Citation Information :
Rajula MP, Narayanan V, Venkatasubbu G, Ravishankar PL, Mani R. Optimization of Nanohydroxyapatite for Bone Tissue Engineering via Wet Chemical Precipitation Method. World J Dent 2024; 15 (3):228-234.
Aim: This study aims to investigate the impact of annealing temperature on the physicochemical properties of chemically precipitated nanohydroxyapatite (nHA). Understanding how annealing parameters influence the crystallinity, morphology, and surface chemistry of HA nanoparticles is crucial for optimizing their performance and functionality in various biomedical applications.
Materials and methods: Nanohydroxyapatite were synthesized using a wet chemical coprecipitation method with high-purity reagents. This involved slowly adding an aqueous phosphoric acid (H3PO4) suspension to a stirred aqueous calcium hydroxide [Ca(OH)2] suspension at room temperature. The resulting precipitate (as-prepared nHA) was then washed and dried in an oven. Subsequently, the nHA was divided into separate groups and annealed at different temperatures (200, 400, and 600°C) for 3 hours in a furnace with subsequent cooling. The samples, including as-prepared and those annealed at 200, 400, and 600°C, underwent comprehensive characterization using high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopic analysis (EDAX), X-ray diffraction (XRD), and Fourier-transform infrared (FTIR).
Results: The HRTEM analysis revealed rod-shaped nHA crystals with agglomeration, and annealing led to increased particle proximity and rounding of crystal tips. EDAX confirmed the stoichiometric composition of calcium (Ca), phophorus (P), and oxygen (O) without impurities. XRD analysis showed distinct peaks for as-prepared HA and enhanced crystallinity in annealed samples. FTIR identified characteristic vibrational modes, including phosphate (PO43−) and carbonate ions (CO32−), indicating high-purity HA.
Conclusion: This study successfully employed wet chemical coprecipitation to synthesize crystalline nHA nanoparticles with rod-like morphologies. Annealing temperature significantly impacted their morphology, crystallinity, and functional groups, as observed through various characterization techniques. These observations highlight the potential of annealing for tailoring nHA properties, paving the way for further exploration in this field.
Clinical significance: The need for improved bone regeneration solutions remains a major challenge in both orthopedics and dentistry. The development of nHA suitable for bone regeneration addresses a critical need in enhancing the effectiveness of bone grafts. By achieving precise control over the nanoparticles’ crystal structure and chemical composition, this approach holds the potential to meet specific clinical requirements. Moreover, the cost-effectiveness of tailoring nHA holds significant translational value, paving the way for future advancements in biofunctionalization and the development of efficient bone repair solutions.
Sadat-Shojai M, Khorasani MT, Dinpanah-Khoshdargi E, et al. Synthesis methods for nanosized hydroxyapatite with diverse structures. Acta Biomater 2013;9(8):7591–7621. DOI: 10.1016/j.actbio.2013.04.012
Silver FH, Christiansen DL, Silver FH, et al. Introduction to biomaterials science and biocompatibility. Springer, New York; 1999.
Kolmas J, Krukowski S, Laskus A, et al. Synthetic hydroxyapatite in pharmaceutical applications. Ceram Int 2016;42(2):2472–2487. DOI: 10.1016/j.ceramint.2015.10.048
Ferraz MP, Monteiro FJ, Manuel CM. Hydroxyapatite nanoparticles: a review of preparation methodologies. J Appl Biomater Biomech 2004;2(2):74–80. DOI: 10.1177/228080000400200202
Zhou H, Lee J. Nanoscale hydroxyapatite particles for bone tissue engineering. Acta Biomater 2011;7(7):2769–2781. DOI: 10.1016/j.actbio.2011.03.019
Bezzi G, Celotti G, Landi E, et al. A novel sol–gel technique for hydroxyapatite preparation. Mater Chem Phy 2003;78(3):816–824. DOI: 10.1016/S0254-0584(02)00392-9
Poinern GE, Brundavanam RK, Mondinos N, et al. Synthesis and characterisation of nanohydroxyapatite using an ultrasound assisted method. Ultrason Sonochem 2009;16(4):469–474. DOI: 10.1016/j.ultsonch.2009.01.007
Liu HS, Chin TS, Lai LS, et al. Hydroxyapatite synthesized by a simplified hydrothermal method. Ceram Int 1997;23(1):19–25. DOI: 10.1016/0272-8842(95)00135-2
Toriyama M, Ravaglioli A, Krajewski A, et al. Synthesis of hydroxyapatite-based powders by mechano-chemical method and their sintering. J Eur Ceram Soc 1996;16(4):429–436. DOI: 10.1016/0955-2219(95)00123-9
