壳聚糖微胶囊的制备与研究
|
摘要
壳聚糖无毒、无害，易于生物降解，不污染环境，在生物医学等领域有着非常广泛的应用。通过正交实验设计，我们首先对壳聚糖的降解进行了实验研究和显著性分析，确定壳聚糖降解的最佳条件为：H_2O_2浓度4％、温度50℃、反应时间4hr、HAc浓度2.5％。并对降解后壳聚糖的两项主要性能指标脱乙酰度和粘度进行了测试。
本课题研究了以正壬烷为囊芯，壳聚糖和明胶为壁材，采用复凝聚法制备明胶-壳聚糖微胶囊的原理和方法。并对影响微胶囊合成的主要因素如系统浓度、pH值、交联时间、复凝聚时间、乳化速度、芯壁比等进行了试验，确定了比较适宜的反应工艺条件。
微胶囊的粒径大小和分布是微胶囊性能的一个重要指标，它不仅影响缓释微胶囊的缓释性能，也影响包覆隔离微胶囊的隔离性能。本实验对所制备的微胶囊颗粒的形貌、粒径等参数进行了测定，发现所制备的微胶囊外观规整圆滑，平均颗粒粒径约数个微米，分布较集中，而且分散均匀。
另外，本课题针对微胶囊囊芯的缓释性能进行了一定的理论研究，讨论了温度、粒径大小、交联度等因素对微胶囊释放速率的影响。通过实验测定了微胶囊分散液对温度、pH值的稳定性。结果表明制备的微胶囊对温度、pH值稳定，可以满足其在后继加工、储存和实用中的要求，是适合生物、医药、食品和化妆品行业的理想材料。
Chitosan is a safe, environment compatible polymer. It does no harm to human being and is easy to be biodegraded. All these characteristics make the chitosan widely used in biochemical and medicinal field. Through orthodox experiment, we analyzed the degraded process of chitosan, found the optimal condition for chitosan degrading is: the concentration of H2O2 is 4%, at the temperature of 50, reaction time is 4hr and HAc concentration is 2.5%. After the chitosan was degraded, the two main parameters were analyzed: D.D and viscosity.
In this thesis, we studied the principle and method of preparing Chitosan-glutin microcapsule by complex coacervation, which was composed of n-nonane as core material, chitosan and glutin as shell material. Then we investigated the main factors affecting the form of microcapsule, such as system concentrations, pH value,association time, complex coacervation time, emulsification speed,
ratio of shell/core materials. Finally, we set suitable reaction
conditions for the reaction.
The size and its distribution of microcapsule particles are important parameters of microcapsules. It would affect not only the slow release property of microcapsule, but also the isolation property of microcapsule. After the microcapsules were prepared, the morphology and size of the microcapsule particle were investigated by electron microscope. The results show that the prepared microcapsules have regular and round appearance with average particle size about several micro -meters, and its size distribution is more narrow.
In addition, we studied the slow release property of core material in microcapsules, such as temperature, particle size and association degree, etc. The stability of microcapsule dispersing
system to temperature and pH value was investigated as well. The results showed that the microcapsule prepared is stable to temperature and pH value, and satisfied the requirements in later process, storage and application, which makes it suitable for biochemical, pharmaceutical, foodstuff and cosmetic industry.
本课题研究了以正壬烷为囊芯，壳聚糖和明胶为壁材，采用复凝聚法制备明胶-壳聚糖微胶囊的原理和方法。并对影响微胶囊合成的主要因素如系统浓度、pH值、交联时间、复凝聚时间、乳化速度、芯壁比等进行了试验，确定了比较适宜的反应工艺条件。
微胶囊的粒径大小和分布是微胶囊性能的一个重要指标，它不仅影响缓释微胶囊的缓释性能，也影响包覆隔离微胶囊的隔离性能。本实验对所制备的微胶囊颗粒的形貌、粒径等参数进行了测定，发现所制备的微胶囊外观规整圆滑，平均颗粒粒径约数个微米，分布较集中，而且分散均匀。
另外，本课题针对微胶囊囊芯的缓释性能进行了一定的理论研究，讨论了温度、粒径大小、交联度等因素对微胶囊释放速率的影响。通过实验测定了微胶囊分散液对温度、pH值的稳定性。结果表明制备的微胶囊对温度、pH值稳定，可以满足其在后继加工、储存和实用中的要求，是适合生物、医药、食品和化妆品行业的理想材料。
Chitosan is a safe, environment compatible polymer. It does no harm to human being and is easy to be biodegraded. All these characteristics make the chitosan widely used in biochemical and medicinal field. Through orthodox experiment, we analyzed the degraded process of chitosan, found the optimal condition for chitosan degrading is: the concentration of H2O2 is 4%, at the temperature of 50, reaction time is 4hr and HAc concentration is 2.5%. After the chitosan was degraded, the two main parameters were analyzed: D.D and viscosity.
