PAN基碳纳米纤维杂化复合材料及其生物特性研究
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摘要
碳纳米纤维(Carbon nanofiber)由于其优异的机械强度、化学稳定性、高的长径比以及易于表面官能化等性能逐渐成为研究的热点。通过静电纺丝-碳化法制备的碳纳米纤维材料还具有与细胞外基质的形态结构相似、无金属催化剂杂质、具有大的比表面积和高孔隙率等特点,被认为在生物医学领域有潜在的应用前景。然而,碳纳米纤维是生物惰性材料,在骨组织修复的过程中,为了使碳纳米纤维支架材料更好的与创伤部位结合,其与其他的生物材料的复合是一种有效的方法。本文利用静电纺丝、溶胶-凝胶以及原位烧结相结合的方法制备了PAN基碳纳米纤维杂化生物复合材料。通过对复合纳米纤维材料的组分、相结构、细胞毒性、细胞相容性以及生物活性等方面的研究,系统地评价这类新型生物材料用于引导骨再生膜／支架材料的可行性和优越性。
本文首先优化了PAN平行纳米纤维的静电纺丝制备工艺,不仅使PAN纳米纤维的直径分布明显变窄,而且还改善了PAN静电纺丝过程的稳定性。经过热牵伸处理后,PAN平行纳米纤维膜的纤维直径减小,纤维间隙变小,平均拉伸强度达到了302 MPa。其次,β-磷酸三钙(β-TCP)是一种可降解的骨修复生物陶瓷材料,其在骨组织修复中能够提供骨再生所必需的钙离子和磷酸根离子。本文以溶胶-凝胶技术为基础,磷酸三乙酯(TEP)和硝酸钙(CN)为磷源和钙源,通过控制水解体系pH值、调整催化剂和溶胶烧结温度,获得了制备高纯度和高结晶度的β-TCP凝胶的工艺。第三,以掺杂了TEP和CN形成的溶胶(TEP-CN)的PAN溶液为纺丝液,用优化的PAN静电纺丝的工艺得到PAN/TEP-CN复合纳米纤维,结合高纯度β-TCP凝胶的制备条件,对该复合纳米纤维进行热牵伸、预氧化和高温碳化烧结,制备了一种由β-TCP提供生物功能和碳纳米纤维提供结构特性的复合纳米纤维。并讨论了负载不同溶胶量对复合纳米纤维微观形貌、生物特性的影响。
研究发现：低溶胶量负载得到的β-TCP@碳纳米纤维,β-TCP纳米颗粒为20-30 nm,主要位于碳纳米纤维的表面；而高溶胶量负载得到的β-TCP@碳纳米纤维,纤维表面比较光滑,通过(透射电子显微镜)TEM分析得知β-TCP纳米颗粒主要位于碳纳米纤维的内部,且粒径较大,与碳纳米纤维共同形成了类似竹节状的结构。通过对高溶胶量负载的β-TCP@碳纳米纤维进行加速降解研究得知：这种类似竹节状的结构可以通过β-TCP纳米颗粒的溶解而使连续的碳纳米纤维的长径比大大缩短。
对上述制备的复合纳米纤维材料进行了MTT细胞毒性试验和人牙周膜细胞(hPDLCs)的体外复合培养等生物相容性检测。MTT检测结果显示所制得的材料细胞相容性良好,没有明显毒性。用激光共聚焦显微镜观察hPDLCs在纳米纤维材料上的铺展和生长情况显示,hPDLCs在β-TCP@碳纳米纤维材料上完全铺展开来,并且细胞沿平行纤维方向生长。扫描电镜结果(SEM)显示,细胞与材料结合紧密,分泌大量的细胞外基质,生长状态良好。
生物活性玻璃(Bioglass)是目前所知唯一可以同时与硬组织和软组织结合良好的骨修复材料。本文以正硅酸四乙酯(TEOS)为硅源、TEP和CN为磷源和钙源、PAN为基体,利用前述优化的制备工艺,将生物活性玻璃纳米颗粒原位掺杂进入碳纳米纤维制得Bioglass@碳纳米纤维。SEM结果显示该复合纤维的平均直径为360nm,其表面负载的Bioglass纳米颗粒的粒径约为20 nm。
对所制备的Bioglass@碳纳米纤维进行了生物活性检测。通过XRD、FTIR、EDX等分析方法对复合纳米纤维在5倍模拟人体体液(5SBF)内生物矿化后的微观形貌和结构进行了表征。6小时矿化后,碳纳米纤维表面的Bioglass纳米颗粒表面有粒状产物隆起,并且随着矿化时间的延长逐渐长大,12-18 h后有些区域产物进一步聚合成球形晶簇。矿化24 h后,球形产物增多并连成片。矿化30 h后,矿化层增厚,厚度达600 nm以上,覆盖整个复合纳米纤维表面。测试结果表明得到的花状结晶为碳酸羟基磷灰石。
综上所述,由静电纺丝-溶胶凝胶-后烧结相结合的方法所制得的PAN基碳纳米纤维复合材料支架具有良好的生物相容性和结构适用性,具有用于临床的引导组织／骨再生治疗的潜能,有望成为新一代纳米复合生物材料。
Carbon nanofibers (CNFs) show good mechanical properties, chemical stability, high aspect ratio and easy surface functionalized capability to be decorated with more biocompatible hydrophilic groups, which are concerned by more and more researchers. And the CNFs prepared by electrospinning-carbonization which mimic the structure of natural extracellular matrix have attracted considerable attention for both fundamental scientific understanding and their potential biomedical applications. In order to form sufficient bonding between CNFs and juxtaposed bone tissue and to minimize motion-induced damage to surrounding tissue in situ, combination of CNFs with biomaterials is a very effective approach. In this study, a new combination of electrospinning, sol-gel and in-situ sintering was used to prepare the PAN-based hybrid carbon nanofibers. To evaluate the feasibility and superiority of the new type of biomaterials for clinical use, the material composition, phase structure, cytotoxicity, biocompatibility and bioactivity were all studied systematically.
