聚乳酸多孔支架的变温降解研究

考察了聚乳酸多孔支架不同温度下的降解行为,提出了一种降解速率的快速外推方法.以DL型丙交酯合成无定型聚乳酸,采用溶剂浇铸-粒子溶出的方法制备高孔隙率的多孔支架,考察了PBS缓冲液中、不同温度下聚乳酸多孔支架的降解行为,测定了特性黏数、质量损失和模量随时间的变化.根据聚乳酸多孔支架降解半衰期随温度的变化曲线,验证了分子量的变化满足Arrhenius方程,计算得到降解的活化能,表明聚乳酸类材料的降解可以采用升温外推的方法来缩短降解实验时间.     

聚乳酸及其共聚物多孔支架的制备及性能比较

采用热致相分离法制备了聚左旋丙交酯(PLLA)、聚左旋丙交酯乙交酯(PLLGA)、单甲氧基聚乙二醇-聚左旋丙交酯乙交酯(MPEG-PLLGA)多孔支架,比较了聚合物溶液浓度、溶剂体系对3种支架孔隙率、孔径、孔的形态和力学性能的影响。结果表明,随聚合物溶液浓度的增大,3种支架的孔隙率、孔径均呈减小趋势,压缩强度增大;在质量浓度为0.05g/mL时,PLLA、PLLGA和MPEG-PLLGA的多孔结构均排列较规整,而质量浓度为0.03g/mL和0.04g/mL时,3种支架的孔结构差异较大。选用二氧六环/水混合溶剂体系时,MPEG-PLLGA支架的孔结构较为规整,而PLLA支架表面为微球状,PLLGA支架的孔壁较厚,孔形态不规整。     

用超临界CO2法制备聚乳酸三维多孔支架材料

在超临界CO2(SC—CO2)条件下制备了生物相容性良好的聚乳酸(PLA)多孔材料，研究了PLA的分子量、SC—CO2的压力、温度和处理时间对多孔材料的结构形态、孔隙率和玻璃化温度的影响。结果表明：支架材料的孔洞分布、结构形态和孔隙率不仅与聚乳酸的分子量有关，而且与处理样品的压力、温度和时间关系密切；经超临界CO2处理后材料的玻璃化温度(Tg)有所升高，与传统的方法所制得的材料相比较，多孔材料不仅杂质少，孔径孔率分布均匀，孔洞表面粗糙，而且在大孔之间几乎布满了直径为10—20μm的微孔，该结构提供了营养物质和新陈代谢的通道，且细胞和生长因子也能通过。     

采用聚醚酯制备多孔支架的条件控制

采用热致相分离(TIPS)结合冷冻干燥技术制备了聚醚酯(聚对苯二甲酸丁二醇酯-co-聚对苯二甲酸环己烷二甲醇酯-b-聚乙二醇)(PTCG)多孔支架,研究了聚合物质量浓度、粗化温度和溶剂组成等相分离参数对多孔支架形貌结构的影响.结果表明,制备出的多孔支架孔间相互贯通,支架表面(与空气接触面)的孔径大于底面(与玻璃接触面)的孔径;随着聚合物质量浓度的增大,支架的孔径和孔隙率减小.由于分相过程中热力学推动力增大和相区融合阻力增加的相互作用,孔径随着粗化温度的降低呈现先升后降的趋势,并在0℃时出现最大值.在DO中加入不良溶剂H2O,溶液分相温度的升高导致多孔支架孔径的增大.通过控制相分离参数可以制备不同形貌结构的PTCG多孔支架.     