In this thesis, we studied the principle and method of preparing Chitosan-glutin microcapsule by complex coacervation, which was composed of n-nonane as core material, chitosan and glutin as shell material. Then we investigated the main factors affecting the form of microcapsule, such as system concentrations, pH value,association time, complex coacervation time, emulsification speed,
ratio of shell/core materials. Finally, we set suitable reaction
conditions for the reaction.
The size and its distribution of microcapsule particles are important parameters of microcapsules. It would affect not only the slow release property of microcapsule, but also the isolation property of microcapsule. After the microcapsules were prepared, the morphology and size of the microcapsule particle were investigated by electron microscope. The results show that the prepared microcapsules have regular and round appearance with average particle size about several micro -meters, and its size distribution is more narrow.
In addition, we studied the slow release property of core material in microcapsules, such as temperature, particle size and association degree, etc. The stability of microcapsule dispersing
system to temperature and pH value was investigated as well. The results showed that the microcapsule prepared is stable to temperature and pH value, and satisfied the requirements in later process, storage and application, which makes it suitable for biochemical, pharmaceutical, foodstuff and cosmetic industry.
引文
1． 鲛岛政羲．粉体工学会志[J]，1989，26(12)：843—849
2. Arshady R. Polymer Engineering & science[J], 1990, 31(5): 905-914
3. Michaels A S. Ind. Engi. Chem. [J], 1965, 57(10): 32-40
4. Finch C A. Ullmann's Encyclopedia of Industrial Chemistry[M], 5th ed, vol A16. New York: VCH Publisher, 1990: 575-588
5. Hiestand EN, et al. (National Cash Register Company)[P], US. 3549555. 1970 A．G．沃德，A．考茨．明胶的科学与工艺学[M]，北京：轻工业出版社，1982：331—342
6． 徐穆卿．纺织学报[J]，1983(4)：235
7. Green B K, Schleicher L. (National Cash Register Company) [P] , US. 2800457:1957
8. Saeki K, et al. JP. Kokai. 74-35278, 1974
9. Becsey J G. (National Register Company)[P], US 3594327. 1971
10． 秦立虎．微胶囊技术及其在乳品加工业中的应用．食品科技．1997(6)：30-32
11. Saeki K, et al. (Imperial Chemical Industries Ltd.)[P], DE 2548879. 1975
12. Tetsuro H, et al. (Kanzaki. Paper Manufacturing Co. Ltd.)[P], US 4336170. 1982
13． 梁治齐．微胶囊技术及其应用[M]．北京：中国轻工业 出版社，1999
14. Hunkeler D. Polymers. for bioartificial organs[J]. Trends Polym Sci, 1997, 5(9); 286-293.
15． 方元超．微胶囊技术及其在茶饮料生产中的应用—冷饮与速冻食品工业．1997(2)：14—17
16. Nixon J R. Preparation of microcapsules with possible pharmaceutical use [J]. Endeavour, 1985, 9(3): 123-128.
17. Thies C. Microencapsulation[J]. Encyclopedia of Polym Sci & Engng, 1987, 9: 724-725.
18. Simon Benita. Microcapsulation: Method and Industrial Application. Marcel Dekker Inc, 1996. 1-21
19． 张可达．微胶囊化方法[J]．功能高分子学报，2001，14(4)，474-480．
20. Finch C A. Polymers for microcapsule wall[J], Chemy Ind, 1985, 22: 752-756
21. Latyxhev V N. Naumov A G, et al. Mechanisms releasing coolant lubricants from microcapsules during friction between metallic surface[J], Trenic Izons, 1999, 20(4): 433-438
