臺灣博碩士論文加值系統

本研究以不同種類的雙醣maltose（α-1,4）、trehalose（α-1,1）、cellobiose（β-1,4）、chitobiose（β-1,4）與不同劑量的臭氧（10mg/min、32mg/min、52mg/min、72mg/min、87mg/min）探討醣苷鍵結對臭氧氧化降解雙醣的影響。
麥芽糖與纖維二糖的單醣產率並無差異，顯示臭氧於降解α-form與β-form之鍵結時，並無顯著性的差異。麥芽糖與纖維二糖的單醣產率均低於海藻糖，顯示α-1,1的鍵結較易受臭氧氧化而斷裂。幾丁二糖（具有胺基）的單醣（葡萄糖胺）產率高於纖維二糖（不具胺基）的單醣（葡萄糖）產率，顯示胺基的存在，有助於單糖的產生。雙醣降解反應速率隨著臭氧劑量的提高而升高，但是會受到雙醣起始反應濃度的影響。在反應溫度70OC下通入不同劑量的臭氧，海藻糖0.5%起始濃度者之葡萄糖產率高於0.06%起始濃度者，顯示雙醣起始反應濃度高者具有較高的單醣產率。而反應的次數介於0.7-1.1之間則與臭氧劑量並無明顯的相關性。利用FT-IR偵測經由臭氧降解所得的產物，發現羧基的存在，顯示臭氧氧化降解雙醣會使醣類產生開環反應而產生酸。

Four different disaccharides, maltose, trehalose, cellobiose, and chitobiose were used to study the effect of glycosidic bond, α-1, 4, α-1, 1, β-1, 4 on the ozonolysis of disaccharides.
The yields of monosaccharides from maltose and cellobiose were similar. That indicated theαorβ form of glycosidic bond did not contribute the difference in ozonolysis. The yield of monosaccharides from trehalose was higher than three from both maltose and cellobiose. The data indicated thatα-1, 1 of glycosidic bond was more favorable during ozonolysis.Chitobiose yield more monosacchadises than cellobiose. The presence of amino group enhanced the production of glucosamine. The degradation rate was increased with the ozone dosade and the initial concentration of disaccharides. At 70℃℃, the yield of glucose from trehalose at initial concentration of 0.5 % was higher than that at the initial concentration of 0.06 %. Nevertheless, the variation in ozone dosage did not alter the reaction orders in the range from 0.7 to 1.1. The analysis from FTIR revealed the presence of carboxylic acid. The formation and inhibitor of carboxylic acid are worthy of further studies.

前言………………………………………………………………….1
文獻回顧……………………………………………………………3
一、 雙醣的介紹…………………………………………………..3
（一） 麥芽糖…………………………………………………3
（二） 纖維二糖………………………………………………5
（三） 海藻糖…………………………………………………5
（四） 幾丁二糖 …………………………………………….7
二、N-乙醯幾丁寡醣與幾丁寡醣的製備…………………….….7
1. 酸水解………………………………………………….11
2. 酵素水解……………………………………………….11
3. 超音波降解…………………………………………….12
4. 氧化降解……………………………………………….12
5. 輻射照射……………………………………………….12
二、 臭氧…………………………………………………………..13
（一） 臭氧的基本性質……………………………………..13
（二） 臭氧自解的機構……………………………………..13
（三） 臭氧與有機物的反應……………………………….18
1. 直接臭氧化反應……………………………………….18
2. 自由基連鎖反應……………………………………….21
（四） 臭氧氧化多醣類之可能機制……………………….23
（五） 溫度對臭氧降解多醣類的影響…………………….30
材料與方法……………………….. ………………………………34
一、 實驗材料……………………………………………………..34
（一） 雙醣…………………………………………………..34
（二） 化學藥品……………………………………………..34
二、 實驗流程………………………. ……………………………34
（一） 臭氧之氧化降解反應……………………………….34
（二） 氧化降解反應裝置………………………………….35
三、 分析方法…………………………………………………….35
（一） 臭氧定量……………………………………………..35
（二） pH值測定…………………………………………… 38
（三） 雙醣與單醣的分析………………………………….39
（四） 單醣產率、雙醣消失率與臭氧降解效率…………55
（五） 臭氧降解雙醣的模式……………………………….55
（六） 臭氧降解雙醣的反應動力學分析…………………56
（七） 官能機鑑定…………………………………………..57
結果與討論………………………………………………………...58
一、 臭氧氧化降解雙醣…………………….. …………………. 58
