高内相/自乳液聚合的共轭亚油酸低聚体的囊泡化及稳定性
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摘要
采用自乳化法制备了高内相共轭亚油酸(CLA)的水包油(O/W)乳液,并通过热引发乳液聚合反应得到共轭亚油酸低聚体(oligo-CLA);将oligo-CLA用于自组装脂肪酸囊泡(FAV).透射电子显微镜和动态激光光散射表征结果均表明,在pH=8. 6～13范围内得到了囊泡粒径为10～30 nm的FAV,此结果对提高FAV的pH适应性具有理论意义.自乳液聚合实验结果表明,该高内相自乳化/热引发低聚反应策略可以使浓度高达75. 3%(质量分数)的CLA完成无外加表面活性剂乳液聚合,并使共轭双键总自交联率达到33%且控制oligoCLA的平均聚合度约为6,对规模化生产oligo-CLA及构筑FAV具有实用价值.与CLA相比,oligo-CLA具有更好的低温溶解性,由其自组装的FAV具有更好的环境适应性,如耐酸性和抗钙皂能力,而且显示出较好的钙响应囊泡体积膨胀率;以极少量非离子表面活性剂Span 40或AEO_2辅助oligo-CLA形成的杂化囊泡具有更宽的pH适应性.因此,所制备的FAV在药物释放体系、日用化学产品、家用洗涤剂和个人护理产品中具有更广阔的应用前景.
High internal phase O/W emulsion of conjugated linoleic acids( CLA) was prepared by selfemulsifying technology,and oligomer of CLA( oligo-CLA) was obtained by thermal self-emulsion polymerization( SEP) of the above emulsion. Furthermore,fatty acid vesicles( FAV) self-assemble by the oligo-CLA showing 10—30 nm diameter at pH = 8. 6—13 that was revealed by both transmission electron microscopy and dynamic light scattering,which has theoretical significance for FAV stable at a broader pH range. The experimental results show that free-surfactant emulsion polymerization was completed in the high internal phase emulsion of 75. 3%( mass fraction) CLA according to the unique self-emulsification/thermal oligomerization strategy,achieving 33% total self-crosslinking degree and the target oligo-CLA with an average polymerization degree of 6,which is instructive for scaling up oligo-CLA and FAV preparation. The oligo-CLA has better low temperature solubility in comparison with CLA itself,and the FAV self-assembling by it has stronger resistance to acidic and calcium conditions and shows calcium responsive size-tunable features. Moreover,the hybrid vesicles of oligo-CLA with a small amount of Span 40 or AEO_2 additives show even broader pH windows for vesiculation. Therefore the FAV self-assembling by oligo-CLA should have a wider application prospect in drug delivery systems,daily chemical products,and household detergents and personal care products.
High internal phase O/W emulsion of conjugated linoleic acids( CLA) was prepared by selfemulsifying technology,and oligomer of CLA( oligo-CLA) was obtained by thermal self-emulsion polymerization( SEP) of the above emulsion. Furthermore,fatty acid vesicles( FAV) self-assemble by the oligo-CLA showing 10—30 nm diameter at pH = 8. 6—13 that was revealed by both transmission electron microscopy and dynamic light scattering,which has theoretical significance for FAV stable at a broader pH range. The experimental results show that free-surfactant emulsion polymerization was completed in the high internal phase emulsion of 75. 3%( mass fraction) CLA according to the unique self-emulsification/thermal oligomerization strategy,achieving 33% total self-crosslinking degree and the target oligo-CLA with an average polymerization degree of 6,which is instructive for scaling up oligo-CLA and FAV preparation. The oligo-CLA has better low temperature solubility in comparison with CLA itself,and the FAV self-assembling by it has stronger resistance to acidic and calcium conditions and shows calcium responsive size-tunable features. Moreover,the hybrid vesicles of oligo-CLA with a small amount of Span 40 or AEO_2 additives show even broader pH windows for vesiculation. Therefore the FAV self-assembling by oligo-CLA should have a wider application prospect in drug delivery systems,daily chemical products,and household detergents and personal care products.
