植酸改性淀粉制备及应用基础研究
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摘要
淀粉的资源丰富，已广泛应用于各个工业领域，随着工业生产技术的发展，原淀粉的性质已难以适用于很多领域，因此有必要对淀粉进行改性，使之能符合应用的要求。本文以植酸钠为改性剂，对淀粉进行酯化改性，通过红外光谱仪，X-射线衍射仪，扫描电镜，粘度计对植酸改性淀粉进行了反应机理和性质的研究，并对改性淀粉的应用基础进行了初步探讨。结论如下：
1．以两种方法进行改性，以取代度为指标，正交试验结果表明，在湿法改性中，得到最大取代度的反应参数为：植酸钠用量2％，pH7，淀粉乳浓度30％，时间9hr，温度50±5℃。在浸渍法改性中，得到最大取代度的反应参数为：植酸钠用量2％，pH 7，时间2hr，温度140℃～160℃。其中植酸钠用量和pH值是主要的影响因素。
2．对两种植酸改性淀粉的性质进行研究，认为所得改性淀粉为植酸交联淀粉，浸渍法改性淀粉的交联度低于湿法改性淀粉。改性淀粉的糊稳定性提高，凝成性弱，由于植酸对人体的安全性高，植酸改性淀粉很适于作食品中的增稠剂和稳定剂。
3．用植酸钠改性时，反应主要发生在淀粉颗粒的无定形区；改性淀粉颗粒的显微形貌保持不变，反应发生在颗粒的表面；推测支淀粉最先起反应，淀粉的C_6的伯醇羟基易于与植酸钠反应。
4．植酸改性淀粉可食性膜的最佳成膜条件是：甘油10％，山梨醇5％，羧甲基纤维素钠3％：植酸钠PVA淀粉膜最佳成膜条件是：PVA为20％，甘油5％，聚乙二醇400为10％，40℃～50℃干燥。
5．湿法植酸改性淀粉制得的膜的耐水性和阻湿性优于浸渍法植酸改性淀粉和原淀粉。大豆及菜籽蛋白质及其水解产物的添加使膜的溶胀性降低，柔韧性增加，蛋白水解液的添加对膜的柔韧性的改善更为明显，但强度都有所下降。菜籽蛋白的添加也使水蒸气透过率降低。蛋白种类的不同会影响膜的性质。
Starch is one of the most abundant substances in nature, which has been widely used in many industry fields. With the development of industrial technology, native starch cannot meet the requirements of certain uses; so it is necessary to develop modified starch. By means of infrared absorption spectroscopy, X-ray diffraction, scanning electron microscope and viscometer, the properties and uses of phytic acid modified starch were discussed. The results show:
1. Result of orthogonal test indicated that reaction parameter of the highest degree of substitute (DS) to wet method PA modified starch was: sodium phytate 2%, starch emulsion concentration 30%, pH7, 50卤5 , 9hour; that reaction parameter of the highest DS to dipping method PA modified starch was: sodium phytate 2%, pH7, 140 ~160 , 2hour.
2. Studying on two kinds of modified starch. It was found that PA modified starch might be esterifying cross-linked starch, and that cross-linking degree of dipping method PA modified starch was lower than wet method PA modified starch. Stability of the paste of modified starch was improved. Because phytic acid was safe to human body, phytic acid modified starch could be used as food thicking agent and food stable agent.
3. Maize starch was modified with sodium phytate, whose morphology was same as those of native starch granules, and the reaction took place in the amorphous size of starch granules. It was supposed that sodium phytate first reacted with amylopectin and hydroxyl groups of primary alcohol of C6 in starch molecular.
4.The optimized preparing condition of edible modified starch membranes was: glycerol 10%, sorbitol 5%, CMC-Na 3%, drying at 40
~50 . And the optimized preparing condition of PVA modified starch membranes was: PVA 20%, glycerol 5%, polyethylene glycol 400 10%, drying at 40~50 .
