掺铜中空生物玻璃纳米球的制备及可控掺杂
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摘要
通过研究铜元素掺杂对中空生物玻璃纳米球形貌结构的影响,进一步探究中空生物玻璃铜掺杂与药物缓释性能的关系,以获得具有一定抗菌作用和药物控释性能的骨组织工程支架。以聚丙烯酸(Polyacrylic acid,PAA)为模板剂,以硅源、磷源、钙源及铜源为无机盐前驱体,结合采用溶胶-凝胶法制备掺铜中空生物玻璃纳米球(Copper substituted hollow bioactive glass, Cu-HBGNs),改变CaO、CuO组分的原料添加量来调控所得掺铜中空生物玻璃纳米球的掺杂量;采用SEM、TEM、EDS、FTIR、XRD、TGA及N_2吸附-脱附等测试表征掺铜中空生物玻璃纳米球的形貌结构、元素组成及热稳定性。结果表明:在生物玻璃体系中引入不同摩尔比的CaO、CuO组分能实现掺铜中空生物玻璃纳米球的可控掺杂,所制备纳米球样品外观形貌及结构基本不变,粒径、孔径均可调。溶胶-凝胶法准备的可控掺铜中空生物玻璃在药物输送和骨组织修复领域具有广阔的应用前景。
The influence of copper doping on morphology and structure of hollow bioactive glass nanospheres(HBGNs) was studied. On this basis, the relationship between copper doping of hollow bioactive glass nanospheres and drug sustained release was explored to gain bone tissue engineering scaffold with certain antibacterial action and controlled release property of drugs. Copper substituted hollow bioactive glass nanospheres(Cu-HBGNs) were prepared with sol-gel method by using polyacrylic acid(PAA) as the template and silicon source, phosphorus source, calcium sources and copper source as inorganic resources. The doping content of Cu-HBGNs was regulated by changing additive amount of CaO and CuO component. Morphology, structure, element composition and thermal stability of Cu-HBGNs were characterized by scanning electron microscope(SEM), transmission electron microscopy(TEM), energy dispersive spectroscopy(EDS), Fourier-transform infrared(FTIR), X-ray diffraction(XRD), thermogravimetric analysis(TGA), and N_2 adsorption-desorption. The results showed that the controlled copper doping of Cu-HBGNs could be realized through introducing different mole ratios of CaO and CuO component in bioactive glass system. The morphology and structure of these samples basically remained unchanged, and the particle size and pore size could be adjusted. Cu-HBGNs prepared with sol-gel method has the wide application prospect in drug delivery and bone tissue repair.
The influence of copper doping on morphology and structure of hollow bioactive glass nanospheres(HBGNs) was studied. On this basis, the relationship between copper doping of hollow bioactive glass nanospheres and drug sustained release was explored to gain bone tissue engineering scaffold with certain antibacterial action and controlled release property of drugs. Copper substituted hollow bioactive glass nanospheres(Cu-HBGNs) were prepared with sol-gel method by using polyacrylic acid(PAA) as the template and silicon source, phosphorus source, calcium sources and copper source as inorganic resources. The doping content of Cu-HBGNs was regulated by changing additive amount of CaO and CuO component. Morphology, structure, element composition and thermal stability of Cu-HBGNs were characterized by scanning electron microscope(SEM), transmission electron microscopy(TEM), energy dispersive spectroscopy(EDS), Fourier-transform infrared(FTIR), X-ray diffraction(XRD), thermogravimetric analysis(TGA), and N_2 adsorption-desorption. The results showed that the controlled copper doping of Cu-HBGNs could be realized through introducing different mole ratios of CaO and CuO component in bioactive glass system. The morphology and structure of these samples basically remained unchanged, and the particle size and pore size could be adjusted. Cu-HBGNs prepared with sol-gel method has the wide application prospect in drug delivery and bone tissue repair.
引文
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[2] 轩肖娜,朱海霖,陈建勇.丝素蛋白/纳米生物玻璃复合多孔支架的结构与性能[J].功能材料,2013,44(2):226-231.
[3] Hench L L.Bioceramics:From concept to clinic[J].Journal of the American Ceramic Society,1991,74(7):1487-1510.
[4] Du X,He J.Spherical silica micro/nanomaterials with hierarchical structures:Synthesis and applications[J].Nanoscale,2011,3(10):3984-4002.
