明胶/CMC复合凝聚微胶囊及新型固化剂研究
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摘要
复合凝聚微法具有有效载量高、可控制释放及缓释等优点。目前的复合凝聚微胶囊多以明胶和阿拉伯胶为壁材,阿拉伯胶价格昂贵且性质不稳定。微胶囊的交联固化通常采用有毒的甲醛,严重限制了产品的应用范围。寻找价格低廉的新型复合凝聚微胶囊壁材,以及开发安全无毒的可食用固化剂意义重大。本论文研究了明胶/羧甲基纤维素(CMC)复合凝聚法制备球形多核微胶囊的工艺,以及以安全无毒的茶多酚作为微胶囊固化剂进行固化条件优化,并对植物多酚的固化机理进行了研究。研究结果如下:
以明胶和CMC为壁材制备肉桂醛微胶囊时,最佳工艺参数如下:明胶/CMC比例9:1,pH 4.6,壁材浓度1%,芯壁比2:1。在此条件下制备得到的微胶囊球形较好,表面光滑,粒径均一,微胶囊的产率、效率可达97.01%和86.55%。热重释放曲线表明芯材肉桂醛经微胶囊化之后在150℃的释放速率大大降低,在高温下具有很好的稳定性;随着芯壁比的上升,微胶囊释放芯材的速度加快。
在以茶多酚为交联剂的固化过程中,反应pH、反应时间、茶多酚添加量都对固化效果有着显著的影响。固化条件优化的结果为:在pH 10.0、反应时间12 h、茶多酚添加量0.1 g/g明胶条件下,微胶囊的固化效果较好。机理研究实验的结果表明:多酚需要氧化为醌才可以与蛋白发生反应;反应没有特定的位点,几乎所有的N末端氨基酸都会参与交联反应。
对不同壁材(明胶/CMC与明胶/阿拉伯胶)制备的微胶囊的性质以及不同固化剂(茶多酚,甲醛和谷氨酰胺转氨酶(TG))的固化效果进行了比较研究,实验结果如下:明胶/CMC微胶囊与明胶/阿拉伯胶微胶囊相比,形态相似,包埋率提高,耐热性好于后者,而壁材成本大大降低。80℃热水中的稳定性实验与TG热释放实验结果显示茶多酚与甲醛和TG固化效果相近,能够很好地替代它们作为复合凝聚微胶囊的固化剂。
对喷雾干燥微胶囊产品的理化性质进行了研究。喷干后微胶囊水分含量为3.32%,易于保存;休止角为38.2°,流动性较好;有效载量为40.74%。扫描电子显微镜观察结果表明微胶囊干燥后结构完整,囊壁没有破坏。热重实验的结果表明喷雾干燥法制备的微胶囊产品具有良好的热稳定性。
Complex coacervation has many advantages such as the high payloads achievable, the controlled release and sustained release possibilities, etc. The most commonly used microcapsule wall materials are gelatin & gum arabic, however, gum arabic is expensive and its quality is irregular. Usually adopted toxic crosslinking agent formaldehyde limited extensive application of microcapsule products. It is of great importance to develop low-cost coacervation wall materials and non-toxic crosslinking agents. Preparation method of spherical multinuclear microcapsules by gelatin/carboxymethyl cellulose (CMC) coacervation was investigated. Cross-linking parameters in the process of tea polyphenols-hardened microcapsules were optimized. Mechanism of polyphenols crosslinking proteins was also studied. The results were as follows:
The optimal technical parameters for preparation of cinnamaldehyde microcapsules by coacervation of gelatin/CMC were as follows: gelatin/CMC ratio 9:1, pH4.6, wall material concentration 1%, core/wall ratio 2:1. Microcapsules made under these parameters have nice spherical shape and uniform particle size. The encapsulation yield and efficiency were 97.01% and 86.55%, respectively. The heat-stability of microcapsules was investigated, TGA curves showed that at 150°C, the release rate of cinnamaldehyde decreased dramatically after microencapsulation, which has direct ratio relations of the core/wall ratio.
