用于稳定Pickering乳液的氨基化明胶纳米颗粒的制备
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摘要
以氨基化改性的B型明胶为原料,通过二次去溶剂法可制得具有良好单分散性(PDI≈0.068)的氨基化明胶纳米颗粒(Aminated gelatin nanoparticles,AGNPs),其粒径约为240 nm,表面带正电荷(ζ≈35 mV),并考察了制备过程中溶液pH对AGNPs粒径以及分散性的影响。结果表明:当pH≈4.0时,制备的AGNPs粒径较小(≈240nm),分散较为均匀。SEM、AFM及TEM测试结果表明:AGNPs为一种粒径窄分布的球形纳米颗粒;相比明胶纳米颗粒(Gelatinnanoparticles,GNPs),AGNPs刚性结构特点增强,且质地较为均匀。颗粒表面润湿性测试结果显示,AGNPs的三相接触角(θow=67?±5?)比GNPs(θow=31?±6?)显著增大,表明AGNPs的表面疏水性有所增强。以AGNPs为稳定剂制备的水包油(O/W)型Pickering乳液4℃下储存9个月未出现分层,表现出较高的稳定性。
Fairly monodispersed aminated gelatin nanoparticles(AGNPs,PDI≈0.068) with an average size of 240 nm were prepared by a two-step desolvation method using amino-modified gelatin of type B as raw materials.The particles were positively charged(z≈35 mV).The effects of pH value of solution on the particle size and dispersity of AGNPs were investigated in the preparation process.The results showed that the prepared AGNPs exhibited uniform particle size distribution with a smaller particle size of approximately 240 nm at pH≈4.AFM,SEM and TEM analysis revealed that the AGNPs exhibited spherical morphology with a narrow particle size distribution.Compared with gelatin nanoparticles(GNPs),AGNPs had stronger rigid structure and more uniform texture.Particle surface wettability test results demonstrated that the three-phase contact angle of AGNPs(θow=67°±5°) was higher than that of GNPs(θow=31°±6°),indicating that the surface hydrophobicity of AGNPs increased.The Pickering emulsion stabilized by AGNPs could be stored for 9 months at 4 ℃ without stratification and showed good stability.
Fairly monodispersed aminated gelatin nanoparticles(AGNPs,PDI≈0.068) with an average size of 240 nm were prepared by a two-step desolvation method using amino-modified gelatin of type B as raw materials.The particles were positively charged(z≈35 mV).The effects of pH value of solution on the particle size and dispersity of AGNPs were investigated in the preparation process.The results showed that the prepared AGNPs exhibited uniform particle size distribution with a smaller particle size of approximately 240 nm at pH≈4.AFM,SEM and TEM analysis revealed that the AGNPs exhibited spherical morphology with a narrow particle size distribution.Compared with gelatin nanoparticles(GNPs),AGNPs had stronger rigid structure and more uniform texture.Particle surface wettability test results demonstrated that the three-phase contact angle of AGNPs(θow=67°±5°) was higher than that of GNPs(θow=31°±6°),indicating that the surface hydrophobicity of AGNPs increased.The Pickering emulsion stabilized by AGNPs could be stored for 9 months at 4 ℃ without stratification and showed good stability.
引文
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[2]Aveyard R,Binks B P,Clint J H.Emulsions stabilised solely by colloidal particles[J].Advances in Colloid and Interface Science,2003,100(2):503-546.
[3]Barbetta A,Cameron N R.Morphology and surface area of emulsion-derived(PolyHIPE)solid foams prepared with oil-phase soluble porogenic solvents:Three-component surfactant system[J].Macromolecules,2004,37(9):3202-3213.
[4]Zhou S Z,Bismarck A,Steinke J H G,et al.Interconnected macroporous glycidyl methacrylate-grafted dextran hydrogels synthesised from hydroxyapatite nanoparticle stabilised high internal phase emulsion templates[J].Journal of Materials Chemistry,2012,22(36):18824-18829.
[5]Gao Q X,Wang C Y,Tong Z.Facile and high efficient fabrication of hybrid microcapsules for urease encapsulation and their use as biomimetic reactors[J].Chemical Research in Chinese Universities,2010,26(5):842-846.
[6]Wang W,Laird E D,Gogotsi Y,et al.Bending single-walled carbon nanotubes into nanorings using a Pickering emulsion-based process[J].Carbon,2012,50(5):1769-1775.
[7]Shinto H,Hirata T,Fukasawa T,et al.Effect of interfacial serum proteins on melanoma cell adhesion to biodegradable poly(L-lactic acid)microspheres coated with hydroxyapatite[J].Colloids Surf BBiointerfaces,2013,108(4),8-15.
[8]Destribats M,Eyharts M,Lapeyre V,et al.Impact of pNIPAMmicrogel size on its ability to stabilize Pickering emulsions[J].Langmuir,2014,30(7):1768-1777.
