Journal of Materials Science: Materials in Medicine

, Volume 22, Issue 9, pp 1993–2004 | Cite as

Reactive calcium-phosphate-containing poly(ester-co-ether) methacrylate bone adhesives: setting, degradation and drug release considerations

  • Xin Zhao
  • Irwin Olsen
  • Jonathan Pratten
  • Jonathan C. Knowles
  • Anne M. Young


This study has investigated novel bone adhesives consisting of fluid photo-polymerizable poly(lactide-co-propylene glycol-co-lactide)dimethacrylate (PGLA-DMA) mixed with systematically varying fillers of β-tricalcium phosphate (β-TCP) and monocalcium phosphate monohydrate (MCPM), for the delivery of an antibacterial drug chlorhexidine (CHX). All formulations were found to polymerize fully within 200 s after exposure to blue light. In addition, water sorption by the polymerized materials catalyzed varying filler conversion to dicalcium phosphate (DCP) (i.e. brushite and monetite). With greater DCP levels, faster degradation was observed. Moreover, increase in total filler content enhanced CHX release, associated with higher antibacterial activity. These findings thus suggest that such rapid-setting and degradable adhesives with controllable drug delivery property could have potential clinical value as bone adhesives with antibacterial activity.


Water Sorption Polymerization Rate Monomer Conversion Monetite Methacryloyl Chloride 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



This research work was supported by a Dorothy Hodgkins Postgraduate Award to Xin Zhao and by the Engineering and Physical Sciences Research Council, UK. This work was supported in part by the WCU Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. R31-10069). The authors would like to thank Drs Tom Frenkiel and Geoff Kelly at the Medical Research Council, Biomedical NMR Centre for their help with the NMR studies.


