Colloid and Polymer Science

, Volume 296, Issue 9, pp 1491–1499 | Cite as

Hydroxyapatite coated poly(lactic acid) microparticles with copper ion doping prepared via the Pickering emulsion route

  • Cho Yin Tham
  • Wen Shyang ChowEmail author
Original Contribution


This work aimed to integrate the ionic substitution feature of hydroxyapatite nanoparticles (HAps) on poly(lactic acid) (PLA) surfaces. HAp-coated PLA microparticles were prepared through the Pickering emulsion route. HAps with adequate surface charge and aggregate size were prepared in a 0.1-M salt dispersion in order to induce oil-water interfacial adsorption of HAps in a Pickering emulsion. A batch sorption process was conducted to evaluate the potential of HAp-coated PLA microparticles to be loaded with copper ions. The concentration of Cu2+ in the supernatant phase was measured by atomic adsorption spectroscopy and their adsorption capacity was determined. The copper ion (Cu2+) adsorption capacity of the microparticles increased with (a) the quantity of HAps adsorbed (consistently increased with HAp solid content) and (b) higher initial Cu2+ concentration of the doping medium. In conclusion, HAp-coated PLA microparticles with the ion doping feature were successfully prepared through the Pickering emulsion route.


Poly(lactic acid) Hydroxyapatite Microparticle Emulsion 



We gratefully acknowledged the financial support provided by Research University grant (RUI, 1001/PBAHAN/814199) from Universiti Sains Malaysia.


