超临界流体制备组织工程细胞支架工艺基础研究
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摘要
细胞支架的制备工艺是组织工程学研究的核心内容。传统细胞支架的制备工艺虽然各有其优势,但存在着有机溶剂残留、制备周期长和孔隙率低等不足。近年来,将超临界流体(简称SCF)技术引入组织工程细胞支架的制备过程已引起研究者广泛关注。利用现有的超临界C02(简称ScCO2)发泡工艺制备细胞支架,虽然没有有机溶剂的残留,但其孔隙率较低、难以控制孔尺寸的范围；利用ScCO2与其他工艺结合制备细胞支架,增加了原工艺的复杂性,使得制备周期延长；利用超临界反溶剂(简称SAS)工艺制备细胞支架,既没有有机溶剂的残留,又可以通过改变工艺参数来控制支架的孔径范围,具有广阔的应用前景。目前对SAS工艺的研究仅停留在实验阶段,主要探讨相关工艺参数对支架性能的影响,缺乏深入系统的理论研究。
本论文首先对现有的ScCO2发泡工艺进行改进,采用多次升温和泄压的方法,以典型的无定型类聚合物—PMMA为模型材料,制备了PMMA多孔支架,考察了主要工艺参数对多孔支架性能的影响,并与现有的ScCO2发泡工艺制备的支架进行了比较。结果表明,与现有ScCO2发泡技术制备的PMMA细胞支架相比,在相同温度、压力、泄压时间、不同保压时间的条件下,改进工艺制备的PMMA细胞支架具有孔径范围大、孔隙率高、孔与孔之间连通性好的特点。
利用SAS工艺,以PCL、PLLA为模型材料,进行了SAS工艺制备细胞支架的实验研究,确定了聚合物浓度、CO2压力和温度对支架形态、孔径分布的影响规律,得出了实验范围内制备上述材料支架的最佳工艺；为了提高单体PLLA支架的孔隙率与抗压强度,分别以PEG和β-TCP为添加剂,在制备单体PLLA细胞支架的基础上,成功制备了PLLA/PEG和PLLA/β-TCP复合材料支架。结果显示,加入PEG后,可以提高支架的孔隙率,最高可达92%；加入β-TCP后,可以提高支架的抗压强度,最高可达1.76MPa。
以Flory-Huggins理论为基础,对SAS工艺的热力学行为进行了研究,建立了适合SAS工艺过程的相平衡热力学模型。利用模型中双节线、旋节线和临界点的计算方法,得到了三元体系相图,分别分析了ScCO2/AC/PCL和ScCO2/CH2C12/PLLA三元体系在制备多孔支架过程中的相行为。结果表明,两种三元体系均在临界点的上方按成核生长机理发生液—液相分离,可制备出具有多孔结构特征的聚合物。随着CO2压力的增加,相互作用参数χ12、χ13均减小,χ23保持不变；随着温度的升高,相互作用参数χ12χ13均增大,X23变化的趋势很小；分相点的计算结果表明,随着压力的增加,非溶剂进入聚合物溶液中的量逐渐增大,而随着温度的升高,非溶剂进入聚合物溶液中的量逐渐减小,两种体系计算结果一致。
基于Reuvers模型,建立了适合SAS工艺过程的传质动力学模型,分别针对ScCO2/AC/PCL和ScCO2/CH2C12/PLLA三元体系给出了相关参数的求取方法,模拟了传质过程,得到了三元相图中的传质路径,描述了不同工艺参数对多孔结构的影响趋势。结果表明：两种三元体系在不同工艺条件下各组分体积分数的变化趋势相似,组分间扩散系数随着CO2压力的增加而减小,随着温度的升高而增大：随着聚合物浓度的增加、CO2压力的减小和温度的升高,传质路径逐渐变短,相分离速度逐渐加快,支架的平均孔径呈逐渐减小的趋势。支架平均孔径的最终变化趋势受相平衡热力学和传质动力学两方面因素的影响；两种三元体系中聚合物不同的物理性质、组分间不同的扩散系数造成了两种支架截面孔结构的不同。
Scaffolds fabrication technique is essential to tissue engineering research. Conventional techniques for scaffolds fabrication have their advantages, but they exist in one or more limitations as follows:residual organic solvent, low porosity and difficulty in controlling pore size. Recently, supercritical fluid has been introduced into scaffolds production, and several processes have been developed. Among these three processes stand out and gain more attention. One of these is the ScCO2foaming process and no solvent is used during the process, while the product obtained by this process has generally low porosity and closed-cells structure. Combing ScCO2with other processes can overcome some disadvantages, but it makes the process more complexited and time consumed. The SAS process has shown great application potential in preparing porous polymer with the advantages of no residual organic solvent and controllable pore size by adjusting process parameters. The present research work on the SAS process is still in the early stage on the process feasibility, and there are seldom reseach on the systemically theoretical research of the process.
