Abstract
The effects of a high energy sterilization treatment on poly-ε-caprolactone/carbonated hydroxyapatite composites have been investigated. Poly-ε-caprolactone is a biodegradable polymer used as long-term bioresorbable scaffold for bone tissue engineering and carbonated hydroxyapatite is a bioactive material able to promote bone growth. The composites were gamma-irradiated in air or under nitrogen atmosphere with doses ranging from 10 to 50 kGy (i.e. to a value higher than that recommended for sterilization). The effects of the irradiation treatment were evaluated by vibrational spectroscopy (IR and Raman spectroscopies) coupled to thermal analysis (Differential Scanning Calorimetry and Thermogravimetry) and Electron Paramagnetic Resonance spectroscopy. Irradiation with the doses required for sterilization induced acceptable structural changes and damaging effects: only a very slight fragmentation of the polymeric chains and some defects in the inorganic component were observed. Moreover, the radiation sensitivity of the composites proved almost the same under the two different atmospheres.
Similar content being viewed by others
References
Chawla JS, Amiji MM. Biodegradable poly(ε-caprolactone) nanoparticles for tumor-targeted delivery of tamoxifen. Int J Pharm. 2002;249:127–38.
Agrawal CM, Ray RB. Biodegradable polymeric scaffolds for musculoskeletal tissue engineering. J Biomed Mater Res. 2001;55:141–50.
Kweon H, Yoo MK, Park IK, Kim TH, Lee HC, Lee HS, et al. A novel degradable polycaprolactone networks for tissue engineering. Biomaterials. 2003;24:801–8.
Corden TJ, Jones IA, Rudd CD, Christian P, Downes S, McDougall KE. Physical and biocompatibility properties of poly-ε-caprolactone produced using in situ polymerisation: a novel manufacturing technique for long-fibre composite materials. Biomaterials. 2000;21:713–24.
Weir NA, Buchanan FJ, Orr JF, Farrar DF, Boyd A. Processing, annealing and sterilisation of poly-l-lactide. Biomaterials. 2004;25:3939–49.
Gogolewski S, Mainil-Varlet P, Dillon JG. Sterility, mechanical properties, and molecular stability of polylactide internal-fixation devices treated with low-temperature plasmas. J Biomed Mater Res. 1996;32:227–35.
Singh A, Silverman J, editors. Radiation processing of polymers. Munich: Hanser Publisher; 1991.
Hilmy N, Febrida A, Basril A. Experiences using IAEA Code of practice for radiation sterilization of tissue allografts: validation and routine control. Radiat Phys Chem. 2007;76:1751–5.
Nguyen H, Morgan DAF, Forwood MR. Sterilization of allograft bone: is 25 kGy the gold standard for gamma irradiation? Cell Tissue Bank. 2007;8:81–91.
Zimek Z, Kaluska I. Sterilization dose auditing for various types of medical products. Radiat Phys Chem. 2002;63:673–4.
Chen BQ, Sun K. Poly(ε-caprolactone)/hydroxyapatite composites: effects of particle size, molecular weight distribution and irradiation on interfacial interaction and properties. Polym Test. 2005;24:64–70.
Gorna K, Gogolewski S. The effect of gamma radiation on molecular stability and mechanical properties of biodegradable polyurethanes for medical applications. Polym Degrad Stab. 2003;79:465–74.
Masson V, Maurin F, Fessi H, Devissaguet JP. Influence of sterilization processes on poly(ε-caprolactone) nanospheres. Biomaterials. 1997;18:327–35.
Rouxhet L, Legras R. Modifications induced by swift heavy ions in poly(hydroxybutyrate–hydroxyvalerate) (PHB/HV) and poly(ε-caprolactone) (PCL) films: part 1. Thermal behaviour and molecular mass modifications. Nucl Instrum Methods Phys Res B. 2000;171:487–98.
Zhu G, Xu Q, Qin R, Yan H, Liang G. Effect of γ-radiation on crystallization of polycaprolactone. Radiat Phys Chem. 2005;74:42–50.
Reggiani M, Taddei P, Tinti A, Fagnano C. Spectroscopic study on the enzymatic degradation of a biodegradable composite periodontal membrane. Biopolymers. 2004;74:146–50.
Narkis M, Sibony-Chaouat MS, Siegmann A, Shkolnok S, Bell JP. Irradiation effects on polycaprolactone. Polymer. 1985;26:50–4.
Ohrlander M, Erickson R, Palmgren R, Wirsen A, Albertsson AC. The effect of electron beam irradiation on PCL and PDXO-X monitored by luminescence and electron spin resonance measurements. Polymer. 2000;41:1277–86.
Andrew William Inc. The effect of sterilisation methods on plastics and elastomers. Morris: Plastic Design library; 1994.
Hooper KA, Cox JD, Kohn J. Comparison of the effect of ethylene oxide and γ-irradiation on selected tyrosine-derived polycarbonates and poly(l-lactic acid). J Appl Polym Sci. 1997;63:1499–510.
Kowalski JB, Herring C, Baryschpolec L, Reger J, Patel J, Feeney M, et al. Field evaluations of the VDmax approach for substantiation of a 25 kGy sterilization dose and its application to other preselected doses. Radiat Phys Chem. 2002;64:411–6.