（一） 纖維二糖之降解……………………………………. 58
（二） 麥芽糖之降解………………………………………. 58
（三） 海藻糖之降解………………………………………. 62
（四） 幾丁二糖之降解……………………………………. 66
二、 雙醣起始反應濃度對反應的影響…………………………74
三、 醣苷鍵結α-form與β-form的比較………………………77
四、 醣苷鍵結1→4與1→1的比較…………………………….77
五、 胺基對臭氧氧化降解的影響………………………………86
六、 降解反應速率的探討……………………………………….92
七、 FT-IR分析……………………………………………………92
結論……………………………………………………………… 106
參考文獻………………………………………………………….108

刁秀華，1993，高級氧化預處理對自來水中含氯有機物生成之影響。國立台灣大學環境工程學研究所碩士論文。台北。
白壽雄、陳蕙蓉，1997，天然生物保存物質-海藻糖的特性、製造及其應用，生物產業8（1）：33-42。
巫健次，1987，水中有機物對O3及ClO2消毒致病微生物的影響研究。國立台灣大學環境工程學研究所。台北。
林淑珍，2001.以臭氧降解幾丁聚醣製備幾丁寡醣之研究.國立台灣大學食品科技研究所碩士論文。台北。
洪佳敬，1998。以臭氧相關程序處理含酚類水溶液反應及臭氧質傳行為之研究。國立台灣科技大學化學工程技術研究所碩士論文。台北。
徐珠璽，1995，水溶性幾丁聚醣的製備與其物化特性，國立台灣海洋大學水產食品科學研究所碩士論文。基隆。
張介林，1995，以臭氧及紫外線/臭氧程序處理含有機磷農藥水溶液反應行為之研究。國立台灣工業技術學院工程技術研究所化學工程技術學程碩士論文。台北。
陳坤上、黃珮芬、陳聰松、陳幸臣，1996，幾丁寡醣製備條件之探討，食品科學，23(6) ，874-883。
陳佳慶，2002。高溫下降解幾丁聚醣製備幾丁寡醣的研究。國立台灣大學食品科技研究所碩士論文。台北。
戴明志，1999。以氧化還原降解法從不同來源幾丁聚醣製備幾丁寡醣之探討。國立海洋大學食品科學研究所碩士論文。
顧洋，1995，紫外線/臭氧氧化程序在廢水處理上之應用。工業污染防制，56：248-261。
Aiba, S.I. 1994. Preparation of N-acetylchitooligosaccharides by hydrolysis of chitosan with chitinase followed by N-acetylation. Carbohydr. Res. 265: 323- 328.
Aiba, S.I. 1992. Studies on chitosan: 4. lysozymic hydrolysis of partially N- acetylated chitosans. Int. J. Biol. Macromol. 14: 225-228.
Allan,G.G. and Peyron,M. 1995. Molecular weight manipulation of chitosan Ⅰ：kinetics of depolymerization by nitrous acid. Carbohydr. Res. 277: 257-272.
Allan,G.G. and Peyron,M. 1995. Molecular weight manipulation of chitosan Ⅱ：prediction and control of depolymerization by nitrous acid. Carbohydr. Res. 277: 273-282.
Beltran, F. J., Encinar, J. M. and Garcia-Araya, J. F., 1990 Ozonation of o-Cresol in aqueous solution. Water Res.,24,1309-1315.
Chang KLB. Lee J. and Fu WR. 2000. HPLC analysis of N-acetyl-chito-oligosaccharides during the acid hydrolysis of chitin. Journal of Food and Drug Analysis. 8(2):75-83.
Choi W.S.,Ahn K J, Lee D W ,Byun M W, Park H J. 2002. Preparation of chitosan oligimers by irradiation. Polymer Degradation and Stability. 78:533-538.
Cotton,F.A.,Wilkinson,G. 1996 Advanced Inorganic Chemistry, 2nd ed., Interscience Publishers, a division of John Wiley & sons, Inc., New York,365-367.
Domard, A., and Cartier, N. 1989. Glucosamine oligomers : 1. Preparation and characterization. Int. J. Biol. Macromol. 11:297-302.
Eisenhauer,H.R.,Dephenolization of Phenolic Wastes. J.WPCF.1968,40,1887-1894.
Grosjean, D., Groshean, E., and Williams, E. L., 1993 "The Reaction of Ozone and MPAN,CH2=C(CH3)C(O)OONO2" Environ. Sci. Techol.,27,2548-2556.
Gurol, M. D. and Nekouinaini, S., 1984 Kinetic Behavior of Ozone in Aqueous Solutions of Substituted Phenols,Ind. Eng. Chem. Fundam.,23,54-62.
Hasegawa,M.,Isogai,A., and Onabe,F.1993.Preparation of low-molecular-weight chitosan using phosphoric acid. Carbohydr. Polym. 20:279-283.