聚乳酸组织工程支架在SBF溶液中的降解和矿化性能

本文利用扫描电镜、X射线衍射仪以及红外漫反射仪,并通过对聚乳酸组织工程支架在模拟体液(SBF)中的失重率、分子量以及模拟体液pH值变化的测试,系统地研究了聚乳酸组织工程支架在模拟体液中的降解和矿化性能。结果发现:在模拟体液中,随着时间的增长,聚乳酸组织工程支架的分子量不断下降;但是其重量并不随着时间的增长而减小,而是有升有降。X-射线衍射图谱和FTIR漫反射图谱研究表明,在模拟体液中,聚乳酸组织工程支架的表面有磷灰石沉积物出现。     

支架结构对聚乳酸组织工程支架在SBF溶液中降解进程的影响

本文通过对不同孔隙率和不同孔径的聚乳酸组织工程支架在模拟体液（SBF）中的降解性能的研究,探讨支架结构对聚乳酸组织工程支架在SBF溶液中降解进程的影响.研究发现：孔径适中的200-300微米致孔剂制得的聚乳酸组织工程支架材料在降解1周后比其它两种孔径（致孔剂粒径100微米以下、致孔剂粒径300-400微米）的支架材料的分子量更高,支架的降解性能更稳定;孔隙率越高支架材料的分子量降低得越慢.聚乳酸组织工程支架的失重率并不随着降解时间的增长而逐步增大,而是呈起伏状态,这是由于组织工程支架在SBF溶液中既有降解进程,又有沉积进程造成的.     

纳米羟基磷灰石/聚酰胺多孔支架材料的制备及性能研究

使用多种致孔剂采用粒子沥滤法制备了纳米羟基磷灰石／聚酰胺多孔支架材料，用IR、XRD、SEM等手段对多孔复合材料的组成结构及形貌进行了表征，并检测了其物理性能指标。结果表明，复合材料中两相分散均匀，且发生了界面结合；材料的孔隙率与致孔剂的含量成正比，支架中大孔与微孔并存且相互贯通；以NaCl作致孔剂且孔隙率达到80％左右时的支架材料可以同时满足组织工程对孔隙率和力学强度的双重要求。     

生物活性玻璃/聚乳酸组织工程支架在SBF溶液中的降解和矿化性能

利用扫描电镜、X衍射仪以及红外漫反射仪,并通过对生物活性玻璃/聚乳酸组织工程支架在模拟体液（SBF）中失重率及模拟体液pH值的变化的检测,系统研究了生物活性玻璃/聚乳酸组织工程支架在SBF中的降解和矿化性能。结果发现：随着含有生物活性玻璃的聚乳酸支架在SBF溶液中浸泡时间的增长,SBF的pH值不断下降;含有生物活性玻璃...     

冷冻抽提相分离法制备聚乳酸多孔支架

为了制备结构和性能满足骨组织工程支架要求的聚乳酸(PLA)多孔支架材料,采用冷冻抽提相分离法,以1,4-二氧六环和水为混合溶剂,聚乙二醇(PEG)为致孔剂,制得一系列PLA多孔支架,探讨了溶剂组成、PLA浓度、PEG添加量对PLA多孔支架结构和性能的影响,结果表明添加PEG有利于形成多孔三维支架,随着PEG含量的增加,...     

分级多孔结构聚乳酸支架的制备与性能研究

以左旋聚乳酸为原料,1,4-二氧六环/水为溶剂,采用热致相分离法制备了具有分级多孔结构的组织工程支架。研究了溶剂配比、粗化时间对支架结构和性能的影响。溶剂比为87/13(1,4-二氧六环/水),PLLA浓度5%,粗化1h时,制备出大孔孔径达300μm,小孔嵌在大孔孔壁上且孔径在10μm以下的高连通分级多孔支架。粗化时间的延长使大孔孔径有所增大。细胞实验表明分级多孔支架有助于细胞长入支架内部,促进细胞的增殖。     

A study on the in vitro degradation of poly(L-lactide)/chitosan microspheres scaffolds

Recent research shows that the addition of chitosan microspheres (CMs) to poly(L-lactide) (PLLA) can result in a composite scaffold material with improved biocompatibility and mechanical properties for tissue engineering applications. However, research regarding the influence of CMs on scaffold degradation is absent in the literature. This paper presents a study on the in vitro degradation of scaffolds made from PLLA with CMs. In this study, the PLLA/CMs scaffolds with a 25% ratio of CMs to PLLA were immersed in phosphate-buffered saline (PBS) solution at 37°C for 8 weeks. The in vitro degradation of the scaffolds was investigated using micro-computed tomography (μCT), weight loss analysis, Raman spectroscopy, and differential scanning calorimetry (DSC). Microstructure changes during degradation were monitored using μCT. The μCT results were consistent with the results obtained from Raman spectra and DSC analysis, which reflected that adding CMs into PLLA can decrease the degradation rate compared with pure PLLA scaffolds. The results suggest that PLLA/CMs scaffold degradation can be regulated and controlled to meet requirements imposed a given tissue engineering application.     

