氧化石墨烯改性形状记忆纤维的尺寸相关性

薛苏桐; 王先流; 易兵成; 郭煦然; 唐寒; 沈炎冰; 张彦中

doi:10.14133/j.cnki.1008-9357.20210411001

氧化石墨烯改性形状记忆纤维的尺寸相关性

doi: 10.14133/j.cnki.1008-9357.20210411001

东华大学化学化工与生物工程学院，上海 201620

基金项目: 国家自然科学基金（31771050、32071345和31570969）；中央高校基本科研业务费专项资金（2232019A3-09）；国家科技部重点研发专项（2016YFC1100203）

详细信息

作者简介:
薛苏桐（1996—），男，山西河津人，硕士，主要研究方向为仿生材料与再生医学。E-mail：18234075077@163.com

通讯作者:
张彦中，E-mail：yzzhang@dhu.edu.cn

中图分类号: R318.08
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出版历程
- 收稿日期: 2021-04-11
- 网络出版日期: 2021-06-18

Lateral Size Dependence of Graphene Oxide in Modifying Shape Memory Polymer Fibers

College of Chemistry, Chemical Engineering &; Biotechnology, Donghua University, Shanghai 201620, China

摘要

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）形状记忆超细纤维中形成GO@PLLA/PHBV复合纤维。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）等对各复合纤维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各复合纤维的形状记忆性能。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的成骨诱导作用。结果表明，小尺寸GO（sGO）的掺入对PLLA/PHBV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%，形状回复应力增强约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纤维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%，钙沉积能力提高了133%。
- 氧化石墨烯 /
- 片层尺寸 /
- 电纺丝 /
- 形状记忆聚合物 /
- 骨组织工程
Abstract: Graphene oxide (GO) with different lateral sizes was doped into the shape memory capable fibers of poly(L-lactic acid)/poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PLLA/PHBV) 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 composite fibers. Thereafter, shape memory properties were determined by performing dynamic mechanical analysis (DMA), shape recovery stress, and photothermal effect tests. Lastly, the effect of GO lateral sizes on the osteodifferentiation capacity of bone marrow stromal cells (BMSCs) cultured on the fibrous PLLA/PHBV mats was examined by conducting cell proliferation and osteodifferentiation relevant assays. It was found that incorporation of small-sized GO (sGO) into the fiber matrix gave rise to the most significant reinforcing effects on the mechanical strengthening and shape recovery capability of the fibrous PLLA/PHBV mats, 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 PLLA/PHBV fibers 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%.
- graphene oxide /
- lateral size /
- electrospinning /
- shape memory polymers /
- bone tissue engineering

HTML全文

图 1 （a）GO的化学结构，（b）sGO、mGO及lGO超声前的Raman光谱图及（c）各GO的FESEM形貌图

Figure 1. （a） Chemical structure of GO, （b） Raman spectra and （c） FESEM images of sGO, mGO and lGO

下载: 全尺寸图片幻灯片

图 2 复合纤维的（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 composite fibers （the white arrows point to GO）

下载: 全尺寸图片幻灯片

图 3 复合纤维的（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 composite fibers

下载: 全尺寸图片幻灯片

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；（d）升温速率

Figure 4. （a） Tensile Young's modulus; （b） Shape fixation ratio and shape recovery ratio; （c） ultimate recovery stress, and （d） the heating rates of composite fibers

下载: 全尺寸图片幻灯片

图 5 BMSCs在复合纤维支架上（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后的ALP和ARS（c）染色及定量

Figure 5. （a） Proliferation of BMSCs assayed at 1, 3, 6 d; （b） Images of cytoskeleton staining at 3 d; （c） ALP and ARS staining, and （d） quantitative measurements of BMSCs cultured on fibrous scaffolds for 14 d

下载: 全尺寸图片幻灯片

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