PLLA–collagen and PLLA–gelatin hybrid scaffolds with funnel-like porous structure for skin tissue engineering

In skin tissue engineering, a three-dimensional porous scaffold is necessary to support cell adhesion and proliferation and to guide cells moving into the repair area in the wound healing process. Structurally, the porous scaffold should have an open and interconnected porous architecture to facilitate homogenous cell distribution. Moreover, the scaffolds should be mechanically strong to protect deformation during the formation of new skin. In this study, the hybrid scaffolds were prepared by forming funnel-like collagen or gelatin sponge on a woven poly(l-lactic acid) (PLLA) mesh. The hybrid scaffolds combined the advantages of both collagen or gelatin (good cell-interactions) and PLLA mesh (high mechanical strength). The hybrid scaffolds were used to culture dermal fibroblasts for dermal tissue engineering. The funnel-like porous structure promoted homogeneous cell distribution and extracellular matrix production. The PLLA mesh reinforced the scaffold to avoid deformation. Subcutaneous implantation showed that the PLLA–collagen and PLLA–gelatin scaffolds promoted the regeneration of dermal tissue and epidermis and reduced contraction during the formation of new tissue. These results indicate that funnel-like hybrid scaffolds can be used for skin tissue regeneration.     

激光熔融静电纺丝法制备PLLA及PLLA/nHA纤维支架及性能研究

利用激光熔融静电纺丝方法制备了PLLA和PLLA/nHA纤维支架,采用FTIR和DSC测试对支架材料的结构和热学性能进行表征,通过熔融电纺对PLLA和PLLA/nHA纤维支架进行体外降解实验,研究了失重率与降解时间的关系。同时对激光熔融和一般溶液电纺得到的PLLA和PLLA/nHA纤维支架进行细胞相容性实验,对两种方法所得支架的安全性进行评价。结果表明:nHA对PLLA的结构和晶型产生影响,并减缓PLLA的降解速度,激光熔融电纺支架更具安全性,其更适合组织工程应用。     

金属氧化物对PLLA降解性能的影响

将分别添加微量金属氧化物CaO、MgO、ZnO 的生物可降解聚酯聚乳酸(PLLA)薄膜放入陕西当地土壤的提取液中进行微生物兹化反应,以研究薄膜中金属氧化物对PLLA降解性能的影响,并通过红外光谱中官能团吸收强度的变化,表征了其降解前后的化学结构。研究结果表明：添加金属氧化物的PLLA在陕西当地土壤的提取液中能够降解,添加微量的 CaO、MgO加快了PLLA的降解速度,而添加ZnO对PLLA 的降解没有太大影响。用显微镜对降解前后膜的观察发现：纯 PLLA 薄膜降解后的膜表面变得明显粗糙,有显著的微生物侵蚀痕迹;而添加微量金属氧化物的薄膜中,由于均匀分散金属氧化物的存在,导致降解后膜表面出现了更大的缺陷和侵蚀痕迹。     

PHB/PLLA共混体系和PHB/PLLA/PEO共混体系冷结晶性的研究

利用DSC研究了聚β-羟基丁酸酯(PHB)与聚乳酸(PLLA)共混物的冷结晶性、相容性和结晶度以及聚氧乙烯(PEO)对PHB/PLLA(质量比为1∶1)共混物冷结晶性、熔融温度和结晶度的影响。结果表明,PHB冷结晶温度及结晶速率不受组分PLLA的影响,而PLLA尽管冷结晶温度不受组分PHB的影响,但其结晶速率随PHB组成增多而变快,共混物结晶度与组分之间的比例相关;PHB与PLLA有一定的相容性,PEO的加入提高了其相容性;同时,PEO的加入,不但显著降低了PHB、PLLA的冷结晶温度,还增进了共混物组分结晶的完善。     

PLLA/HA复合微球的制备

采用了一种新的微球制备方法液滴-冷凝法,以左旋聚乳酸[Poly(L-lactic-acid),PLLA]和羟基磷灰石(Hydroxyaptite,HA)为原料制备了复合微球。采用正交试验,以复合微球的粒径、球形度、成球率和孔隙率为考察指标,研究了PLLA溶液浓度、PLLA/HA质量比及冷凝液的温度梯度对复合微球成型和性能的影响,应用扫描电镜(SEM)对聚乳酸微球的微观形貌、孔隙结构进行了观察和表征。研究结果表明,应用该工艺制备的微球粒径均一,球径可控,其表面和内部都存在丰富的微孔,且孔间互相贯通。当采用较低浓度的PLLA溶液和适中的冷凝液温度梯度时,复合微球的各项指标均较好。该微球材料有望在骨缺损填充等领域得到应用。     

PLLA/CNTs复合材料的非等温冷结晶

通过溶液共混法制备了聚乳酸/碳纳米管(PLA/CNTs)复合材料,并利用差示扫描量热分析(DSC)研究了CNTs的种类、长度、直径和质量分数对不同升温速度下PLA非等温冷结晶性能的影响,结果表明,PLA/CNTs复合材料的玻璃化转变温度(Tg)和结晶峰温度(Tc)都随升温速度降低而逐渐降低,而结晶度和熔融温度(Tm)则升高。添加质量分数为0.1%的多壁碳纳米管(MWNTs)即可有效促进PLA的异相成核,提高其结晶速度和结晶度,以10℃/min升温冷结晶时,当CNTs用量达1%时会阻碍PLA的非等温结晶过程,并导致PLA复合材料的Tg、Tm和结晶度降低。MWNTs对PLA非等温结晶的促进作用比SWNTs或DWNTs明显,而较短的MWNTs比长MWNTs的作用略为明显。     