The hardening effectiveness was significantly affected by the change of the hardening pH, time and tea polyphenols concentration. The optimum hardening parameters were as follows: hardening pH 10.0, hardening time 12 h, tea polypenols concentration 0.1 g/g gelatin. The mechanism research showed that polyphenols can only react with proteins after they were oxidized to polyquinones, there were no specific reaction sites and almost all N-terminal amino acid participated in the crosslinking reaction.
Properties of microcapsules made of different wall materials (gelatin/CMC and gelatin/gum arabic) and the hardening effect of different crosslinking agents (polypenols, formaldehyde and transglutaminase (TG)) were compared. Comparing with gelatin/gum arabic microcapsules, gelatin/CMC microcapsules have similar morphology, better embedding effect, thermal stability, and much lower cost. The result of 80℃water-bath and TGA showed that compared with formaldehyde and TG, tea polyphenols exhibited similar hardening effectiveness, and can replace them as crosslinking agent of coacervation microcapsules.
Physical and chemical properties of sprydried microcapsules were studied. The moisture was 3.32% and fit for storage; the repose angle was 38.2°, and the fluid was good; The loading of microcapsules was 40.74%. The microstructure valued by scanning electron microscope showed that microcapsules were integral and the surface was not destroyed through sprydrying. TGA curves showed that microcapsules made by sprydrying have fine thermal stability.
以明胶和CMC为壁材制备肉桂醛微胶囊时,最佳工艺参数如下:明胶/CMC比例9:1,pH 4.6,壁材浓度1%,芯壁比2:1。在此条件下制备得到的微胶囊球形较好,表面光滑,粒径均一,微胶囊的产率、效率可达97.01%和86.55%。热重释放曲线表明芯材肉桂醛经微胶囊化之后在150℃的释放速率大大降低,在高温下具有很好的稳定性;随着芯壁比的上升,微胶囊释放芯材的速度加快。
在以茶多酚为交联剂的固化过程中,反应pH、反应时间、茶多酚添加量都对固化效果有着显著的影响。固化条件优化的结果为:在pH 10.0、反应时间12 h、茶多酚添加量0.1 g/g明胶条件下,微胶囊的固化效果较好。机理研究实验的结果表明:多酚需要氧化为醌才可以与蛋白发生反应;反应没有特定的位点,几乎所有的N末端氨基酸都会参与交联反应。
对不同壁材(明胶/CMC与明胶/阿拉伯胶)制备的微胶囊的性质以及不同固化剂(茶多酚,甲醛和谷氨酰胺转氨酶(TG))的固化效果进行了比较研究,实验结果如下:明胶/CMC微胶囊与明胶/阿拉伯胶微胶囊相比,形态相似,包埋率提高,耐热性好于后者,而壁材成本大大降低。80℃热水中的稳定性实验与TG热释放实验结果显示茶多酚与甲醛和TG固化效果相近,能够很好地替代它们作为复合凝聚微胶囊的固化剂。
对喷雾干燥微胶囊产品的理化性质进行了研究。喷干后微胶囊水分含量为3.32%,易于保存;休止角为38.2°,流动性较好;有效载量为40.74%。扫描电子显微镜观察结果表明微胶囊干燥后结构完整,囊壁没有破坏。热重实验的结果表明喷雾干燥法制备的微胶囊产品具有良好的热稳定性。
Complex coacervation has many advantages such as the high payloads achievable, the controlled release and sustained release possibilities, etc. The most commonly used microcapsule wall materials are gelatin & gum arabic, however, gum arabic is expensive and its quality is irregular. Usually adopted toxic crosslinking agent formaldehyde limited extensive application of microcapsule products. It is of great importance to develop low-cost coacervation wall materials and non-toxic crosslinking agents. Preparation method of spherical multinuclear microcapsules by gelatin/carboxymethyl cellulose (CMC) coacervation was investigated. Cross-linking parameters in the process of tea polyphenols-hardened microcapsules were optimized. Mechanism of polyphenols crosslinking proteins was also studied. The results were as follows:
The optimal technical parameters for preparation of cinnamaldehyde microcapsules by coacervation of gelatin/CMC were as follows: gelatin/CMC ratio 9:1, pH4.6, wall material concentration 1%, core/wall ratio 2:1. Microcapsules made under these parameters have nice spherical shape and uniform particle size. The encapsulation yield and efficiency were 97.01% and 86.55%, respectively. The heat-stability of microcapsules was investigated, TGA curves showed that at 150°C, the release rate of cinnamaldehyde decreased dramatically after microencapsulation, which has direct ratio relations of the core/wall ratio.
