研究论文

磷酸钙纳米材料的制备、性能及应用

  • 漆超 ,
  • 朱英杰 ,
  • 吴进 ,
  • 陈峰
展开
  • 中国科学院上海硅酸盐研究所, 上海200050
漆超,博士研究生,研究方向为纳米生物材料,电子信箱:qichao@student.sic.ac.cn

收稿日期: 2014-09-15

  修回日期: 2014-10-26

  网络出版日期: 2015-03-19

Preparation, properties and applications of calcium phosphate nanostructured materials

  • QI Chao ,
  • ZHU Yingjie ,
  • WU Jin ,
  • CHEN Feng
Expand
  • Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received date: 2014-09-15

  Revised date: 2014-10-26

  Online published: 2015-03-19

摘要

磷酸钙作为生物体硬组织中主要的无机成分,具有良好的生物相容性、生物活性及生物可降解性,广泛应用于骨组织与牙齿修复和替换、药物输运和控制释放、基因转染及诊断成像等生物医学领域。人工合成磷酸钙材料的组成、结构、尺寸、形貌和结晶度等特性均与材料的制备方法有关,且材料的这些特性对其应用起到决定性作用。因此,发展不同的方法制备出具有特定组成、结构、尺寸、形貌、结晶度和性能的磷酸钙纳米材料对其应用至关重要。本文综述近年来在磷酸钙纳米材料的制备、表征、性能和应用研究方面所取得的最新进展,讨论室温制备法、溶剂热/水热合成法、微波辅助快速合成法、静电纺丝法及含磷生物分子磷源合成法等制备方法,分析磷酸钙纳米材料的性能及其在药物装载和可控释放、蛋白质吸附及释放、生物成像等领域的应用,展望磷酸钙纳米材料研究领域的发展趋势。

本文引用格式

漆超 , 朱英杰 , 吴进 , 陈峰 . 磷酸钙纳米材料的制备、性能及应用[J]. 科技导报, 2015 , 33(4) : 111 -119 . DOI: 10.3981/j.issn.1000-7857.2015.04.019

Abstract

As the important inorganic component of biological hard tissues, calcium phosphate materials have high biocompatibility, bioactivity and biodegradability. Therefore, they are widely investigated and used in various biomedical fields, such as bone and tooth repair and replacement, drug delivery, gene transfection and diagnostic imaging. The chemical composition, structure, crystallite size, morphology, and crystallinity of the synthetic calcium phosphate materials, which are strongly influenced by their preparation methods, play a decisive role in their applications. Therefore, to develop various synthetic methods for the desirable materials is important for their applications. This paper reviews recent research progress of our group in the preparation, characterization, properties and applications of calcium phosphate nanostructured materials, focusing on the preparation methods, including room-temperature synthesis, solvothermal/hydrothermal synthesis, microwave-assisted rapid synthesis, electrospinning, and phosphorus-containing biomolecules based synthesis, and their applications in drug delivery, protein adsorption and release, and bioimaging. The future research trends are also discussed.