Hayashi,J.I.,Ikeda,J.,Kusakabe,k.,Morooka,S. 1993 Decomposition Rate of Volatile Organochlorines by Ozone and Utilization Efficiency of Ozone with Ultraviolet Radiation in a Bubble-Column Contactor.Water Res.,27,1091-1102.
Hoigne, J. and Bader, H., 1983a Rate Constants of Reactions of Ozone with Organic and Inorganic Compounds in Water I. Non-Dissociating Organic Compounds, Water Res., 17,173-181.
Hoigne, J. and Bader, H., 1983b Rate Constants of Reactions of Ozone with Organic and Inorganic Compounds in Water II. Dissociating Organic Compounds, Water Res., 17,185-192.
Hoigne, J., Bader, H., Hagg, W. R. and Staehelin, J., 1985. "Rate Constants of Reactions of Ozone with Organic and Inorganic Compounds in Water III. Inorganic Compounds and Radicals," Water Res., Vol., 19,993-1005.
Jeon, Y. J., and Kim, S.K. 2000. Continuous production of chitooligosaccharides using a dual reactor system. Process Biochem.35:623-632.
Joshi,M.G.,Shambaugh,R.L.1982. The Kinetic of Ozone-Phenol Reaction in Aqueoes Solutions.Water Res., 16,933-938.
Joy,P.,Gilbert,E.,Eberle,S.H., 1980. A Quantitative Investigation of the Reaction of Ozone with p-Toluenesulfonic Acid in Aqueous Solution as a Model Compound for Anionic Detergents.Water Res.,14,1509-1516.
Kabal'nova NN, Murinov KY, Mullagaliev IR, Krasnogorskaya NN,Shereshovets VV, Monakov YB, Zaikov GE. 2001.Oxidative destruction of chitosan under the effect of ozone and hydrogen peroxide. J. Appl. Polym. Sci. 81(4): 875-881.
Langlais, B., Reckhow, D.A., and Brink, D.R. 1991. Ozone in Water Treatment: Application and Engineering: Lewis,Ann Arbor,Michigan, 11-13.
Li, K.Y., Kuo, C.H., Weeks, J.L.Jr., 1979 A Kinetic Study of Ozone-phenol Reaction in Aqueous Solutions. AIChE J.,25,583-589.
Otake, T., Tone, S., Kono, K. and Nakao, K.,1979 Photo-Oxidation of Phenols with Ozone, J. Chem. Eng. Jpn.,12,289-297.
Pantaleone,D.,Yalpani,M.and Scollar,M.1992.Unusual susceptibility of chitosan to enzymic hydrolysis. Carbohydr. Res. 37:325-332.
Rakovsky SK,Zaikov G.1999.Ozonolysis of alkenes in liquid phase.Chap. 3 in:Kinetics and Mechanism of Ozone Reactions with Organic and Polymeric Compounds in Liquid Phase.(eds. S.K. Rakovsky and G. Zaikov) Nova Science Publishers, Inc.
Sehested K. Corfitzen H. Holcman J. Fischer CH. Hart EJ.1991. The Primary Reaction in the Decomposition of Ozone in Acidic Aqueous Solution. Environ. Sci. Technol. 25:1589-1596.
Solomons T.W., Fundamentals of Organic Chemistry Third Edition.
Sotelo JL. Beltran FJ. Beltran HJ. Encinar JM.1989.Azo dye ozonation film theory ultilization for kinetic studies. Ozone Sci. & Eng. 11:391-402.
Staehelin J. Buhler RE. Hoigné J. 1984. Ozone decomposition in water studied by Pulse Radiolysis. 2. OH‧ And HO2— as Chain Intermediates.J. Phys. Chem. 88:5999.
Staehelin, J. and Hoigné, J. 1985. Decomposition of ozone in water in the presence of organic solutes acting as promotors and inhibitors of radical chain reactions. Envir. Sci. Technol.,19:1206-1213.
Tomiyasu H. Fukutomi H. Gordon G.1985. Kinetics and mechanism of ozone decomposition in basic aqueous solution. Inorg. Chem. 24:2962-2974.
Wang, Y., Hollingsworth, R. I., and Kasper, D. L. 1998. Ozonolysis for selectively depolymerizing polysaccharides containing ß-D-aldosidic linkages. Proc. Natl. Acad. Sci. U.S. 95: 6584-6589.
Wang, Y., Hollingsworth, R.I., and Kasper, D.L. 1999. Ozonolytic depolymerization of polysaccharides in aqueous solution. Carbohydr. Res. 319:141-147.
McCarthy,J.J.,Smith,C.H.,1974. A ”Review of Ozone and Its Application to Domestic Waste water Treatment.” J.AWWA.,66,718-726.