研究生: |
李嘉修 Chia-hsiu Lee |
---|---|
論文名稱: |
酵素催化合成肉桂酸衍生物 Enzymatic synthesis of Cinnamic Acid Derivatives |
指導教授: |
朱義旭
Yi-Hsu Ju |
口試委員: |
陳志平
none 陳秀美 none |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
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 radical, antioxidant |
相關次數: | 點閱:144 下載:0 |
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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.
Reference
Abella, A., J. Chalas, C. Claise, D. Laurent, L. Vergne, S. Labidalle and A. Lindenbaum (1997), Interest of ethyl esters of polyphenolic acids in prevention of atherosclerosis, Atherosclerosis, 199
Andreasen, M.F., L.P. Christensen, A.S. Meyer and A. Hansen (1999), Release of hydroxycinnamic and hydroxyl-benzoic acids in rye by commercial plant cell wall degrading enzyme preparations. J Sci Food Agr, 79, 411-413
Brzozowski, A.M., U. Derewenda, Z.S. Derewenda, G.G. Godson, D.M. Lawson, J.P. Turkenburg, F. Bjorkling, B. Huge–Jensen, S.A. Patkar and L. Thim (1991), A model for interfacial activation in lipases from the structure of a fungal lipase-inhibitor complex. Nature, 351, 491-494
Buisman, G.J.H., C.T.W. van Helteren, G.F.H. Kramer, J.W. Veldink, J.T.P. Derksen and F.P. Cuperus (1998), Enzymatic esterifications of functionalized phenols for the synthesis of lipophilic actioxidants, Biotechnol Lett, 131-136
Chimi, H, J. Cillard, P. Cillard and M. Rahmani (1991), Peroxyl and hydroxyl radical scavenging activity of some natural phenolic antioxidants, J Am Oil Chem Soc, 68, 307-312.
Chimi, H, A. Sadik, B. Letutour, and M. Rahmani, (1988) Antioxydant activity of tyrosol, hydroxytyrosol, caffeic acid, oleuropein and BHT in olive oil, Revue Francaise Des Corps Gras, 35, 339-344
Compton, D.L., J.A. Laszlo and M.A. Berhow (2000), Lipase-catalyzed synthesis of ferulate esters, J Am Oil Chem Soc, 513-519
Compton, D.L., J.A. Laszlo and T.A. Isbell (2004), Cinnamoyl esters of lesquerella and castor oil: novel sunscreen active ingredients, J Am Oil Chem Soc, 945-951
Denisov, E.T. and I.V. Khudyakov (1987), Mechanisms of action and reactivities of the free-radicals of inhibitors, Chem Rev, 87, 1313
Dziedzic, S.Z., B.J.F. Hudson (1984), Phenolic acids and related compounds as antioxidants for edible oils, Food Chem, 14, 45-51
Gandhi, N.N. (1997), Applications of lipase, J Am Oil Chem Soc, 74, 621-633.
Garcia, T., A. Coteron, M. Martinez and J. Aracil, Kinetic model for the esterification of oleic acid and cetyl alcohol using an immobilized lipase as catalyst, Chem Eng Sci 55 (2000) 1411-1423
Giuliani, S., C. Piana, L. Setti, A. Hochkoeppler, P.G. Pifferi, G. Williamson and C.B. Faulds (2001), Synthesis of pentylferulate by a feruloyl esterase from Aspergillus niger using water-in-oil microemulsions, Biotechnol Lett, 23, 325–330.
Graf, E. (1992), Antioxidant potential of ferulic acid, Free Radical Bio Med, 13, 435-448
Guyot, B., B. Bosquette, M. Pina and J. Graille (1997), Esterification of phenolic acids from green coffee with an immobilized lipase from Candida antarctica in solvent-free medium, Biotechnol Lett, 529-532
Hansch, C., A. Leo, and D. Hoekman (1995), Exploring QSAR. Hydrophobic, Electronic and Steric Constants. ACS Professional Reference Book, Washington, D.C.
Hatzakis, N.S., D. Daphnomili, I. Smonou (2003), Ferulic acid esterase from Humicola insolens catalyzes enantioselective transesterifcation of secondary alcohols, J Mol Catal B: Enzym, 21, 309-311
Howard, J.A. (1972), Electron-spin resonance-spectrum of tert-butylperoxy radical, Can J Chem, 50, 1981.
Hsiao, G., M.Y. Shen, W.C. Chang, Y.W. Cheng, S.L. Pan, Y.H. Kuo, T.F. Chen and J.R. Sheu (2003), A novel antioxidant, octyl caffeate, suppression of LPS/IFN-r-induced inducible nitric oxide synthase gene expression in rat aortic smooth muscle cells, Biochem Pharmacol, 1383-1392
Ishigami, T., K. Nakazato, M. Uehara and T. Endo (1979), Marked ependence of multiplicity in direst Z,E photoisomerization of a series of methyl cinnamates on their para-substitutents, Tetrahedron Lett, 20, 863–866.
Jayaprakasha, G.K. and L.J. Rao (2000), Phenolic constituents from lichen Parmotrema stuppeum (Nyl.) Hale and their antioxidant activity. , 55, 1018–1022.