参考文献

[1] Dorozhkin S V. Calcium orthophosphates[J]. Journal of Materials Science, 2007, 42(4): 1061-1095.
[2] Dorozhkin S V. Calcium orthophosphates in nature, Biology and Medicine[J]. Materials, 2009, 2(2): 399-498.
[3] Palmer L C, Newcomb C J, Kaltz S R, et al. Biomimetic systems for hydroxyapatite mineralization inspired by bone and enamel[J]. Chemical Reviews, 2008, 108(11): 4754-4783.
[4] Cai Y R, Tang R K. Calcium phosphate nanoparticles in biomineralization and biomaterials[J].JournalofMaterialsChemistry,2008,18:3775-3787.
[5] Dorozhkin S V, Epple M. Biological and medical significance of calcium phosphates[J]. Angewandte Chemie International Edition, 2002, 41: 3130-3146.
[6] Chen F, Zhu Y J, Wu J, et al. Nanostructured calcium phosphates: Preparation and their application in biomedicine[J]. Nano Biomedicine and Engineering, 2012, 4(1): 41-49.
[7] Anselme K. Osteoblast adhesion on biomaterials[J]. Biomaterials, 2000, 21: 667-681.
[8] Valletregi M. Calcium phosphates as substitution of bone tissues[J]. Progress in Solid State Chemistry, 2004, 32(1/2): 1-31.
[9] Wang K W, Zhou L Z, Sun Y, et al. Calcium phosphate/PLGA-mPEG hybrid porous nanospheres: A promising vector with ultrahigh gene loading and transfection efficiency[J]. Journal of Materials Chemistry, 2010, 20(6): 1161-1166.
[10] Wu G J, Zhou L Z, Wang K W, et al. Hydroxylapatite nanorods: An efficient and promising carrier for gene transfection[J]. Journal of Colloid and Interface Science, 2010, 345(2): 427-432.
[11] Tang Q L, Zhu Y J, Wu J, et al. Calcium phosphate drug nanocarriers with ultrahigh and adjustable drug-loading capacity: One-step synthesis, in situ drug loading and prolonged drug release[J]. Nanomedicine: Nanotechnology, Biology, and Medicine, 2011, 7(4): 428-434.
[12] Qi C, Zhu Y J, Zhao X Y, et al. High surface area carbonate apatite nanorod bundles: Surfactant-free sonochemical synthesis and drug loading and release properties[J]. Materials Research Bulletin, 2013, 48(4): 1536-1540.
[13] Lin K L, Wu C T. Chang J. Advances in synthesis of calcium phosphate crystals with controlled size and shape[J]. Acta Biomaterialia, 2014, 10 (10): 4071-4102.
[14] Chen F, Zhu Y J. Multifunctional Calcium Phosphate Nanostructured Materials and Biomedical Applications[J]. Current Nanoscience, 2014, 10: 465-485.
[15] Chen X, Tang Q L, Zhu Y J, et al. Synthesis and antibacterial property of zinc loaded hydroxyapatite nanorods[J]. Materials Letters, 2012, 89: 233-235.
[16] Zhao X Y, Zhu Y J, Chen F, et al. Calcium phosphate nanocarriers dual-loaded with bovine serum albumin and ibuprofen: facile synthesis, sequential drug loading and sustained drug release[J]. Chemistry-An Asian Journal, 2012, 7(7): 1610-1615.
[17] Cao S W, Zhu Y J, Wu J, et al. Preparation and sustained-release property of triblock copolymer/calcium phosphate nanocomposite as nanocarrier for hydrophobic drug[J]. Nanoscale Research Letters, 2010, 5(4): 781-785.
[18] Tang Q L, Zhu Y J, Duan Y R, et al. Porous nanocomposites of PEGPLA/ calcium phosphate: room-temperature synthesis and its application in drug delivery[J]. Dalton Transactions, 2010, 39(18): 4435-4439.
[19] Chen F, Zhu Y J, Zhang K H, et al. Europium-doped amorphous calcium phosphate porous nanospheres: preparation and application as luminescent drug carriers[J]. Nanoscale Research Letters, 2011, 6(1): 67-75.
[20] Wang K W, Zhu Y J, Chen F, et al. Calcium phosphate/block copolymer hybrid porous nanospheres: Preparation and application in drug delivery[J]. Materials Letters, 2010, 64(21): 2299-2301.
[21] Shang H B, Chen F, Wu J, et al. Multifunctional biodegradable terbiumdoped calcium phosphate nanoparticles: facile preparation, pHsensitive drug release and in vitro bioimaging[J]. RSC Advances, 2014, 4: 53122-53129.
