纳米缺钙羟基磷灰石/壳聚糖复合微球的原位均匀制备
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摘要
针对纳米缺钙羟基磷灰石/壳聚糖(nCDHA/CS)复合微球中,nCDHA在微球中分布不均和含量不足的问题,在油包水(W/O)体系中,运用均匀沉淀法原位制备了nCDHA/CS复合微球。利用扫描电镜(SEM)、粒度分析仪、X射线衍射(XRD)、傅里叶红外光谱仪(FT-IR)、热重分析(TG)、X射线光电子能谱仪(XPS)等对复合微球的理化性能进行了表征。结果显示,所制得的nCDHA/CS复合微球中,nCDHA均匀分布于复合微球中,其含量高达43%;复合微球粒径分布较窄,球形度良好,分散性指数(PDI)为0.291,平均粒径18.6μm。仿生矿化结果显示,复合微球表面矿化是从nCDHA生成nHA的过程,仿生矿化14 d后,微球表面形成大量均匀的片状类骨磷灰石,表明该复合微球具有较好的生物学性能,对骨组织再生修复具有较大的潜力。
Aimed at the problem of nano calcium-deficient hydroxyapatite(nCDHA) uneven distribution and insufficient content in nano calcium-deficient hydroxyapatite/chitosan(CS) composite microspheres, nCDHA/CS composite microspheres were firstly fabricated in situ by homogeneous precipitation method in a water-in-oil(W/O) emulsion. The physicochemical properties of composite microspheres were investigated by scanning electronic microscopy(SEM), laser particle size analyzer, X-ray diffraction(XRD), Fourier infrared spectrum(FT-IR), thermogravimetric analysis(TG) and X-ray photoelectron spectroscopy(XPS). The results indicate that the nCDHA was uniformly distributed in the nCDHA/CS composite microspheres, and the content was up to 43%. Moreover, the composite microspheres had a narrow size distribution, good sphericity with PDI 0.291 and average size of 18.6 μm. The result of biomimetic mineralization shows that the surface mineralization of composite microspheres was a process from nCDHA to nHA. After 14 d of biomimetic mineralizationr, a large number of even sheets of bone-like apatite were formed on the surface of the microspheres, indicating that the composite microspheres had good biological properties and great potential for bone tissue regeneration and repair.
Aimed at the problem of nano calcium-deficient hydroxyapatite(nCDHA) uneven distribution and insufficient content in nano calcium-deficient hydroxyapatite/chitosan(CS) composite microspheres, nCDHA/CS composite microspheres were firstly fabricated in situ by homogeneous precipitation method in a water-in-oil(W/O) emulsion. The physicochemical properties of composite microspheres were investigated by scanning electronic microscopy(SEM), laser particle size analyzer, X-ray diffraction(XRD), Fourier infrared spectrum(FT-IR), thermogravimetric analysis(TG) and X-ray photoelectron spectroscopy(XPS). The results indicate that the nCDHA was uniformly distributed in the nCDHA/CS composite microspheres, and the content was up to 43%. Moreover, the composite microspheres had a narrow size distribution, good sphericity with PDI 0.291 and average size of 18.6 μm. The result of biomimetic mineralization shows that the surface mineralization of composite microspheres was a process from nCDHA to nHA. After 14 d of biomimetic mineralizationr, a large number of even sheets of bone-like apatite were formed on the surface of the microspheres, indicating that the composite microspheres had good biological properties and great potential for bone tissue regeneration and repair.
引文
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[2] Lei Y,Guan J J,Chen W,et al.Fabrication of hydroxyapatite/chitosan porous materials for Pb (II) removal from aqueous solution[J].Rsc Advances,2015,5(32):25462-25470.
[3] Winand L,Dallemagne M J.Hydrogen bonding in the calcium phosphates[J].Nature,1962,193(4813):368-369.
[4] Guo H,Su J,Wei J,et al.Biocompatibility and osteogenicity of degradable Ca-deficient hydroxyapatite scaffolds from calcium phosphate cement for bone tissue engineering [J].Acta Biomaterialia,2009,5(1):268-278.
[5] Hu X X,Shen H,Yang F,et al.Modified composite microspheres of hydroxyapatite and poly (lactide-co-glycolide) as an injectable scaffold[J].Applied Surface Science,2014,292:764-772.
[6] Lee J U,Kim G H.Calcium-deficient hydroxyapatite/collagen/platelet-rich plasma scaffold with controlled release function for hard tissue regeneration [J].ACS Biomaterials Science & Engineering,2018,4(1):278-289.
[7] Zhao J,Wang S Y,Bao J Q,et al.Trehalose maintains bioactivity and promotes sustained release of BMP-2 from lyophilized CDHA scaffolds for enhanced osteogenesis in vitro and in vivo[J].PLoS One,2013,8(1):e54645.
[8] Liu T Y,Chen S Y,Li J H,et al.Study on drug release behaviour of CDHA/chitosan nanocomposites—effect of CDHA nanoparticles[J].Journal of controlled release,2006,112(1):88-95.
[9] Lim H N,Huang N M,Loo C H.Facile preparation of graphene-based chitosan films:Enhanced thermal,mechanical and antibacterial properties[J].Journal of Non-crystalline Solids,2012,358(3):525-530.
[10] Buschmann M D,Merzouki A,Lavertu M,et al.Chitosans for delivery of nucleic acids[J].Advanced Drug Delivery Reviews,2013,65(9):1234-1270.
[11] Shavandi A,Bekhit A E D A,Sun Z,et al.A novel squid pen chitosan/hydroxyapatite/β-tricalcium phosphate composite for bone tissue engineering[J].Materials Science and Engineering:C,2015,55:373-383.
[12] Paul W,Sharma C P.Development of porous spherical hydroxyapatite granules:application towards protein delivery[J].Journal of Materials Science:Materials in Medicine,1999,10(7):383-388.
[13] Lee J,Yun H S.Hydroxyapatite-containing gelatin/chitosan microspheres for controlled release of lysozyme and enhanced cytocompatibility[J].Journal of Materials Chemistry B,2014,2(9):1255-1263.
[14] Cai B,Zou Q,Zuo Y,et al.Fabrication and cell viability of injectable n-HA/chitosan composite microspheres for bone tissue engineering[J].Rsc Advances,2016,6(89):85735-85744.
[15] Ding C C,Teng S H,Pan H.In-situ generation of chitosan/hydroxyapatite composite microspheres for biomedical application[J].Materials Letters,2012,79:72-74.
[16] Li Jian,Han Zhijun,Wei Yan,et al.In situ biomimetic fabrication and characterization of nano-hydroxyapatite/chitosan composite microspheres[J].Journal of Inorganic Materials,2014,29(12):1327-1332(in Chinese).李健,韩志军,魏延,等.纳米羟基磷灰石/壳聚糖复合微球的原位仿生制备及表征[J].无机材料学报,2014,29(12):1327-1332.
[17] Kokubo T,Takadama H.How useful is SBF in predicting in vivo bone bioactivity[J].Biomaterials,2006,27(15):2907-2915.