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Low temperature aqueous precipitation of needle-like nanophase hydroxyapatite

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Abstract

The use of tissue engineered biodegradable porous scaffolds has become an important focus of the biomedical research field. The precursor materials used to form these structures play a vital role in their overall performance thus making the study and synthesis of these selected materials imperative. The authors present a comparison and characterisation of hydroxyapatite (HA), a popular calcium phosphate (CaP) biomaterial, synthesised by an aqueous precipitation (AP) method. The influence of various reaction conditions on the phase, crystallinity, particle size as well as morphology, molecular structure, potential in-vivo bioactivity and cell viability were assessed by XRD, SEM and TEM, FTIR, a simulated body fluid (SBF) test and a live/dead assay using MC3T3 osteoblast precursor cells, respectively. Naturally carbonated nanoparticles of HA with typically needle-like morphology were synthesised by the reported AP method. Initial pH was found to influence the crystallisation process and determine the CaP phase formed as well as the resultant particle and crystallite sizes. A marked change in particle morphology was also observed above pH 9. The use of toluene as a replacement solvent for water up to 60 % was found to reduce the crystallinity of as-synthesised HA. This has marked influence on the effect of ethanolamine (5 wt%), which was found to improve HA crystallinity. SEM and EDS were used to confirm the growth of carbonated apatite on the surface of HA pellets immersed in SBF for up to 28 days. Cell culture results revealed viable cells on all samples where pH was controlled and maintained at 10–11 during precipitation, including those that used ethanolamine and toluene in preparation. When the initial alkali pH was not maintained non-viable cells were observed on HA substrates.

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References

  1. Shepherd JH, Best SM. Calcium phosphate scaffolds for bone repair. JOM. 2011;63(4):83–92.

    Article  Google Scholar 

  2. Kumta PN, et al. Nanostructured calcium phosphates for biomedical applications: novel synthesis and characterization. Acta Biomater. 2005;1(1):65–83.

    Article  Google Scholar 

  3. Pramanik S, et al. Development of high strength hydroxyapatite by solid-state-sintering process. Ceram Int. 2007;33(3):419–26.

    Article  Google Scholar 

  4. Rao RR, Roopa HN, Kannan TS. Solid state synthesis and thermal stability of HAP and HAP - beta-TCP composite ceramic powders. J Mater Sci-Mater Med. 1997;8(8):511–8.

    Article  Google Scholar 

  5. Liu DM, Troczynski T, Tseng WJ. Water-based sol–gel synthesis of hydroxyapatite: process development. Biomaterials. 2001;22(13):1721–30.

    Article  Google Scholar 

  6. Bezzi G, et al. A novel sol–gel technique for hydroxyapatite preparation. Mater Chem Phys. 2003;78(3):816–24.

    Article  Google Scholar 

  7. Cunniffe GM, et al. The synthesis and characterization of nanophase hydroxyapatite using a novel dispersant-aided precipitation method. J Biomed Mater Res, Part A. 2010;95A(4):1142–9.

    Article  Google Scholar 

  8. Ferraz MP, Monteiro FJ, Manuel CM. Hydroxyapatite nanoparticles: a review of preparation methodologies. J Appl Biomater Biomech. 2004;2(2):74–80.

    Google Scholar 

  9. Wang PP, et al. Effects of synthesis conditions on the morphology of hydroxyapatite nanoparticles produced by wet chemical process. Powder Technol. 2010;203(2):315–21.

    Article  Google Scholar 

  10. Niu JL (2007) Hydrothermal synthesis of nano-crystalline hydroxyapatite. Bioceramics, Vol 19, Pts 1 and 2. 330–332: p. 247–250.

  11. Wang YJ, et al. Investigations on the formation mechanism of hydroxyapatite synthesized by the solvothermal method. Nanotechnology. 2006;17(17):4405–12.