Firstly, the electrospinning of PAN nanofibers were optimized by using mixture solutions. As a result, not only the fiber diameters were narrower obviously, but also the process stability was improved. After hot stretching treatment, the fiber diameters were reduced and the fiber gaps become smaller while the maximum tensile strength reached 302 MPa. Secondly,β-tricalcium phosphate (β-TCP) is a biodegradable bio-ceramic materials for bone repair, which can provide the necessary calcium and phosphate ions. By controlling the pH value of hydrolysis system, adjusting the catalyst and sol-sintering temperature, high purity and high crystallinity ofβ-TCP crystals with triethyl phosphate (TEP) and calcium nitrate (CN) as the phosphorus and calcium source were prepared. Thirdly, PAN/TEP-CN composite nanofibers were prepared by electrospinning. After the hot strenching treatment, stabilization and carbonization of the PAN/TEP-CN composite nanofibers, a type of nanofibers with biological properties provided byβ-TCP and the structural properties provided by CNFs was fabricated. And the morphology and biological characteristics of the composite nanofibers with different sol volumes were studied.
The results show that theβ-TCP nanoparticles are mainly on the surface of the CNFs when the composite fibers were prepared at low sol volume, and the diameter of the nanoparticles is 20-30 nm. TEM analysis shows that the nanoparticles are maily located inside the nanofiber when prepared at high sol volume, and finally form a bamboo-like structure. The accelerated degradation of composite nanofibers with high sol volume was studied. The long-continued nanofibers can be effectively degraded into small CNFs with aspect ratio due to the degradation of (3-TCP nanoparticles.
The biocompatibility test was carried on the above-mentioned composite nanofibrous scaffolds, including cytotoxicity test (MTT test) and human periodontal ligament cells (hPDLCs) in vitro co-culture experiments. MTT test results indicate that the prepared materials have good biocompatibility, and no apparent toxicity. Confocal laser microscope observation shows that the PDLCs adhere favorably onβ-TCP/CNFs membranes with proliferating preferencely along the aligned longitudinal direction of nanofibers. Scanning electron microscopy (SEM) shows that the PDLCs were in close combination with materials, and produces large amounts of extracellular matrix.
It is generally believed that bioglass is a widely-used bone repair material, which has shown an excellent behavior when it is in contact with physiological fluids. In addition, bioglass is the only one, which can bond to both hard and soft tissue. In this study, carbon nanofibers decorated with bioglass nanoparticles have been prepared by sintering electrospun polyacrylonitrile fibers with calcium nitrate tetrahydrate as the calcium source, tetraethoxysilane (TEOS) as the silica source and triethyl phosphate as the phosphorus source. The SEM reveals that the average diameter of the nanofibers is 360 nm, and the diameter of nanoparticles on the surface of the composite nanofibers is about 20 nm. The results of mineralization in five-timed simulated body fluid (5SBF) characterized by XRD, FTIR and EDX analysis indicate that this kind of hybrid nanofibers possesses good bioactivity. After immersion in 5SBF for 6 h, granular crystals grow from the bioglass nanoparticles which are on the surface of the nanofiber. With the mineralization time extending, the granular crystals become more and more spherical, and after 30 h, the mineral layer are thicker than 600 nm, completely covering the surface of the composite nanofibers. The results show that the obtained flower-like crystals are carbonated hydroxyapatite.
