因子……………………………………...13 (1) 包覆物濃度…………………………………………………….14 (2) 包覆物性質…………………………………………………….14 (3) 離子濃度……………………………………………………….14 (4) 溶液pH值……………………………………………………..14 三、蛋白質與陰電性多醣類之交互作用……………………………………15 (一) 動物膠的結構與特性………………………………………………...15 (二) 陰電性多醣類結構與特性…………………………………………...19 (1) 羧甲基纖維素…………………………………………………….19 (2) 紅藻膠…………………………………………………………….21 (3) 褐藻膠…………………………………………………………….23 (三) 蛋白質與多醣類之交互作用對乳化安定性的影響………………...25 第三章 材料與方法……………………………………………………….. 27 一、實驗材料…………………………………………………………………27 (一) 阿斯巴甜及其裂解產物標準品……………………………………...27 (二) 溶劑及其他試藥……………………………………………………...27 二、樣品製備…………………………………………………………………28 (一) 動物膠之鹼處理……………………………………………………...28 (二) 複合物相分離條件之評估…………………………………………...28 (三) 混合膠體的配製……………………………………………………...29 (四) 超微膠囊的製備……………………………………………………...31 三、分析方法…………………………………………………………………31 (一) 物性分析……………………………………………………………...31 (二) 流變性分析…………………………………………………………...32 (三) 超微膠囊顆粒大小及分布分析……………………………………...32 (四) 示差掃描熱分析……………………………………………………...33 (五) 阿斯巴甜及其裂解產物之定量測定………………………………...35 (1) 標準溶液配製…………………………………………………….35 (2) 動相配製………………………………………………………….35 (3) 阿斯巴甜及其裂解產物之定量分析…………………………….35 (六) HPLC分析阿斯巴甜含量…………………………………………….36 (七) HPLC分析超微膠囊化阿斯巴甜含量……………………………….37 (八) 超微膠囊中阿斯巴甜之釋放動力學………………………………...37 (九) 統計分析……………………………………………………………...38 第四章 結果與討論………………………………………………………...39 一、複合物相分離條件之評估………………………………………………39 二、混合膠體的交互作用……………………………………………………44 (一) 物性分析……………………………………………………………...45 (二) 流變性分析…………………………………………………………...51 三、超微膠囊分析……………………………………………………………57 (一) 超微膠囊熱穩定性…………………………………………………...59 (二) 超微膠囊顆粒大小及分布…………………………………………...62 (三) 冷凍解凍安定性……………………………………………………...68 (四) HPLC分析超微膠囊之包覆率……………………………………….71 (五) 超微膠囊化阿斯巴甜的控制釋放動力學…………………………...72 (六) 加熱過程中阿斯巴甜降解動力學研究……………………………...78 第五章 結論…………………………………………………………………88 第六章 參考文獻…………………………………………………………...89 附錄一…………………………………………………………………………..100 附錄二…………………………………………………………………………..101 附錄三…………………………………………………………………………..102
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