[5] Wang F,Tang Y,Zhang B,et al.Preparation of novel magnetic hollow mesoporous silica microspheres and their efficient adsorption[J].Journal of Colloid and Interface Sscience,2012,386(1):129-134.
[6] Yang Y H,Liu C H,Liang Y H,et al.Hollow mesoporous hydroxyapatite nanoparticles (hmHANPs) with enhanced drug loading and pH-responsive release properties for intracellular drug delivery[J].Journal of Materials Chemistry B,2013,1(19):2447-2450.
[7] Wu C,Chang J,Xiao Y.Mesoporous bioactive glasses as drug delivery and bone tissue regeneration platforms[J].Therapeutic Delivery,2011,2(9):1189-1198.
[8] Pappas G S,Bilalis P,Kordas G C.Synthesis and characterization of SiO2-CaO-P2O5 hollow nanospheres for biomedical applications[J].Materials Letters,2012,67(1):273-276.
[9] Li B,Luo W,Wang Y,et al.Bioactive SiO2-CaO-P2O5 hollow nanospheres for drug delivery[J].Journal of Non-Crystalline Solids,2016,447:98-103.
[10] Wu C,Zhou Y,Xu M,et al.Copper-containing mesoporous bioactive glass scaffolds with multifunctional properties of angiogenesis capacity,osteostimulation and antibacterial activity[J].Biomaterials,2013,34(2):422-433.
[11] Ye J,He J,Wang C,et al.Copper-containing mesoporous bioactive glass coatings on orbital implants for improving drug delivery capacity and antibacterial activity[J].Biotechnology Letters,2014,36(5):961-968.
[12] 杜瑞林,常江.含Zn,Mg生物玻璃的制备及性能研究[J].无机材料学报,2004,19(6):1353-1358.
[13] Solgi S,Khakbiz M,Shahrezaee M,et al.Synthesis,characterization and in vitro biological evaluation of Sol-gel derived Sr-containing nano bioactive glass[J].Silicon,2017,9(4):535-542.
[14] Carta D,Jones J R,Lin S,et al.Neutron diffraction study of antibacterial bioactive calcium silicate sol-gel glasses containing silver[J].International Journal of Applied Glass Science,2017,8(4):364-371.
[15] Hu G.Copper stimulates proliferation of human endothelial cells under culture[J].Journal of Cellular Biochemistry,1998,69(3):326-335.
[16] Hoppe A,Meszaros R,St?hli C,et al.In vitro reactivity of Cu doped 45S5 Bioglass? derived scaffolds for bone tissue engineering[J].Journal of Materials Chemistry B,2013,1(41):5659-5674.
[17] Ruparelia J P,Chatterjee A K,Duttagupta S P,et al.Strain specificity in antimicrobial activity of silver and copper nanoparticles[J].Acta Biomaterialia,2008,4(3):707-716.
[18] Neel E A A,Ahmed I,Pratten J,et al.Characterisation of antibacterial copper releasing degradable phosphate glass fibres[J].Biomaterials,2005,26(15):2247-2254.
[19] 孙志娟,陈雪莲,蒋春跃.自组装法制备中空二氧化硅纳米粒子减反射薄膜[J].无机材料学报,2014,29(9):947-955.
[20] 黄世斌,董亚明,郭旭虹.以纳米球形聚电解质刷为模板制备PS/SiO2核-壳纳米杂化粒子和SiO2空心微球[J].华东理工大学学报:自然科学版,2011,37(6):655-658
[21] 万勇.二氧化硅空心球及核壳结构的制备与形成机理研究[D].合肥:中国科学技术大学,2007:1-18.
[22] 陈晓峰,王迎军,赵娜如,等.溶胶-凝胶生物玻璃多孔材料显微结构和生物活性的扫描电镜及红外光谱分析[J].电子显微学报,2003,22(4):304-310.
[23] Zhu Y,Shi J.A mesoporous core-shell structure for pH-controlled storage and release of water-soluble drug[J].Microporous and Mesoporous Materials,2007,103(1/3):243-249.
[24] Liu J,Qiao S Z,Budi Hartono S,et al.Monodisperse yolk-shell nanoparticles with a hierarchical porous structure for delivery vehicles and nanoreactors[J].Angewandte Chemie International Edition,2010,49(29):4981-4985.