Jimenez, M.M., J. Pelletier, M.F. Bobin and M.C. Martini (2004), Influence of encapsulation on the in vitro percutaneous absorption of octyl methoxycinnamate, Int J Pharm, 45-55
Klibanov A.M. (2001), Improving enzymes by using them in organic solvents, Nature, 409, 241-246
Kikuzaki, H., M. Hisamoto, K. Hirose, K. Akiyama and H. Taniguchi (2002), Antioxidant properties of ferulic acid and its related compounds, Agri Food Chem, 2161-2168
Koseki, T., Y. Ito, S. Furuse, K. Itoand K. Iwano, Conversion of ferulic acid into 4-vinylguaiacol, vanillin and vanillic acid in model solutions of Shochu, J Ferment Bioeng, 82 (1996) 42-50
Kovac, A., H. Scheib, J. Pleiss, R.D. Schmid and F. Paltauf, Molecular basis of lipase stereoselectivity, Eur J Lipid Sci Technol 102 (2000) 61-77
Langner, R. and H. Surburg (1997), Naturally Occurring Isoamyl p-Methoxycinnamate: An effective organic-chemical UV absorber can be detected in a plant, Cosmetics and Toiletries, 74, 112.
Lee, Y.J., H.C. Kuo, C.Y. Chu, C.J. Wang, W.C. Lin and T.H. Tseng (2003), Involvement of tumor suppressor protein p53 and p38 MAPK in caffeic acid phenethyl ester-induced apoptosis of C6 glioma cells, Biochem Pharmacol, 2281-2289
Liu, L., W.R. Hudgins, S. Shack, M.Q. Yin and D. Samid (1995), Cinnamic acid - a natural product with potential use in cancer intervention, Int J Cancer, 62, 345-350
Lue, B.M., S. Karboune, F.K. Yeboah and S. Kermasha (2005), Lipase catalyzed esterification of cinnamic acid and oleyl alcohol in organic solvent media, J Chem Technol Biot, 80, 462-468
Mahapatro, A., B. Kalra, A. Kumar and R.A. Gross (2003), Lipase catalyzed polycondensations: effect of substrates and solvent on chain formation, dispersity, and end-group structure, Biomacromolecules, 4, 544-551
Mahoney, L.R. (1969), 98Antioxidants, Angew Chem Int Edit, 8, 547
Margovich, M.J., A. Jimenez, K. Gray and G.J. Kellof (2000), Efficacy of potential chemopreventive agents on rat colon aberrant crypt formation and progression, Carcinogenesis, 1149
MartiMestres, G., C. Fernandez, N. Parsotam, F. Nielloud, J.P. Mestres and H. Maillols (1997), Stability of UV filters in different vehicles: Solvents and emulsions, Drug Dev Ind Pharm, 23, 647–655.
Marty, A., W. Chulalaksananukul, R.M. Willemot and J.S. Condoret (1992), Kinetics of lipase-catalyzed esterification in supercritical CO2. Biotechnol Bioeng 39, 273–280
Mori, H., K. Kawabata, N. Yoshimi, T. Tanaka, T. Murakami, T. Okada and H. Muray (1999), Chemopreventive effects of ferulic acid on oral and rice germ on large bowel carcinogenesis, Anticancer Res, 3775
Narayan, V. S. and A. M. Klibanov (1993), Are water immiscibility and apolarity of the solvent relevant to enzyme efficiency? Biotechnol Bioeng, 41, 390-393
Novozym 435 product sheet, Enzyme Business, Novo Nordisk company (1999).
Otterstedt, J.E. (1973), Photostability and molecular structure, J Phys Chem, 58, 5716- 5725
Pattanaargson, S., T. Munhapol, P. Hirunsupachot, P. Luangthongaram (2004), Photoisomerization of octyl methoxycinnamate, J Photoch Photobio A, 161, 269–274
Pokorny, J. (1988) in Autoxidation of Unsaturated Lipids (Chan, H., ed.), Academic Press, London, pp. 141-206
Porter, N.A. (1986), Mechanisms for the autoxidation of polyunsaturated lipids, Acc Chem Res, 19, 262-268
Priya, K. and A. Chadha (2003), Synthesis of hydrocinnamic esters by Pseudomonas cepacia lipase, Enzyme Microb Tech, 485-490
Pyysalo, T., H. Torkkeli and E. Honkanen (1997), The thermal decarboxyboxylation of some substituted cinnamic acids. Lebens-Wissensch Technol, 10, 438-441
Ramamurthi, S. and A.R. McCurdy (1994), Lipase-catalyzed esterification of oleic acid and methanol in hexane. A kinetic study. J Am Oil Chem Soc, 71, 927-930.
Reyes, H. R. and C.G.J. Hill (1994), Kinetic modeling of interesterification reactions catalyzed by immobilized lipase. Biotechnol Bioeng, 43, 171-182
Rybka, K., J. Sitarski and K. Raczynska-Bojanowska (1993), Ferulic acid in rye and wheat grain and grain dietary fiber. Cereal Chem, 70, 55–59.
