European Polymer Congress 2011 XII Congress of the Specialized Group of Polymers
Congress Program
European Polymer Federation Specialized Group of Polymers (GEP) Institute of Polymer Science and Technology (ICTP-CSIC)
ISBN: 978-84-694-3124-5
3267(5&2175,%87,216
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T5-115 T5-116 T5-117 T5-118
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T5-120 T5-121 T5-122
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T5-128 T5-129 T5-130
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Sphere-to-cylinder transition in mixed PS-b-PEO/TiO2 micellar systems. D. Scalarone; M. Lazzari; F. Caldera; O. Chiantore Microstructure analysis of the layers containing nanoparticles hybrids ZnO-SiO2 , TiO2 -SiO2 on textile fabrics. J. Sojka-Ledakowicz; J. Olczyk; A. Walawska; T. Jesionowski Synthesis of multi-walled carbon nanotubes using hydrocarbon as carbon sources in an arc discharge. M. Teymourzade; H. Kangarlou; K. Kazemikia; Synthesis of novel macroporous copolymer resins via aggregation/ breakage and post-polymerization. A. Lamprou; I. Koese; M. Soos; G. Storti; M. Morbidelli Crystallization kinetics of polypropylene nanocomposites. H. P. Nogueira; E. M. Alexandrino; M. I. Felisberti Magnetite-montmorillonite hybrid materials for wastewater treatment. G. Marcelo; I. Larraza; M. Lopez; T. Corrales; C. Peinado Analysis of the dispersion of nanofillers in PVC plastisols via rheological and morphological characterizations. C. Barres; A. Gueye; J. Duchet-Rumeau Intermolecular Interactions in polyacrylic acid solutions and gels. D. Shaltykova; E. Kalacheva; E. Shadrova; D. Kaldybekov; Z. Konyrbayeva Polymeric ionic liquids: homo- and copolymers in water. E. Karjalainen; H. Tenhu Functional poly(vinyl pyrrolidone)s for the controlled synthesis of Ag nanoparticles . A. Ledo-Suárez; I. Rielo-Rodríguez; M. A. López-Quintela; M. Lazzari; M. G. Tardajos; H. Reinecke; A. Gallardo Study of nanocomposites processing containing polyaniline and carbon nanotube as use with radar absorbing structures. L. Folgueras; M. Rezende Single macromolecule as neural network. S. Panchenko; I. Suleimenov Novel fluorescence properties of syndiotactic polystyrene and its derivative. T. Sago; H. Itagaki Polymers as nanocarbon presursors in template method characterization and sorption properties of the obtained products. M. Sobiesiak, B. Podkościelna, M. Podgórski, A.M. Puziy, O.I. Poddubnaya, C.A. Reinish, M.M. Tsyba How affect the shape and modifier of clay on polymer blends?. R. Gallego; D. García-López; J. C. Merino Senovilla; J. M. Pastor Role of polymer-to-filler grafting in dispersion of CNTs in rubbers.. P. Verge; S. Peeterbroeck; L. Bonnaud; P. Dubois Synthesis of colloidal stable silica containing blockcopolymer -nanoparticles. N. Köken Öz; K. Tauer; N. Weber Characterization of conducting polymer nanocomposites with poly(vinylidene fluoride) used in devices electroluminescents. A. Linardi Gomes; J. Sinézio de C. Campos; E. Armelin; C. Aleman; R. A. Ricci Jr; M. Beny P. Zakia; M. A. Canesqui; A. R. Vaz; J. G. Filho; J. A. Diniz Formation and size tuning of colloidal microcapsules via host-guest molecular recognition at the liquid-liquid interface. K. M. Turksoy; A. Sanyal Characterization, bioactivity and in vitro cellular response of sol-gel silica-polymer hybrid nanocomposites. S. Iváshchenko; D. M. García Cruz; A. Campillo Fernández; M. Monleón Pradas; J. L. Escobar Ivirico; G. Gallego Ferrer
EPF 2011, XII GEP Congress, 26th June - 1st July 2011, Granada, Spain
T5 – 133
Characterization, bioactivity and in vitro cellular response of sol-gel silica-polymer hybrid nanocomposites S. Iváshchenko 1 , D. M. García Cruz2,1 , A. Campillo Fernández3 , M. Monleón Pradas1,2,4 , J. L. Escobar Ivirico 1,2 , G. Gallego Ferrer1,2,4 1
Centro de Biomateriales e Ingeniería Tisular, Universitat Politècnica de València, 46022, Valencia, Spain 2 Centro de Investigación Príncipe Felipe, Autopista del Saler 16, 46013 Valencia, Spain 3 Metis Biomaterials, Parc Tecnològic, Av. Franklin, 12, 46980 Paterna, Valencia, Spain 4 CIBER en Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN), Spain