22. Thies C. Microcapsulation[J], Encyclopedia of Polym Sci & Engi, 1987, 9: 724-725
23． 阎世翔．化妆品科学(下册)[M]，北京，科学技术出版社，1998：299—302
24. Hong K, Park. Preparation of polyurea microcapsules containing ovalbuntin[J], Mater Chem Phys, 2000, 64: 20-24
25． 段林东．赵良患．曾传广．微胶囊复合果蔬饮料研究食品工业科技．1994(6)：25—29，8
26. Larionova N V, Ponchel G, et al. Biodegradable cross-linked starch/protein microcapsules containing protenase inhibitor for oral protein administration [J], Int Pharm, 1999, 189: 171-178
27． 于西全．左晖等．复方双氯灭痛微胶囊的制备及缓释效果研究．海峡药学．1997(1)：17—18
28. Kimiko Kakinno, Mebae Umetsu, et al. Two-layer structures of microcapsule membrane as predicted from electrophoretic stuies[J], J Collid Interface Science, 1999, 218: 275-281
29． 檀亦兵．奚广生．迟景波．微胶囊化芝麻油的研制．中国油脂．1998(5)：35-366
30. Water A, Rehage H, et al. Shear-induced deformations of polyamide microcapsules[J]. Collid Polym Sci. 2000, 278: 169-175
31. Stere Lubetikin, Patrick Mulqeen, et al. Communication to the editor[J], Plastic Sci, 1999, 55: 1123-25
32． 崔凯．丁宵霖．苏子油的微胶囊化技术研究，中国粮油学报，1997(6)：36—397
33. Hans W H, Michad J H, et al. Process for the preparation of microcapsules[P], US patent, 5 8866 153, 1996
34. Becher D Z, Magin R W. High concentration encapsulation by interfacial polycondasation[p], Eur patent, 148 149
35． 余纲哲．吴克刚．鳗骨油微胶囊技术的研究，中国粮油学报，1996(4)：56—608
36． 陈雄，马丽，乔昕．大蒜油微胶囊的制备，中国调味品．2000(1)：137-139
37. Choi H J, Lee Y H, et al. Microcapsulated polyamide for electroecological materials[J], J Mater Sci lett, 2000, 19: 533-535
38. Kokufuta Etsuo. Polyelectrolyte-coated microcasules and their potential applications to biotechnology[J], Bioseparation, 1998, 7(4): 241-252
39． 雍国平．徐丽．金翔．薄荷素油的微胶囊的研制，烟草科技化学，1995(1)：16—17
40． 黄恩平，马林，黄小燕．微胶囊抗氧化剂对油脂稳定性作用约研究．食品工业科技．2000(1)：14—15
41． 马小军．解玉冰等．APA生物微胶囊的制备条件与膜强度的关，中华器官移植杂志．1995(4)：156—157
42. Daly M M, Keown R, et al. Preparation of capsules from chitsan and algnic acid ester for increase wall permeability[P], US patent 48
43． 林家莲．应向东．李玉林．微胶囊技术在烘烤食品中的应用．广州食品工业科技．1997(3)：42-45
44. Kiougasa, Hitoshi. Deterioration mechanism for tea infusion aroma by retort pasteurization[J], Agric Biol Chem. 1990, 54(10): 2537-2547
45. Borders Solubilizing tea cream, U. S. Patent, 3787590
46. Evans Pavid N. Process for anon-clouding concerntrated tea extract, U. S. Patent 4797293
47. Kinugasa, Hitashi. Prevention of retort odor formation in green tea drinke with cyclodextrin, Gekkan Fudo Kemikaru(Japan),
1994，10(10)
48. Coggon, Philip Cold water soluble tea, Brit. Patent 1 380 135
49. Clarification of tea extraces. JP Patent 77 033 958
50. Lofisson T, Fridriksdottir H, et al. Acta Pharm Nord, 1991(3): 215-217
51. Allan R. H., Wen J S., Christopher T. S.. ACS Symp. Ser, 1995, 590: 60-71
52. Amstrong D. W. Procedings of the Fourth International Symposiom on Cy clodextria Kluwer Academic. Dordrecht, Holland 1998, 437-440
53． 王伟，日用化学工业，1989，2：36
2. Arshady R. Polymer Engineering & science[J], 1990, 31(5): 905-914
3. Michaels A S. Ind. Engi. Chem. [J], 1965, 57(10): 32-40
4. Finch C A. Ullmann's Encyclopedia of Industrial Chemistry[M], 5th ed, vol A16. New York: VCH Publisher, 1990: 575-588
5. Hiestand EN, et al. (National Cash Register Company)[P], US. 3549555. 1970 A．G．沃德，A．考茨．明胶的科学与工艺学[M]，北京：轻工业出版社，1982：331—342