5. Water tolerance and moisture resistance of wet method PA modified starch were higher than those of native and dipping method PA modified starch. Swellability of the membrane decreased with the adding of soybean protein, rapeseed protein and their hydrolysates; its flexibility increased too. The increasing of flexibility was more obvious when protein hydrolysates added, but tensile strength of membrane decreased in a degree. Adding of rapeseed protein made water vapor transmission reduced. Species of protein would affect properties of membranes.
1．以两种方法进行改性，以取代度为指标，正交试验结果表明，在湿法改性中，得到最大取代度的反应参数为：植酸钠用量2％，pH7，淀粉乳浓度30％，时间9hr，温度50±5℃。在浸渍法改性中，得到最大取代度的反应参数为：植酸钠用量2％，pH 7，时间2hr，温度140℃～160℃。其中植酸钠用量和pH值是主要的影响因素。
2．对两种植酸改性淀粉的性质进行研究，认为所得改性淀粉为植酸交联淀粉，浸渍法改性淀粉的交联度低于湿法改性淀粉。改性淀粉的糊稳定性提高，凝成性弱，由于植酸对人体的安全性高，植酸改性淀粉很适于作食品中的增稠剂和稳定剂。
3．用植酸钠改性时，反应主要发生在淀粉颗粒的无定形区；改性淀粉颗粒的显微形貌保持不变，反应发生在颗粒的表面；推测支淀粉最先起反应，淀粉的C_6的伯醇羟基易于与植酸钠反应。
4．植酸改性淀粉可食性膜的最佳成膜条件是：甘油10％，山梨醇5％，羧甲基纤维素钠3％：植酸钠PVA淀粉膜最佳成膜条件是：PVA为20％，甘油5％，聚乙二醇400为10％，40℃～50℃干燥。
5．湿法植酸改性淀粉制得的膜的耐水性和阻湿性优于浸渍法植酸改性淀粉和原淀粉。大豆及菜籽蛋白质及其水解产物的添加使膜的溶胀性降低，柔韧性增加，蛋白水解液的添加对膜的柔韧性的改善更为明显，但强度都有所下降。菜籽蛋白的添加也使水蒸气透过率降低。蛋白种类的不同会影响膜的性质。
Starch is one of the most abundant substances in nature, which has been widely used in many industry fields. With the development of industrial technology, native starch cannot meet the requirements of certain uses; so it is necessary to develop modified starch. By means of infrared absorption spectroscopy, X-ray diffraction, scanning electron microscope and viscometer, the properties and uses of phytic acid modified starch were discussed. The results show:
1. Result of orthogonal test indicated that reaction parameter of the highest degree of substitute (DS) to wet method PA modified starch was: sodium phytate 2%, starch emulsion concentration 30%, pH7, 50卤5 , 9hour; that reaction parameter of the highest DS to dipping method PA modified starch was: sodium phytate 2%, pH7, 140 ~160 , 2hour.
2. Studying on two kinds of modified starch. It was found that PA modified starch might be esterifying cross-linked starch, and that cross-linking degree of dipping method PA modified starch was lower than wet method PA modified starch. Stability of the paste of modified starch was improved. Because phytic acid was safe to human body, phytic acid modified starch could be used as food thicking agent and food stable agent.
3. Maize starch was modified with sodium phytate, whose morphology was same as those of native starch granules, and the reaction took place in the amorphous size of starch granules. It was supposed that sodium phytate first reacted with amylopectin and hydroxyl groups of primary alcohol of C6 in starch molecular.
4.The optimized preparing condition of edible modified starch membranes was: glycerol 10%, sorbitol 5%, CMC-Na 3%, drying at 40
~50 . And the optimized preparing condition of PVA modified starch membranes was: PVA 20%, glycerol 5%, polyethylene glycol 400 10%, drying at 40~50 .
5. Water tolerance and moisture resistance of wet method PA modified starch were higher than those of native and dipping method PA modified starch. Swellability of the membrane decreased with the adding of soybean protein, rapeseed protein and their hydrolysates; its flexibility increased too. The increasing of flexibility was more obvious when protein hydrolysates added, but tensile strength of membrane decreased in a degree. Adding of rapeseed protein made water vapor transmission reduced. Species of protein would affect properties of membranes.