介孔纳米羟基磷灰石/左旋聚乳酸复合材料的制备及性能

为考察介孔纳米羟基磷灰石(MHA)/左旋聚乳酸(PLLA)复合材料的性能,以十六烷基三甲基溴化铵(CTAB)为模板合成MHA,采用溶液相分离结合粒子沥滤法制备了不同纳米粒子含量的MHA/PLLA多孔支架复合材料,考察了其抗压缩性能和淬断面微观结构。采用溶液浇注法制备了MHA/PLLA复合膜,并对其拉伸性能和拉伸断面微观结构进行了研究。FTIR、XRD、TEM和氮气吸附测试等结果显示:合成的MHA具有典型的晶体结构、介孔结构和较高的比表面积。力学测试结果显示:在发生10%压缩形变时,填料含量为1%、5%和10%的MHA/PLLA多孔支架复合材料的抗压缩强度随填料含量增加而提高,与相应含量的纳米羟基磷灰石(HA)/PLLA多孔支架复合材料相比,分别提高了约37.0%、67.7%和144.7%。在填料含量为5%和10%时,MHA/PLLA复合膜的拉伸强度较HA/PLLA复合膜分别提高约38.7%和46.1%,拉伸模量分别提高约35.4%和14.5%。而且MHA/PLLA复合膜具有更高的断裂伸长率,填料含量为1%、5%和10%时断裂伸长率分别较HA/PLLA复合膜提高约91.3%、79.7%和96.1%。FESEM结果显示:尤其当填料含量较高时,MHA/PLLA多孔支架复合材料或复合膜中填料粒子分布较HA/PLLA中均匀。结果表明:与HA/PLLA复合材料相比,随着MHA含量增加,MHA/PLLA复合材料具有更好的力学性能,MHA在PLLA基体中分布相对更均匀。     

微波辐射D,L-丙交酯开环聚合制备聚乳酸

为得到聚乳酸的最佳制备工艺,利用微波辐射技术实现D,L-丙交酯开环聚合制备聚乳酸,实验考查了催化剂种类和用量,微波辐照功率和时间等工艺参数对产物分子量的影响,以及反应过程中体系温度的变化.研究表明,以连续微波炉作为反应器,催化剂Sn(Oct)2用量为丙交酯单体用量的0.56%(质量分数),在功率为90 W的连续微波辐射下反应10 m in,可获得粘均分子量(Mη)为15.92×104的聚乳酸(PDLLA).与家用微波炉相比,采用连续微波炉反应器,可在较短的反应时间内获得较高产率的聚乳酸产物.     

Thermal degradation behavior and kinetic analysis of poly(L-lactide) in nitrogen and air atmosphere

The non-isothermal and isothermal degradation behaviors and kinetics of poly(L-lactide) (PLLA) were studied by using thermogravimetry analysis (TGA) in nitrogen and air atmosphere, respectively. At lower heating rate ((5–10)°C/min), PLLA starts to decompose in air at lower temperature than those in nitrogen atmosphere; however, at higher heating rate ((20–40)°C/min), the starting decomposition temperature in air are similar to those in nitrogen atmosphere, not only showing that PLLA has better thermal stability in nitrogen than in air atmosphere, but also suggesting that the faster heating rate will decrease the decomposition of PLLA in thermal processing. Whether in air or in nitrogen atmosphere, the decomposition of PLLA has only one-stage degradation with a first-order decomposed reaction, suggesting that the molecular chains of PLLA have the similar decomposed kinetics. The average apparent activation energy of non-isothermal thermal degradation (Ē_non) calculated by Ozawa theory are 231.7kJ·mol⁻¹ in air and 181.6kJ·mol⁻¹ in nitrogen; while the average apparent activation energy of isothermal degradation (Ē_iso) calculated by Flynn method are 144.0kJ·mol⁻¹ in air and 129.2kJ·mol⁻¹ in nitrogen, also suggesting that PLLA is easier to decompose in air than in nitrogen. Moreover, the decomposed products of PLLA are also investigated by using thermogravimetry-differential scanning calorimetry-mass spectrometry (TG-DSC-MS). In air atmosphere the volatilization products are more complex than those in nitrogen because the oxidation reaction occurring produces some oxides groups.     

