为合成较高取代度的丁酸酐改性淀粉,探究其乳化性和乳化稳定性,该研究以酶改性多孔淀粉(porous starch,PS)为主体,丁酸酐(butyric acid,BA)为客体,在碱性水相体系中制备了取代度为0.023~0.148的丁酸酐改性多孔淀粉(butyric anhydride porous starch ester,BA-PS),并以其作为稳定剂制备Pickering乳液。扫描电子显微镜和N2-吸附/脱附结果表明,PS表面分布着较为均匀的孔洞结构,平均孔径为11.13 nm,颗粒比表面积为3.914 4 m2/g,酯化改性后BA-PS仍保留PS原有的颗粒形态;傅立叶红外光谱和核磁共振氢谱谱图的结果相互印证了BA对PS酯化改性的成功;X射线衍射结果表明,PS和BA-PS都保留了天然淀粉原有的结晶形态;制备的Pickering乳液贮存20 d后观察结果表明,天然淀粉(native starch,NS)不具有乳化性,酶改性赋予PS一定的乳化性能,但其乳化能力仍然有限,而BA-PS的乳化性要远优于NS和PS,且改性程度越高,制备的乳液液滴均匀性越好,尺寸越小,乳化能力越强。该研究表明,丁酸酐改性淀粉具备较好的乳化性和乳化稳定性,对以其为稳定剂制备的Pickering乳液,可进一步进行药物或活性物质的递送研究。
[1] 吴昱春, 陈小草, 张琦, 等.Pickering乳液稳定机理及其在食品中的应用研究进展[J].食品科学, 2021, 42(7):275-282.
WU Y C, CHEN X C, ZHANG Q, et al.Stability mechanism of Pickering emulsion and its application in food industry[J].Food Science, 2021, 42(7):275-282.
[2] HALMOS E P, MACK A, GIBSON P R.Review article:Emulsifiers in the food supply and implications for gastrointestinal disease[J].Alimentary Pharmacology & Therapeutics, 2019, 49(1):41-50.
[3] 曹雁平, 许朵霞, 侯占群.食品乳状液及乳化新技术[M].北京:化学工业出版社, 2014.
CAO Y P, XU D X, HOU Z Q.Food Emulsion and New Emulsification Technology[M].Beijing:Chemical Industry Press, 2014.
[4] RAYNER M, MARKU D, ERIKSSON M, et al.Biomass-based particles for the formulation of Pickering type emulsions in food and topical applications[J].Colloids & Surfaces A:Physicochemical & Engineering Aspects, 2014, 458(1):48-62.
[5] 汤洋, 高成成, 张岩, 等.多糖基颗粒稳定的Pickering乳液凝胶研究进展[J].食品科学, 2022,43(3):341-351.
TANG Y, GAO C C, ZHANG Y, et al.Pickering emulsion gel stabilized by polysaccharide-based particles[J].Food Science, 2022,43(3):341-351.
[6] RUAN H, CHEN Q H, FU M L, et al.Preparation and properties of octenyl succinic anhydride modified potato starch[J].Food Chemistry, 2009, 114(1):81-86.
[7] 王秋丽. 辛烯基琥珀酸淀粉酯构建乳化微胶囊体系及其包埋应用的研究[D].广州:华南理工大学, 2018.
WANG Q L.Study on the emulsified microcapsule system made by octenyl succinic anhydride modified starch and its embedded application[D].Guangzhou:South China University of Technology, 2018.
[8] SIMSEK S, OVANDO-MARTINEZ M, MAREFATI A, et al.Chemical composition, digestibility and emulsification properties of octenyl succinic esters of various starches[J].Food Research International, 2015, 75:41-49.
[9] GARCÍA-TEJEDA Y V, LEAL-CASTAÑEDA E J, ESPINOSA-SOLIS V, et al.Synthesis and characterization of rice starch laurate as food-grade emulsifier for canola oil-in-water emulsions[J].Carbohydrate Polymers, 2018, 194:177-183.
[10] LU X X, LIU H S, HUANG Q R.Fabrication and characterization of resistant starch stabilized Pickering emulsions[J].Food Hydrocolloids, 2020, 103:105703.