Taddei P, Tinti A, Reggiani M, Fagnano C. In vitro mineralization of bioresorbable poly(ε-caprolactone)/apatite composites for bone tissue engineering: a vibrational and thermal investigation. J Mol Struct. 2005;744–747:135–43.
Taddei P, Di Foggia M, Causa F, Ambrosio L, Fagnano C. In vitro bioactivity of poly(ε-caprolactone)-apatite (PCL-AP) scaffolds for bone tissue engineering: the influence of the PCL/AP ratio. Int J Artif Organs. 2006;29:719–25.
Guarino V, Causa F, Taddei P, Di Foggia M, Ciapetti G, Martini D, et al. Polylactic acid fibre reinforced polycaprolactone scaffolds for bone tissue engineering: morphology, degradation properties and human bone cell interaction. Biomaterials. 2008;29:3662–70.
Affatato S, Zavalloni M, Taddei P, Di Foggia M, Fagnano C, Viceconti M. Comparative study on the wear behaviour of different conventional and cross-linked polyethylenes for total hip replacement. Trib Int. 2008;41:813–22.
Ciapetti G, Ambrosio L, Savarino L, Granchi D, Cenni E, Baldini N, et al. Osteoblast growth and function in porous poly ε-caprolactone matrices for bone repair: a preliminary study. Biomaterials. 2003;24:3815–24.
Crescenzi V, Manzini G, Calzolari G, Borri C. Thermodynamics of fusion of poly-β-propiolactone and poly-ε-caprolactone comparative analysis of the melting of aliphatic polylactone and polyester chains. Eur Polym J. 1972;8:449–63.
Baji A, Wong SC, Liu T, Li T, Srivatsan TS. Morphological and X-ray diffraction studies of crystalline hydroxyapatite-reinforced polycaprolactone. J Biomed Mater Res B. 2007;81B:343–50.
Miller LM, Vairavamurthy V, Chance MR, Mendelsohn R, Paschalis EP, Betts F, et al. In situ analysis of mineral content and crystallinity in bone using infrared micro-spectroscopy of the ν4 PO4 3− vibration. Biochim Biophys Acta. 2001;1527:11–9.
Hubner W, Blume A, Pushjakova R, Dekhtyar Y, Hein HJ. The influence of X-ray radiation on the mineral/organic matrix interaction of bone tissue: an FT-IR microscopic investigation. Int J Artif Organs. 2005;28:66–73.
Kister G, Cassanas G, Bergounhon M, Hoarau D, Vert M. Structural characterization and hydrolytic degradation of solid copolymers of d,l-lactide-co-ε-caprolactone by Raman spectroscopy. Polymer. 2000;41:925–32.
Kirchner MT, Edwards HGM, Lucy D, Pollard AM. Ancient and modern specimens of human teeth: a Fourier Transform Raman spectroscopic study. J Raman Spectrosc. 1997;28:171–8.
Kubisz L, Polomska M. FT NIR Raman studies on γ-irradiated bone. Spectrochim Acta A. 2007;66:616–25.
Awonusi A, Morris MD, Tecklenburg MMJ. Carbonate assignment and calibration in the Raman spectrum of apatite. Calcif Tissue Int. 2007;81:46–52.
Jie W, Li Y. Tissue engineering scaffold material of nano apatite crystals and polyamide composite. Eur Polym J. 2004;40:509–15.
Gupta MC, Deshmukh VG. Radiation effects on poly(lactic acid). Polymer. 1983;24:827–30.
Carden A, Morris MD. Application of vibrational spectroscopy to the study of mineralized tissues. J Biomed Opt. 2000;5:259–68.
Schramm DU, Rossi AM. Electron spin resonance (ESR) studies of CO2 − radicals in irradiated A and B-type carbonate-containing apatites. Appl Rad Isot. 2000;52:1085–91.
Da Costa ZM, Pontuschka WM, Campos LL. Study of the ESR signal of gamma irradiated hydroxyapatite for dose assessment. Nucl Instrum Methods Phys Res B. 2004;218:283–8.
Bacquet G, Truong VQ, Vignoles M, Trombe JC, Bonel G. ESR of CO. Calcif Tissue Int. 1981;33:105–9.
Mitomo H, Sasada K, Nishimura K, Yoshii F, Nagasawa N. Radiation effects on blends of poly(ε-caprolactone) and diatomites. J Polym Environ. 2004;12:95–103.
Filipczak K, Janik I, Kozicki M, Ulanski P, Rosiak JM, Pajewski LA, et al. Porous polymeric scaffolds for bone regeneration. e-Polymers. 2005;11:1–13.
Plikk P, Odelius K, Hakkarainen M, Albertsson AC. Finalizing the properties of porous scaffolds of aliphatic polyesters through radiation sterilization. Biomaterials. 2006;27:5335–47.
Acknowledgement
We thank Dr. Angelo Alberti and Dr. Giorgio Fuochi (ISOF-CNR) for the critical reading of the paper.
Author information
Authors and Affiliations
Corresponding authors
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Di Foggia, M., Corda, U., Plescia, E. et al. Effects of sterilisation by high-energy radiation on biomedical poly-(ε-caprolactone)/hydroxyapatite composites. J Mater Sci: Mater Med 21, 1789–1797 (2010). https://doi.org/10.1007/s10856-010-4046-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10856-010-4046-0