蔗汁美拉德反应及其抑制研究
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摘要
褐变色素的形成贯穿于提汁到结晶的制糖全过程。由于有色
杂质的出现，对制糖工业有显著影响。美拉德反应是制糖过程中
色素形成的重要原因。本文对美拉德反应及其抑制进行了研究，
取得了以下结果：
1．通过正交试验对美拉德反应的影响因素进行研究，实验结果
表明：pH值、温度是对美拉德反应有关键影响的条件因素，果糖、
赖氨酸是对美拉德反应有关键影响的成分因素。在弱碱性、低温。
情况下，美拉德反应不明显。
2.通过试验添加不同抑制剂研究了美拉德反应褐变抑制的规
律。研究表明，在一定条件下抑制剂（包括还原剂、氧化剂、吸
附剂）能有效抑制美拉德反应，降低色值。脱色效果顺序为：
Na_2S_2O_4、H_2O_2、NaCLO、NaHSO_3、Na_2SO_3、以及吸附剂活性炭。
通过对试验数据的计算，得出了抑制剂加入量和脱色率的关系曲
线。
3．通过紫外分光光度计研究了吸收光谱和吸光度的变化。对抑
制美拉德反应可能的机理进行了讨论。研究表明：还原剂并没有
破坏色素基团，氧化剂则破坏色素基团。
4．在清汁中选用正交试验优化工艺条件以降低色值，对影响色
值的主要因素如：pH值、温度、时间、添加量进行了考查。试验
数据通过方差分析，得出影响因素和色值关系曲线。
Brown pigments are formed during the processing of sugarcane from the initial juice extraction to crystallization. The presence of these colored impurities is of considerable significance to the sugar industry. Maillard reaction make a major contribution to color formation during the processing of sugar juice. In this paper, Maillard reaction and its inhibition were studied, and some results were got:
1. On the basis of orthogonal test, this paper discuss the composition factors and the conditional factors. From experiments results we know that PH value, temperature are the key conditional factors in Millard reaction, and fructose and lysine are the key composition factors in Millard reaction, and by analyzed experiments results, found that in low temperature, slight alkalinity, Millard reaction is restrained.
2. The law of inhibiting browning stain of Maillard reaction were studied by experiments of adding different browning inhibitors. It is found that browning inhibitors (including the reducing agent, oxidizing agent and active carbon) can effectively retard the Maillard reaction and decrease the color value under the certain parameter conditions . The sequences of decolorization were:
Na2S2O4 H202... NaCLO% NaHSO3, Na2SO3 and active carbon. Moreover, plots of the decoloraration rate versus inhibitor adding quantity were draw on the basis of the experimental data.
3. The changes of absorption spectra and absorbance were also presented by using UV spectrummeter. Possible mechanisms of inhibiting browning reaction were described. The results of study
-3-
suggest that reducing agents can not destroy colored impurities; and oxidizing agents can destroy colored impurities.
4. Orthogonal test was selected to optimum technology condition to decrease the color value in clarified juice. The main factors affecting the color value such as PH value, temperature, time, adding quantity were examined. Experimental data were analysed, variance analysis calculus and curves of factors and color value were drawn.
杂质的出现，对制糖工业有显著影响。美拉德反应是制糖过程中
色素形成的重要原因。本文对美拉德反应及其抑制进行了研究，
取得了以下结果：
1．通过正交试验对美拉德反应的影响因素进行研究，实验结果
表明：pH值、温度是对美拉德反应有关键影响的条件因素，果糖、
赖氨酸是对美拉德反应有关键影响的成分因素。在弱碱性、低温。
情况下，美拉德反应不明显。
2.通过试验添加不同抑制剂研究了美拉德反应褐变抑制的规
律。研究表明，在一定条件下抑制剂（包括还原剂、氧化剂、吸
附剂）能有效抑制美拉德反应，降低色值。脱色效果顺序为：
Na_2S_2O_4、H_2O_2、NaCLO、NaHSO_3、Na_2SO_3、以及吸附剂活性炭。
通过对试验数据的计算，得出了抑制剂加入量和脱色率的关系曲
线。
3．通过紫外分光光度计研究了吸收光谱和吸光度的变化。对抑
制美拉德反应可能的机理进行了讨论。研究表明：还原剂并没有
破坏色素基团，氧化剂则破坏色素基团。
4．在清汁中选用正交试验优化工艺条件以降低色值，对影响色
值的主要因素如：pH值、温度、时间、添加量进行了考查。试验
数据通过方差分析，得出影响因素和色值关系曲线。
Brown pigments are formed during the processing of sugarcane from the initial juice extraction to crystallization. The presence of these colored impurities is of considerable significance to the sugar industry. Maillard reaction make a major contribution to color formation during the processing of sugar juice. In this paper, Maillard reaction and its inhibition were studied, and some results were got:
1. On the basis of orthogonal test, this paper discuss the composition factors and the conditional factors. From experiments results we know that PH value, temperature are the key conditional factors in Millard reaction, and fructose and lysine are the key composition factors in Millard reaction, and by analyzed experiments results, found that in low temperature, slight alkalinity, Millard reaction is restrained.