Saija, A., A. Tomaino, D. Tromdetta, A. De Pasquale, N. Uccella, T. Barbuzzi, D. Paolino and F. Bonita (2000), In vitro and in vivo evaluation of caffeic and ferulic acids as topical photoprotective agents, Int J Pharm, 39
Scapagnini, G., D.A. Butterfield, C. Colombrita, R. Sultana, A. Pascale and V. Calabrese (2004), Ethyl ferulate, a lipophilic polyphenol, induces HO-1 and protects rat neurons against oxidative stress, Antioxid Redox Signal, 811-818
Scharfetter-Kochanek, K., J. Wenk, B. Brenneisen, R. Blaudschun and M. Wlaschek, Molecular role of reactive oxygen species in photoaging and tumor progression. In: P. Altmeyer et al. (Eds.). Skin Cancer and Radiation. Springer, Berlin-Heidelberg (1997) pp. 115–127
Schmid, R.D., and R. Verger (1998), Lipases: interfacial enzymes with attractive applications, Angew. Chem. Int. Ed., 37, 1608-1633.
Schudel, P., Grut, R. Schwarzenbach, Winterthur, Hans U. Gonzenbach, Geneva (1987), Process for treating 2-ethylhexyl p-methoxycinnamate in the presence of a phenol, U.S. Patent.
Schuler, P., and B.J.F. Hudson, Food antioxidants, Elsevier, London, 1990 113-127
Serkedjieva J., N. Manolova and V. Bankova (1992), Anti-influenza virus effect of some propolis constituents and their analogues (esters of substituted cinnamic acids), J Natl Prod, 55, 294-302.
Shahidi, F., Natural antioxidants (1996), 102
Stamatis, H., V. Sereti and F.N. Kolisis (2001), Enzymatic synthesis of hydrophilic and hydrophobic derivatives of natural phenolic acids in organic media, J Mol Catal B: Enzym, 323-328
Stamatis, H., V. Sereti, and F.N. Kolisis (1999), Studies on the enzymatic synthesis of lipophilic derivatives of natural antioxidants, J Am Oil Chem Soc, 1505-1510
Streilein, J.W., J.R. Taylor, V. Vincek, I. Kurimoto, T. Shimizu, C. Tie and C. Coulomb (1994), Immune surveillance and sunlight-induced skin cancer. Immunol Today, 15, 174–179
Soumanou, M.M. and U.T. Bornscheuer (2003), Improvement in lipase-catalyzed synthesis of fatty acid methyl esters from sunflower oil, Enzyme and Microbial Technology, 33, 97–103
Susuki, A., D. Kagawa, A. Futji, R. Ochiai, I. Tokimitsu and I. Saito (2002), Short- and long-term effects of ferulic acid on blood pressure in spontaneously hypertensive rats, Am J Hypertens, 351
Taniguchi, H., Wakayama-ken, E. Nomura, Wakayama, T. Tsuno and S. Minami, Ferulic acid ester antioxidant/UV absorbent, United States Patent, 1999
Tarras-Wahlberg, N., G. Stenhagen, O. Larko, A. Rosen, A.M. Wennberg and O. Wennerstrom (1999), Changes in ultraviolet absorption of sunscreens after ultraviolet irradiation, J Invest Dermatol, 113, 547– 553.
Timasheff, S. N. (1993), The control of protein stability and associations by weak interactions with water: how do solvents affect these processes? Annu Rev Bioph Biom Struct, 22, 67-97
Topakas, E., H. Stamatis, P. Biely, D. Kekos, B.J. Macris, P. Christakopoulos (2003), Purification and characterization of a feruloyl esterase from Fusarium oxysporum catalyzing esterification of phenolic acids in ternary water-organic solvent mixtures, J Biotechnol, 102, 33-44.
Volkin, D. B., A. Staubli, R. Langer and A.M. Klibanov (1991), Enzyme thermoinactivation in anhydrous organic solvent. Biotechnol Bioeng 37, 843-853
Watanabe, Y., Y. Shimada, A. Sugihara, and Y. Tominaga (1999), Stepwise ethanolysis tuna oil using immobilized Candida antarctica lipase, Journal of Bioscience and Bioengineering, 6, 622-626.
Yadav, G.D. and A.H. Trivedi, Kinetic modeling of immobilized-lipase catalyzed transesterification of n-octanol with vinyl acetate in non-aqueous media, Enzyme Microb Technol 32 (2003) 783–789
Zaidi, A., J.L. Gainer, G. Carta, A. Mrani, T. Kadiri, Y. Belarbi and A. Mir (2002), Esterification of fatty acids using nylon-immobilized lipase in n-hexane: kinetic parameters and chain-length effects, J Biotechnol 93, 209-216
Zaks, A. and A.M. Klibanov (1988), The effect of water on enzyme action in organic media. J Biol Chem 263, 8017-8021
Zupfer, J.M., K.E. Churchill, D.C. Rasmusson and R.G. Fulcher (1998), Variation in ferulic acid concentration among diverse barley cultivars measured by HPLC and microspectrophotometry. J Agr Food Chem, 46, 1350–1354.