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dc.description.abstract白藜蘆醇(Resveratrol)具有抑制血小板非正常凝聚、抗氧化等多種有益效應的天然成分。白藜蘆醇在油及乳化劑等親油性的系統中,會因為其偏低的溶解度,而降低其抗氧化的功能及生物吸收率。然而,可藉由轉酯化的方式來提升其脂溶性,以增加其生物利用度、穩定度。本研究利用商業化脂解固定酵素Novozym ®435 (EC; Candida antarctica) 在2-甲基-2-丁醇溶劑中進行白藜蘆醇與醋酸乙烯酯的轉酯化反應。第一階段先以反應曲面法及五階層四變數之中心混層實驗設計,在搖瓶系統中,分析反應變數對合成白藜蘆醇乙醯化轉換率之影響。由統計分析及脊型分析之最適化莫耳轉化率為103%,其最佳反應條件為反應時間60 h、反應溫度64 ℃、基質莫耳比1:56、酵素用量為 2293 PLU (propyl laurate unit),以其條件進行反應其實驗結果之莫耳轉化率為95%。結果顯示Novozym® 435能有效的選擇在4′-OH位置乙醯化白藜蘆醇,而白藜蘆醇的抗氧化的主要功能是由3-OH來提供,因此4′-OH位置乙醯化後,除可增加脂溶性外,並可保留白藜蘆醇原本的抗氧化活性。第二階段,在超音波輔助系統合成乙醯化白藜蘆醇,超音波於液相溶液中產生空穴現象,造成許多微小氣泡,進而增加了酵素與基質的接觸機會,提高轉酯化效用及縮短合成時間。而根據統計分析及脊型分析合成乙醯化白藜蘆醇之最適化莫耳轉化率為96%,其最佳反應條件為反應時間10.78 h、酵素用量為 5492 PLU及超音波功率為147.80 W,以其條件進行反應其實驗結果之莫耳轉化率為95%。此外,本研究之動力學遵循Ping-Pong Bi-Bi的模式,探討在搖瓶及超音波系統下利用酵素催化合成乙醯化白藜蘆醇之動力學參數。在搖瓶系統中Vmax =10.58 mM 和Km=121.26 mM/h,而在超音波系統中Vmax=41.84 mM和Km=187.80 mM/h ,超音波系統下的轉酯化反應之Vmax值約增加3.95倍 。由Vmax值增加,可發現在超音波輔助反應下,確實增進了酵素與基質間的質傳效果而縮短了合成時間。zh_TW
dc.description.abstractThe use of immobilized lipase from Candida antarctica (Novozym® 435) to catalyze synthesis of 4'-O-acetyl resveratrol from resveratrol and vinyl acetate was investigated in this study. Response surface methodology and five-level-four-factor central composite rotatable design were adopted to evaluate the effects of synthesis variables, including reaction time (24-72 h), temperature (25-65 °C), substrate molar ratio (1:15-1:75; RV:VA), and enzyme amount (600-3000 PLU) on the percentage molar conversion of 4'-O-acetyl resveratrol. The results showed that reaction temperature and enzyme amount were the most important parameters on percent molar conversion. Based on ridge max analysis, the optimum conditions for synthesis were: reaction time 60 h, reaction temperature 64 oC, substrate molar ratio 1:56 and enzyme amount 2293 PLU. The molar conversions of predicted and actual experimental values were 103% and 95%, respectively. In the second part, ultrasonication provided a very effective mixing in the reaction solution due to cavitations in the liquid medium. The 3-level-3-variables Box-Behnken design was adopted to evaluate the effects of synthesis variables, and the optimum conditions were as follows: reaction time 10.78 h, enzyme amount 5492 PLU, and ultrasonic power 147.8 W. The molar conversions of predicted and actual experimental values were 96% and 95%, respectively. The reaction kinetic was agreed with Ping-Pong mechanism, and the kinetic constants of the shaker and ultrasonic system were studied. Vmax obtained were 10.58 mM for shaker system and 41.84 mM for ultrasonic system; According to our results, we found using ultrasound could accelerate synthesis 4'-O-acetyl resveratrol.en_US
dc.description.tableofcontents第一章、緒論 1 第二章、文獻回顧 4 2.1 白藜蘆醇(Resveratrol) 4 2.1.1 多酚類物質的種類 4 2.1.2白藜蘆醇 6 2.1.3白藜蘆醇基本之化學性質 9 2.1.4 白藜蘆醇之抗氧化作用 9 2.1.5白藜蘆醇之抗發炎能力 10 2.1.6白藜蘆醇之抗癌能力 10 2.2 酵素 11 2.2.1酵素簡介 11 2.2.2酵素催化反應之優點 12 2.2.3脂解酵素 12 2.2.4 Candida antarctica lipase-B (CALB) 15 2.3超音波於酵素轉酯化之研究 16 2.3.1超音波的基本性質 16 2.3.2超音波反應器應用的型態 16 2.3.3 超音波對於合成酯類之研究 19 第三章、材料與方法 20 3.1實驗藥品 20 3.2儀器設備 20 3.3在搖瓶反應系統下之實驗設計與合成方法 21 3.3.1實驗設計-反應曲面法 (RSM) 21 3.3.2合成4′-OH乙醯化白藜蘆醇 21 3.4在超音波反應系統下之實驗設計與合成方法 24 3.4.1實驗設計-反應曲面法 (RSM) 24 3.4.2超音波輔助合成4′-OH乙醯化白藜蘆醇 24 3.5分析分法 26 3.5.1 分析條件 26 3.5.2產物之莫耳轉化率 26 3.5.3 統計分析 27 第四章、結果與討論 28 4.1HPLC分析 28 4.2質譜分析 28 4.3核磁共振光譜儀 (Nuclear Magnetic Resonance Spectrometry, NMR) 28 4.4以反應曲面法探討在搖瓶系統中合成乙醯化白藜蘆醇之最優化反應條件 32 4.4.1反應時間對轉酯化轉化率的影響 32 4.4.2反應曲面法(Response Surface Methodology, RSM) 34 4.4.3 Novozym 435合成4′-OH乙醯化白藜蘆醇之變數分析 35 4.4.4 Novozym 435合成4′-OH乙醯化白藜蘆醇之最適化條件探討 41 4.5以反應曲面法探討超音波輔助合成乙醯化白藜蘆醇之最優化反應條件 44 4.5.1超音波輔助對轉酯化轉化率的影響 44 4.5.2超音波輔助合成4′-OH乙醯化白藜蘆醇之變數分析 46 4.5.3 超音波輔助合成4′-OH乙醯化白藜蘆醇之最適化條件探討 52 4.6酵素動力學 57 4.6.1 Ping-Pong Bi-Bi mechanism 57 4.6.2 Alberty速率方程式之通式 58 4.6.3 動力模式探討 59 4.3.4 動力學模型 64 第五章、結論與未來展望 66 5.1 結論 66 5.2 未來展望 67  zh_TW
dc.subjectresponse surface methodologyen_US
dc.titleLipase Catalyzed Synthesis of 4'-O-Acetyl Resveratrol - Optimization and Kinetics Studyen_US
dc.typeThesis and Dissertationzh_TW
item.openairetypeThesis and Dissertation-
item.fulltextno fulltext-
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