doi:

DOI: 10.3724/SP.J.1077.2014.13532

Journal of Inorganic Materials (无机材料学报) 2014/29:7 PP.769-775

Synthesis and Characterization of Copper-substituted Hydroxyapatite Micrspheres


Abstract:
As the second essential trace element in human body, copper plays vital roles in metabolism and antimicrobial. Therefore, synthesis of copper-substituted hydroxyapatite (Cu-HA) is expected to create bioceramics with improved biological and antimicrobial properties. In this study, Cu-HA was prepared by hydrothermal reactions using Ca(NO3)2·4H2O, Cu(NO3)2·3H2O and Na2HPO4·12H2O. Products were characterized by scanning electron microscope, transmission electron microscope, X-ray diffraction, Fourier transform infrared spectroscope and atomic absorption spectrometry. Results show that copper is incorporated into the HA crystals. Correspondingly, the products retain a HA structure but their morphologies transform from ribbons to flower-like microspheres. Moreover, when Cu/(Cu+Ca) (molar ratio) of the reaction solution is greater than 0.05, the thermal stability of the HA product is decreased.

Key words:hydroxyapatite,copper substitution,microspheres,hydrothermal synthesis

ReleaseDate:2016-07-11 11:25:05



[1] VALLET-REGí M, GONZáLEZ-CALBET J M. Calcium phosphates as substitution of bone tissues. Progress in Solid State Chemistry, 2004, 32(1): 1-31.

[2] FRAGA C G. Relevance, essentiality and toxicity of trace elements in human health. Molecular Aspects of Medicine, 2005, 26(4): 235-244.

[3] HU G. Copper stimulates proliferation of human endothelial cells under culture. Journal of Cellular Biochemistry, 1998, 69(3): 326-335.

[4] RODRíGUEZ J P, RIOS S, GONZALEZ M. Modulation of the proliferation and differentiation of human mesenchymal stem cells by copper. Journal of Cellular Biochemistry, 2002, 85(1): 92-100.

[5] STRAUSE L, SALTMAN P, GLOWACKI J. The effect of deficiencies of manganese and copper on osteoinduction and on resorption of bone particles in rats. Calcified Tissue International, 1987, 41(3): 145-150.

[6] MEHTAR S, WIID I, TODOROV S D. The antimicrobial activity of copper and copper alloys against nosocomial pathogens and Mycobacterium tuberculosis isolated from healthcare facilities in the Western Cape: an in-vitro study. Journal of Hospital Infection, 2008, 68(1): 45-51.

[7] STANI? V, DIMITRIJEVI? S, ANTI?-STANKOVI? J, et al. Synthesis, characterization and antimicrobial activity of copper and zinc-doped hydroxyapatite nanopowders. Applied Surface Science, 2010, 256(20): 6083-6089.

[8] POGOSOVA M A, KAZIN P E, TRETYAKOV Y D. Synthesis and characterisation of copper doped Ca-Li hydroxyapatite. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 2012, 284: 33-35.

[9] LI JI-DONG, LI YU-BAO, ZUO Yi, et al. Preparation and antibacterial properties valuation of copper-substituted nano-hydroxyapatite. Functional Materials, 2006, 37(4): 635-638.

[10] LI Y, HO J, OOI C P. Antibacterial efficacy and cytotoxicity studies of copper (II) and titanium (IV) substituted hydroxyapatite nanoparticles. Materials Science and Engineering: C, 2010, 30(8): 1137-1144.

[11] LI J, LI Y, ZHANG L, et al. Composition of calcium deficient Na-containing carbonate hydroxyapatite modified with Cu (II) and Zn (II) ions. Applied Surface Science, 2008, 254(9): 2844-2850.

[12] LIU J, YE X, WANG H, et al. The influence of pH and temperature on the morphology of hydroxyapatite synthesized by hydrothermal method. Ceramics international, 2003, 29(6): 629-633.

[13] JOKI? B, MITRI? M, RADMILOVI? V, et al. Synthesis and characterization of monetite and hydroxyapatite whiskers obtained by a hydrothermal method. Ceramics International, 2011, 37(1): 167-173.

[14] JEMAL J, TOUNSI H, CHAARI K, et al. NO reduction with NH3 under oxidizing atmosphere on copper loaded hydroxyapatite. Applied Catalysis B: Environmental, 2012, 113: 255-260.

[15] CORAMI A, D’ACAPITO F, MIGNARDI S, et al. Removal of Cu from aqueous solutions by synthetic hydroxyapatite: EXAFS investigation. Materials Science and Engineering: B, 2008, 149(2): 209-213.

