PHBV神经导管的静电纺丝法制备
发布时间：2018-07-25 11:49
【摘要】：周围神经损伤以后的修复、再生和功能恢复一直是神经科学研究的热点,组织工程学的出现为神经损伤的修复提供了一个新的思路。目前,神经导管已经成为修复周围神经损伤的途径之一。如何制备出有利于神经再生、分化和生长的神经导管支架一直是神经组织工程学的难点。静电纺丝技术所制备的电纺纳米纤维支架材料具有孔隙率高、比表面积大等优点,能够从纳米尺度上模仿天然细胞外基质,可作为细胞生长的多孔支架,促进细胞的迁移和增殖。 本文利用羟基丁酸-羟基戊酸共聚酯(PHBV)、聚乙二醇(PEG)、聚己内酯(PCL)为支架材料,通过静电纺丝、熔融纺丝、等离子体改性等技术制备三层静电纺丝有序纤维神经导管。其特征在于,由静电纺PHBV/PEG有序亚微米纤维薄膜卷绕而成的内层管、由熔融纺丝制备的PCL单丝编织成的中间层网状导管和由静电纺丝法直接喷射而成的PHBV高比表面积、高孔隙率外层管。通过扫描电镜(SEM)、差示扫描量热仪(DSC)、广角X射线衍射(WAXD)、偏振红外光谱、万能试验机等手段对静电纺丝制备的PHBV纤维的形态、纤维排列有序性、结晶性能、取向度、力学性能进行表征；通过SEM、动态力学分析(DMA)、热重分析(TG)、DSC、WAXD、傅里叶变换红外光谱(FTIR)、偏光显微镜(PLM)等手段对PHBV/PEG纤维的形态、纤维排列有序性、相容性、结晶性能及晶体形态进行表征；通过SEM、万能试验机、接触角仪等测试对神经导管的表面微观形态、力学性能及亲水性进行表征。主要研究结果如下： (1)PHBV可溶于氯仿(CHCl3)/DMF (10//1)混合溶剂中进行静电纺丝,纺丝的最佳工艺参数为：浓度6%,电压12KV,推进速度0.5ml/h。 (2)转轴法制备静电纺有序PHBV纤维过程中,随着转轴表面线速度的提高,纤维的排列有序度、晶区取向度及分子链取向度、结晶度以及力学强度增大,10.5m/s时达到最大值,其后又有所降低。转轴表面线速度的提高一方面促进纤维排列有序度的提高,另一方面也会对纤维进行拉伸,使纤维的平均直径减小,取向度进一步提高,晶粒尺寸减小。电纺有序PHBV纤维在拉伸过程中经过屈服点以后没有明显的“细颈”现象,而是随着应变的增大应力逐渐降低直至完全断裂。 (3)以氯仿/DMF(10/1)为溶剂,静电纺丝制备PHBV/PEG纤维的最佳纺丝参数为：浓度8%,电压10KV,出样速率为0.8ml/h,接收距离18cm。当PEG的比例小于50wt%时,PHBV/PEG共混物的可纺性都比较好,纺出的纤维表面光滑,直径比较均匀；当PEG增加到70wt%以后,PHBV/PEG溶液仍然能够纺丝,但是纺出的丝断头很多。静电纺丝制备PHBV/PEG有序纤维的最佳转轴表面线速度为9.5m/s,其纤维的排列有序度较纯PHBV稍差。 (4)DMA和FTIR分析证明了PHBV与PEG是不相容的。在氮气气氛中,PEG的加入改善了PHBV的热稳定性；在空气气氛中,当PEG得含量超过50wt%时,共混物的热稳定性变差。通过DSC、XRD、POM分析表明在PHBV/PEG共混体系中随着PEG含量的提高,PHBV熔点稍微降低,晶粒变小,结晶温度显著降低；当PEG的含量不超过50wt%时,PHBV的结晶度基本不变,超过50wt%以后其结晶度显著降低。 (5)在卷绕PHBV/PEG内管过程中,卷绕层数以5层为佳,每层厚度约为8μm；中间层导管的最佳编织参数为：纤度为32.43tex的PCL单丝,编织锭数为8锭；神经导管外层PHBV纤维膜其表面的纤维排列有序度较低,外层导管的孔隙率较高,为81%左右。水接触角测试结果显示,随着PEG含量的增加,PHBV/PEG内管的亲水性增加；经过等离子改性以后,PHBV外管的亲水性显著增强。
[Abstract]:The repair, regeneration and functional recovery of peripheral nerve injury have been the focus of neuroscience research. The appearance of tissue engineering provides a new idea for the repair of nerve injury. At present, the nerve conduit has become one of the ways to repair the peripheral nerve injury. Transcatheter stent is a difficult problem in neural tissue engineering. Electrospun electrospun nanofiber scaffold has the advantages of high porosity and large surface area. It can mimic natural extracellular matrix from nanoscale, which can be used as a porous scaffold for cell growth and promote cell migration and proliferation.