This study was funded by Universiti Sains Malaysia (grant number RUI, 1001/PBAHAN/814199).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Huang Y, Zhang X, Zhao R, Mao H, Yan Y, Pang X (2015) Antibacterial efficacy, corrosion resistance, and cytotoxicity studies on copper-substituted carbonated hydroxyapatite coating on titanium substrate. J Mater Sci 50(4):1688–1700CrossRefGoogle Scholar
  2. 2.
    Li Y, Ho J, Ooi CP (2010) Antibacterial efficacy and cytotoxicity studies of copper (II) and titanium (IV) substituted hydroxyapatite nanoparticles. Mater Sci Eng C 30(8):1137–1144CrossRefGoogle Scholar
  3. 3.
    Yang L, Perez-Amodio S, FYFB-d G, Everts V, Blitterswijk CAC, Habibovic P (2010) The effects of inorganic additives to calcium phosphate on in vitro behavior of osteoblasts and osteoclasts. Biomaterials 31:2976–2989CrossRefPubMedGoogle Scholar
  4. 4.
    Ewald A, Käppel C, Vorndran E, Moseke C, Gelinsky M, Gbureck U (2012) The effect of Cu(II)-loaded brushite scaffolds on growth and activity of osteoblastic cells. J Biomed Mater Res A 100(9):2392–2400PubMedGoogle Scholar
  5. 5.
    Barralet J, Gbureck U, Habibovic P, Vorndran E, Gerard C, Doillon CJ (2009) Angiogenesis in calcium phosphate scaffolds by inorganic copper ion release. Tissue Eng A 15(7):1601–1609CrossRefGoogle Scholar
  6. 6.
    Lima IRD, Alves GG, Soriano CA, Campaneli AP, Gasparoto TH, Junior ESR, Sean LÁD, Rossi AM, Granjeiro JM (2011) Understanding the impact of divalent cation substitution on hydroxyapatite: an in vitro multiparametric study on biocompatibility. J Biomed Mater Res A 98A:351–358CrossRefGoogle Scholar
  7. 7.
    Ho ML, Fu YC, Wang GJ, Chen HT, Chang JK, Tsai TH, Wang CK (2008) Controlled release carrier of BSA made by W/O/W emulsion method containing PLGA and hydroxyapatite. J Control Release 128(2):142–148CrossRefPubMedGoogle Scholar
  8. 8.
    Zhu Y, Wang Z, Zhou H, Li L, Zhu Q, Zhang P (2017) An injectable hydroxyaptite/poly(lactide-co-glycolide) composites reinforced by micro/nano-hybrid poly(glycolide). Mater Sci Eng C 80:326–334CrossRefGoogle Scholar
  9. 9.
    Nagata F, Miyajima T, Kato K (2016) Preparation of phylloquinone-loaded poly(lactic acid)/hydroxyapatite core-shell particles and their drug release behavior. Adv Powder Technol 27(3):903–907CrossRefGoogle Scholar
  10. 10.
    Wang X, Song G, Lou T (2010) Fabrication and characterization of nano composite scaffold of poly(L-lactic acid)/hydroxyapatite. J Mater Sci Mater Med 21(1):183–188CrossRefPubMedGoogle Scholar
  11. 11.
    Danoux CB, Barbieri D, Yuan H, Bruijn JDD, Blitterswijk CAV, Habibovic P (2014) In vitro and in vivo bioactivity assessment of a polylactic acid/hydroxyapatite composite for bone regeneration. Biomatter 4(1):e27664CrossRefPubMedPubMedCentralGoogle Scholar
  12. 12.
    Rakmae S, Ruksakulpiwat Y, Sutapun W, Suppakarn N (2012) Effect of silane coupling agent treated bovine bone based carbonated hydroxyapatite on in vitro degradation behavior and bioactivity of PLA composites. Mater Sci Eng C 32(6):1428–1436CrossRefGoogle Scholar
  13. 13.
    Trinkunaite-Felsen J, Prichodko A, Semasko M, Skaudzius R, Beganskiene A, Kareiva A (2015) Synthesis and characterization of iron-doped/substituted calcium hydroxyapatite from seashells Macoma balthica (L.). Adv Powder Technol 26(5):1287–1293CrossRefGoogle Scholar
  14. 14.
    Chevalier Y, Bolzinger M-A (2013) Emulsions stabilzed with solid nanoparticles: Pickering emulsion. Colloids Surf A Physicochem Eng Asp 439:23–34CrossRefGoogle Scholar
  15. 15.
    Arditty S, Whitby CP, Binks BP, Schmitt V, Leal-Calderon F (2003) Some general features of limited coalescence in solid-stabilized emulsions. Eur Phys J E Soft Matter 11(3):273–281CrossRefPubMedGoogle Scholar
  16. 16.
    Okada M, Maeda H, Fujii S, Nakamura Y, Furuzono T (2012) Formation of Pickering emulsions stabilized via interaction between nanoparticles dispersed in aqueous phase and polymer end groups dissolved in oil phase. Langmuir 28(25):9405–9412CrossRefPubMedGoogle Scholar
  17. 17.
    Zhang M, Wang A-j, J-m L, Song N, Song Y, He R (2017) Factors influencing the stability and type of hydroxyapatite stabilized Pickering emulsion. Mater Sci Eng C 70:396–404CrossRefGoogle Scholar
  18. 18.
    Wei Z, Wang C, Liu H, Zou S, Tong Z (2012) Facile fabrication of biocompatible PLGA drug-carrying microspheres by Pickering emulsions. Colloids Surf, B Biointerfaces 91:97–105CrossRefPubMedGoogle Scholar
  19. 19.
    Tham CY, Chow WS (2017) Poly(lactic acid) microparticles with controllable morphology by hydroxyapatite stabilized Pickering emulsions: effect of pH, salt and amphiphilic agents. Colloids Surf A Physicochem Eng Asp 533:275–285CrossRefGoogle Scholar
  20. 20.
    Marinova KG, Alargova RG, Denkov ND, Velev OD, Petsev DN, Ivanov IB, Borwankar R (1996) Charging of oil-water interfaces due to spontaneous adsorption of hydroxyl ions. Langmuir 12(8):2045–2051CrossRefGoogle Scholar
  21. 21.
    Lin Y, Böker A, Skaff H, Cookson D, Dinsmore AD, Emrick T, Russell TP (2005) Nanoparticle assembly at fluid interfaces: structure and dynamics. Langmuir 21(1):191–194CrossRefPubMedGoogle Scholar
  22. 22.
    Juárez JA, Whitby CP (2012) Oil-in-water Pickering emulsion destabilisation at low particle concentrations. J Colloid Interface Sci 368(1):319–325CrossRefPubMedGoogle Scholar
  23. 23.
    Lin MY, Lindsay HM, Weitz DA, Ball RC, Klein R, Meakin P (1989) Universality in colloid aggregation. Nature 339(3):360–362CrossRefGoogle Scholar
  24. 24.
    Tsabet EM, Fradette L (2015) Effect of processing parameters on the production of Pickering emulsions. Ind Eng Chem Res 54(7):2227–2236CrossRefGoogle Scholar
  25. 25.
    Bile J, Bolzinger M-A, Vigne C, Boyron O, Valour J-P, Fessi H, Chevalier Y (2015) The parameters influencing the morphology of poly(ɛ-caprolactone) microspheres and the resulting release of encapsulated drugs. Int J Pharm 494(1):152–166CrossRefPubMedGoogle Scholar
  26. 26.
    Holmes JM, Beebe RA (1971) Surface areas by gas adsorption on amorphous calcium phosphate and crystalline hydroxyapatite. Calcif Tissue Res 7(1):163–174CrossRefPubMedGoogle Scholar
  27. 27.
    Yang L, Wei Z, Zhong W, Cui J, Wei W (2016) Modifying hydroxyapatite nanoparticles with humic acid for highly efficient removal of cu(II) from aqueous solution. Colloids Surf A Physicochem Eng Asp 490:9–21CrossRefGoogle Scholar
  28. 28.
    Zhu R, Yu R, Yao J, Mao D, Xing C, Wang D (2008) Removal of Cd2+ from aqueous solutions by hydroxyapatite. Catal Today 139(1):94–99CrossRefGoogle Scholar
  29. 29.
    Vitale-Brovarone C, Miola M, Balagna C, Verné E (2008) 3D-glass-ceramic scaffolds with antibacterial properties for bone grafting. Chem Eng J 137(1):129–136CrossRefGoogle Scholar
  30. 30.
    ASTM F 1185–03 (2003) Standard specification for composition of hydroxyapatite for surgical implants. ASTM International, West ConshohockenGoogle Scholar
  31. 31.
    ASTM F 1088 – 04a (2004) Standard specification for beta-tricalcium phosphate for surgical implantation. ASTM International, West ConshohockenGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Materials and Mineral Resources Engineering, Engineering CampusUniversiti Sains MalaysiaPenangMalaysia

Personalised recommendations