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Effect of interface on mechanical properties and biodegradation of PCL HAp supramolecular nano-composites

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Abstract

This research explores the correlation between the structural properties of supramolecular biocomposites and their mechanical strength. Hybrid biocomposites composed of surface-modified hydroxyapatite nano-particles and supramolecular polycaprolactone (SP PCL), were prepared at different compositions, and their mechanical, thermal and viscoelastic properties as well as biodegradability, biocompatibility and cytotoxicity were evaluated in vitro. The results were compared with those for SP PCL/naked hydroxyapatite nano-composites. We show that surface modification of hydroxyapatite nanoparticles resulted in outstanding improvement of tensile strength and modulus up to 3.6 and 2.2-fold, respectively. At above 10 wt% HAp and 20 wt% HApUPy, heterogeneous nano-composites with inferior mechanical properties were obtained. Based on rheological (in steady shear mode) and small/wide angle X-ray scattering measurements, unusual improved mechanical properties were ascribed to the formation of supramolecular clusters around nanoparticles. In-vitro degradation of the supramolecular nano-composites was also studied to investigate the overall product biodegradation as well as toxicity of the degradation product(s).

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References

  1. Farokhi M, et al. Porous crosslinked poly(ε-caprolactone fumarate)/nanohydroxyapatite composites for bone tissue engineering. J Biomed Mater Res Part A. 2012;100A(4):1051–60.

    Article  Google Scholar 

  2. Kim SS, et al. Poly (lactide-co-glycolide)/hydroxyapatite composite scaffolds for bone tissue engineering. Biomaterials. 2006;27(8):1399–409.

    Article  Google Scholar 

  3. Kunze C, et al. Surface modification of tricalcium phosphate for improvement of the interfacial compatibility with biodegradable polymers. Biomaterials. 2003;24(6):967–74.

    Article  Google Scholar 

  4. Corno M, et al. Hydroxyapatite as a key biomaterial: quantum-mechanical simulation of its surfaces in interaction with biomolecules. Phys Chem Chem Phys. 2010;12(24):6309–29.

    Article  Google Scholar 

  5. Torres N, et al. Stability of antibacterial self-assembled monolayers on hydroxyapatite. Acta Biomater. 2010;6(8):3242–55.

    Article  Google Scholar 

  6. Bach LG, Rafiqul Islam MD, et al. Poly(allyl methacrylate) functionalized hydroxyapatite nanocrystals via a combination of surface initiated RAFT polymerization and tiol ene protocol; a potential anticancer drug carrier. J Colloid Interface Sci. 2013;394:132–40.

    Google Scholar 

  7. Aissa A, et al. Covalent modification of calcium hydroxyapatite surface by grafting phenyl phosphonate moieties. J Solid State Chem. 2007;180(8):2273–8.

    Article  Google Scholar 

  8. Borum-Nicholas L, Wilson O. Surface modification of hydroxyapatite. Part I. Dodecyl alcohol. Biomaterials. 2003;24(21):3671–9.

    Article  Google Scholar 

  9. Borum L, Wilson O. Surface modification of hydroxyapatite. Part II. Silica. Biomaterials. 2003;24(21):3681–8.

    Article  Google Scholar 

  10. Hong Z, et al. Grafting polymerization of L-lactide on the surface of hydroxyapatite nano-crystals. Polymer. 2004;45(19):6699–706.

    Article  Google Scholar 

  11. Qiu X, et al. Surface-modified hydroxyapatite linked by L-lactic acid oligomer in the absence of catalyst. J Polym Sci Part A: Polym Chem. 2005;43(21):5177–85.

    Article  Google Scholar 

  12. Zeng L, et al. A new approach for synthesis of the comb-shaped poly (<i> ε </i>-caprolactone) brushes on the surface of nano-hydroxyapatite by combination of ATRP and ROP. J Colloid Interface Sci. 2010;352(1):36–42.

    Article  Google Scholar 

  13. Wang Y, et al. Improved mechanical properties of hydroxyapatite/poly (ɛ-caprolactone) scaffolds by surface modification of hydroxyapatite. Appl Surf Sci. 2010;256(20):6107–12.

    Article  Google Scholar 

  14. Miltner HE, et al. Quantifying the degree of nanofiller dispersion by advanced thermal analysis: application to polyester nanocomposites prepared by various elaboration methods. J Mater Chem. 2010;20(42):9531–42.