[11] RUSSO R, SANTARCANGELO C, BADOLATI N, et al.In vivo bioavailability and in vitro toxicological evaluation of the new butyric acid releaser N-(1-carbamoyl-2-phenyl-ethyl) butyramide[J].Biomedicine & Pharmacotherapy, 2021, 137:111385.
[12] DAI D D, SUN S L, HONG Y, et al.Structural and functional characteristics of butyrylated maize starch[J].LWT-Food Science and Technology, 2019, 112:108254.
[13] DURA A, BLASZCZAK W, ROSELL C M.Functionality of porous starch obtained by amylase or amyloglucosidase treatments[J].Carbohydrate Polymers, 2014, 101:837-845.
[14] ZHANG K R, CHENG F, ZHANG K, et al.Synthesis of long-chain fatty acid starch esters in aqueous medium and its characterization[J].European Polymer Journal, 2019, 119:136-147.
[15] NAMAZI H, FATHI F, DADKHAH A.Hydrophobically modified starch using long-chain fatty acids for preparation of nanosized starch particles[J].Scientia Iranica, 2011, 18(3):439-445.
[16] LEE Y K, CHANG Y H.Structural and in vitro digestibility properties of esterified maca starch with citric acid and its application as an oil-in-water (O/W) Pickering emulsion stabilizer[J].International Journal of Biological Macromolecules, 2019, 134:798-806.
[17] 张盼盼, 夏文, 王飞, 等.多孔淀粉制备方法及其应用的研究进展[J].广东化工, 2015, 42(17):102-105.
ZHANG P P, XIA W, WANG F, et al.Development of porous starch preparation and application[J].Guangdong Chemical Industry, 2015, 42(17):102-105.
[18] GARCIA M A V T, GARCIA C F, FARACO A A G.Pharmaceutical and biomedical applications of native and modified starch:A review[J].Starch-Starke, 2020, 72(7-8):1900270.
[19] LI H Y, MA Y X,YU L Y.Construction of octenyl succinic anhydride modified porous starch for improving bioaccessibility of β-carotene in emulsions[J].RSC Advances, 2020, 10(14):8 480-8 489.
[20] WEN Y, YE F Y, ZHU J F, et al.Corn starch ferulates with antioxidant properties prepared by N, N′-carbonyldiimidazole-mediated grafting procedure[J].Food Chemistry, 2016, 208:1-9.
[21] ZHANG B, MEI J Q, CHEN B, et al.Digestibility, physicochemical and structural properties of octenyl succinic anhydride-modified cassava starches with different degree of substitution[J].Food Chemistry, 2017, 229:136-141.
[22] LI J L, ZHOU M, CHENG F, et al.Characterization and properties of long-chain fatty acid starch esters prepared with regenerated starch by dry method[J].Starch-Starke, 2019, 71(11-12):1900143.
[23] 苟丽娜, 马云翔, 王宇霞, 等.高比表面积阿魏酸多孔淀粉酯结构表征及体外消化特性[J].食品与发酵工业, 2021,47(22):76-83.
GOU L N, MA Y X, WANG Y X, et al.Structural characterization and in vitro digestibility of ferulic acid porous starch ester with high specific surface area[J].Food and Fermentation Industries, 2021,47(22):76-83.
[24] 冯鑫, 马良, 戴宏杰, 等.食品级Pickering乳液的稳定性及β-胡萝卜素的装载研究[J].食品与发酵工业, 2021, 47(6):18-25.
FENG X, MA L, DAI H J, et al.The study on stability of food-grade Pickering emulsion and the loading of β-carotene[J].Food and Fermentation Industries, 2021, 47(6):18-25.
[25] LIU Z Q, LI Y, CUI F J, et al.Production of octenyl succinic anhydride-modified waxy corn starch and its characterization[J].Journal of Agricultural & Food Chemistry, 2008, 56(23):11 499-11 506.
[26] LI S N, ZHANG B, TAN C P, et al.Octenylsuccinate quinoa starch granule-stabilized Pickering emulsion gels:Preparation, microstructure and gelling mechanism[J].Food Hydrocolloids, 2019, 91:40-47.
[27] 罗文波, 魏宇清, 邵苗, 等.淀粉脂质复合物纳米粒子的制备、结构表征及其在Pickering乳液中的应用[J].粮油食品科技, 2021, 29(4):122-129.