In this paper, three layers of electrospun fibers were prepared by using hydroxybutyrate Hydroxyvalerate copolyester (PHBV), polyethylene glycol (PEG) and polyhexyl ester (PCL) as scaffolds, which were prepared by electrostatic spinning, melt spinning, and plasma modification. It was characterized by an inner tube rolled by a electrostatic spinning PHBV/PEG ordered submicron fiber film. The PHBV high specific surface area, high porosity surface area, and high porosity outer tube formed by PCL monofilament made by melt spinning and direct injection by electrostatic spinning method, and by means of scanning electron microscopy (SEM), differential scanning calorimeter (DSC), wide-angle X ray diffraction (WAXD), partial vibration infrared spectroscopy, universal testing machine and so on, the PHBV prepared by electrostatic spinning The morphology, ordering, crystallization, orientation, and mechanical properties of fibers are characterized by SEM, dynamic mechanical analysis (DMA), thermogravimetric analysis (TG), DSC, WAXD, Fourier transform infrared (FTIR), polarization microscope (PLM) and other means for the morphology, ordering, compatibility, crystallization and crystal morphology of PHBV/ PEG fibers The surface micromorphology, mechanical properties and hydrophilicity of the nerve conduits were characterized by SEM, universal testing machine and contact angle meter. The main results were as follows:
(1) PHBV can be electrospun in mixed solvents of chloroform (CHCl3) /DMF (10//1). The best spinning parameters are: concentration 6%, voltage 12KV, advancing speed 0.5ml/h.
(2) in the process of preparing the ordered PHBV fiber by the rotating shaft method, the order degree of the fiber, the orientation degree of the crystal area, the degree of molecular chain orientation, the crystallinity and the mechanical strength increase with the increase of the surface line speed of the rotating shaft, and the maximum value is reached at the time of 10.5m/s. The increase of the speed of the axis of the rotating shaft promotes the arrangement of the fibers on the one hand. On the other hand, the fiber will be stretched, the average diameter of the fiber is reduced, the orientation degree is further improved, and the grain size decreases. After the yield point of the electrospun ordered PHBV fiber, there is no obvious "fine neck" phenomenon after the yield point, but the stress gradually decreases to the complete fracture with the increase of strain.
(3) with chloroform /DMF (10/1) as solvent, the optimum spinning parameters for the preparation of PHBV/PEG fibers by electrostatic spinning are as follows: the concentration is 8%, the voltage 10KV, the sample rate is 0.8ml/h, the receiving distance 18cm. when the proportion of PEG is less than 50wt%, the spinnability of the PHBV/PEG blends is better, the fiber surface is smooth and the diameter is more uniform; PEG increases to 70wt%, The PHBV/PEG solution can still spin, but the spun yarn has a lot of broken ends. The optimal axis speed of the electrostatic spinning PHBV/PEG ordered fiber is 9.5m/s, and the order degree of the fiber is slightly worse than that of the pure PHBV.
(4) DMA and FTIR analysis showed that PHBV was incompatible with PEG. In the nitrogen atmosphere, the addition of PEG improved the thermal stability of PHBV. In the air atmosphere, when the content of PEG exceeded 50wt%, the thermal stability of the blends became worse. The analysis of DSC, XRD, POM analysis showed that the melting point decreased slightly in the PHBV/PEG co mixing system with the increase of the content. Grain size decreased and crystallization temperature decreased significantly. When the content of PEG was not more than 50wt%, the crystallinity of PHBV remained almost unchanged, and its crystallinity decreased significantly after 50wt%.
(5) in the process of winding PHBV/PEG inner tube, the number of winding layers is good with 5 layers, and the thickness of each layer is about 8 mu m; the best weaving parameters of the middle layer catheter are PCL monofilament with the size of 32.43tex, the number of weave ingot is 8, the fiber arrangement of the PHBV fiber membrane on the outer layer of the nerve conduit is lower, the porosity of the outer tube is higher, and is about 81%. The contact angle test results show that the hydrophilicity of the PHBV/PEG inner tube increases with the increase of the PEG content, and the hydrophilicity of the PHBV tube is significantly enhanced after the plasma modification.