引文
1．于九皋，高建平，林通．淀粉细化改性及其与聚乙烯增容性的研究。开发与应用，1997(3)：25-29
2．于炎湖，吴谋成．饲料毒物学附毒物分析。农业出版社，1992
3．大连轻工业学院，华南理工大学等合编．食品分析。中国轻工业出版社，1994
4．马涛，宗旭等．酸变性淀粉生产工艺及在部分食品中应用的研究。食品工业科技，1996(6)：35-40
5．王萍．大豆植物性化学活性成分。粮食与油脂，1999(3)：53—54
6．叶梁，王焘，宋艳茹．转基因植物生产可降解塑料的研究进展。科学通报，1999(6)：1244-1256
7．伍强贤．耐水性淀粉塑料的研制。[硕士学位论文]。武汉，华中农业大学，1998
8．关颍男，施大德编译．试验设计方法入门。冶金工业出版社，1985
9．刘峰，于九皋．淀粉在泡沫塑料制品中的应用。化学工业与工程，2000(2)：43-48
10．刘通讯，曾庆孝，何慧华．可食性褐藻酸的成膜性及其应用的研究。食品工业科技，1996(6)：6-8
11．刘惠君．羟丙基直链扩增，蜡性和正常玉米淀粉性能性质的研究。中国粮油学报，1998(1)：16-20
12．朱晓康，王文选．食品加工用变性淀粉。淀粉与淀粉糖，1998(3)：11-13
13．吴加根等．食用变性淀粉及其发展。淀粉与淀粉糖，1996(3)：9-12
14．吴田端，杨林．食用变性淀粉的性质及用途。陕西粮油科技，1995(4)：16-18
15．张力田．交联淀粉。淀粉与淀粉糖，1991(4)：1-8
16．张力田．变性淀粉。华南理王大学出版社，1999
17．张力田．淀粉的化学变性。淀粉与淀粉糖，1999(4)：1-2
18．张力田．淀粉磷酸酯。淀粉与淀粉糖，1988(1)：1-6
19．张友松主编．变性淀粉生产与应用手册。中国轻工业出版社，1999，636
20．李广兰．交联乙酰化淀粉用作食品增稠剂的研究。淀粉与淀粉糖，1999(4)：21—23
21．李志达，朱秋李，陈为旭等．可食性淀粉薄膜材料与性能的研究(Ⅰ)。中国粮油学报，1997(3)：28-31
22．李志达，朱秋李，陈为旭等．可食性淀粉薄膜材料与性能的研究(Ⅱ)。中国粮油学报，1997(4)：20-22
23．李波．魔芋葡苷聚糖及其改性产物水溶胶成膜性的研究。[硕士学位论文]。武汉，华中农业大学，1998
24．陈燕燕，顾正彪．淀粉与蛋白质塑料包装材料。食品科学，1996(9)：62-65
25．周世英．乙酰化二淀粉磷酸酯性质的研究。无锡轻工业学院学报，1990，9(4)：37
26．林江涛，刘国琴等．微孔性变性淀粉的研究。郑州粮食学院学报，1999(4)：45-50
27．郑丽萍，姚献平．阴离子型淀粉磷酸酯的研制及其在造纸上的应用。淀粉与淀粉糖，1991(4)：13-18
28．段梦林，段铁铃．日本生物降解性塑料的开发动向与进展。淀粉与淀粉糖，1996(3)：1-4
29．胡爱军，吴加根等．淀粉深加工三种方式概述。粮食与油脂，1997(1)：14—16
30．莫尊理，陈红，弓巧娟．交联酯化双重变性淀粉的合成与性能研究。西北师范大学学报，1998(1)：55-58
31．黄立新，周家华等．酯化交联淀粉反应及性质的研究。无锡轻工业学院学报，2001，20(1)：9-10
32．惠思特勒等．淀粉的化学与工艺学。中国食品出版社，1987，368
33．程梅霞．全降解淀粉—聚乙烯酯薄膜的研究。[硕士学位论文]。武汉，华中农业大学，1998
34．葛文光等．天然食品添加剂—植酸在食品工业中的应用。无锡轻工业学院学报，1990(2)：24-25
35．颜栋美．变性淀粉的特性及其在食品中的应用。广西轻工业，1997(2)：9-11
36．魏文珑，李和平等．新型复合变性淀粉的合成与结构表征。中国粮油学报，2000(2)：14-17．
37. Feliciano P. Beijosano, Harold Corke. Effect of Amaranthus and Buckwheat Proteins on the Rheological Properties of Maize Starch. Food Chemistry, 1999, 65, 493-501
38. Godshall, M. A. and Solms, J. Flavor and Sweetener Interactions with Starch. Food Technology, 1992, 46(6), 140-145
39. Hamnker B. R. Griffin, V. K. & Moldenhauer, K. A. K. Potential Influence of a Starch Granule—Associated Protein on Cooked Rice Stickness. Journal Of Food Science, 1991, 56, 1327-1329, 1346