    Article  Google Scholar 

  15. Cui Y, et al. The nanocomposite scaffold of poly (lactide-co-glycolide) and hydroxyapatite surface-grafted with L-lactic acid oligomer for bone repair. Acta Biomater. 2009;5(7):2680–92.

    Article  Google Scholar 

  16. Lee HJ, et al. Modification of hydroxyapatite nanosurfaces for enhanced colloidal stability and improved interfacial adhesion in nanocomposites. Chem Mater. 2006;18(21):5111–8.

    Article  Google Scholar 

  17. Liu A, et al. Surface modification of bioactive glass nanoparticles and the mechanical and biological properties of poly (L-lactide) composites. Acta Biomater. 2008;4(4):1005–15.

    Article  Google Scholar 

  18. Liu Q, de Wijn JR, van Blitterswijk CA. Surface modification of nano-apatite by grafting organic polymer. Biomaterials. 1998;19(11–12):1067–72.

    Google Scholar 

  19. Xie J et al. Controlled biomineralization of electrospun poly(ε-caprolactone) fibers to enhance their mechanical properties. Acta Biomater. 2013;9(3):5698–707.

    Google Scholar 

  20. Keledi G, Hári J, Pukánszky B. Polymer nanocomposites: structure, interaction, and functionality. Nanoscale. 2012;4(6):1919–38.

    Article  Google Scholar 

  21. Jancar J, et al. Current issues in research on structure–property relationships in polymer nanocomposites. Polymer. 2010;51(15):3321–43.

    Article  Google Scholar 

  22. Bhattacharya P et al. Exploiting the physicochemical properties of dendritic polymers for environmental and biological applications. Phys Chem Chem Phys. 2013;15:4477–90.

    Google Scholar 

  23. Zhang W, et al. Correlation of polymer-like solution behaviors with electrospun fiber formation of hydroxypropyl-[small beta]-cyclodextrin and the adsorption study on the fiber. Phys Chem Chem Phys. 2012;14(27):9729–37.

    Article  Google Scholar 

  24. Appel WPJ, Meijer E, Dankers PYW. Enzymatic activity at the surface of biomaterials via supramolecular anchoring of peptides: the effect of material processing. Macromol Biosci. 2011;11(12):1706–12.

    Article  Google Scholar 

  25. Dankers PYW, et al. Bioengineering of living renal membranes consisting of hierarchical, bioactive supramolecular meshes and human tubular cells. Biomaterials. 2011;32(3):723–33.

    Article  Google Scholar 

  26. Li YY, et al. Supramolecular polymer micelles prepared by steric effect tuned self-assembly: a new strategy for self-assembly. Soft Matter. 2011;7(10):4839–44.

    Article  Google Scholar 

  27. Yang C, et al. A supramolecular gene carrier composed of multiple cationic α-cyclodextrins threaded on a PPO–PEO–PPO triblock polymer. Polymer. 2009;50(6):1378–88.

    Article  Google Scholar 

  28. Zhang X, et al. Structure and properties of polysaccharide nanocrystal-doped supramolecular hydrogels based on cyclodextrin inclusion. Polymer. 2010;51(19):4398–407.

    Article  Google Scholar 

  29. Shokrollahi P, et al. Biological and mechanical properties of novel composites based on supramolecular polycaprolactone and functionalized hydroxyapatite. J Biomed Mater Res Part A. 2010;95(1):209–21.

    Article  Google Scholar 

  30. Shokrollahi P, et al. Effect of self-complementary motifs on phase compatibility and material properties in blends of supramolecular polymers. Polymer. 2010;51(26):6303–12.

    Article  Google Scholar 

  31. Mehmanchi M, et al. Supramolecular polycaprolactone nanocomposite based on functionalized hydroxyapatite. J Bioactive Compat Polym. 2012;27(5):467–80.

    Article  Google Scholar 

  32. Chen J, et al. Controlled surface-initiated ring-opening polymerization of L-lactide from risedronate-anchored hydroxyapatite nanocrystals: novel synthesis of biodegradable hydroxyapatite/poly (L-lactide) nanocomposites. J Polym Sci Part A: Polym Chem. 2011;49(20):4379–86.

    Article  Google Scholar 

  33. Tsuji H, Ikada Y. Blends of aliphatic polyesters. II. Hydrolysis of solution-cast blends from poly (L-lactide) and poly (E-caprolactone) in phosphate-buffered solution. J Appl Polym Sci. 1998;67(3):405–15.