The hardening effectiveness was significantly affected by the change of the hardening pH, time and tea polyphenols concentration. The optimum hardening parameters were as follows: hardening pH 10.0, hardening time 12 h, tea polypenols concentration 0.1 g/g gelatin. The mechanism research showed that polyphenols can only react with proteins after they were oxidized to polyquinones, there were no specific reaction sites and almost all N-terminal amino acid participated in the crosslinking reaction.
Properties of microcapsules made of different wall materials (gelatin/CMC and gelatin/gum arabic) and the hardening effect of different crosslinking agents (polypenols, formaldehyde and transglutaminase (TG)) were compared. Comparing with gelatin/gum arabic microcapsules, gelatin/CMC microcapsules have similar morphology, better embedding effect, thermal stability, and much lower cost. The result of 80℃water-bath and TGA showed that compared with formaldehyde and TG, tea polyphenols exhibited similar hardening effectiveness, and can replace them as crosslinking agent of coacervation microcapsules.
Physical and chemical properties of sprydried microcapsules were studied. The moisture was 3.32% and fit for storage; the repose angle was 38.2°, and the fluid was good; The loading of microcapsules was 40.74%. The microstructure valued by scanning electron microscope showed that microcapsules were integral and the surface was not destroyed through sprydrying. TGA curves showed that microcapsules made by sprydrying have fine thermal stability.
引文
1.张峻,齐崴,韩志慧.食品微胶囊,超微粉碎加工技术[M].北京:化学工业出版社, 2005. 1-5
2.宋健,陈磊,李效军.微胶囊化技术及应用[M].北京:化学工业出版社,2001.1-5
3. Shefer A, Shefer D. Multi component controlled release system for oral care, food products, nutraceutical, and beverages[P].US 6887493.2005-05-03
4. Daniel J W, Soper, Theodore T P. Method of flavoring and mechanically processing foods with polymer encapsulated flavor oils[P].US 5759599.1998-06-02
5. Merchant Z M, Behringer M U, Hill L G, et al. Low temperature cooking cereal based products [P].US 6599550.2003-07-29
6. Gouin S. Microencapsulation: industrial appraisal of existing technologies and trends[J].Trends in Food Science and Technology,2004,15(7-8):330-347
7.丁洁,李博生.微胶囊技术及其在食品工业中的应用[J].中国食物与营养, 2010,3(3): 29-31
8.彭姣凤,李庆廷.香精微胶囊化及控制释放[Z].第七届中国香料香精学术研讨会论文集,2008-05-17
9.井乐刚,赵新淮.复合维生素微胶囊制备中壁材用量及浓度对成品的影响[J].农业工程学报,2008,24(1):303-306
10.朱选,汪洋.微胶囊技术及其在食品工业中的应用[J].粮食与饲料工业, 1999(11): 47-49
11.田云,卢向阳,何小解,等.微胶囊制备技术及其应用研究[J].科学技术与工程, 2005, 5(1):44-47
12.周文华,杨辉荣,岳庆磊,等.香精香料微胶囊的研究新进展[J].香料香精化妆品, 2003 (4):29-33
13. M.梅勒马.包含亲脂性核的复合凝聚层胶囊[P].CN 1747784,2006-03-15
14.许时婴,张晓鸣,夏书芹,等.微胶囊技术-原理与应用[M].北京:化学工业出版社, 2006.1-169
15. Green B K, Schleicher L. Oil-containing microscopic capsules and method of making them [P].US 2800457,1957-07-23
16. Weinbreck F, Minor M, Kruif C G. Microencapsulation of oils using whey protein/ gum arabic coacervates [J]. Microencapsulation, 2004,21(6):667-669