Bose S, Saha SK. Synthesis and characterization of hydroxyapatite nanopowders by emulsion technique. Chem Mater 2003;15(23):4464–4469. DOI: 10.1021/cm0303437
Mishra VK, Srivastava SK, Asthana BP, et al. Structural and spectroscopic studies of hydroxyapatite nanorods formed via microwave-assisted synthesis route. J Am Ceram Soc 2012;95(9):2709–2715. DOI: 10.1111/j.1551-2916.2012.05134.x
S’lo'sarczyk A, Paszkiewicz Z, Paluszkiewicz C. FTIR and XRD evaluation of carbonated hydroxyapatite powders synthesized by wet methods. J Mol Struct 2005;744–747:657–661. DOI: 10.1016/j.molstruc.2004.11.078
Rodríguez-Lugo V, Angeles-Chavez C, Mondragon G, et al. Synthesis and structural characterization of hydroxyapatite obtained from CaO and CaHP04 by a hydrothermal method. Mater Res Innov 2005;9(1):20–22. DOI: 10.1080/14328917.2005.11784875
Tang XL, Xiao XF, Liu RF. Structural characterization of silicon-substituted hydroxyapatite synthesized by a hydrothermal method. Mater Lett 2005;59(29–30):3841–3846. DOI: 10.1016/j. matlet.2005.06.060
Rodríguez-Lugo V, Karthik TV, Mendoza-Anaya D, et al. Wet chemical synthesis of nanocrystalline hydroxyapatite flakes: effect of pH and sintering temperature on structural and morphological properties. Royal Soc Open Sci 2018;5(8). DOI: 10.1098/rsos.180962
Venkatasubbu GD, Ramasamy S, Ramakrishnan V, et al. Hydroxyapatite-alginate nanocomposite as drug delivery matrix for sustained release of ciprofloxacin. J Biomed Nanotechnol 2011;7(6):759–767. DOI: 10.1166/jbn.2011.1350
Loo SC, Siew YE, Ho S, et al. Synthesis and hydrothermal treatment of nanostructured hydroxyapatite of controllable sizes. J Mater Sci Mater Med 2008;19(3):1389–1397. DOI: 10.1007/s10856-007-3261-9
Mateus AYP, Ferraz MP, Monteiro FJ. Microspheres based on hydroxyapatite nanoparticles aggregates for bone regeneration. Key Eng Mater 2007;330–332:243–246. DOI: 10.4028/www.scientific.net/KEM.330-332.243
Scherrer P. Nachrichten von der Gesellschaft der Wissenschaften zu Göttingen. Mathematisch-Physikalische Klasse 1918;2:98–100. DOI: 10.1590/sajs.2013/a0019
Porter JR, Ruckh TT, Popat KC. Bone tissue engineering: a review in bone biomimetics and drug delivery strategies. Biotechnol Prog 2009;25(6):1539–1560. DOI: 10.1002/btpr.246
Dorozhkin SV. Calcium Orthophosphates: Applications in Nature, Biology, and Medicine. Florida, USA: CRC Press; 2012.
Kehoe S. Optimisation of hydroxyapatite (HAp) for orthopaedic application via the chemical precipitation technique (Doctoral dissertation, Dublin City University).
Subramanian R, Murugan P, Chinnadurai G, et al. Experimental studies on caffeine mediated synthesis of hydroxyapatite nanorods and their characterization. Mater Res Express 2020;7(1):015022. DOI: 10.1088/2053-1591/ab619a
Venkatasubbu GD, Ramasamy S, Avadhani GS, et al. Size-mediated cytotoxicity of nanocrystalline titanium dioxide, pure and zinc-doped hydroxyapatite nanoparticles in human hepatoma cells. J Nanoparticle Res 2012;14:1–8. DOI: 10.1007/s11051-012-0819-3
Sebastiammal S, Fathima AS, Devanesan S, et al. Curcumin-encased hydroxyapatite nanoparticles as novel biomaterials for antimicrobial, antioxidant and anticancer applications: a perspective of nano-based drug delivery. J Drug Deliv Sci Technol 2020;57:101752. DOI: 10.1016/j.jddst.2020.101752
Salarian M, Solati-Hashjin M, Shafiei SS, et al. Surfactant-assisted synthesis and characterization of hydroxyapatite nanorods under hydrothermal conditions. Mater Sci-Poland 2009;27(4/1):961–971.
Azzaoui K, Lamhamdi A, Mejdoubi E, et al. Synthesis of nanostructured hydroxyapatite in presence of polyethylene 1000glycol. J Chem Pharm Res 2013;5(12):1209–1216.
Abidi SS, Murtaza Q. Synthesis and characterization of nano-hydroxyapatite powder using wet chemical precipitation reaction. J Mater Sc Technol 2014;30(4):307–310. DOI: 10.1016/j.jmst.2013.10.011
Arami H, Mohajerani M, Mazloumi M, et al. Rapid formation of hydroxyapatite nanostrips via microwave irradiation. J Alloy Compound 2009;469(1–2):391–394. DOI: 10.1016/j.jallcom.2008.01.116
Li L, Liu Y, Tao J, et al. Surface modification of hydroxyapatite nano crystallite by a small amount of terbium provides a biocompatible fluorescent probe. J Phy Chem C 2008;112(32):12219–12224. DOI: 10.1021/jp8026463
Ficai A, Andronescu E, Voicu G, et al. Self-assembled collagen/hydroxyapatite composite materials. Chem Eng J 2010;160(2):794–800. DOI: 10.1016/j.cej.2010.03.088