引文
[1]Gebicki J.M.,Hicks M.,Nature,1973,243(5404),232-234
[2]Morigaki K.,Walde P.,Curr.Opin.Colloid Interface Sci.,2007,12(2),75-80
[3]Morigaki K.,Walde P.,Misran M.,Robinson B.H.,Colloids Surf.A,2003,213(1),37-44
[4]Ruiz-Mirazo K.,Briones C.,de la Escosura A.,Chem.Rev.,2014,114(1),285-366
[5]Chen I.A.,Walde P.,Cold Spring Harbor Perspect.Biol.,2010,2(7),a002107-a002121
[6]Namani T.,Deamer D.W.,Orig.Life Evol.Biosph.,2008,38(4),329-341
[7]Picker A.,Nuss H.,Guenoun P.,Chevallard C.,Langmuir,2011,27(7),3213-3218
[8]Adamala K.,Szostak J.W.,Science,2013,342(29),1098-1100
[9]Hanczyc M.M.,Fujikawa S.M.,Szostak J.W.,Science,2003,302(5645),618-622
[10]Fan Y.,Ma J.,Fang Y.,Liu T.T.,Hu X.Y.,Xia Y.M.,Colloids Surf.B,2018,167,385-391
[11]Caschera F.,Bernardino de la Serna J.,Loffler P.M.,Langmuir,2011,27(23),14078-14090
[12]Suga K.,Yokoi T.,Kondo D.,Langmuir,2014,30(43),12721-12728
[13]Song A.,Dong S.,Jia X.,Angew.Chem.Int.Ed.,2005,44(26),4018-4021
[14]Liang X.D.,Fan Y.,Fang Y.,Xia Y.M.,Chen R.H.,Chem.J.Chinese Universities,2017,38(9),1639-1644(梁潇丹,樊晔,方云,夏咏梅,程若辉.高等学校化学学报,2017,38(9),1639-1644)
[15]Namani T.,Walde P.,Langmuir,2005,21(14),6210-6219
[16]Fan Y.,Han Y.C.,Xia Y.M.,Bo C L.,Fang Y.,Chinese J.Appl.Chem.,2018,35(12),1478-1484(樊晔,韩贻陈,夏咏梅,薄纯玲,方云.应用化学,2018,35(12),1639-1644)
[17]Liu M.S.,Gao K.Q.,Lin L.,Phys.Chem.Chem.Phys.,2015,17(8),5959-5965
[18]Du N.,Song R.Y.,Li H.P.,Song S.,Zhang R.J.,Hou W.G.,Langmuir,2015,31(20),12579-12586
[19]Abe M.,Koike T.,Nishiyama H.,J.Colloid Interface Sci.,2009,330(1),250-253
[20]Sakai K.,Izumi K.,Sakai H.,J.Colloid Interface Sci.,2010,343(2),491-495
[21]Abe M.,Tsubone K.,Koike T.,Langmuir,2006,22(20),8293-8297
[22]Fan Y.,Zheng Y.Z.,Fang Y.,Xia Y.M.,Gao D.,Wang J.,Chem.J Chinese Universities,2018,39(7),1484-1489(樊晔,郑艺洲,方云,夏咏梅,高迪,王杰.高等学校化学学报,2018,39(7),1484-1489)
[23]Meraz-Torres.,Hernandez-Sanchez H.,Am.J.Food Technol.,2012,7(4),176-179
[24]Vélez M.A.,Perotti M.C.,Zanel P.,J.Food Eng.,2017,212,174-180
[25]Fan Y.,Fang Y.,Ma L.,Jiang H.,J.Surfact.Deterg.,2015,18(1),179-188
[26]Israelachvili J.N.,Mitchell D.J.,Ninham B.W.,J.Chem.Soc.,Faraday Trans.2,1976,72(24),1525-1568
[2]Morigaki K.,Walde P.,Curr.Opin.Colloid Interface Sci.,2007,12(2),75-80
[3]Morigaki K.,Walde P.,Misran M.,Robinson B.H.,Colloids Surf.A,2003,213(1),37-44
[4]Ruiz-Mirazo K.,Briones C.,de la Escosura A.,Chem.Rev.,2014,114(1),285-366
[5]Chen I.A.,Walde P.,Cold Spring Harbor Perspect.Biol.,2010,2(7),a002107-a002121
[6]Namani T.,Deamer D.W.,Orig.Life Evol.Biosph.,2008,38(4),329-341
[7]Picker A.,Nuss H.,Guenoun P.,Chevallard C.,Langmuir,2011,27(7),3213-3218
[8]Adamala K.,Szostak J.W.,Science,2013,342(29),1098-1100
[9]Hanczyc M.M.,Fujikawa S.M.,Szostak J.W.,Science,2003,302(5645),618-622
[10]Fan Y.,Ma J.,Fang Y.,Liu T.T.,Hu X.Y.,Xia Y.M.,Colloids Surf.B,2018,167,385-391
[11]Caschera F.,Bernardino de la Serna J.,Loffler P.M.,Langmuir,2011,27(23),14078-14090
[12]Suga K.,Yokoi T.,Kondo D.,Langmuir,2014,30(43),12721-12728
[13]Song A.,Dong S.,Jia X.,Angew.Chem.Int.Ed.,2005,44(26),4018-4021
[14]Liang X.D.,Fan Y.,Fang Y.,Xia Y.M.,Chen R.H.,Chem.J.Chinese Universities,2017,38(9),1639-1644(梁潇丹,樊晔,方云,夏咏梅,程若辉.高等学校化学学报,2017,38(9),1639-1644)
[15]Namani T.,Walde P.,Langmuir,2005,21(14),6210-6219
[16]Fan Y.,Han Y.C.,Xia Y.M.,Bo C L.,Fang Y.,Chinese J.Appl.Chem.,2018,35(12),1478-1484(樊晔,韩贻陈,夏咏梅,薄纯玲,方云.应用化学,2018,35(12),1639-1644)
[17]Liu M.S.,Gao K.Q.,Lin L.,Phys.Chem.Chem.Phys.,2015,17(8),5959-5965
[18]Du N.,Song R.Y.,Li H.P.,Song S.,Zhang R.J.,Hou W.G.,Langmuir,2015,31(20),12579-12586
[19]Abe M.,Koike T.,Nishiyama H.,J.Colloid Interface Sci.,2009,330(1),250-253
[20]Sakai K.,Izumi K.,Sakai H.,J.Colloid Interface Sci.,2010,343(2),491-495
[21]Abe M.,Tsubone K.,Koike T.,Langmuir,2006,22(20),8293-8297
[22]Fan Y.,Zheng Y.Z.,Fang Y.,Xia Y.M.,Gao D.,Wang J.,Chem.J Chinese Universities,2018,39(7),1484-1489(樊晔,郑艺洲,方云,夏咏梅,高迪,王杰.高等学校化学学报,2018,39(7),1484-1489)
[23]Meraz-Torres.,Hernandez-Sanchez H.,Am.J.Food Technol.,2012,7(4),176-179
[24]Vélez M.A.,Perotti M.C.,Zanel P.,J.Food Eng.,2017,212,174-180
[25]Fan Y.,Fang Y.,Ma L.,Jiang H.,J.Surfact.Deterg.,2015,18(1),179-188
[26]Israelachvili J.N.,Mitchell D.J.,Ninham B.W.,J.Chem.Soc.,Faraday Trans.2,1976,72(24),1525-1568