【学位授予单位】：东华大学
【学位级别】：硕士
【学位授予年份】：2011
【分类号】：R318.08
本文编号：2143731
[Abstract]:The repair, regeneration and functional recovery of peripheral nerve injury have been the focus of neuroscience research. The appearance of tissue engineering provides a new idea for the repair of nerve injury. At present, the nerve conduit has become one of the ways to repair the peripheral nerve injury. Transcatheter stent is a difficult problem in neural tissue engineering. Electrospun electrospun nanofiber scaffold has the advantages of high porosity and large surface area. It can mimic natural extracellular matrix from nanoscale, which can be used as a porous scaffold for cell growth and promote cell migration and proliferation.
In this paper, three layers of electrospun fibers were prepared by using hydroxybutyrate Hydroxyvalerate copolyester (PHBV), polyethylene glycol (PEG) and polyhexyl ester (PCL) as scaffolds, which were prepared by electrostatic spinning, melt spinning, and plasma modification. It was characterized by an inner tube rolled by a electrostatic spinning PHBV/PEG ordered submicron fiber film. The PHBV high specific surface area, high porosity surface area, and high porosity outer tube formed by PCL monofilament made by melt spinning and direct injection by electrostatic spinning method, and by means of scanning electron microscopy (SEM), differential scanning calorimeter (DSC), wide-angle X ray diffraction (WAXD), partial vibration infrared spectroscopy, universal testing machine and so on, the PHBV prepared by electrostatic spinning The morphology, ordering, crystallization, orientation, and mechanical properties of fibers are characterized by SEM, dynamic mechanical analysis (DMA), thermogravimetric analysis (TG), DSC, WAXD, Fourier transform infrared (FTIR), polarization microscope (PLM) and other means for the morphology, ordering, compatibility, crystallization and crystal morphology of PHBV/ PEG fibers The surface micromorphology, mechanical properties and hydrophilicity of the nerve conduits were characterized by SEM, universal testing machine and contact angle meter. The main results were as follows:
(1) PHBV can be electrospun in mixed solvents of chloroform (CHCl3) /DMF (10//1). The best spinning parameters are: concentration 6%, voltage 12KV, advancing speed 0.5ml/h.
(2) in the process of preparing the ordered PHBV fiber by the rotating shaft method, the order degree of the fiber, the orientation degree of the crystal area, the degree of molecular chain orientation, the crystallinity and the mechanical strength increase with the increase of the surface line speed of the rotating shaft, and the maximum value is reached at the time of 10.5m/s. The increase of the speed of the axis of the rotating shaft promotes the arrangement of the fibers on the one hand. On the other hand, the fiber will be stretched, the average diameter of the fiber is reduced, the orientation degree is further improved, and the grain size decreases. After the yield point of the electrospun ordered PHBV fiber, there is no obvious "fine neck" phenomenon after the yield point, but the stress gradually decreases to the complete fracture with the increase of strain.
(3) with chloroform /DMF (10/1) as solvent, the optimum spinning parameters for the preparation of PHBV/PEG fibers by electrostatic spinning are as follows: the concentration is 8%, the voltage 10KV, the sample rate is 0.8ml/h, the receiving distance 18cm. when the proportion of PEG is less than 50wt%, the spinnability of the PHBV/PEG blends is better, the fiber surface is smooth and the diameter is more uniform; PEG increases to 70wt%, The PHBV/PEG solution can still spin, but the spun yarn has a lot of broken ends. The optimal axis speed of the electrostatic spinning PHBV/PEG ordered fiber is 9.5m/s, and the order degree of the fiber is slightly worse than that of the pure PHBV.
(4) DMA and FTIR analysis showed that PHBV was incompatible with PEG. In the nitrogen atmosphere, the addition of PEG improved the thermal stability of PHBV. In the air atmosphere, when the content of PEG exceeded 50wt%, the thermal stability of the blends became worse. The analysis of DSC, XRD, POM analysis showed that the melting point decreased slightly in the PHBV/PEG co mixing system with the increase of the content. Grain size decreased and crystallization temperature decreased significantly. When the content of PEG was not more than 50wt%, the crystallinity of PHBV remained almost unchanged, and its crystallinity decreased significantly after 50wt%.
(5) in the process of winding PHBV/PEG inner tube, the number of winding layers is good with 5 layers, and the thickness of each layer is about 8 mu m; the best weaving parameters of the middle layer catheter are PCL monofilament with the size of 32.43tex, the number of weave ingot is 8, the fiber arrangement of the PHBV fiber membrane on the outer layer of the nerve conduit is lower, the porosity of the outer tube is higher, and is about 81%. The contact angle test results show that the hydrophilicity of the PHBV/PEG inner tube increases with the increase of the PEG content, and the hydrophilicity of the PHBV tube is significantly enhanced after the plasma modification.
【学位授予单位】：东华大学
【学位级别】：硕士
【学位授予年份】：2011
【分类号】：R318.08
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