An improvement is made on the ScCO2foaming process. Porous PMMA scaffolds are produced by repeated heating and pressure reducing. The influences of the different operation parameters on the properties of porous scaffolds are examined and a comparison is made between conventional SCCO2foaming process and the improved one. The results show that the porosity, pore size and pore connectivity of PMMA scaffolds prepared by improved ScCO2foaming process are higher than those prepared by conventional one at the operation conditions of the same temperature, pressure, pressure release time, and different maitaining times.
The scaffolds of PCL and PLLA polymer are successfully prepared by SAS process. The influences of operation parameters (polymer concentration, CO2pressure and temperature) on the scaffolds morphology, pore size and size distribution are investigated. The optimal operation conditions for these materials are obtained. In order to improve the porosity and the compressive strength of the PLLA scaffolds, the PLLA composite scaffolds are fabricated with PEG and β-TCP as additive respectively. The porosity increases with the adding of the PEG and the highest porosity of PLLA/PEG composite scaffolds can reach92%. The compressive strength increases with the adding of the β-TCP and the highest compressive strength of PLLA/β-TCP composite scaffolds can reach1.76MPa.
Based on Flory-Huggins theory, a thermodynamic model suitable for SAS process is established. Through the calculation of binodal line, spinodal line and critical point, the ternary phase diagram is obtained. The thermodynamics behaviors of ScCO2/AC/PCL and ScCO2/CH2Cl2/PLLA systems in the process of preparing porous scaffolds are analyzed by means of the ternary phase diagram. The results show that both systems have liquid-liquid phase separation in the upper part of the critical point following the nuclear growth mechanism, and they are suitable for the preparation of porous scaffolds. The interaction parameters χ12and χ13reduce, but χ23remains unchanged with the increase of CO2pressure. As the temperature increases, the interaction parameters χ12and χ13increase, the change of χ23is very small. The calculation results of split phase point show that the solvent quantity of polymer solution increases gradually with the increase of pressure and the decrease temperature. Similar calculations are obtained in these two systems.
Based on Reuvers model, a mass transfer dynamics model suitable for SAS process is established. The computing methods of model parameters are given, the mass transfer processes of ScCO2/AC/PCL and ScCO2/CH2Cl2/PLLA system are simulated, and the influences of the operation parameters on the scaffolds morphology, pore size and size distribution are investigated according to the mass transfer path obtained by the calculation. The result shows that the change of volume fraction of the different component is similar in the two systems. The diffusion coefficients decrease with the increase of CO2pressure, while they increase with the increase of temperature. The mass transfer path gradually becomes short with the increase of the polymer concentration or temperature or with the decrease of CO2pressure. So the speed of phase sepatation gradually accelerate, then the mean pore size of scaffolds gradually decrease. The formation of scaffolds is the result of the combination of the equilibrium thermodynamics and membrane formation kinetics. The different porous structures of these two scaffolds can be explained with different physical properties and component different diffusion coefficients of the polymers.
本论文首先对现有的ScCO2发泡工艺进行改进,采用多次升温和泄压的方法,以典型的无定型类聚合物—PMMA为模型材料,制备了PMMA多孔支架,考察了主要工艺参数对多孔支架性能的影响,并与现有的ScCO2发泡工艺制备的支架进行了比较。结果表明,与现有ScCO2发泡技术制备的PMMA细胞支架相比,在相同温度、压力、泄压时间、不同保压时间的条件下,改进工艺制备的PMMA细胞支架具有孔径范围大、孔隙率高、孔与孔之间连通性好的特点。
利用SAS工艺,以PCL、PLLA为模型材料,进行了SAS工艺制备细胞支架的实验研究,确定了聚合物浓度、CO2压力和温度对支架形态、孔径分布的影响规律,得出了实验范围内制备上述材料支架的最佳工艺；为了提高单体PLLA支架的孔隙率与抗压强度,分别以PEG和β-TCP为添加剂,在制备单体PLLA细胞支架的基础上,成功制备了PLLA/PEG和PLLA/β-TCP复合材料支架。结果显示,加入PEG后,可以提高支架的孔隙率,最高可达92%；加入β-TCP后,可以提高支架的抗压强度,最高可达1.76MPa。
以Flory-Huggins理论为基础,对SAS工艺的热力学行为进行了研究,建立了适合SAS工艺过程的相平衡热力学模型。利用模型中双节线、旋节线和临界点的计算方法,得到了三元体系相图,分别分析了ScCO2/AC/PCL和ScCO2/CH2C12/PLLA三元体系在制备多孔支架过程中的相行为。结果表明,两种三元体系均在临界点的上方按成核生长机理发生液—液相分离,可制备出具有多孔结构特征的聚合物。随着CO2压力的增加,相互作用参数χ12、χ13均减小,χ23保持不变；随着温度的升高,相互作用参数χ12χ13均增大,X23变化的趋势很小；分相点的计算结果表明,随着压力的增加,非溶剂进入聚合物溶液中的量逐渐增大,而随着温度的升高,非溶剂进入聚合物溶液中的量逐渐减小,两种体系计算结果一致。
基于Reuvers模型,建立了适合SAS工艺过程的传质动力学模型,分别针对ScCO2/AC/PCL和ScCO2/CH2C12/PLLA三元体系给出了相关参数的求取方法,模拟了传质过程,得到了三元相图中的传质路径,描述了不同工艺参数对多孔结构的影响趋势。结果表明：两种三元体系在不同工艺条件下各组分体积分数的变化趋势相似,组分间扩散系数随着CO2压力的增加而减小,随着温度的升高而增大：随着聚合物浓度的增加、CO2压力的减小和温度的升高,传质路径逐渐变短,相分离速度逐渐加快,支架的平均孔径呈逐渐减小的趋势。支架平均孔径的最终变化趋势受相平衡热力学和传质动力学两方面因素的影响；两种三元体系中聚合物不同的物理性质、组分间不同的扩散系数造成了两种支架截面孔结构的不同。