40. Hattori M., Yang W. and Takahashi K. Functional Changes of Carboxymethyl Potato Starch by Conjugation with Whey Protein. Journal of Agricultural and Food Chemistry, 1995, 43(8), 2007-2011
41. J. J. Kestev and O. R. Fenema. Edible Films and Coatings: A Review. Food Technology, 1986, 40(12), 47-59
42. Ling, L. H. Effect of Heat Denaturation of Whey Proteins on the Rheological Properties of Corn Starch-milk Systems. Dissertation Abstracts International, 1984, B44 (12), 131
43. Mahmoud, M. I. Physicochemical and Function Properties of Protein Hydrolysates In Nutritional Products. Food Technology, 1994, 48(10), 89-95
44. Pradeep K. Goel, Rekha S. Singhal, Pushpa R. Kalkarni. Studies on Interactions of Corn Starch with Casein and Casein Hydrolysates. Food Chemistry, 1999, Vol.64, 383-389
45. S. L. Karper and O. Fennema, Water Vapor Permeability of Edible Bilayer Films, J. of Food Sci., 1984, Vol. 49, 1478-1485
46. Shamsuddin A. M. Inositol Phosphates Have Novel Anticancer Function. J. Nutr. 1995, 125: 725s-732s
2．于炎湖，吴谋成．饲料毒物学附毒物分析。农业出版社，1992
3．大连轻工业学院，华南理工大学等合编．食品分析。中国轻工业出版社，1994
4．马涛，宗旭等．酸变性淀粉生产工艺及在部分食品中应用的研究。食品工业科技，1996(6)：35-40
5．王萍．大豆植物性化学活性成分。粮食与油脂，1999(3)：53—54
6．叶梁，王焘，宋艳茹．转基因植物生产可降解塑料的研究进展。科学通报，1999(6)：1244-1256
7．伍强贤．耐水性淀粉塑料的研制。[硕士学位论文]。武汉，华中农业大学，1998
8．关颍男，施大德编译．试验设计方法入门。冶金工业出版社，1985
9．刘峰，于九皋．淀粉在泡沫塑料制品中的应用。化学工业与工程，2000(2)：43-48
10．刘通讯，曾庆孝，何慧华．可食性褐藻酸的成膜性及其应用的研究。食品工业科技，1996(6)：6-8
11．刘惠君．羟丙基直链扩增，蜡性和正常玉米淀粉性能性质的研究。中国粮油学报，1998(1)：16-20
12．朱晓康，王文选．食品加工用变性淀粉。淀粉与淀粉糖，1998(3)：11-13
13．吴加根等．食用变性淀粉及其发展。淀粉与淀粉糖，1996(3)：9-12
14．吴田端，杨林．食用变性淀粉的性质及用途。陕西粮油科技，1995(4)：16-18
15．张力田．交联淀粉。淀粉与淀粉糖，1991(4)：1-8
16．张力田．变性淀粉。华南理王大学出版社，1999
17．张力田．淀粉的化学变性。淀粉与淀粉糖，1999(4)：1-2
18．张力田．淀粉磷酸酯。淀粉与淀粉糖，1988(1)：1-6
19．张友松主编．变性淀粉生产与应用手册。中国轻工业出版社，1999，636
20．李广兰．交联乙酰化淀粉用作食品增稠剂的研究。淀粉与淀粉糖，1999(4)：21—23
21．李志达，朱秋李，陈为旭等．可食性淀粉薄膜材料与性能的研究(Ⅰ)。中国粮油学报，1997(3)：28-31
22．李志达，朱秋李，陈为旭等．可食性淀粉薄膜材料与性能的研究(Ⅱ)。中国粮油学报，1997(4)：20-22
23．李波．魔芋葡苷聚糖及其改性产物水溶胶成膜性的研究。[硕士学位论文]。武汉，华中农业大学，1998
24．陈燕燕，顾正彪．淀粉与蛋白质塑料包装材料。食品科学，1996(9)：62-65