β-偏磷酸钙晶须增强左旋聚乳酸材料的体外降解

对用于骨折内固定的β-偏磷酸钙晶须/左旋聚乳酸(β-CMP_W/PLLA)复合材料在体外降解过程中强度的变化、 分子量和微观形貌进行了初步研究。结果表明: 在人体模拟体液(SBF)中浸泡, 前8周材料的强度变化较小, 25wt%β-CMP_W/75wt%PLLA降解20周后的抗压强度值仍高达103MPa; 45wt%β-CMP_W/55wt%PLLA降解12周后抗压强度约为初始值的88%。扫描电镜图表明, 随降解时间的延长, 因聚乳酸溶解而在样品中形成孔洞。在降解周期内, SBF溶液的pH值随β-CMP_W/PLLA降解时间的延长基本保持稳定。凝胶渗透色谱检测结果表明, PLLA的数均相对分子质量和重均相对分子质量随降解时间的延长而降低, 降解20周后数均相对分子质量约为20万, 重均相对分子质量下降了32%。     

聚乳酸熔体中缠结网络的形成

采用冷冻萃取法制备了不同相对分子质量的部分解缠结聚乳酸试样。通过流变学的方法实时检测了聚乳酸熔体中缠结网络的形成和发展演变过程。结果表明,部分解缠结聚乳酸分子链的缠结过程分为快速穿插阶段和慢速穿插阶段。同时考察了在可控外场作用下缠结网络的形成,结果表明,预剪切和快速熔融会促进分子链缠结网络的形成,而检测频率则对缠结形成没有影响。     

可降解碳纳米管/聚乳酸复合材料的制备及性能

利用丙交酯的开环聚合反应成功地制备了单壁碳纳米管/聚乳酸复合材料, 研究了其降解性和热稳定性。通过红外光谱(FTIR)、 Raman光谱、 热失重分析(TGA)和扫描电子显微镜(SEM)研究, 证明乙二醇功能化的单壁碳纳米管能够参与丙交酯的开环聚合反应, 并在碳纳米管侧壁成功接枝聚乳酸链, 得到的复合材料在碱性溶液中容易降解。差示热分析(DSC)表明, 功能化单壁碳纳米管/聚乳酸复合材料的玻璃化转变温度与纯聚乳酸相比有所提高。      

Formation of bone-like apatite on poly(L-lactide) to improve osteoblast-like compatibility in vitro and in vivo

The biomimetic apatite coating process was adopted to modify poly(L-lactide) (PLLA) surfaces with osteoblasts-like cell compatibility. The apatite coating was formed on the pre-hydrolyzed PLLA film and scaffold surfaces by incubating in simulated body fluid (SBF). Scanning electron microscopy and energy dispersive X-ray analyzer were utilized to characterize the composition and the structure of the apatite coating. The cytocompatibility of the modified PLLA films was investigated by testing osteoblast-like attachment, proliferation, alkaline phosphatase (ALP) activity, and cell cycle. Subsequently, the modified PLLA scaffolds were co-cultured with the osteoblasts-like in vitro and subcutaneously implanted into nude mice. The experimental results showed that the formed apatite had a nano-sized particle and matrix configuration. The surface modification of PLLA with apatite coating significantly promoted osteoblast-like compatibility. After a four-week culture in vivo, no significant inflammatory signs were observed in the implanted regions and osteoblast-like congeries with bone-like structure began to form in the scaffolds. The positive results of this study suggest a good way to produce desirable PLLA biomaterials for bone tissue engineering.