Therefore, theβ-TCP or bioglass decorated CNF nanofibrous materials with good biocompatibility and structural properties can be used as promising biomaterials for guide tissue/bone regeneration.
本文首先优化了PAN平行纳米纤维的静电纺丝制备工艺,不仅使PAN纳米纤维的直径分布明显变窄,而且还改善了PAN静电纺丝过程的稳定性。经过热牵伸处理后,PAN平行纳米纤维膜的纤维直径减小,纤维间隙变小,平均拉伸强度达到了302 MPa。其次,β-磷酸三钙(β-TCP)是一种可降解的骨修复生物陶瓷材料,其在骨组织修复中能够提供骨再生所必需的钙离子和磷酸根离子。本文以溶胶-凝胶技术为基础,磷酸三乙酯(TEP)和硝酸钙(CN)为磷源和钙源,通过控制水解体系pH值、调整催化剂和溶胶烧结温度,获得了制备高纯度和高结晶度的β-TCP凝胶的工艺。第三,以掺杂了TEP和CN形成的溶胶(TEP-CN)的PAN溶液为纺丝液,用优化的PAN静电纺丝的工艺得到PAN/TEP-CN复合纳米纤维,结合高纯度β-TCP凝胶的制备条件,对该复合纳米纤维进行热牵伸、预氧化和高温碳化烧结,制备了一种由β-TCP提供生物功能和碳纳米纤维提供结构特性的复合纳米纤维。并讨论了负载不同溶胶量对复合纳米纤维微观形貌、生物特性的影响。
研究发现：低溶胶量负载得到的β-TCP@碳纳米纤维,β-TCP纳米颗粒为20-30 nm,主要位于碳纳米纤维的表面；而高溶胶量负载得到的β-TCP@碳纳米纤维,纤维表面比较光滑,通过(透射电子显微镜)TEM分析得知β-TCP纳米颗粒主要位于碳纳米纤维的内部,且粒径较大,与碳纳米纤维共同形成了类似竹节状的结构。通过对高溶胶量负载的β-TCP@碳纳米纤维进行加速降解研究得知：这种类似竹节状的结构可以通过β-TCP纳米颗粒的溶解而使连续的碳纳米纤维的长径比大大缩短。
对上述制备的复合纳米纤维材料进行了MTT细胞毒性试验和人牙周膜细胞(hPDLCs)的体外复合培养等生物相容性检测。MTT检测结果显示所制得的材料细胞相容性良好,没有明显毒性。用激光共聚焦显微镜观察hPDLCs在纳米纤维材料上的铺展和生长情况显示,hPDLCs在β-TCP@碳纳米纤维材料上完全铺展开来,并且细胞沿平行纤维方向生长。扫描电镜结果(SEM)显示,细胞与材料结合紧密,分泌大量的细胞外基质,生长状态良好。
生物活性玻璃(Bioglass)是目前所知唯一可以同时与硬组织和软组织结合良好的骨修复材料。本文以正硅酸四乙酯(TEOS)为硅源、TEP和CN为磷源和钙源、PAN为基体,利用前述优化的制备工艺,将生物活性玻璃纳米颗粒原位掺杂进入碳纳米纤维制得Bioglass@碳纳米纤维。SEM结果显示该复合纤维的平均直径为360nm,其表面负载的Bioglass纳米颗粒的粒径约为20 nm。
对所制备的Bioglass@碳纳米纤维进行了生物活性检测。通过XRD、FTIR、EDX等分析方法对复合纳米纤维在5倍模拟人体体液(5SBF)内生物矿化后的微观形貌和结构进行了表征。6小时矿化后,碳纳米纤维表面的Bioglass纳米颗粒表面有粒状产物隆起,并且随着矿化时间的延长逐渐长大,12-18 h后有些区域产物进一步聚合成球形晶簇。矿化24 h后,球形产物增多并连成片。矿化30 h后,矿化层增厚,厚度达600 nm以上,覆盖整个复合纳米纤维表面。测试结果表明得到的花状结晶为碳酸羟基磷灰石。
综上所述,由静电纺丝-溶胶凝胶-后烧结相结合的方法所制得的PAN基碳纳米纤维复合材料支架具有良好的生物相容性和结构适用性,具有用于临床的引导组织／骨再生治疗的潜能,有望成为新一代纳米复合生物材料。
Carbon nanofibers (CNFs) show good mechanical properties, chemical stability, high aspect ratio and easy surface functionalized capability to be decorated with more biocompatible hydrophilic groups, which are concerned by more and more researchers. And the CNFs prepared by electrospinning-carbonization which mimic the structure of natural extracellular matrix have attracted considerable attention for both fundamental scientific understanding and their potential biomedical applications. In order to form sufficient bonding between CNFs and juxtaposed bone tissue and to minimize motion-induced damage to surrounding tissue in situ, combination of CNFs with biomaterials is a very effective approach. In this study, a new combination of electrospinning, sol-gel and in-situ sintering was used to prepare the PAN-based hybrid carbon nanofibers. To evaluate the feasibility and superiority of the new type of biomaterials for clinical use, the material composition, phase structure, cytotoxicity, biocompatibility and bioactivity were all studied systematically.