6． 徐穆卿．纺织学报[J]，1983(4)：235
7. Green B K, Schleicher L. (National Cash Register Company) [P] , US. 2800457:1957
8. Saeki K, et al. JP. Kokai. 74-35278, 1974
9. Becsey J G. (National Register Company)[P], US 3594327. 1971
10． 秦立虎．微胶囊技术及其在乳品加工业中的应用．食品科技．1997(6)：30-32
11. Saeki K, et al. (Imperial Chemical Industries Ltd.)[P], DE 2548879. 1975
12. Tetsuro H, et al. (Kanzaki. Paper Manufacturing Co. Ltd.)[P], US 4336170. 1982
13． 梁治齐．微胶囊技术及其应用[M]．北京：中国轻工业 出版社，1999
14. Hunkeler D. Polymers. for bioartificial organs[J]. Trends Polym Sci, 1997, 5(9); 286-293.
15． 方元超．微胶囊技术及其在茶饮料生产中的应用—冷饮与速冻食品工业．1997(2)：14—17
16. Nixon J R. Preparation of microcapsules with possible pharmaceutical use [J]. Endeavour, 1985, 9(3): 123-128.
17. Thies C. Microencapsulation[J]. Encyclopedia of Polym Sci & Engng, 1987, 9: 724-725.
18. Simon Benita. Microcapsulation: Method and Industrial Application. Marcel Dekker Inc, 1996. 1-21
19． 张可达．微胶囊化方法[J]．功能高分子学报，2001，14(4)，474-480．
20. Finch C A. Polymers for microcapsule wall[J], Chemy Ind, 1985, 22: 752-756
21. Latyxhev V N. Naumov A G, et al. Mechanisms releasing coolant lubricants from microcapsules during friction between metallic surface[J], Trenic Izons, 1999, 20(4): 433-438
22. Thies C. Microcapsulation[J], Encyclopedia of Polym Sci & Engi, 1987, 9: 724-725
23． 阎世翔．化妆品科学(下册)[M]，北京，科学技术出版社，1998：299—302
24. Hong K, Park. Preparation of polyurea microcapsules containing ovalbuntin[J], Mater Chem Phys, 2000, 64: 20-24
25． 段林东．赵良患．曾传广．微胶囊复合果蔬饮料研究食品工业科技．1994(6)：25—29，8
26. Larionova N V, Ponchel G, et al. Biodegradable cross-linked starch/protein microcapsules containing protenase inhibitor for oral protein administration [J], Int Pharm, 1999, 189: 171-178
27． 于西全．左晖等．复方双氯灭痛微胶囊的制备及缓释效果研究．海峡药学．1997(1)：17—18
28. Kimiko Kakinno, Mebae Umetsu, et al. Two-layer structures of microcapsule membrane as predicted from electrophoretic stuies[J], J Collid Interface Science, 1999, 218: 275-281
29． 檀亦兵．奚广生．迟景波．微胶囊化芝麻油的研制．中国油脂．1998(5)：35-366
30. Water A, Rehage H, et al. Shear-induced deformations of polyamide microcapsules[J]. Collid Polym Sci. 2000, 278: 169-175
31. Stere Lubetikin, Patrick Mulqeen, et al. Communication to the editor[J], Plastic Sci, 1999, 55: 1123-25
32． 崔凯．丁宵霖．苏子油的微胶囊化技术研究，中国粮油学报，1997(6)：36—397
33. Hans W H, Michad J H, et al. Process for the preparation of microcapsules[P], US patent, 5 8866 153, 1996
34. Becher D Z, Magin R W. High concentration encapsulation by interfacial polycondasation[p], Eur patent, 148 149
35． 余纲哲．吴克刚．鳗骨油微胶囊技术的研究，中国粮油学报，1996(4)：56—608
36． 陈雄，马丽，乔昕．大蒜油微胶囊的制备，中国调味品．2000(1)：137-139
37. Choi H J, Lee Y H, et al. Microcapsulated polyamide for electroecological materials[J], J Mater Sci lett, 2000, 19: 533-535
38. Kokufuta Etsuo. Polyelectrolyte-coated microcasules and their potential applications to biotechnology[J], Bioseparation, 1998, 7(4): 241-252
39． 雍国平．徐丽．金翔．薄荷素油的微胶囊的研制，烟草科技化学，1995(1)：16—17
40． 黄恩平，马林，黄小燕．微胶囊抗氧化剂对油脂稳定性作用约研究．食品工业科技．2000(1)：14—15
41． 马小军．解玉冰等．APA生物微胶囊的制备条件与膜强度的关，中华器官移植杂志．1995(4)：156—157
42. Daly M M, Keown R, et al. Preparation of capsules from chitsan and algnic acid ester for increase wall permeability[P], US patent 48
43． 林家莲．应向东．李玉林．微胶囊技术在烘烤食品中的应用．广州食品工业科技．1997(3)：42-45
44. Kiougasa, Hitoshi. Deterioration mechanism for tea infusion aroma by retort pasteurization[J], Agric Biol Chem. 1990, 54(10): 2537-2547
45. Borders Solubilizing tea cream, U. S. Patent, 3787590
46. Evans Pavid N. Process for anon-clouding concerntrated tea extract, U. S. Patent 4797293
47. Kinugasa, Hitashi. Prevention of retort odor formation in green tea drinke with cyclodextrin, Gekkan Fudo Kemikaru(Japan),
1994，10(10)
48. Coggon, Philip Cold water soluble tea, Brit. Patent 1 380 135
49. Clarification of tea extraces. JP Patent 77 033 958
50. Lofisson T, Fridriksdottir H, et al. Acta Pharm Nord, 1991(3): 215-217
51. Allan R. H., Wen J S., Christopher T. S.. ACS Symp. Ser, 1995, 590: 60-71
52. Amstrong D. W. Procedings of the Fourth International Symposiom on Cy clodextria Kluwer Academic. Dordrecht, Holland 1998, 437-440
53． 王伟，日用化学工业，1989，2：36