25．周世英．乙酰化二淀粉磷酸酯性质的研究。无锡轻工业学院学报，1990，9(4)：37
26．林江涛，刘国琴等．微孔性变性淀粉的研究。郑州粮食学院学报，1999(4)：45-50
27．郑丽萍，姚献平．阴离子型淀粉磷酸酯的研制及其在造纸上的应用。淀粉与淀粉糖，1991(4)：13-18
28．段梦林，段铁铃．日本生物降解性塑料的开发动向与进展。淀粉与淀粉糖，1996(3)：1-4
29．胡爱军，吴加根等．淀粉深加工三种方式概述。粮食与油脂，1997(1)：14—16
30．莫尊理，陈红，弓巧娟．交联酯化双重变性淀粉的合成与性能研究。西北师范大学学报，1998(1)：55-58
31．黄立新，周家华等．酯化交联淀粉反应及性质的研究。无锡轻工业学院学报，2001，20(1)：9-10
32．惠思特勒等．淀粉的化学与工艺学。中国食品出版社，1987，368
33．程梅霞．全降解淀粉—聚乙烯酯薄膜的研究。[硕士学位论文]。武汉，华中农业大学，1998
34．葛文光等．天然食品添加剂—植酸在食品工业中的应用。无锡轻工业学院学报，1990(2)：24-25
35．颜栋美．变性淀粉的特性及其在食品中的应用。广西轻工业，1997(2)：9-11
36．魏文珑，李和平等．新型复合变性淀粉的合成与结构表征。中国粮油学报，2000(2)：14-17．
37. Feliciano P. Beijosano, Harold Corke. Effect of Amaranthus and Buckwheat Proteins on the Rheological Properties of Maize Starch. Food Chemistry, 1999, 65, 493-501
38. Godshall, M. A. and Solms, J. Flavor and Sweetener Interactions with Starch. Food Technology, 1992, 46(6), 140-145
39. Hamnker B. R. Griffin, V. K. & Moldenhauer, K. A. K. Potential Influence of a Starch Granule—Associated Protein on Cooked Rice Stickness. Journal Of Food Science, 1991, 56, 1327-1329, 1346
40. Hattori M., Yang W. and Takahashi K. Functional Changes of Carboxymethyl Potato Starch by Conjugation with Whey Protein. Journal of Agricultural and Food Chemistry, 1995, 43(8), 2007-2011
41. J. J. Kestev and O. R. Fenema. Edible Films and Coatings: A Review. Food Technology, 1986, 40(12), 47-59
42. Ling, L. H. Effect of Heat Denaturation of Whey Proteins on the Rheological Properties of Corn Starch-milk Systems. Dissertation Abstracts International, 1984, B44 (12), 131
43. Mahmoud, M. I. Physicochemical and Function Properties of Protein Hydrolysates In Nutritional Products. Food Technology, 1994, 48(10), 89-95
44. Pradeep K. Goel, Rekha S. Singhal, Pushpa R. Kalkarni. Studies on Interactions of Corn Starch with Casein and Casein Hydrolysates. Food Chemistry, 1999, Vol.64, 383-389
45. S. L. Karper and O. Fennema, Water Vapor Permeability of Edible Bilayer Films, J. of Food Sci., 1984, Vol. 49, 1478-1485
46. Shamsuddin A. M. Inositol Phosphates Have Novel Anticancer Function. J. Nutr. 1995, 125: 725s-732s