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研究生:李嘉修
研究生(外文):Chia-hsiu Lee
論文名稱:酵素催化合成肉桂酸衍生物
論文名稱(外文):Enzymatic synthesis of Cinnamic Acid Derivatives
指導教授:朱義旭
指導教授(外文):I-hsu Chu
學位類別:碩士
校院名稱:國立臺灣科技大學
系所名稱:化學工程系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2005
畢業學年度:93
語文別:英文
論文頁數:55
中文關鍵詞:自由基抗氧化
外文關鍵詞:free radicalantioxidant
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阿魏酸(ferulic acid, 4-hydroxy 3-methoxy cinnamic acid)研究證實具有抗氧化、抗UV、抗癌及降血壓等活性,普遍存在於許多植物中,分子本身para-hydroxyl的結構更增加其抗氧化性,阿魏酸為有效之自由基清除劑,可防止自由基對神經元細胞的攻擊而不損害細胞本身。OMC是目前研究最為廣泛的UVB防曬劑,也是最不易引起過敏之化學防曬劑。本研究選用阿魏酸及4-甲基肉桂酸(4-methoxycinnamic acid)為基質,以Novozym 435酵素催化酯化反應分別進行合成乙基阿魏酸酯(ethyl ferulate)及辛基肉桂酸酯(octyl methoxycinnamate)。目前文獻有關酵素催化合成上述產物的結果僅達低轉化率且反應時間長,本研究尋求最適化的操作條件而在合理反應時間下達到高轉化率。本研究並探討Novozym 435之重複使用性。
Ferulic acid (4-hydroxy 3-methoxy cinnamic acid), which occurred naturally in many plants, has been shown to possess photoprotective, antioxidant, antitumor and hypertensive activities. Octyl methoxycinnamate (OMC) is the most widely used non-allergic sunscreen agent in the market. Most literatures reported low conversion and long reaction time in the syntheses of ethyl ferulate and OMC. In his study, Novozym 435 was selected as the catalyst for the syntheses of ethyl ferulate from ferulic acid and ethanol, and OMC from 4-methoxycinnamic acid and 2-ethyl hexanol. Parameters that affect the conversion of these reactions as well as the reusability of Novozym 435 were systematically investigated.
Subjects catalog

Chapter 1 Introduction...…………………………………………….........1
1-1 Phenolic acid………………......…………………………........1
1-2 Antioxidants………………………..……………...…..…........2
1-3 Radical scavenging……………………….……………...........3
1-4 UV………………………………...……………...……………6
1-5 Enzyme………………...………………………………...........9
1-6 Ferulic acid and ethyl ferulate………………...……………...12
1-7 p-Methoxycinnamic acid and octyl methoxycinnamate..........13
1-8 About this research………………………...…………………13
1-9 Chemical structure…………...………………………………14

Chapter 2 Literature survey…………………….…………….…………16

Chapter 3 Chemicals, equipments and procedures……...........................18
3-1 Chemicals…………………………………………………….18
3-2 Equipments…………………………………………………...19
3-3 Procedures…………………………………………..………..19
3-4 HPLC analysis………………………………………………..20
3-5 NMR analysis…………………………………………...........22
3-6 Purification…………………………………………………...25
3-7 Determine the conversion…………………………………….25
3-8 Reused lipase activity assay…………………………….........25



Chapter 4 Results and discussions …………………..…………….........27
4-1 Effect of log P…………………….…….……………………28
4-2 Effect of temperature…………………………………………29
4-3 The effects of stirring on enzymatic esterification..…….........31
4-4 Reproducibility problems…………………………..………...31
4-5 Effect of substrate ratio………………………………..……..32
4-6 Effect of water………………………………………………..34
4-7 Effect of alcohol chain length………………………………..35
4-8 Reusabiliy of Novozym 435………………………………….40
4-9 Thermal decarboxylation of ferulic acid……..………………44

Chapter 5 Conclusion…………………………………………………...46

Reference…………...…………………………………...........................47









Figure catalog
Fig. 1.1 Resonance stabilization of ferulic acid radical………………..…4
Fig. 1.2 Penetration of UV radiation into the skin………………………..7
Fig. 1.3 Mechanism of UV protection by absorption…………………….8
Fig. 1.4 Structure of octyl-p-methoxy-trans-cinnamate (E-OMC) and octyl-p-methoxy-cis-cinnamate (Z-OMC)……………..……………9
Fig. 1.5 Reaction route having a smaller activation energy is provided by enzyme catalysis…………………………………………………...11
Fig. 1.6 Process of enzyme catalyzed reaction…………………………..12
Fig. 3.1 HPLC separation of ferulic acid and ethyl ferulate………….…21
Fig. 3.2 HPLC separation of p-methoxycinnamic acid and octyl methoxycinnamate…………………………………………………22
Fig. 3.3 1H NMR spectrum of EF……………………………………….23
Fig. 3.4 1H NMR spectrum of OMC……………………………………24
Fig. 4.1 The effect of solvent on lipase-catalyzed synthesis of OMC…..29
Fig. 4.2 The effect of temperature on lipase-catalyzed synthesis of ethyl ferulate……………………………………………………………..30
Fig. 4.3 The effect of temperature on lipase-catalyzed synthesis of OMC…………………………………………………………….…31
Fig. 4.4 The effect of molar ratio of substrate on lipase-catalyzed synthesis of ethyl ferulate…………………………………………………….33
Fig. 4.5 The effect of water content on the synthesis of EF…………….35
Fig. 4.6 Effect of water on the lipase-catalyzed synthesis of OMC…….35
Fig. 4.7 The effect of n-alcohol chain length on the esterification of p-methoxycinnamic acid…………………………………………...37
Fig. 4.8 The effect of linear and branched chain alcohols on the synthesis of p-methoxycinnamic acid ester derivatives……………………...38
Fig. 4.9 Effect of n-alcohol chain length on the esterification of ferulic acid………………………………………………………………...39
Fig. 4.10 The effect of linear and branched chain alcohols on the synthesis of ferulic acid ester derivatives…………………………………….40
Fig. 4.11 Relative activity of Novozym 435 versus temperature…….…41
Fig. 4.12 Reusability study of Novozym 435 in the synthesis of OMC…………………………………………………………….…42
Fig. 4.13 Mechanism for the conversion of ferulic acid………………...45












Table catalog
Table 2.1 Results of enzymatic cinnamic acid esters syntheses in the literature……………………………………………………………17
Table 3.1 Conversion (%) for OMC between calculation and peak ratio………………………………………………………………...25
Table 3.1 Conversion (%) for EF between calculation and peak ratio.…25
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