17. Li W G, Wu G, Chen H Z, et al, Preparation and characterization of gelatin/SDS /NaCMC microcapsules with compact wall structure by complex coacervation [J].Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2009, 333(1-3): 133-137
18. Iwasaki H, Shioi S, Kouno J. Process for producing microcapsules [P].US 4010038, 1977-03-01
19. Miyake M, Shiozaki T, Shioi S, et al. Method of making oil-containing microcapsules [P].US 4219439,1980-08-26
20. Strauss G, Suzanne M G. Plant phenolics as cross-linkers of gelatin gels and gelatin- based coacervates for use as food ingredients [J].Food Hydrocolloids, 2004, 18(1): 81-89
21. David J, Lefrancois C, Ridoux C. Microcapsules based on gelatin and polysaccharides and process for obtaining same[P]. US 5051304.1991-09-24
22. Bakker, Galema, Visser. Microcapsules of gelatin and carboxy methyl cellulose [P].EP 0937496A2,1999-08-25
23.黄耀洲,徐勇,王小明.车前子胶—明胶复凝聚法包囊的研究[J].中成药研究, 1986(7): 1-4
24.李强,吴彩娥.明胶/壳聚糖复凝聚法制备八角茴香油微胶囊[J].中国粮油学报, 2007, 22(3):122-130
25.闫向阳,李光水,雍国平.凝聚法制备薄荷脑微胶囊技术研究[J].食品科学, 2005, 26(3):116-119
26.王广远,罗明科.复合凝聚法制备辛硫磷微胶囊剂的研究[J].农药,1998,37(11):14-16
27.曹正国,李成章.常用蛋白交联方法及其对胶原的影响[J].国外医学生物医学工程分册,2001,.24(4):187-191
28. Bigi A, Cojazzi G, Panzavolta S, et, al. Mechanical and thermal properties of gelatin films at different degrees of glutaraldehyde crosslinking[J].Biomaterials, 2001, 22(8): 763-768
29. Bayomi M A, Suwayeh S A, Helw A M, et, al. Preparation of casein–chitosan microspheres containing diltiazem hydrochloride by an aqueous coacervation technique[J]. Pharmaceutica Acta Helvetiae,1998,73(4):187-192
30. Maji T K, Baruah I, Dube S, et, al. Microencapsulation of zanthoxylum limonella oil (ZLO) in glutaraldehyde crosslinked gelatin for mosquito repellent application [J]. Bioresource Technology,2007,98(4):840-844
31. Sung H W, Huang R N, Huang L H, et, al. Feasibility study of a natural crosslinking reagent for biological tissue fixation[J].Journal of Biomedical Materials Research, 1998,42(4):560-567
32. Dong Z J, Xia S Q, Hua S, et, al. Optimization of crosslinking parameters during production of transglutaminase-hardened spherical multinuclear microcapsules by complex coacervation[J].Colloids and Surfaces B:Biointerfaces, 2008,63(1):41-47
33. Huang Y I, Cheng Y H, Yu C C, et, al. Microencapsulation of extract containing shikonin using gelatin–acacia coacervation method: A formaldehyde-free approach [J]. Colloids and Surfaces B:Biointerfaces,2007,58(2):290-297
34. Vandelli M A, Rivasi F, Guerra P, et, al. Gelatin microspheres crosslinked with D,L-glyceraldehyde as a potential drug delivery system: preparation, characterization, in vitro and in vivo studies [J].International Journal of Pharmaceutics, 2001, 215 (1-2): 175-184
35. Cortesi R, Esposito E, Osti M, et, al. Dextran cross-linked gelatin microspheres as a drug delivery system [J].European Journal of Pharmaceutics and Biopharmaceutics, 1999,47(2):153-160
36. Kyogoku N, Saeki T, Fujikawa S. Process for producing microcapsules [P]. US 5023024,1997-07-11
37.姚芳莲,李学强,于潇,等.京尼平对壳聚糖及明胶的交联反应[J].天津大学学报, 2007, 40(12):1485-1489