Firstly, the electrospinning of PAN nanofibers were optimized by using mixture solutions. As a result, not only the fiber diameters were narrower obviously, but also the process stability was improved. After hot stretching treatment, the fiber diameters were reduced and the fiber gaps become smaller while the maximum tensile strength reached 302 MPa. Secondly,β-tricalcium phosphate (β-TCP) is a biodegradable bio-ceramic materials for bone repair, which can provide the necessary calcium and phosphate ions. By controlling the pH value of hydrolysis system, adjusting the catalyst and sol-sintering temperature, high purity and high crystallinity ofβ-TCP crystals with triethyl phosphate (TEP) and calcium nitrate (CN) as the phosphorus and calcium source were prepared. Thirdly, PAN/TEP-CN composite nanofibers were prepared by electrospinning. After the hot strenching treatment, stabilization and carbonization of the PAN/TEP-CN composite nanofibers, a type of nanofibers with biological properties provided byβ-TCP and the structural properties provided by CNFs was fabricated. And the morphology and biological characteristics of the composite nanofibers with different sol volumes were studied.
The results show that theβ-TCP nanoparticles are mainly on the surface of the CNFs when the composite fibers were prepared at low sol volume, and the diameter of the nanoparticles is 20-30 nm. TEM analysis shows that the nanoparticles are maily located inside the nanofiber when prepared at high sol volume, and finally form a bamboo-like structure. The accelerated degradation of composite nanofibers with high sol volume was studied. The long-continued nanofibers can be effectively degraded into small CNFs with aspect ratio due to the degradation of (3-TCP nanoparticles.
The biocompatibility test was carried on the above-mentioned composite nanofibrous scaffolds, including cytotoxicity test (MTT test) and human periodontal ligament cells (hPDLCs) in vitro co-culture experiments. MTT test results indicate that the prepared materials have good biocompatibility, and no apparent toxicity. Confocal laser microscope observation shows that the PDLCs adhere favorably onβ-TCP/CNFs membranes with proliferating preferencely along the aligned longitudinal direction of nanofibers. Scanning electron microscopy (SEM) shows that the PDLCs were in close combination with materials, and produces large amounts of extracellular matrix.
It is generally believed that bioglass is a widely-used bone repair material, which has shown an excellent behavior when it is in contact with physiological fluids. In addition, bioglass is the only one, which can bond to both hard and soft tissue. In this study, carbon nanofibers decorated with bioglass nanoparticles have been prepared by sintering electrospun polyacrylonitrile fibers with calcium nitrate tetrahydrate as the calcium source, tetraethoxysilane (TEOS) as the silica source and triethyl phosphate as the phosphorus source. The SEM reveals that the average diameter of the nanofibers is 360 nm, and the diameter of nanoparticles on the surface of the composite nanofibers is about 20 nm. The results of mineralization in five-timed simulated body fluid (5SBF) characterized by XRD, FTIR and EDX analysis indicate that this kind of hybrid nanofibers possesses good bioactivity. After immersion in 5SBF for 6 h, granular crystals grow from the bioglass nanoparticles which are on the surface of the nanofiber. With the mineralization time extending, the granular crystals become more and more spherical, and after 30 h, the mineral layer are thicker than 600 nm, completely covering the surface of the composite nanofibers. The results show that the obtained flower-like crystals are carbonated hydroxyapatite.
Therefore, theβ-TCP or bioglass decorated CNF nanofibrous materials with good biocompatibility and structural properties can be used as promising biomaterials for guide tissue/bone regeneration.
引文
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