2. The law of inhibiting browning stain of Maillard reaction were studied by experiments of adding different browning inhibitors. It is found that browning inhibitors (including the reducing agent, oxidizing agent and active carbon) can effectively retard the Maillard reaction and decrease the color value under the certain parameter conditions . The sequences of decolorization were:
Na2S2O4 H202... NaCLO% NaHSO3, Na2SO3 and active carbon. Moreover, plots of the decoloraration rate versus inhibitor adding quantity were draw on the basis of the experimental data.
3. The changes of absorption spectra and absorbance were also presented by using UV spectrummeter. Possible mechanisms of inhibiting browning reaction were described. The results of study
-3-
suggest that reducing agents can not destroy colored impurities; and oxidizing agents can destroy colored impurities.
4. Orthogonal test was selected to optimum technology condition to decrease the color value in clarified juice. The main factors affecting the color value such as PH value, temperature, time, adding quantity were examined. Experimental data were analysed, variance analysis calculus and curves of factors and color value were drawn.
引文
[1] L Spencer, P Meade Cane Sugar Handbook eight edition 798—803
[2] Carolyn, S B, Simon, P R, Contribution of enzymic browning to color in sugarcane juice J Agric Food Chem 1994, 42, 257—261。
[3] M Shore et al Factors affecting white sugar colour Sugar Tech Reviews,1984,12,1—99
[4] G Mantovani et al，“蔗糖结晶中的色素包裹体”，《国际甘蔗糖学会第十九届年会论文选集》(中译本)6—9
[5] 霍汉镇主编．《现代制糖工业技术》(第一分册)中国轻工业出版社1992，221—253。
[6] 陈维钧，“脱色剂对糖厂某些色素的作用及机理研究”，《广东制糖学会年会论文选集》。1992，15—19。
[7] 沈参秋 《糖品色香味化学》华南理工大学出版社 1996，45—77。
[8] 陈树功 《现代制糖工艺理论》轻工业出版社 1988，124—202
[9] 中美甘蔗糖业专家学术交流会议专辑(二)《甘蔗糖业》。1985，2，1—27
[10] James, C P Chan, Cane Sugar Handbook, John Wiley and sons, N Y eleventh edition 56—82
[11] 宁正祥、赵谋明：《食品生物化学》华南理工大学出版社 1995，293—297。
[12] Coombs, J, Baldry, c W Formation of color in cane juice by enzyme catalyzed reaction Partl Mechanism and chemical inhibition Int sugar J 1978,80, 291—294
[13] Hodge, J E Chemistry of browning reactions in model system J Agric Food Chem 1953, 1,928—943
[14] Lee, H S Nagy, S Relative reactivities of sugars in the formation of 5-hydroxymethyl furfural in sugar —catalyst model systems J Food Process 1990,14, 171—178
[15] Buera, M P Karel M Effect of physical changes on the rates of nonenzymatic browning and related reactions Food Chem 1995, 28, 359—365
[16] Wolfrom, M L Kashimura, N Horton, D Factors affecting the Maillard
browning reaction between sugars and amino acids studies on the nonenzymatic browning of dehydrated orange juice J Agric Food Chem 1974, 22, 796—800
[17] Karmas, R Buera, M P Karel, M Effect of glass transition on rates of nonenzymatic browning in food systems J Agric Food Chem 1992, 40,873—879