38. Filippa A M. On enzyme inhibition by oxidized chlorogenic acid [J].Life Sciences, 1964,3(1):49-54
39. Mason H S, Peterson E W. The reaction of quinones with protamine and nucleoprotamine: N-terminal proline [J]. The Journal of Biological Chemistry, 1955, 212:485-493
40. Haider K, Rfrederick L, Flaig W. Reactions between amino acid compounds and phenols during oxidation [J].Plant and Soil,1965,22(1):49-64
41. Pierpoint W S. o-Quinones formed in plant extracts their reaction with bovine serum albumin [J].Biochemical Journal,1969,112(5):609-616
42.石碧,狄莹.植物多酚[M].北京:科学出版社,2000.81-91
43.杨贤强,王岳飞,陈留记,等.茶多酚化学[M].上海:上海科学技术出版社,2003.48-50
44.孙宝山,郭成勋.几种抑制剂对酶促褐变抑制机制的探讨[J].食品与发酵工业, 1988(4):56-59
45. Gibson S M, Strauss G, Wasserman. Heat stable fat substitute composition and process [P].US 5374441,1994-12-20
46. Gibson S M, Strauss G. Process for production heat-stable protein microcapsules [P]. US 5993888,1999-11-30
47. Subramaniam A, Reilly A. Process for the preparation of flavor or fragrancemicrocapsules [P].US 2004/0032036 A1,2004-02-19
48.黄凤洪,夏伏建,王江薇,等.亚麻油粉末油脂制备的研究[J].中国油料作物学报, 2002, 24(4):65-68
49.王俊强,顾震,马天贵,等.微胶囊壁材的选择及其在食品工业中的应用[J].江西科学, 2008,26(2):242-247
50.阮海燕.肉桂醛在香精香料、日用化学品及食品添加剂行业中的应用[J].精细与专用化学品,2005,12(3/4):9-10
51.谭龙飞,武伟,杨连生.喷雾干燥法制备肉桂醛微胶囊工艺条件的研究[J].华南师范大学学报(自然科学版),2001(4):84-87
52.谢小梅,方建茹,许杨.肉桂醛柠檬醛抗黄曲霉作用的研究[J].食品科学, 2004, 25(9): 32-34
53.王燕.无吡啶盐酸羟胺肟化法测定肉桂醛含量的探讨[J].徐州师范大学学报(自然科学版),1997,15(3):34-36
54.谢艳丽,蒋敏,陈鸿雁.复凝聚法制备明胶/阿拉伯胶含油微胶囊工艺过程的研究[J].化学世界,2010(1):33-37
55. Ducel V, Richard J, Saulnier P, et, al .Evidence and characterization of complex coacervates containing plant proteins: application to the microencapsulation of oil droplets [J].Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2004,223(2-3):239-247
56. Schmitt C, Sancheza C, Thomas F, et, al. Complex coacervation betweenβ- lactoglobulin and acacia gum in aqueous medium[J].Food Hydrocolloids, 1999, 13(6): 483-496
57. Kruif K D, Weinbreck F, Vireos R D. Complex coacervation of proteins and anionic polysaccharides [D]. Netherlands: Utrecht University,2004
58. Weinbreck F, Roland H W, Nieuwenhuijse H, et, al. Rheological properties of whey protein/gum arabic coacervates[J].Journal of Rheology,2004,48(6):1215-1228
59. Ijichi K, Yoshizawa H, Uemura Y. Multi-layered gelatin/acacia microcapsules by complex coacervation method [J]. Journal of chemical engineering of Japan,1997, 30(5):793-798
60. Dong Z J, TouréA, Jia C S, et, al. Effect of processing parameters on the formation of spherical multinuclear microcapsules encapsulating peppermint oil by coacervation[J]. Journal of Microencapsulation ,2007,24(7):634-646
61. Burgess D J, Carless J E. Microelectrophoretic studies of gelatin and acacia for the prediction of complex coacervation [J].Journal of Colloid and Interface Science, 1984,98(1):1-8
62.朱丽云,李素芳,邵慧娟.复凝聚喷雾干燥法制备香精香料微胶囊的研究[J].食品科技,2006(4):25-33
63. Huang Y Y, Chung T W, Tzeng T W. Drug release from PLA/PEG microparticulates [J].International journal of pharmaceutics,1977,156:9-15
