Lateral Size Dependence of Graphene Oxide in Modifying Shape Memory Fibers
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摘要: 将不同片层大小的氧化石墨烯（GO）通过电纺丝方法掺杂到左旋聚乳酸/聚（3-羟基丁酸酯-co-3-羟基戊酸酯）（PLLA/PHBV）形状记忆复合纤维中形成GO@PLLA/PHBV复合纤维膜。通过拉曼光谱（Raman）、场发射扫描电镜（FESEM）、透射电镜（TEM）、X射线衍射（XRD）及差示扫描量热（DSC）等对复合纤维膜的形貌、结构和热性能进行了表征。采用动态热机械分析（DMA）、形状回复应力测试及光热升温实验分析了复合纤维膜的形状记忆性能。通过细胞增殖和成骨分化实验检测GO片层大小对复合纤维膜的成骨诱导作用。结果表明，小尺寸GO（sGO）的掺入对PLLA/PHBV复合纤维膜的力学增强及形状回复效果最为显著，可使拉伸杨氏模量提高约124%，形状回复应力增大约29%，形状回复率增大约47%，热响应速率提高约30倍；但在成骨诱导方面，掺入大尺寸GO（lGO）的PLLA/PHBV复合纤维膜则具有最优的成骨诱导性能，使骨髓间充质干细胞（BMSCs）中的碱性磷酸酶（ALP）分泌量提高了92%，钙沉积提高了133%。Abstract: Graphene oxide (GO) with different lateral sizes was doped into the shape memory capable fibrous membranes of poly(L-lactic acid)/poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PLLA/PHBV) composite via electrospinning. A series of characterizing techniques such as Raman spectroscopy (Raman), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC) were employed to characterize the structure and thermal properties of the fibrous composite membranes. Thereafter, shape memory properties were determined by dynamic mechanical analysis (DMA), shape recovery stress, and photothermal effect test. Finally, the effect of GO lateral sizes on the osteodifferentiation capacity of bone mesenchymal stem cells (BMSCs) cultured on the fibrous composite membranes was examined by conducting cell proliferation and osteodifferentiation relevant assays. It was found that incorporation of small-sized GO (sGO) into the fibrous composite membranes gave rise to the most significant reinforcing effects on the mechanical strengthening and shape recovery capability of the fibrous PLLA/PHBV membranes, with the tensile Young's modulus increased by about 124%, the shape recovery stress increased by about 29%, the shape recovery rate increased by about 47%, and the thermal responsive rate increased by about 30 fold. In terms of osteogenic performance, the fibrous PLLA/PHBV membranes doped with large-sized GO (lGO) demonstrated the best osteogenic induction capacity in BMSCs, with the secreted alkaline phosphatase (ALP) increased by 92% and the calcium deposits by 133%.
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Key words:
- graphene oxide /
- lateral size /
- electrospinning /
- shape memory polymer /
- bone tissue engineering
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图 1 GO的（a）化学结构，（b）Raman光谱图及（c）FESEM形貌图
Figure 1. （a） Chemical structure, （b） Raman spectra and （c） FESEM images of GO
图 2 复合纤维膜的（a）FESEM和（b）TEM形貌图（白色箭头所指为GO）
Figure 2. （a） FESEM and （b） TEM images of fibrous composite membranes （The white arrows point to GO）
图 3 复合纤维膜的（a）拉曼光谱图、（b）热失重曲线、（c）XRD图谱和（d）DSC图谱
Figure 3. （a） Raman spectra, （b） TG curves, （c） XRD patterns and （d） DSC curves of the fibrous composite membranes
图 4 复合纤维膜的（a）拉伸杨氏模量、（b）形状固定率和形状回复率、（c）最大回复应力和（d）升温速率
Figure 4. （a） Tensile Young's modulus, （b） shape fixation rate and shape recovery rate, （c） ultimate recovery stress and （d） the heating rates of fibrous composite membranes
图 5 BMSCs在复合纤维膜上（a）培养1、3、6 d的增殖情况；（b）培养3 d的骨架染色图；培养14 d后（c）ALP和ARS的染色图及（d）定量测定结果
Figure 5. （a） Proliferation assayed at 1, 3, 6 d; （b） Images of cytoskeleton staining at 3 d; （c） ALP and ARS staining and （d） quantitative measurements for 14 d of BMSCs cultured on the fibrous composite membranes
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