[18] 五十岚侑著，刘继生、奚印慈译 《食品化学》科学出版社1994，144—155。
[19] 黄梅丽、江小梅 《食品色香味化学》轻工业出版社1984，64—74。
[20] Buera, M P Chirife, J Nonenzymatic browning in liqid model systems of high water activity J Food Sci 1987, 52, 1063—1067
[21] Tsai, C H Kong, M S Water activity and temperature effects on nonenzymic browning of amino acids in dried squid and simulated model system J food Sci 1991, 56, 665—677
[22] Smith, N H Inhibition of enzymic browning in cane sugar processing Int Sugar J 1976, 78, 259—263。
[23] N H Paton等，糖厂生产过程中色素生成的机理。《甘蔗糖业》。1988，2，43—50
[24] Mendel Friedman, Food browning and its prevention an overview J Agric Food Chem 1996, 44, 631—648。
[25] 沈淑娟，方绮云 《波谱分析的基本原理及应用》高等教育出版社1988，1—33。
[26] 华南工学院等编．《制糖工业分析》轻工业出版社1984
[27] Sharma S C, Johary, P C Studies on the adsorption of sugar colorants India Sugar 1987, 4, 19—31
[28] Sapers, G M Browning of foods control by sulfites, antioxidants, and other means Food Tech 1993, 47, 75—84
[29] Meweeny, D J et al The Maillard reaction and its inhibition by sulfite J Food Sci 1969, 34, 641—643
[30] 霍汉镇 《制糖工艺与装备的新概念与新实践》(第一分册)(内部资料)601—631。
[31] 张小平，钱宇，张献忠，“保险粉在机木浆漂白中的应用”，华南理工大学化学工程研究所技术报告(内部资料)。6—36。
[32] 梁汉平，《原糖溶液氧化脱色的研究》华南工学院硕士学位论文1982。
[33] 梁汉平，“糖品色素氧化脱色的研究”，《广东制糖学会年会论文选集》。1982，15—21。
[34] C A Accoral, Ⅰ Galban, Decolonzation of beet sugar juices with hydrogen peroxide Int Sugar J 1993, 95,399—403。
[35] Martingez, P J Munoz, R An approach to the characterization of betanine oxidation catalyzed by horseradish peroxidase J Agri Food Chem 1997, 45,2984—2987
[36] 兰淑澄 《活性炭水处理技术》中国环境科学出版社1991，1—13。
[37] 赖凤英，林庆生，许喜林，许斯欣，陈焕章，“活性炭对糖浆脱色效果的研究”，《中国甜菜糖业》。1999，10 2—9。
[38] 沈参秋，赖凤英，“用吸附等温线评价活性炭和离子交换树脂对糖浆脱色性能的探讨”，《广东制糖学会年会论文选集》。1982，22—32。
[39] 郭尧君 《分光光度技术及其在生物化学中的应用》 科学出版社1987，1—53。
[40] 清水俊秀，洒井重男，“关于精制砂糖的研究糖和氨基酸的反应(第一部份)”，《制糖译丛》。1963，1 48—51。
[41] 汪荣鑫．《数理统计》西安交通大学出版社1986，148—166。
[42] 上海市科学技术交流站组编，《正交试验设计法》上海人民出版社1975，24—55。
[43] 闫胜文，孙由芳，扶雄，“降低玉米低聚糖(饴糖)色值的工艺条件优化”，《淀粉与淀粉糖》。1999，1 22—27。
[44] 郭成宇，陈士学，高文娜，刘毅，“正交试验在清净中的应用”，《中国甜菜糖业》。 1994，4．27—29。
[2] Carolyn, S B, Simon, P R, Contribution of enzymic browning to color in sugarcane juice J Agric Food Chem 1994, 42, 257—261。
[3] M Shore et al Factors affecting white sugar colour Sugar Tech Reviews,1984,12,1—99
[4] G Mantovani et al，“蔗糖结晶中的色素包裹体”，《国际甘蔗糖学会第十九届年会论文选集》(中译本)6—9
[5] 霍汉镇主编．《现代制糖工业技术》(第一分册)中国轻工业出版社1992，221—253。
[6] 陈维钧，“脱色剂对糖厂某些色素的作用及机理研究”，《广东制糖学会年会论文选集》。1992，15—19。
[7] 沈参秋 《糖品色香味化学》华南理工大学出版社 1996，45—77。
[8] 陈树功 《现代制糖工艺理论》轻工业出版社 1988，124—202
[9] 中美甘蔗糖业专家学术交流会议专辑(二)《甘蔗糖业》。1985，2，1—27
[10] James, C P Chan, Cane Sugar Handbook, John Wiley and sons, N Y eleventh edition 56—82
[11] 宁正祥、赵谋明：《食品生物化学》华南理工大学出版社 1995，293—297。
[12] Coombs, J, Baldry, c W Formation of color in cane juice by enzyme catalyzed reaction Partl Mechanism and chemical inhibition Int sugar J 1978,80, 291—294