64. Lee S J, Rosenberg M .Microencapsulation of theophylline in whey proteins: effects of core to wall ratio [J].International Journal of Pharmaceutics,2000,205(1-2): 147– 158
65.梁治齐.微胶囊技术及其应用[M].北京:中国轻工业出版社,1999.47-53
66.黄晓丹,张晓鸣,董志俭,等.复凝聚法制备肉桂醛微胶囊的研究[J].食品工业科技, 2008,29(3):63-69
67.王静,戚向阳,朱学良,等.表棓儿茶素棓酸酯体外氧化及其低聚产物形成的研究[J].林产化学与工业,2007,27(5):62-66
68. Chang C P, Leung T K, Lin S M, et al. Release properties on gelatin-gum arabic microcapsules containing camphor oil with added polystyrene [J].Collids and Surfaces B:Biointerfaces,2006,50:136-140
69. Bachtsi A R, Kiparissides C. Synthesisand release studies of oil-containing poly (vinyl alcohol) microcapsules prepared by coacervation [J]. Journal of controlled release, 1996, 38: 49-58
70.伍红.蘑菇多酚氧化酶的性质及其催化反应动力学的研究[J].广州化学,1994(34)24-29
71.赵东海,王云,张建平.果蔬酶促褐变的条件及控制方法研究[J].长江蔬菜, 2005(7): 32-34
2.宋健,陈磊,李效军.微胶囊化技术及应用[M].北京:化学工业出版社,2001.1-5
3. Shefer A, Shefer D. Multi component controlled release system for oral care, food products, nutraceutical, and beverages[P].US 6887493.2005-05-03
4. Daniel J W, Soper, Theodore T P. Method of flavoring and mechanically processing foods with polymer encapsulated flavor oils[P].US 5759599.1998-06-02
5. Merchant Z M, Behringer M U, Hill L G, et al. Low temperature cooking cereal based products [P].US 6599550.2003-07-29
6. Gouin S. Microencapsulation: industrial appraisal of existing technologies and trends[J].Trends in Food Science and Technology,2004,15(7-8):330-347
7.丁洁,李博生.微胶囊技术及其在食品工业中的应用[J].中国食物与营养, 2010,3(3): 29-31
8.彭姣凤,李庆廷.香精微胶囊化及控制释放[Z].第七届中国香料香精学术研讨会论文集,2008-05-17
9.井乐刚,赵新淮.复合维生素微胶囊制备中壁材用量及浓度对成品的影响[J].农业工程学报,2008,24(1):303-306
10.朱选,汪洋.微胶囊技术及其在食品工业中的应用[J].粮食与饲料工业, 1999(11): 47-49
11.田云,卢向阳,何小解,等.微胶囊制备技术及其应用研究[J].科学技术与工程, 2005, 5(1):44-47
12.周文华,杨辉荣,岳庆磊,等.香精香料微胶囊的研究新进展[J].香料香精化妆品, 2003 (4):29-33
13. M.梅勒马.包含亲脂性核的复合凝聚层胶囊[P].CN 1747784,2006-03-15
14.许时婴,张晓鸣,夏书芹,等.微胶囊技术-原理与应用[M].北京:化学工业出版社, 2006.1-169
15. Green B K, Schleicher L. Oil-containing microscopic capsules and method of making them [P].US 2800457,1957-07-23
16. Weinbreck F, Minor M, Kruif C G. Microencapsulation of oils using whey protein/ gum arabic coacervates [J]. Microencapsulation, 2004,21(6):667-669
17. Li W G, Wu G, Chen H Z, et al, Preparation and characterization of gelatin/SDS /NaCMC microcapsules with compact wall structure by complex coacervation [J].Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2009, 333(1-3): 133-137
18. Iwasaki H, Shioi S, Kouno J. Process for producing microcapsules [P].US 4010038, 1977-03-01
19. Miyake M, Shiozaki T, Shioi S, et al. Method of making oil-containing microcapsules [P].US 4219439,1980-08-26
20. Strauss G, Suzanne M G. Plant phenolics as cross-linkers of gelatin gels and gelatin- based coacervates for use as food ingredients [J].Food Hydrocolloids, 2004, 18(1): 81-89
21. David J, Lefrancois C, Ridoux C. Microcapsules based on gelatin and polysaccharides and process for obtaining same[P]. US 5051304.1991-09-24
22. Bakker, Galema, Visser. Microcapsules of gelatin and carboxy methyl cellulose [P].EP 0937496A2,1999-08-25