[22] Zhou R, Xu W, Chen F, et al. Amorphous calcium phosphate nanospheres/ polylactide composite coated tantalum scaffold: Facile preparation, fast biomineralization and subchondral bone defect repair application[J]. Colloids and Surfaces B: Biointerfaces, 2014, 123: 236-245.
[23] Zhao X Y, Zhu Y J, Chen F, et al. Calcium phosphate hybrid nanoparticles: Self-assembly formation, characterization, and application as an anticancer drug nanocarrier[J]. Chemistry-An Asian Journal, 2013, 8 (6): 1306-1312.
[24] Chen F, Huang P, Zhu Y J, et al. Multifunctional Eu3+/Gd3+ dual-doped calcium phosphate vesicle-like nanospheres for sustained drug release and imaging[J]. Biomaterials, 2012, 33(27): 6447-6455.
[25] Ma M Y, Zhu Y J, Li L, et al Nanostructured porous hollow ellipsoidal capsules of hydroxyapatite and calcium silicate: preparation and application in drug delivery[J]. Journal of Materials Chemistry, 2008, 18(23): 2722-2727.
[26] Zhao X Y, Zhu Y J, Zhao J, et al. Hydroxyapatite nanosheet-assembled microspheres: Hemoglobin-templated synthesis and adsorption for heavy metal ions[J]. Journal of Colloid and Interface Science, 2014, 416: 11-18.
[27] Qi C, Zhu Y J, Lu B Q, et al. Hydroxyapatite nanosheet-assembled porous hollow microspheres: DNA-templated hydrothermal synthesis, drug delivery and protein adsorption[J]. Journal of Materials Chemistry, 2012, 22(42): 22642-22650.
[28] Lu B Q, Zhu Y J, Chen F. Highly flexible and nonflammable inorganic hydroxyapatite paper[J]. Chemistry-A European Journal, 2014, 20(5): 1242-1246.
[29] Lu B Q, Zhu Y J, Chen F, et al. Solvothermal transformation of a calcium oleate precursor into large-sized highly ordered arrays of ultralong hydroxyapatite microtubes[J]. Chemistry-A European Journal, 2014, 20 (23): 7116-7121.
[30] Ma M G, Zhu Y J, Chang J. Solvothermal preparation of hydroxyapatite microtubes in water/N, N-dimethylformamide mixed solvents[J]. Materials Letters, 2008, 62(10/11): 1642-1645.
[31] Chen F, Zhu Y J, Wang K W, et al. Surfactant-free solvothermal synthesis of hydroxyapatite nanowire/nanotube ordered arrays with biomimetic structures[J]. CrystEngComm, 2011, 13(6): 1858-1863.
[32] Zhu Y J, Chen F. Microwave-assisted preparation of inorganic nanostructures in liquid phase[J]. Chemical Reviews, 2014, 114: 6462-6555.
[33] Tang Q L, Wang K W, Zhu Y J, et al. Single-step rapid microwaveassisted synthesis of polyacrylamide-calcium phosphate nanocomposites in aqueous solution[J]. Materials Letters, 2009, 63(15): 1332-1334.
[34] Ma M G, Zhu Y J, Chang J. Monetite formed in mixed solvents of water and ethylene glycol and its transformation to hydroxyapatite[J]. Journal of Physical Chemistry B, 2006, 116: 14226-14230.
[35] Wang K W, Zhu Y J, Chen F, et al. Microwave-assisted synthesis of hydroxyapatite hollow microspheres in aqueous solution[J]. Materials Letters, 2011, 65(15/16): 2361-2363.
[36] Zhao X Y, Zhu Y J, Chen F, et al. Nanosheet-assembled hierarchical nanostructures of hydroxyapatite: surfactant-free microwavehydrothermal rapid synthesis, protein/DNA adsorption and pHcontrolled release[J]. CrystEngComm, 2013, 15(1): 206-212.
[37] Chen F, Li C, Zhu Y J, et al. Magnetic nanocomposite of hydroxyapatite ultrathin nanosheets/Fe3O4 nanoparticles: Microwave-assisted rapid synthesis and application in pH-responsive drug release[J]. Biomaterials Science, 2013, 1(10): 1074-1081.
[38] Wang K W, Zhu Y J, Chen X Y, et al. Flower-like hierarchically nanostructured hydroxyapatite hollow spheres: Facile preparation and application in anticancer drug cellular delivery[J]. Chemistry-An Asian Journal, 2010, 5(12): 2477-2482.
[39] Chen F, Huang P, Zhu Y J, et al. The photoluminescence, drug delivery and imaging properties of multifunctional Eu3+/Gd3+ dual-doped hydroxyapatite nanorods[J]. Biomaterials, 2011, 32(34): 9031-9039.
[40] Chen F, Tang Q L, Zhu Y J, et al. Hydroxyapatite nanorods/poly(vinyl pyrolidone) composite nanofibers, arrays and three-dimensional fabrics: Electrospun preparation and transformation to hydroxyapatite nanostructures[J]. Acta Biomaterialia, 2010, 6(8): 3013-3020.