[13] Hodge, J E Chemistry of browning reactions in model system J Agric Food Chem 1953, 1,928—943
[14] Lee, H S Nagy, S Relative reactivities of sugars in the formation of 5-hydroxymethyl furfural in sugar —catalyst model systems J Food Process 1990,14, 171—178
[15] Buera, M P Karel M Effect of physical changes on the rates of nonenzymatic browning and related reactions Food Chem 1995, 28, 359—365
[16] Wolfrom, M L Kashimura, N Horton, D Factors affecting the Maillard
browning reaction between sugars and amino acids studies on the nonenzymatic browning of dehydrated orange juice J Agric Food Chem 1974, 22, 796—800
[17] Karmas, R Buera, M P Karel, M Effect of glass transition on rates of nonenzymatic browning in food systems J Agric Food Chem 1992, 40,873—879
[18] 五十岚侑著，刘继生、奚印慈译 《食品化学》科学出版社1994，144—155。
[19] 黄梅丽、江小梅 《食品色香味化学》轻工业出版社1984，64—74。
[20] Buera, M P Chirife, J Nonenzymatic browning in liqid model systems of high water activity J Food Sci 1987, 52, 1063—1067
[21] Tsai, C H Kong, M S Water activity and temperature effects on nonenzymic browning of amino acids in dried squid and simulated model system J food Sci 1991, 56, 665—677
[22] Smith, N H Inhibition of enzymic browning in cane sugar processing Int Sugar J 1976, 78, 259—263。
[23] N H Paton等，糖厂生产过程中色素生成的机理。《甘蔗糖业》。1988，2，43—50
[24] Mendel Friedman, Food browning and its prevention an overview J Agric Food Chem 1996, 44, 631—648。
[25] 沈淑娟，方绮云 《波谱分析的基本原理及应用》高等教育出版社1988，1—33。
[26] 华南工学院等编．《制糖工业分析》轻工业出版社1984
[27] Sharma S C, Johary, P C Studies on the adsorption of sugar colorants India Sugar 1987, 4, 19—31
[28] Sapers, G M Browning of foods control by sulfites, antioxidants, and other means Food Tech 1993, 47, 75—84
[29] Meweeny, D J et al The Maillard reaction and its inhibition by sulfite J Food Sci 1969, 34, 641—643
[30] 霍汉镇 《制糖工艺与装备的新概念与新实践》(第一分册)(内部资料)601—631。
[31] 张小平，钱宇，张献忠，“保险粉在机木浆漂白中的应用”，华南理工大学化学工程研究所技术报告(内部资料)。6—36。
[32] 梁汉平，《原糖溶液氧化脱色的研究》华南工学院硕士学位论文1982。
[33] 梁汉平，“糖品色素氧化脱色的研究”，《广东制糖学会年会论文选集》。1982，15—21。
[34] C A Accoral, Ⅰ Galban, Decolonzation of beet sugar juices with hydrogen peroxide Int Sugar J 1993, 95,399—403。
[35] Martingez, P J Munoz, R An approach to the characterization of betanine oxidation catalyzed by horseradish peroxidase J Agri Food Chem 1997, 45,2984—2987
[36] 兰淑澄 《活性炭水处理技术》中国环境科学出版社1991，1—13。
[37] 赖凤英，林庆生，许喜林，许斯欣，陈焕章，“活性炭对糖浆脱色效果的研究”，《中国甜菜糖业》。1999，10 2—9。
[38] 沈参秋，赖凤英，“用吸附等温线评价活性炭和离子交换树脂对糖浆脱色性能的探讨”，《广东制糖学会年会论文选集》。1982，22—32。
[39] 郭尧君 《分光光度技术及其在生物化学中的应用》 科学出版社1987，1—53。
[40] 清水俊秀，洒井重男，“关于精制砂糖的研究糖和氨基酸的反应(第一部份)”，《制糖译丛》。1963，1 48—51。
[41] 汪荣鑫．《数理统计》西安交通大学出版社1986，148—166。
[42] 上海市科学技术交流站组编，《正交试验设计法》上海人民出版社1975，24—55。
[43] 闫胜文，孙由芳，扶雄，“降低玉米低聚糖(饴糖)色值的工艺条件优化”，《淀粉与淀粉糖》。1999，1 22—27。
[44] 郭成宇，陈士学，高文娜，刘毅，“正交试验在清净中的应用”，《中国甜菜糖业》。 1994，4．27—29。