    Article  Google Scholar 

  12. Lim GK, et al. Processing of hydroxyapatite via microemulsion and emulsion routes. Biomaterials. 1997;18(21):1433–9.

    Article  Google Scholar 

  13. Yang JH, et al. Synthesis of spherical hydroxyapatite granules with interconnected pore channels using camphene emulsion. J Biomed Mater Res Part B. 2011;99B(1):150–7.

    Article  Google Scholar 

  14. Rho JY, Kuhn-Spearing L, Zioupos P. Mechanical properties and the hierarchical structure of bone. Med Eng Phys. 1998;20(2):92–102.

    Article  Google Scholar 

  15. Zhang LJ, Webster TJ. Nanotechnology and nanomaterials: promises for improved tissue regeneration. Nano Today. 2009;4(1):66–80.

    Article  Google Scholar 

  16. Liu YK, et al. In vitro effects of nanophase hydroxyapatite particles on proliferation and osteogenic differentiation of bone marrow-derived mesenchymal stem cells. J Biomed Mater Res, Part A. 2009;90A(4):1083–91.

    Article  Google Scholar 

  17. Huang J, et al. In vitro assessment of the biological response to nano-sized hydroxyapatite. J Mater Sci-Mater Med. 2004;15(4):441–5.

    Article  Google Scholar 

  18. Sadat-Shojai M, et al. Synthesis methods for nanosized hydroxyapatite in diverse structures. Acta Biomaterialia. 2013;9(8):7591–621.

    Article  Google Scholar 

  19. Cardoso DA, Jansen JA, Leeuwenburgh SCG. Synthesis and application of nanostructured calcium phosphate ceramics for bone regeneration. J Biomed Mater Res Part B. 2012;100B(8):2316–26.

    Article  Google Scholar 

  20. Cao LY, Zhang CB, Huang HF. Synthesis of hydroxyapatite nanoparticles in ultrasonic precipitation. Ceram Int. 2005;31(8):1041–4.

    Article  Google Scholar 

  21. Kong LB, Ma J, Boey F. Nanosized hydroxyapatite powders derived from coprecipitation process. J Mater Sci. 2002;37(6):1131–4.

    Article  Google Scholar 

  22. Dorozhkin SV, Epple M. Biological and medical significance of calcium phosphates. Angewandte Chemie-International Edition. 2002;41(17):3130–46.

    Article  Google Scholar 

  23. Driessens FCM. Formation and stability of calcium phosphates in relation to the phase composition of the mineral in calcified tissue. In: DeGroot K, editor. Bioceramics of calcium phosphate. Florida: CRC Press; 1983. p. 1–33.

    Google Scholar 

  24. Jha LJ, et al. Preparation and characterization of fluoride-substituted apatites. J Mater Sci-Mater Med. 1997;8(4):185–91.

    Article  Google Scholar 

  25. Barralet J, Best S, Bonfield W. Carbonate substitution in precipitated hydroxyapatite: an investigation into the effects of reaction temperature and bicarbonate ion concentration. J Biomed Mater Res. 1998;41(1):79–86.

    Article  Google Scholar 

  26. Barralet JE, Best SM, Bonfield W. Preparation and sintering of carbonate-substituted apatite. Bioceramics. 1993;6:179–84.

    Google Scholar 

  27. Bigi A, Boanini E, Gazzano M. Ionic substitutions in calcium phosphates synthesized at low temperature. Acta Biomater. 2010;6(6):1882–94.

    Article  Google Scholar 

  28. Bouyer E, Gitzhofer F, Boulos MI. Morphological study of hydroxyapatite nanocrystal suspension. J Mater Sci-Mater Med. 2000;11(8):523–31.

    Article  Google Scholar 

  29. LeGeros RZ, et al. Zinc effect on the in vitro formation of calcium phosphates: relevance to clinical inhibition of calculus formation. Am J Dent. 1999;12(2):65–71.

    Google Scholar 

  30. Aoki H (1991) Science and medical applications of hydroxyapatite. Ishiyaku Euroamerica.

  31. Raynaud S, et al. Calcium phosphate apatites with variable Ca/P atomic ratio I. Synthesis, characterisation and thermal stability of powders. Biomaterials. 2002;23(4):1065–72.