23.黄耀洲,徐勇,王小明.车前子胶—明胶复凝聚法包囊的研究[J].中成药研究, 1986(7): 1-4
24.李强,吴彩娥.明胶/壳聚糖复凝聚法制备八角茴香油微胶囊[J].中国粮油学报, 2007, 22(3):122-130
25.闫向阳,李光水,雍国平.凝聚法制备薄荷脑微胶囊技术研究[J].食品科学, 2005, 26(3):116-119
26.王广远,罗明科.复合凝聚法制备辛硫磷微胶囊剂的研究[J].农药,1998,37(11):14-16
27.曹正国,李成章.常用蛋白交联方法及其对胶原的影响[J].国外医学生物医学工程分册,2001,.24(4):187-191
28. Bigi A, Cojazzi G, Panzavolta S, et, al. Mechanical and thermal properties of gelatin films at different degrees of glutaraldehyde crosslinking[J].Biomaterials, 2001, 22(8): 763-768
29. Bayomi M A, Suwayeh S A, Helw A M, et, al. Preparation of casein–chitosan microspheres containing diltiazem hydrochloride by an aqueous coacervation technique[J]. Pharmaceutica Acta Helvetiae,1998,73(4):187-192
30. Maji T K, Baruah I, Dube S, et, al. Microencapsulation of zanthoxylum limonella oil (ZLO) in glutaraldehyde crosslinked gelatin for mosquito repellent application [J]. Bioresource Technology,2007,98(4):840-844
31. Sung H W, Huang R N, Huang L H, et, al. Feasibility study of a natural crosslinking reagent for biological tissue fixation[J].Journal of Biomedical Materials Research, 1998,42(4):560-567
32. Dong Z J, Xia S Q, Hua S, et, al. Optimization of crosslinking parameters during production of transglutaminase-hardened spherical multinuclear microcapsules by complex coacervation[J].Colloids and Surfaces B:Biointerfaces, 2008,63(1):41-47
33. Huang Y I, Cheng Y H, Yu C C, et, al. Microencapsulation of extract containing shikonin using gelatin–acacia coacervation method: A formaldehyde-free approach [J]. Colloids and Surfaces B:Biointerfaces,2007,58(2):290-297
34. Vandelli M A, Rivasi F, Guerra P, et, al. Gelatin microspheres crosslinked with D,L-glyceraldehyde as a potential drug delivery system: preparation, characterization, in vitro and in vivo studies [J].International Journal of Pharmaceutics, 2001, 215 (1-2): 175-184
35. Cortesi R, Esposito E, Osti M, et, al. Dextran cross-linked gelatin microspheres as a drug delivery system [J].European Journal of Pharmaceutics and Biopharmaceutics, 1999,47(2):153-160
36. Kyogoku N, Saeki T, Fujikawa S. Process for producing microcapsules [P]. US 5023024,1997-07-11
37.姚芳莲,李学强,于潇,等.京尼平对壳聚糖及明胶的交联反应[J].天津大学学报, 2007, 40(12):1485-1489
38. Filippa A M. On enzyme inhibition by oxidized chlorogenic acid [J].Life Sciences, 1964,3(1):49-54
39. Mason H S, Peterson E W. The reaction of quinones with protamine and nucleoprotamine: N-terminal proline [J]. The Journal of Biological Chemistry, 1955, 212:485-493
40. Haider K, Rfrederick L, Flaig W. Reactions between amino acid compounds and phenols during oxidation [J].Plant and Soil,1965,22(1):49-64
41. Pierpoint W S. o-Quinones formed in plant extracts their reaction with bovine serum albumin [J].Biochemical Journal,1969,112(5):609-616
42.石碧,狄莹.植物多酚[M].北京:科学出版社,2000.81-91
43.杨贤强,王岳飞,陈留记,等.茶多酚化学[M].上海:上海科学技术出版社,2003.48-50
44.孙宝山,郭成勋.几种抑制剂对酶促褐变抑制机制的探讨[J].食品与发酵工业, 1988(4):56-59
45. Gibson S M, Strauss G, Wasserman. Heat stable fat substitute composition and process [P].US 5374441,1994-12-20