[41] Ma Z, Chen F, Zhu Y J, et al. Amorphous calcium phosphate/poly(D, L-lactic acid) composite nanofibers: electrospinning preparation and biomineralization[J]. Journal of Colloid and Interface Science, 2011, 359(2): 371-379.
[42] Qi C, Zhu Y J, Zhao X Y, et al. Highly stable amorphous calcium phosphate porous nanospheres: Microwave-assisted rapid synthesis using ATP as phosphorus source and stabilizer, and their application in anticancer drug delivery[J]. Chemistry-A European Journal, 2013, 19(3): 981-987.
[43] Qi C, Tang Q L, Zhu Y J, et al. Microwave-assisted hydrothermal rapid synthesis of hydroxyapatite nanowires using adenosine 5'-triphosphate disodium salt as phosphorus source[J]. Materials Letters, 2012, 85: 71-73.
[44] Chen F, Huang P, Qi C, et al. Multifunctional biodegradable mesoporous microspheres of Eu3+-doped amorphous calcium phosphate: microwaveassisted preparation, pH-sensitive drug release, and bioimaging application[J]. Journal of Materials Chemistry B, 2014, 2: 7132-7140.
[45] Lu B Q, Zhu Y J, Chen F, et al. Core–shell hollow microspheres of magnetic iron oxide@amorphous calcium phosphate synthesis using adenosine 5'-triphosphate and application in pH-responsive drug delivery[J]. Chemistry -An Asian Journal, 2014, 9: 2908-2914.
[46] Zhao J, Zhu Y J, Zheng J Q, et al. Microwave-assisted hydrothermal preparation using adenosine 5'-triphosphate disodium salt as a phosphate source and characterization of zinc-doped amorphous calcium phosphate mesoporous microspheres[J]. Microporous and Mesoporous Materials, 2013, 180: 79-85.
[47] Qi C, Zhu Y J, Chen F. Microwave hydrothermal transformation of amorphous calcium carbonate nanospheres and application in protein adsorption[J]. ACS Applied Materials & Interfaces, 2014, 6(6): 4310-4320.
[48] Qi C, Zhu Y J, Chen F. Fructose 1,6-bisphosphate trisodium salt as a new phosphorus source for the rapid microwave synthesis of porous calcium-phosphate microspheres and their application in drug delivery[J]. Chemistry-An Asian Journal, 2013, 8(1): 88-94.
[49] Qi C, Huang J J, Chen F, et al. Synthesis, characterization and applications of calcium carbonate/fructose 1, 6-bisphosphate composite nanospheres and carbonated hydroxyapatite porous nanospheres[J]. Journal of Materials Chemistry B, 2014, 2: 8378-8389.
[50] Qi C, Zhu Y J, Lu B Q, et al. Hydroxyapatite hierarchically nanostructured porous hollow microspheres: rapid, sustainable microwavehydrothermal synthesis by using creatine phosphate as an organic phosphorus source and application in drug delivery and protein adsorption[J]. Chemistry-A European Journal, 2013, 19(17): 5332-5341.
[51] Chen F, Zhu Y J, Zhao X Y, et al. Solvothermal synthesis of oriented hydroxyapatite nanorod/nanosheet arrays using creatine phosphate as phosphorus source[J]. CrystEngComm, 2013, 15(22): 4527-4531.
[52] Zhao J, Zhu Y J, Cheng G F, et al. Microwave-assisted hydrothermal rapid synthesis of amorphous calcium phosphate nanoparticles and hydroxyapatite microspheres using cytidine 5'-triphosphate disodium salt as a phosphate source[J]. Materials Letters, 2014, 124: 208-211.
[53] Zhao X Y, Zhu Y J, Lu B Q, et al. Hydrothermal synthesis of hydroxyapatite nanorods using pyridoxal-5'-phosphate as a phosphorus source[J]. Materials Research Bulletin, 2014, 55: 67-70.
[54] Zhao X Y, Zhu Y J, Qi C, et al. Hierarchical hollow hydroxyapatite microspheres: microwave-assisted rapid synthesis by using pyridoxal-5'-phosphate as a phosphorus source and application in drug delivery[J]. Chemistry -An Asian Journal, 2013, 8(6): 1313-1320.
[55] Zhao X Y, Zhu Y J, Chen F, et al. Hydrothermal synthesis of hydroxyapatite nanorods and nanowires using riboflavin-5'-phosphate monosodium salt as a new phosphorus source and their application in protein adsorption[J]. CrystEngComm, 2013, 15(39): 7926-7935.
文章导航

/