    Article  Google Scholar 

  34. Kautz H, et al. Cooperative end-to-end and lateral hydrogen-bonding motifs in supramolecular thermoplastic elastomers. Macromolecules. 2006;39(13):4265.

    Article  Google Scholar 

  35. Qiu X, et al. Hydroxyapatite surface modified by L-lactic acid and its subsequent grafting polymerization of L-lactide. Biomacromolecules. 2005;6(3):1193–9.

    Article  Google Scholar 

  36. Utracki LA, Sepehr MM, Carreau PJ. Rheology of polymers with nanofillers. In: Utracki LA, Jamieson AM, editors. Polymer physics: from suspensions to nanocomposites and beyond. Hoboken, NJ: John Wiley & Sons, Inc.; 2010. p. 639–708.

  37. Ray SS, Okamoto K, Okamoto M. Structure-property relationship in biodegradable poly (butylene succinate)/layered silicate nanocomposites. Macromolecules. 2003;36(7):2355–67.

    Article  Google Scholar 

  38. Ray SS, et al. New polylactide/layered silicate nanocomposites. 3. High-performance biodegradable materials. Chem Mater. 2003;15(7):1456–65.

    Article  Google Scholar 

  39. Kagarise C, et al. Transient shear rheology of carbon nanofiber/polystyrene melt composites. J Nonnewton Fluid Mech. 2010;165(3):98–109.

    Article  Google Scholar 

  40. Wietor JL, et al. Effects of branching and crystallization on rheology of polycaprolactone supramolecular polymers with ureidopyrimidinone end groups. Macromolecules. 2011;44(5):1211.

    Article  Google Scholar 

  41. Van Beek D, et al. Unidirectional dimerization and stacking of ureidopyrimidinone end groups in polycaprolactone supramolecular polymers. Macromolecules. 2007;40(23):8464–75.

    Article  Google Scholar 

  42. Ahn SH, Lee HJ, Kim GH. Polycaprolactone scaffolds fabricated with an advanced electrohydrodynamic direct-printing method for bone tissue regeneration. Biomacromolecules. 2011;12(12):4256–63.

    Article  Google Scholar 

  43. Herbst F, et al. Aggregation and chain dynamics in supramolecular polymers by dynamic rheology: cluster formation and self-aggregation. Macromolecules. 2010;43(23):10006–16.

    Article  Google Scholar 

  44. Woodruff MA, Hutmacher DW. The return of a forgotten polymer—polycaprolactone in the 21st century. Prog Polym Sci. 2010;35(10):1217–56.

    Article  Google Scholar 

  45. Kim WS, et al. Evaluation of mechanical interlock effect on adhesion strength of polymer–metal interfaces using micro-patterned surface topography. Int J Adhes Adhes. 2010;30(6):408–17.

    Article  Google Scholar 

  46. Shen L, Liu T, Lv P. Polishing effect on nanoindentation behavior of nylon 66 and its nanocomposites. Polym Testing. 2005;24(6):746–9.

    Article  Google Scholar 

  47. Shokrollahi P. Supramolecular approaches to materials with tunable biological and mechanical properties: composite and blending. PhD thesis, Cambridge University.

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Acknowledgments

We would like to thank Ms. Mohsen Asl Rahimi for his excellent technical assistance and Dr Mahmood Rajabian for a fruitful discussion on rheological measurements.

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Authors and Affiliations

  1. Department of Biomaterials, Iran Polymer and Petrochemical Institute, P.O. Box 14965/159, Tehran, Iran

    Parvin Shokrollahi & Mohammad Mehmanchi

  2. Department of Polymer Science, Iran Polymer and Petrochemical Institute, P.O. Box 14965/159, Tehran, Iran

    Mohammad Atai

  3. Department of Pharmaceutical Sciences, Nova Southeastern University, Fort Lauderdale, FL, USA

    Hossein Omidian

  4. Department of Petrochemical Synthesis, Iran Polymer and Petrochemical Institute, P.O. Box 14965/159, Tehran, Iran

    Fateme Shokrolahi

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  1. Parvin Shokrollahi
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  2. Mohammad Mehmanchi
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Correspondence to Parvin Shokrollahi.

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Shokrollahi, P., Mehmanchi, M., Atai, M. et al. Effect of interface on mechanical properties and biodegradation of PCL HAp supramolecular nano-composites. J Mater Sci: Mater Med 25, 23–35 (2014). https://doi.org/10.1007/s10856-013-5039-6

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  • DOI: https://doi.org/10.1007/s10856-013-5039-6

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