46. Gibson S M, Strauss G. Process for production heat-stable protein microcapsules [P]. US 5993888,1999-11-30
47. Subramaniam A, Reilly A. Process for the preparation of flavor or fragrancemicrocapsules [P].US 2004/0032036 A1,2004-02-19
48.黄凤洪,夏伏建,王江薇,等.亚麻油粉末油脂制备的研究[J].中国油料作物学报, 2002, 24(4):65-68
49.王俊强,顾震,马天贵,等.微胶囊壁材的选择及其在食品工业中的应用[J].江西科学, 2008,26(2):242-247
50.阮海燕.肉桂醛在香精香料、日用化学品及食品添加剂行业中的应用[J].精细与专用化学品,2005,12(3/4):9-10
51.谭龙飞,武伟,杨连生.喷雾干燥法制备肉桂醛微胶囊工艺条件的研究[J].华南师范大学学报(自然科学版),2001(4):84-87
52.谢小梅,方建茹,许杨.肉桂醛柠檬醛抗黄曲霉作用的研究[J].食品科学, 2004, 25(9): 32-34
53.王燕.无吡啶盐酸羟胺肟化法测定肉桂醛含量的探讨[J].徐州师范大学学报(自然科学版),1997,15(3):34-36
54.谢艳丽,蒋敏,陈鸿雁.复凝聚法制备明胶/阿拉伯胶含油微胶囊工艺过程的研究[J].化学世界,2010(1):33-37
55. Ducel V, Richard J, Saulnier P, et, al .Evidence and characterization of complex coacervates containing plant proteins: application to the microencapsulation of oil droplets [J].Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2004,223(2-3):239-247
56. Schmitt C, Sancheza C, Thomas F, et, al. Complex coacervation betweenβ- lactoglobulin and acacia gum in aqueous medium[J].Food Hydrocolloids, 1999, 13(6): 483-496
57. Kruif K D, Weinbreck F, Vireos R D. Complex coacervation of proteins and anionic polysaccharides [D]. Netherlands: Utrecht University,2004
58. Weinbreck F, Roland H W, Nieuwenhuijse H, et, al. Rheological properties of whey protein/gum arabic coacervates[J].Journal of Rheology,2004,48(6):1215-1228
59. Ijichi K, Yoshizawa H, Uemura Y. Multi-layered gelatin/acacia microcapsules by complex coacervation method [J]. Journal of chemical engineering of Japan,1997, 30(5):793-798
60. Dong Z J, TouréA, Jia C S, et, al. Effect of processing parameters on the formation of spherical multinuclear microcapsules encapsulating peppermint oil by coacervation[J]. Journal of Microencapsulation ,2007,24(7):634-646
61. Burgess D J, Carless J E. Microelectrophoretic studies of gelatin and acacia for the prediction of complex coacervation [J].Journal of Colloid and Interface Science, 1984,98(1):1-8
62.朱丽云,李素芳,邵慧娟.复凝聚喷雾干燥法制备香精香料微胶囊的研究[J].食品科技,2006(4):25-33
63. Huang Y Y, Chung T W, Tzeng T W. Drug release from PLA/PEG microparticulates [J].International journal of pharmaceutics,1977,156:9-15
64. Lee S J, Rosenberg M .Microencapsulation of theophylline in whey proteins: effects of core to wall ratio [J].International Journal of Pharmaceutics,2000,205(1-2): 147– 158
65.梁治齐.微胶囊技术及其应用[M].北京:中国轻工业出版社,1999.47-53
66.黄晓丹,张晓鸣,董志俭,等.复凝聚法制备肉桂醛微胶囊的研究[J].食品工业科技, 2008,29(3):63-69
67.王静,戚向阳,朱学良,等.表棓儿茶素棓酸酯体外氧化及其低聚产物形成的研究[J].林产化学与工业,2007,27(5):62-66
68. Chang C P, Leung T K, Lin S M, et al. Release properties on gelatin-gum arabic microcapsules containing camphor oil with added polystyrene [J].Collids and Surfaces B:Biointerfaces,2006,50:136-140
69. Bachtsi A R, Kiparissides C. Synthesisand release studies of oil-containing poly (vinyl alcohol) microcapsules prepared by coacervation [J]. Journal of controlled release, 1996, 38: 49-58
70.伍红.蘑菇多酚氧化酶的性质及其催化反应动力学的研究[J].广州化学,1994(34)24-29
71.赵东海,王云,张建平.果蔬酶促褐变的条件及控制方法研究[J].长江蔬菜, 2005(7): 32-34