    Article  Google Scholar 

  32. Pang YX, Bao X. Influence of temperature, ripening time and calcination on the morphology and crystallinity of hydroxyapatite nanoparticles. J Eur Ceram Soc. 2003;23(10):1697–704.

    Article  Google Scholar 

  33. Santos MH, et al. Synthesis control and characterization of hydroxyapatite prepared by wet precipitation process. Mater Res. 2004;7(4):625–30.

    Article  Google Scholar 

  34. Slosarczyk A, Paszkiewicz Z, Paluszkiewicz C. FTIR and XRD evaluation of carbonated hydroxyapatite powders synthesized by wet methods. J Mol Struct. 2005;744:657–61.

    Article  Google Scholar 

  35. Landi E, et al. Carbonated hydroxyapatite as bone substitute. J Eur Ceram Soc. 2003;23(15):2931–7.

    Article  Google Scholar 

  36. Kokubo T, Takadama H. How useful is SBF in predicting in vivo bone bioactivity? Biomaterials. 2006;27(15):2907–15.

    Article  Google Scholar 

  37. Panda RN, et al. FTIR, XRD, SEM and solid state NMR investigations of carbonate-containing hydroxyapatite nano-particles synthesized by hydroxide–gel technique. J Phys Chem Solids. 2003;64(2):193–9.

    Article  Google Scholar 

  38. Koutsopoulos S. Synthesis and characterization of hydroxyapatite crystals: a review study on the analytical methods. J Biomed Mater Res. 2002;62(4):600–12.

    Article  Google Scholar 

  39. Bohner M. Calcium orthophosphates in medicine: from ceramics to calcium phosphate cements. Inj-Int J Care Inj. 2000;31:S37–47.

    Article  Google Scholar 

  40. Afshar A, et al. Some important factors in the wet precipitation process of hydroxyapatite. Mater Des. 2003;24(3):197–202.

    Article  Google Scholar 

  41. Girija EK, et al. Role of material processing on the thermal stability and sinterability of nanocrystalline hydroxyapatite. Powder Technol. 2012;225:190–5.

    Article  Google Scholar 

  42. Salimi MN, et al. Effect of processing conditions on the formation of hydroxyapatite nanoparticles. Powder Technol. 2012;218:109–18.

    Article  Google Scholar 

  43. Gross KA, Berndt CC (1991) Thermal spraying of hydroxyapatite for bioceramic applications. International ceramic conference: Austceram 90, 53–5: p. 124–129.

  44. Liu DM. Fabrication of hydroxyapatite ceramic with controlled porosity. J Mater Sci-Mater Med. 1997;8(4):227–32.

    Article  Google Scholar 

  45. Rehman I, Bonfield W. Characterization of hydroxyapatite and carbonated apatite by photo acoustic FTIR spectroscopy. J Mater Sci-Mater Med. 1997;8(1):1–4.

    Article  Google Scholar 

  46. Legeros RZ, Bonel G, Legros R. Types of H2o in human enamel and in precipitated apatites. Calcif Tissue Res. 1978;26(2):111–8.

    Article  Google Scholar 

  47. Yin G, et al. Impacts of the surface charge property on protein adsorption on hydroxyapatite. Chem Eng J. 2002;87(2):181–6.

    Article  Google Scholar 

  48. Chen L, et al. The role of surface charge on the uptake and biocompatibility of hydroxyapatite nanoparticles with osteoblast cells. Nanotechnology. 2011;22(10):105708.

    Article  Google Scholar 

Download references

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Correspondence to Kajal K. Mallick.

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Cox, S.C., Jamshidi, P., Grover, L.M. et al. Low temperature aqueous precipitation of needle-like nanophase hydroxyapatite. J Mater Sci: Mater Med 25, 37–46 (2014). https://doi.org/10.1007/s10856-013-5042-y

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  • DOI: https://doi.org/10.1007/s10856-013-5042-y

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