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Introduction Caprolactone derived materials are good candidates for tissue engineering. Although previous works demonstrate that methacrylate-endcapped caprolactone (CLMA) and 2hydroxyethyl acrylate (HEA) copolymer networks present good response when cultured with chondrocytes [1], they lack of sufficient mechanical properties for hard tissue engineering applications like bone. The hybridation of the organic matrix with silica (SiO2 ) by the polymerization of the organic phase during the simultaneous in situ sol-gel polymerization of a silica precursor has been presented as and strategy for mechanical reinforcement and bioactivity improvement [2]. The aim of the present work is the synthesis, characterization and evaluation of the cellular response of new CLMA-co-HEA/SiO2 hybrids. Materials and Methods The hybrids were obtained through the co-polymerization reaction of CLMA and HEA in monomers ratio 60/40% (w/w) and the simultaneous acid-catalyzed sol-gel polymerization of TEOS as described elsewhere [2]. 1 mm thickness sheets were obtained with different proportions of SiO2 (up to 30 wt.%). Effective silica network formation was confirmed by infrared spectroscopy (FTIR). Thermogravimetry (TGA) allowed determining the real quantity of SiO2 in the hybrids. The glass transition temperature of the samples was assessed by differential scanning calorimetry (DSC). Dynamic mechanical measurements (DMA) allowed measuring the storage modulus as a function of temperature. The ability of the samples to form a layer of hydroxyapatite (HAp) on their surface was tested in vitro by soaking them in a simulated body fluid (SBF) [3]. MC3T3-E1 pre-osteoblastic cells were cultured in vitro on the materials to evaluate their osteogenic potential. Results and Discussion The weights of the inorganic residual at 650ºC of the TGA curves agree well with the nominal ones. FTIR spectra show the characteristic peaks of the silica network: at 1060–1100 and 800 cm-1 (attributed to the Si-O-Si asymmetric and symmetric stretching vibration, respectively) and at 950 cm-1 (characteristic of the Si-OH stretching vibration). Their intensities increase proportionally to the silica content, mainly at silica contents above 15%. This abrupt increase is correlated with the percolation of the silica network. The copolymer is amorphous and random showing a single glass transition at -23ºC. It monotonously shifts to higher temperatures with the increase of the silica content, up to 9.48ºC for the 30% SiO2 sample. The rubbery modulus does not vary
significantly up to 15% SiO2 content when it markedly increases due to the formation of a continuous inorganic network. Scanning electron microscopy (SEM) images of the samples after 7 days of immersion in SBF show few hydroxyapatite nuclei grown on their surface. After 14 and 21 days the copolymer and the hybrid with a 15% SiO 2 are completely covered by a layer of HAp (formed by the typical needle-shape crystals) with aggregates of a second and third layer (Figure 1 left). On the contrary, although the sample with a 30% SiO2 is bioactive it presents a HAp layer with some imperfections. Electron dispersive X-ray spectroscopy shows that the coatings are mainly composed of calcium and phosphorous, with Ca/P atomic ratio close to the stoichiometric apatite, 1.67. The MTS proliferation assay shows an increment in the number of cells at 7 days of culture, being the number of cells independent of the silica content. Confocal laser scanning microscopy imag es of the immuno-histochemistries (Figure 1 right) show cells producing osteocalcin and collagen type I, typical markers of osteoblastic differentiated cells.
100 μm
Figure 1. Left: SEM image of the hydroxyapatite layer grown on the 15% SiO 2 hybrid, 14 days immersed in SBF; right: double immunofluorescence image showing staining of osteocalcin (green) and collagen type I (red) of pre-osteoblastic cells cultured on the 15% SiO 2 hybrid at 14 days. Cell nucleus is stained with Dapi (blue). Bar equal to 75 μm.
Conclusions The new silica hybrids have improved mechanical properties in comparison to pure copolymers, are bioactive and induce the osteoblastic differentiation as good candidates for bone tisuue engineering. Acknowledments: this work is supported by the Spanish Ministry of Science and Innovation trough the DPI201020399-C04-03 and PTQ08-08-06321 projects. References [1] Escobar Ivirico J.L. et al. J Biomed M ater Res Part B: Appl Biomater, 2007;83B:266-75 [2] Vallés-Lluch A. et al. Eur Polym J, 2010;46:1446-55 [3] Kokubo T. Biomaterials, 1991;12:155–63
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