Dziadek Michal, Menaszek Elzbieta, Zagrajczuk Barbara, Pawlik Justyna, Cholewa-Kowalska Katarzyna
AGH University of Science and Technology, Faculty of Materials Science and Ceramics, Department of Glass Technology and Amorphous Coatings, 30 Mickiewicza Ave., 30-059 Krakow, Poland.
Jagiellonian University, Collegium Medicum, Department of Cytobiology, 9 Medyczna St., 30-688 Krakow, Poland.
Mater Sci Eng C Mater Biol Appl. 2015 Nov 1;56:9-21. doi: 10.1016/j.msec.2015.06.020. Epub 2015 Jun 11.
Poly(ε-caprolactone) (PCL) based composite films containing 12 and 21vol.% bioactive glass (SBG) microparticles were prepared by solvent casting method. Two gel-derived SBGs of SiO2-CaO-P2O5 system differing in SiO2 and CaO contents were applied (mol%): S2: 80SiO2, 16CaO, 4P2O5 and A2: 40SiO2, 54CaO, 6P2O5. The surfaces of the films in contact with Petri dish and exposed to the gas phase during casting were denoted as GS and AS, respectively. Both surfaces of films were characterised in terms of their morphology, micro- and nano-topography as well as wettability. Also mechanical properties (tensile strength, Young's modulus) and PCL matrix crystallinity (degree of crystallinity, crystal size) were evaluated. Degradation behaviour was examined by incubation of materials in UHQ-water at 37°C for 56weeks. The crystallinity, melting temperature and mass loss of incubated materials and pH changes of water were monitored. Furthermore, proliferation of MG-63 osteoblastic cells by direct contact and cytotoxic effect of obtained materials were investigated. Results showed that opposite surfaces of the same polymer and composite films differ in studied surface parameters. The addition of SBG particles into PCL matrix improves nano- and micro-roughness of both surfaces, enhances the hydrophilicity of GS surfaces (67° for 21A2-PCL compared to ~78° for pure PCL) and also makes AS surface more hydrophobic (94° for 21S2-PCL compared to 86° for pure PCL). The nucleation density of PCL was increased with increasing content of SBG particles, which results in the large number of fine spherulites on composite AS surfaces observed using polarized optical (POM), scanning electron (SEM), and atomic force (AFM) microscopies. Higher content of SBG particles causes a notable increase of Young's modulus (from 0.38GPa for pure PCL, 0.90GPa for 12A2-PCL to 1.31GPa for 21A2-PCL), which also depends on SBG chemical composition. After 56-week degradation test, considerably higher crystallinity increase (Δχc ~148% for 21S2-PCL, ~81% for 21A2-PCL) and weight loss (17% for both) were found for composite materials, depending on SBG composition, in contrast to value variations for pure PCL film (Δχc ~43%, weight loss ~1.6%). Furthermore, it seems that both SBG could neutralize acidic degradation by-products of PCL at later incubation stages. Obtained SBG-PCL composites show excellent biocompatibility, support cell proliferation also may modulate cell response depending on the glass composition. The results indicate the possibility to use different contents and/or chemical compositions of SBG to obtain composite materials with various, but controlled, surface and mechanical properties as well as degradation kinetics.
采用溶液浇铸法制备了含12体积%和21体积%生物活性玻璃(SBG)微粒的聚(ε-己内酯)(PCL)基复合薄膜。应用了两种SiO₂和CaO含量不同的SiO₂-CaO-P₂O₅体系的凝胶衍生SBG(摩尔%):S2:80SiO₂、16CaO、4P₂O₅和A2:40SiO₂、54CaO、6P₂O₅。在浇铸过程中与培养皿接触并暴露于气相的薄膜表面分别标记为GS和AS。对薄膜的两个表面进行了形态、微观和纳米形貌以及润湿性的表征。还评估了力学性能(拉伸强度、杨氏模量)和PCL基体结晶度(结晶度、晶体尺寸)。通过将材料在37°C的超纯水(UHQ-水)中孵育56周来研究降解行为。监测孵育材料的结晶度、熔点温度和质量损失以及水的pH变化。此外,研究了所制备材料通过直接接触对MG-63成骨细胞的增殖作用和细胞毒性作用。结果表明,相同聚合物和复合薄膜的相对表面在所研究的表面参数上存在差异。向PCL基体中添加SBG颗粒提高了两个表面的纳米和微观粗糙度,增强了GS表面的亲水性(21A2-PCL为67°,而纯PCL为78°),也使AS表面更疏水(21S2-PCL为94°,而纯PCL为86°)。随着SBG颗粒含量的增加,PCL的成核密度增加,这导致在使用偏光光学显微镜(POM)、扫描电子显微镜(SEM)和原子力显微镜(AFM)观察时,复合AS表面出现大量细小球晶。较高含量的SBG颗粒导致杨氏模量显著增加(从纯PCL的0.38GPa、12A2-PCL的0.90GPa增加到21A2-PCL的1.31GPa),这也取决于SBG的化学成分。经过56周的降解试验,发现复合材料的结晶度增加幅度(21S2-PCL的Δχc约为148%,21A2-PCL的约为81%)和重量损失(两者均约为17%)明显更高,这取决于SBG的组成,而纯PCL薄膜的值变化为(Δχc约为43%,重量损失约为1.6%)。此外,似乎两种SBG都可以在孵育后期中和PCL的酸性降解副产物。所制备的SBG-PCL复合材料表现出优异的生物相容性,支持细胞增殖,还可能根据玻璃组成调节细胞反应。结果表明,有可能使用不同含量和/或化学成分的SBG来获得具有各种但可控的表面和力学性能以及降解动力学的复合材料。