Colloidal Hydroxyapatite/Poly(Acrylic Acid) Hybrids Using Calcium Sucrate and Ammoniumdihydrogen Orthophosphate


  • W.P.S.L. Wijesinghe Department of Chemistry, Faculty of Science, University of Peradeniya
  • M.M.M.G.P.G. Mantilaka Department of Chemistry, Faculty of Science, University of Peradeniya
  • A.M.C.P. Weerasinghe Department of Botany, Faculty of Science, University of Peradeniya
  • K.M. Nalin de Silva Sri Lanka Institute of Nanotechnology, Nanotechnology and Science Park, Mahenwatta, Pitipana, Homagama
  • T.P. Gamagedara Department of Chemistry, Faculty of Science, University of Peradeniya
  • R.M.G. Rajapakse Postgraduate Institute of Science, University of Peradeniya



Hydroxyapatite, Poly(acrylic acid), Stable colloids, Hybrid materials, Calcium sucrate.


This manuscript is concerned with a simple and novel method to synthesize hydroxyapatite-poly(acylic acid) hybrid materials for broad range of applications. In this method, hydroxyapatite nanoparticles are synthesized using calcium sucrate and ammoniumdihydrogen orthophosphate in the presence of poly(acrylic acid). Increase in poly(acrylic acid) concentration in the synthesis medium results in the increase in the hydrodynamic radius of particle size allowing increased hydration. Poly(acylic acid) tends to control both crystallite size and colloidal stability. Increase in poly(acrylic acid) concentration decreases the crystallite size of the products but considerably increases their shelf life as stable colloidal solutions. Thermo gravimetric analysis shows that there are no combustible or volatile impurities present in these samples. This is further supported by FT-IR studies, which show three types of interactions between hydroxyapatite nanoparticles and poly(acrylic acid).