Scaffolds fabrication technique is essential to tissue engineering research. Conventional techniques for scaffolds fabrication have their advantages, but they exist in one or more limitations as follows:residual organic solvent, low porosity and difficulty in controlling pore size. Recently, supercritical fluid has been introduced into scaffolds production, and several processes have been developed. Among these three processes stand out and gain more attention. One of these is the ScCO2foaming process and no solvent is used during the process, while the product obtained by this process has generally low porosity and closed-cells structure. Combing ScCO2with other processes can overcome some disadvantages, but it makes the process more complexited and time consumed. The SAS process has shown great application potential in preparing porous polymer with the advantages of no residual organic solvent and controllable pore size by adjusting process parameters. The present research work on the SAS process is still in the early stage on the process feasibility, and there are seldom reseach on the systemically theoretical research of the process.
An improvement is made on the ScCO2foaming process. Porous PMMA scaffolds are produced by repeated heating and pressure reducing. The influences of the different operation parameters on the properties of porous scaffolds are examined and a comparison is made between conventional SCCO2foaming process and the improved one. The results show that the porosity, pore size and pore connectivity of PMMA scaffolds prepared by improved ScCO2foaming process are higher than those prepared by conventional one at the operation conditions of the same temperature, pressure, pressure release time, and different maitaining times.
The scaffolds of PCL and PLLA polymer are successfully prepared by SAS process. The influences of operation parameters (polymer concentration, CO2pressure and temperature) on the scaffolds morphology, pore size and size distribution are investigated. The optimal operation conditions for these materials are obtained. In order to improve the porosity and the compressive strength of the PLLA scaffolds, the PLLA composite scaffolds are fabricated with PEG and β-TCP as additive respectively. The porosity increases with the adding of the PEG and the highest porosity of PLLA/PEG composite scaffolds can reach92%. The compressive strength increases with the adding of the β-TCP and the highest compressive strength of PLLA/β-TCP composite scaffolds can reach1.76MPa.
Based on Flory-Huggins theory, a thermodynamic model suitable for SAS process is established. Through the calculation of binodal line, spinodal line and critical point, the ternary phase diagram is obtained. The thermodynamics behaviors of ScCO2/AC/PCL and ScCO2/CH2Cl2/PLLA systems in the process of preparing porous scaffolds are analyzed by means of the ternary phase diagram. The results show that both systems have liquid-liquid phase separation in the upper part of the critical point following the nuclear growth mechanism, and they are suitable for the preparation of porous scaffolds. The interaction parameters χ12and χ13reduce, but χ23remains unchanged with the increase of CO2pressure. As the temperature increases, the interaction parameters χ12and χ13increase, the change of χ23is very small. The calculation results of split phase point show that the solvent quantity of polymer solution increases gradually with the increase of pressure and the decrease temperature. Similar calculations are obtained in these two systems.
Based on Reuvers model, a mass transfer dynamics model suitable for SAS process is established. The computing methods of model parameters are given, the mass transfer processes of ScCO2/AC/PCL and ScCO2/CH2Cl2/PLLA system are simulated, and the influences of the operation parameters on the scaffolds morphology, pore size and size distribution are investigated according to the mass transfer path obtained by the calculation. The result shows that the change of volume fraction of the different component is similar in the two systems. The diffusion coefficients decrease with the increase of CO2pressure, while they increase with the increase of temperature. The mass transfer path gradually becomes short with the increase of the polymer concentration or temperature or with the decrease of CO2pressure. So the speed of phase sepatation gradually accelerate, then the mean pore size of scaffolds gradually decrease. The formation of scaffolds is the result of the combination of the equilibrium thermodynamics and membrane formation kinetics. The different porous structures of these two scaffolds can be explained with different physical properties and component different diffusion coefficients of the polymers.
引文
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