[9]Lu X,Xiao J,Huang Q.Pickering emulsions stabilized by media-milled starch particles[J].Food Research International,2017,105:140-149.
[10]Werner A,Schmitt V,Sèbe G,et al.Synthesis of surfactant-free micro-and nanolatexes from Pickering emulsions stabilized by acetylated cellulose nanocrystals[J].Polymer Chemistry,2017,8(39):6064-6072.
[11]Mwangi W W,Ho K W,Tey B T,et al.Effects of environmental factors on the physical stability of Pickering-emulsions stabilized by chitosan particles[J].Food Hydrocolloids,2016,60:543-550.
[12]Zhu X F,Zhang N,Lin W F,et al.Freeze-thaw stability of Pickering emulsions stabilized by soy and whey protein particles[J].Food Hydrocolloids,2017,69:173-184.
[13]Tan H,Sun G,Lin W,et al.Gelatin particle-stabilized high internal phase emulsions as nutraceutical containers[J].ACS Applied Materials&Interfaces,2014,6(16):13977-13984.
[14]Pawlik A,Kurukji D,Norton I,et al.Food-grade Pickering emulsions stabilised with solid lipid particles[J].Food&Function,2016,7(6):2712-2721.
[15]Tan H,Wei J,Sun G,et al.Interconnected macroporous 3D scaffolds templated from gelatin nanoparticle-stabilized high internal phase emulsions for biomedical applications[J].Soft Matter,2017,13(21):3871-3878.
[16]Yang Lan(杨岚),Wang Chunhua(王春华),Li Changpeng(李昌朋),et al.Preparation of gelatin nanoparticles[J].Fine Chemicals(精细化工),2017,34(7):774-779.
[17]Nan F,Wu J,Qi F,et al.Uniform chitosan-coated alginate particles as emulsifiers for preparation of stable Pickering emulsions with stimulus dependence[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2014,456:246-252.
[18]Morimoto K,Chono S,Kosai T,et al.Design of novel injectable cationic microspheres based on aminated gelatin for prolonged insulin action[J].Journal of Pharmacy&Pharmacology,2005,57(7):839-844.
[19]Azarmi S,Huang Y,Chen H,et al.Optimization of a two-step desolvation method for preparing gelatin nanoparticles and cell uptake studies in 143B osteosarcoma cancer cells[J].Journal of Pharmacy&Pharmaceutical Sciences,2006,9(1):124-132.
[20]Habeeb A F.Determination of free amino groups in proteins by trinitrobenzenesulfonic acid[J].Analytical Biochemistry,1966,14(3):328-336.
[21]Li B,Kennedy J F,Jiang Q G,et al.Quick dissolvable,edible and heatsealable blend films based on konjac glucomannan-gelatin[J].Food Research International,2006,39(5):544-549.
[22]Binks B P,Horozov T S.Colloidal particles at liquid interfaces[M].UK:Cambridge University Press,2006:60-61.
[23]Vignati E,Piazza R,Lockhart T P.Pickering emulsions:?Interfacial tension,colloidal layer morphology,and trapped-particle motion[J].Langmuir,2003,19(17):6650-6656.
[24]Kesavan S,Alamelu B S.Effect of surfactant on the release of ciprofloxacin from gelatin microspheres[J].Ars Pharmaceutica,2010,51(2):1-16.
[25]Chen Mingde(陈明德).The relationship between color and molecular structure of organic reagents[J].Analytical Chemistry(分析化学),1982,(8):58-64.
[26]Ishida N,Inoue T,Minoru Miyahara A,et al.Nano bubbles on a hydrophobic surface in water observed by tapping-mode atomic force microscopy[J].Langmuir,2000,16(16):6377-6380.
[27]Dickinson E.Stabilising emulsion-based colloidal structures with mixed food ingredients[J].Journal of The Science of Food&Agriculture,2013,93(4):710-721.
[28]Binks B P,Lumsdon S O.Influence of particle wettability on the type and stability of surfactant-free emulsions[J].Langmuir,2000,16(23):8622-8631.
[29]Inoue M,Hashizaki K,Taguchi H.Emulsion preparation using b-cyclodextrin and its derivatives acting as an emulsifier[J],Chemical&Pharmaceutical Bulletin,2008,56(9):1335-1337.
[30]Williams M,Warren N J,Fielding L A,et al.Preparation of double emulsions using hybrid polymer/silica particles:New Pickering emulsifiers with adjustable surface wettability[J].ACS Applied Materials&Interfaces,2014,6(23):20919-20927.
[31]Wei W,Wang L Y,Yuan L,et al.Preparation and application of novel microspheres possessing autofluorescent properties[J].Advanced Functional Materials,2007,17(16):3153-3158.
[32]Farrugia C A,Groves M J.Gelatin Behaviour in dilute aqueous solution:Designing a nanoparticulate formulation[J].Journal of Pharmacy&Pharmacology,1999,51(6):643-649.