[1] Li C, Li G, Liu S, bai J, Zhang A. Spherical hydroxyapatite with colloidal stability prepared in aqueous solutions containing polymer/surfactant pair, Colloid Surf A 2010; 366: 27-33.
[2] Xiao XF, Liu RF. Effect of suspension stability on electrophoretic deposition of hydroxyapatite coatings , Mater Lett 2006; 60: 2627-32.
[3] Malmsten M, Zauscher S. Colloids and surfaces in biology, Curr Opin In 2013; 18: 379-80.
[4] Shojaia MS, Ataia M, Nodehia A, Khanlar LN. Hydroxyapatite nanorods as novel fillers for improving the properties of dental adhesives: Synthesis and application, Dent Mater 2010; 26: 471-82.
[5] Zhou R, Si S, Zhang Q. Water-dispersible hydroxyapatite nanoparticles synthesized in aqueous solution containing grape seed extract, Appl Surf Sci 2012; 258: 3578-83.
[6] Han Y, Li S, Wang X, Bauer I, Yin M. Sonochemical preparation of hydroxyapatite nanoparticles stabilized by glycosaminoglycans, Ultrason Sonochem 2007; 14: 286-90.
[7] Cengiz B, Gokce Y, Yildiz N, Aktas Z, Calimli A. Synthesis and characterization of hydroxyapatite nanoparticles. Colloid Surf A 2008; 32: 229-33.
[8] Peters F, Schwarz K, Epple M. The structure of bone studied with synchrotron X-ray diffraction, X-ray absorption spectroscopy, thermal analysis, Thermochim Acta 2000; 361: 131-8.
[9] Paschalis EP, Carlo ED, Betts F, Sherman P, Mendelsohn R, Boskey AL. FTIR Microspectroscopic analysis of human osteonal bone. Calcif Tissue Int 1996; 59: 480-7.
[10] Tseng Y, Kuo C, Li Y, Huang C. Polymer-assisted synthesis of hydroxyapatite nanoparticle, Mater Sci Eng C 2009; 29: 819-22.
[11] Habraken WJEM, Wolke JGC, Jansen JA. Ceramic composites as matrices and scaffolds for drug delivery in tissue engineering, Adv Drug Deliver Rev 2007; 59: 234-48.
[12] Zhi S, Wan L, Xu Z. Poly(vinylidene fluoride)/poly(acrylic acid)/calcium carbonate composite membranes via mineralization, J Membrane Sci 2014; 454: 144-54.
[13] Liou S, Chen S, Liu D. Synthesis and characterization of needle like apatitic nanocomposite with controlled aspect ratios. Biomaterials 2003; 24: 3981-8.
[14] Niu X, Feng Q, Wang M, Guo X, Zheng Q. Porous nanoHA/collagen/PLLA scaffold containing chitosan microspheres for controlled delivery of synthetic peptide derived from BMP- 2, J Controll Release 2009; 134: 111–7.
[15] Esfahani SR, Khorasani S, Lu Z, Appleyard R, Zreiqat H. The influence hydroxyapatite nanoparticle shape and size on the properties of biphasic calcium phosphate scaffolds coated with hydroxyapatite PCL composites, Biomaterials 2010; 31: 5498-509.
[16] Peter M, Ganesh N, Selvamurugan N, Nair SV, Furuike T, Tamura H, Jayakumar R. Preparation and characterization of chitosan–gelatin/nanohydroxyapatite composite scaffolds for tissue engineering applications, Carbohyd Polym 2010; 80: 687-94.
[17] Mohamed KR, El-Rashidy ZM, Salama AA. Preparation and characterization of nano hydroxyapatite/polymeric composites materials. Part I, Mater Chem Phys 2011;130: 561-8.
[18] Hentze HP, Antonietti M. Porous polymers and resins for biotechnological and biomedical applications. Rev Mol Biotechnol 2002; 90: 27-53.
[19] Murugan R, Ramakrishna S. Development of nanocomposites for bone grafting Compos Sci Technol 2005; 65: 2385-406.
[20] Asran AS, Henning S, Michler GH. Polyvinyl alcohol– collagen–hydroxyapatite biocomposite nanofibrous scaffold: Mimicking the key features of natural bone at the nanoscale level. Polymer 2010; 51: 868-76.
[21] Lee S, Shin H. Matrices and scaffolds for delivery of bioactive molecules in bone and cartilage tissue engineering. Adv Drug Deliver Rev 2007; 59: 339-59.
[22] Heinemann S, Rössler S, Lemm M, Ruhnow M, Nies B. Properties of injectable ready-to-use calcium phosphate cement based on water-immiscible liquid. Acta Biomater 2013; 9: 6199-207.
[23] Luo J, Qiu S, Zhou X, Lai R, Dong P, Xie X. In situ grafting polyethylene glycol chains onto amorphous calcium phosphate nanoparticles to improve the storage stability and organic solvent redispersibility. Colloid Surface A 2014; 444: 81-8.
[24] Adnadjevic B, Jovanovic J. A comparative kinetics study of isothermal drug release from poly(acrylic acid) and poly(acrylic-co-methacrylic acid) hydrogels. Colloid Surface B 2009; 69: 31-42.
[25] Nho Y, Park Jk, Lim Y. Preparation of poly(acrylic acid) hydrogel by radiation crosslinking and its application for mucoadhesives. Polymer 2014; 6: 890-8.
[26] Chena W, Jub C, Wanga J, Hunga C, Lin JC. Brittle and ductile adjustable cement derived from calcium phosphate cement/polyacrylic acid composites. Dent Mater 2008; 24: 1616-22.
[27] Es-Souni M, Brandies HF, Zaporojshenko V. On the interaction of polyacrylic acid as a conditioning agent with bovine enamel. Biomaterials 2002; 23: 2871-8.
[28] Witono JR, Noordergraaf IW, Heeres HJ, Janssen LPBM. Water absorption, retention and the swelling characteristics of cassava starch grafted with polyacrylic acid. Carbohyd Polym 2014; 103: 325-32.
[29] Hosseinzadeh H, Sadeghzadeh M, Babazadeh M. Preparation and properties of carrageenan-g-poly(acrylic acid)/bentonite superabsorbent composite. J Biomater Nanobiotechnol 2011; 2: 311-7.
[30] Mantilaka MMMGPG, Karunaratne DGGP, Rajapakse RMG, Pitawala HMTGA. Precipitated calcium carbonate/ poly(methyl methacrylate) nanocomposite using dolomite: synthesis, characterization and properties. Powder Technol 2013; 235: 628-32.
[31] Mantilaka MMMGPG, Pitawala HMTGA, Rajapakse RMG, Karunaratne DGGP. Upul Wijayantha KG. Formation of hollow bone-like morphology of calcium carbonate on surfactant/polymer templates. J Cryst Growth 2014; 392: 52- 9.
[32] Mantilaka MMMGPG, Pitawala HMTGA, Karunaratne, DGGP Rajapakse RMG. Nanocrystalline magnesium oxide from dolomite via poly(acrylate) stabilized magnesium hydroxide colloids. Colloid Surface A 2014; 443: 201-8.
[33] Mantilaka MMMGPG, Wijesinghe WPSL, Pitawala HMTGA, Rajapakse RMG, Karunaratne DGGP. Surfactant-assisted synthesis of pure calcium carbonate nanoparticles from Sri Lankan dolomite. J Natn Sci Foundation Sri Lanka 2014; 42: 221-8.
[34] Dorozhkin SV. Amorphous calcium (ortho)phosphates. Acta Biomater 2010; 6: 4457-75.
[35] Mantilaka MMMGPG, Rajapakse RMG, Pitawala HMTGA, Karunaratne, DGGP. Preparation of amorphous calcium carbonate nanoparticles from impure dolomitic marble with the aid of poly(acrylic acid) as a stabilizer. Adv Powder Technol 2014; 25: 591-8.
[36] Wijesinghe WPSL, Mantilaka MMMGPG, Premalal EVA, et al. Facile synthesis of both needle-like and spherical hydroxyapatite nanoparticles: Effect of synthetic temperature and calcination on morphology, crystallite size and crystallinity. Mater Sci Eng C 2014; 42: 83-90.
[37] 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: 1697-704.
[38] Gu C, Katti DR, Katti KS. Photoacoustic FTIR spectroscopic study of undisturbed human cortical bone. Spectrochim Acta A 2013; 103: 25-37.
[39] El-Bahy GS, Abdelrazek EM, Allam MA, Hezma AM. Characterization of in situ prepared nanohydroxyapatite/polyacrylic acid (HAp/PAAc) biocomposites. J Appl Polym Sci 2011; 122: 3270-6.
[40] Katti KS, Turlapati P, Verma D, Bhowmik R, Gujjula PK, Katti DR. Static and dynamic mechanical behavior of hydroxyapatite-polyacrylic acid composites under simulated body fluid. Am J Biochem Biotechnol 2006; 2: 73-9.
[41] Liu Q, Wijn JR, Blitterswijk CAV. Nano-apatite/polymer composites: mechanical and physicochemical characteristics. Biomaterials 1997; 18: 1263-70.
[42] Wang P, Li C, Gong H, Jiang X, Wang H, Li K. Effects of synthesis conditions on the morphology of hydroxyapatite nanoparticles produced by wet chemical process. Powder Technol 2010; 203: 315-21.
[43] Bhowmik R, Katti KS, Katti D. Molecular dynamics simulation of hydroxyapatite polyacrylic acid interfaces. Polymer 2007; 48: 664-74.






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