[16] GADALETA S J, PASCHALIS E P, CAMACHO N P, et al. Fourier Transform Infrared Spectroscopy of Synthetic and Bbiological Apatites. In: Amjad Z, editor. Mineral Scale Formation and Inhibition. New York: Plenum Press, 1995: 283-294.

[17] KLEE W E, ENGEL G. Infrared spectra of the phosphate ions in various apatites. Journal of Inorganic Nuclear Chemistry, 1970, 32(6): 1837-1843.

[18] ?LóSARCZYK A, PASZKIEWICZ Z, PALUSZKIEWICZ C. FTIR and XRD evaluation of carbonated hydroxyapatite powders synthesized by wet methods. Journal of Molecular Structure, 2005, 744: 657-661.

[19] MEYER J L, FOWLER B O. Lattice defects in nonstoichiometric calcium hydroxylapatites: a chemical approach. Inorganic Chemistry, 1982, 21(8): 3029-3035.

[20] LAFON J P, CHAMPION E, BERNACHE-ASSOLLANT D. Processing of AB-type carbonated hydroxyapatite Ca10-x(PO4)6-x (CO3)x(OH)2-x-2y(CO3)y, ceramics with controlled composition. Journal of the European Ceramic Society, 2008, 28(1): 139-147.

[21] WENK H R, HEIDELBACH F. Crystal alignment of carbonated apatite in bone and calcified tendon: results from quantitative texture analysis. Bone, 1999, 24(4): 361-369.

[22] KAWASAKI T, NIIKURA M, KOBAYASHI Y. Fundamental study of hydroxyapatite high-performance liquid chromatography. III, Direct experimental confirmation of the existence of two types of absorbing surface on the hydroxyapatite crystal. Journal of Chromatography A, 1990, 515: 125-148.

[23] BARAVELLI S, BIGI A, RIPAMONTI A, et al. Thermal behavior of bone and synthetic hydroxyapatites submitted to magnesium interaction in aqueous medium. Journal of Inorganic Biochemistry, 1984, 20(1): 1-12.

[24] LI Z Y, LAM W M, YANG C, et al. Chemical composition, crystal size and lattice structural changes after incorporation of strontium into biomimetic apatite. Biomaterials, 2007, 28(7): 1452-1460.

[25] GALERA MARTíNEZ M, PHAM MINH D, Weiss-Hortala E, et al. Synthesis, characterization, and thermo-mechanical properties of copper-loaded apatitic calcium phosphates. Composite Interfaces, 2013, 20(8): 647-660.

[26] GINEBRA M P, FERNANDEZ E, DE MAEYER E A P, et al. Setting reaction and hardening of an apatitic calcium phosphate cement. Journal of Dental Research, 1997, 76(4): 905-912.

[27] NEIRA I S, KOLEN’KO Y V, LEBEDEV O I, et al. An effective morphology control of hydroxyapatite crystals via hydrothermal synthesis. Crystal Growth and Design, 2009, 9(1): 466-474.

[28] LU X, WANG Y, WANG J, et al. Calcium phosphate crystal growth under controlled environment through urea hydrolysis. Journal of crystal growth, 2006, 297(2): 396-402.

[29] WANG Y, HASSAN M S, GUNAWAN P, et al. Polyelectrolyte mediated formation of hydroxyapatite microspheres of controlled size and hierarchical structure. Journal of Colloid and Interface Science, 2009, 339(1): 69-77.

[30] HE Q J, HUANG Z L. Template-directed growth and characterization of flowerlike porous carbonated hydroxyapatite spheres. Crystal Research and Technology, 2007, 42(5): 460-465.

[31] YANG L X, YIN J J, WANG L L, et al. Hydrothermal synthesis of hierarchical hydroxyapatite: preparation, growth mechanism and drug release property. Ceramics International, 2012, 38(1): 495-502.

[32] MAYER I, CUISINIER F J G, GDALYA S, et al. TEM study of the morphology of Mn2+ doped calcium hydroxyapatite and β-tricalcium phosphate. Journal of Inorganic Biochemistry, 2008, 102(2): 311-317.

[33] BOANINI E, GAZZANO M, BIGI A. Ionic substitutions in calcium phosphates synthesized at low temperature. Acta biomaterialia, 2010, 6(6): 1882-1894.

[34] ZHANG Y, DAWE R A. Influence of Mg2+ on the kinetics of calcite precipitation and calcite crystal morphology. Chemical Geology, 2000, 163(1): 129-138.

[35] WANG F, GUO Y, WANG H, et al. Facile preparation of hydroxyapatite with a three dimensional architecture and potential application in water treatment. CrystEngComm, 2011, 13(19): 5634-5637.