  1. 1.
    Ho SM, Young AM. Synthesis, polymerisation and degradation of poly(lactide-co-propylene glycol)dimethacrylate adhesives. Eur Polym J. 2006;42:1775–85.CrossRefGoogle Scholar
  2. 2.
    Young AM, Ho SM, Abou Neel EA, Ahmed I, Barralet JE, Knowles JC, Nazhat SN. Chemical characterization of a degradable polymeric bone adhesive containing hydrolysable fillers and interpretation of anomalous mechanical properties. Acta Biomater. 2009;5:2072–83.CrossRefGoogle Scholar
  3. 3.
    Zhao X, Olsen I, Li HY, Gellynck K, Buxton PG, Knowles JC, Salih V, Young AM. Reactive calcium-phosphate-containing poly(ester-co-ether) methacrylate bone adhesives: Chemical, mechanical and biological considerations. Acta Biomater. 2010;6:845–55.CrossRefGoogle Scholar
  4. 4.
    Bohner M. Reactivity of calcium phosphate cements. J Mater Chem. 2007;17:3980–6.CrossRefGoogle Scholar
  5. 5.
    Mourino V, Boccaccini AR. Bone tissue engineering therapeutics: controlled drug delivery in three-dimensional scaffolds. J R Soc Interface. 2010;7:209–27.CrossRefGoogle Scholar
  6. 6.
    Young AM, Ho SM. Drug release from injectable biodegradable polymeric adhesives for bone repair. J Control Release. 2008;127:162–72.CrossRefGoogle Scholar
  7. 7.
    Mandal S, Berendt AR, Peacock SJ. Staphylococcus aureus bone and joint infection. J Infect. 2002;44:143–51.CrossRefGoogle Scholar
  8. 8.
    Nair SP, Williams RJ, Henderson B. Advances in our understanding of the bone and joint pathology caused by Staphylococcus aureus infection. Rheumatology. 2000;39:821–34.CrossRefGoogle Scholar
  9. 9.
    Nascimento AP, Tanomaru JMG, Matoba F, Watanabe E, Tanomaru M, Ito IY. Maximum inhibitory dilution of mouthwashes containing chlorhexidine and polyhexamethylene biguanide against salivary Staphylococcus aureus. J Appl Oral Sci. 2008;16:336–9.CrossRefGoogle Scholar
  10. 10.
    Harris LG, Mead L, Muller-Oberlander E, Richards RG. Bacteria and cell cytocompatibility studies on coated medical grade titanium surfaces. J Biomed Mater Res A. 2006;78A:50–8.CrossRefGoogle Scholar
  11. 11.
    Lee DY, Spangberg LSW, Bok YB, Lee CY, Kum KY. The sustaining effect of three polymers on the release of chlorhexidine from a controlled release drug device for root canal disinfection. Oral Surg Oral Med Oral Pathol Oral Radiol Endod. 2005;100:105–11.CrossRefGoogle Scholar
  12. 12.
    Riggs PD, Braden M, Patel M. Chlorhexidine release from room temperature polymerising methacrylate systems. Biomaterials. 2000;21:345–51.CrossRefGoogle Scholar
  13. 13.
    Nerurkar MJ, Zentner GM, Rytting JH. Effect of chloride on the release of chlorhexidine salts from methyl-methacrylate—2-hydroxyethyl methacrylate copolymer reservoir devices. J Control Release. 1995;33:357–63.CrossRefGoogle Scholar
  14. 14.
    Leung D, Spratt DA, Pratten J, Gulabivala K, Mordan NJ, Young AM. Chlorhexidine-releasing methacrylate dental composite materials. Biomaterials. 2005;26:7145–53.CrossRefGoogle Scholar
  15. 15.
    Mehdawi I, Abou Neel EA, Valappil SP, Palmer G, Salih V, Pratten J, Spratt DA, Young AM. Development of remineralizing, antibacterial dental materials. Acta Biomater. 2009;5:2525–39.CrossRefGoogle Scholar
  16. 16.
    O’Dell LA, Guerry P, Wong A, Abou Neel EA, Pham TN, Knowles JC, Brown SP, Smith ME. Quantification of crystalline phases and measurement of phosphate chain lengths in a mixed phase sample by P-31 refocused INADEQUATE MAS NMR. Chem Phys Lett. 2008;455:178–83.CrossRefGoogle Scholar
  17. 17.
    Andrews JM, BSAC Working PS. BSAC standardized disc susceptibility testing method (version 7). J Antimicrob Chemoth. 2008;62:256–78.CrossRefGoogle Scholar
  18. 18.
    Grover LM, Gbureck U, Young AM, Wright AJ, Barralet JE. Temperature dependent setting kinetics and mechanical properties of beta-TCP-pyrophosphoric acid bone cement. J Mater Chem. 2005;15:4955–62.CrossRefGoogle Scholar
  19. 19.
    Elliott JC. General chemistry of the calcium orthophosphate. In: Structure and chemistry of the apatites and other calcium orthophosphates (studies in inorganic chemistry). Elsevier; 1994. p. 1–61.Google Scholar
  20. 20.
    Ripamonti U. Osteoinduction in porous hydroxyapatite implanted in heterotopic sites of different animal models. Biomaterials. 1996;17:31–5.CrossRefGoogle Scholar
  21. 21.
    Lin M, Wang HT, Meng S, Zhong W, Li ZL, Cai R, Chen Z, Zhou XY, Du QG. Structure and release behavior of PMMA/silica composite drug delivery system. J Pharm Sci. 2007;96:1518–26.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2011

Authors and Affiliations

  • Xin Zhao
    • 1
  • Irwin Olsen
    • 1
  • Jonathan Pratten
    • 2
  • Jonathan C. Knowles
    • 1
    • 3
  • Anne M. Young
    • 1
  1. 1.Biomaterials and Tissue Engineering Research DepartmentUCL Eastman Dental InstituteLondonUK
  2. 2.Microbial Diseases Research DepartmentUCL Eastman Dental InstituteLondonUK
  3. 3.WCU Research Centre of Nanobiomedical ScienceDankook UniversityCheonan-siSouth Korea

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