Controlled release of brefeldin A from electrospun PEG–PLLA nanofibers and their in vitro antitumor activity against HepG2 cells

In this work, PEG–PLLA electrospun fibers were developed as a new controlled release system for macrolide antibiotic drug brefeldin A (BFA). SEM and XRD analyses of the BFA-loaded PEG–PLLA fibers revealed that the average diameter of fibers was below 950 nm with smooth surfaces, and the drug was well incorporated into the fibers in amorphous form. The release profiles of BFA in PBS were measured by HPLC, demonstrating that the controlled release of BFA could be gained for long time. The in vitro antitumor activity against human liver carcinoma HepG2 cells of the fibers containing 3%, 6%, 9%, 12% and 15% BFA were examined by MTT method, and the results showed that cell growth inhibition rates at 72 h were 64%, 77%, 80%, 81% and 85%, respectively. These results strongly suggested that the BFA/PEG–PLLA fibers had an effect of controlled release of BFA and were suitable for postoperative chemotherapy of cancers.     

TMC-300对PLLA/PPC合金性能的影响

为了改善聚L-乳酸(PLLA)/聚碳酸亚丙酯(PPC)合金的结晶等性能,利用熔融共混法在合金中添加PLLA专用酰肼类成核剂TMC-300。采用差示扫描量热仪(DSC)、广角X射线衍射仪(WAXD)、小角X射线散射仪(SAXS)、偏光显微镜(POM)、扫描电子显微镜(SEM)及力学分析方法考察了PLLA专用酰肼类成核剂TMC-300对PLLA/PPC合金的结晶及力学性能的影响。结果显示,添加质量分数为0.5%的TMC-300对PLLA/PPC合金之间的相容性影响甚微,但可提高PLLA/PPC合金的结晶度,使合金中PLLA的长周期减小,且添加TMC-300的合金中PLLA晶核数目增多,球晶尺寸减小。此外,添加0.5%的TMC-300可提高PLLA/PPC合金整体的断裂伸长率。在质量比为80/20的PLLA/PPC合金中加入0.5%的TMC-300后,该三元共混材料的冲击韧性达到最佳。     

CPP/PLLA软骨组织工程支架复合材料初步研究

采用溶媒投放、颗粒滤取技术制备出CPP/PLLA软骨组织工程支架复合材料,测试了该复合材料的物理力学性能和降解性能。研究结果表明,CPP/PLLA软骨组织工程支架复合材料具有高的孔隙率(90%)、良好的生物降解性能和物理力学性能,以及三维连通、微孔、网状微观结构,故该复合材料有希望成为软骨组织工程支架材料之一。     

Tailoring impact toughness of poly(L-lactide)/poly(ε-caprolactone) (PLLA/PCL) blends by controlling crystallization of PLLA matrix

Melt blending poly(L-lactide) (PLLA) with various biodegradable polymers has been thought to be the most economic and effective route to toughen PLLA without compromising its biodegradability. Unfortunately, only very limited improvement in notched impact toughness can be achieved, although most of these blends show significant enhancement in tensile toughness. In this work, biodegradable poly(ε-caprolactone) (PCL) was used as an impact modifier to toughen PLLA and a nucleating agent was utilized to tailor the crystallization of PLLA matrix. Depending on the nucleating agent concentrations in the matrix and mold temperatures in injection molding, PLLA/PCL blends with a wide range of matrix crystallinity (10-50%) were prepared by practical injection molding. The results show that there is a linear relationship between PLLA matrix crystallinity and impact toughness. With the increase in PLLA crystalline content, toughening becomes much easier to achieve. PLLA crystals are believed to provide a path for the propagation of shear yielding needed for effective impact energy absorption, and then, excellent toughening effect can be obtained when these crystals percolate through the whole matrix. This investigation provides not only a new route to prepare sustainable PLLA products with good impact toughness but also a fresh insight into the importance of matrix crystallization in the toughening of semicrystalline polymers with a flexible polymer.     

PLLA/PBLG嵌段共聚物的合成及其结构表征

以L-丙交酯(LLA)为原料,在催化剂辛酸锡酯Sn(Oct)2的作用下,利用聚(γ-谷氨酸苄酯)的活性端氨基引发LLA进行开环聚合,合成了聚L-丙交酯 (PLLA)与聚(γ-谷氨酸苄酯)(PBLG)的共聚物,对反应条件的各项因素进行了讨论,确定了最佳反应条件是:m(催化剂):m(PBLG)=1:1;反应温度120℃;反应时间6h.并利用红外、核磁和凝胶渗透色谱方法对产物的结构进行表征.结果表明,所制备的共聚物为PLLA/PBLG/PLLA三嵌段共聚物.     

改性纳米MgO/PLLA复合薄膜的制备及性能

为了改善左旋聚乳酸(PLLA)的降解性,采用溶液共混法将PLLA和MgO纳米颗粒(MgO-NPs)进行复合,制备了一种具有良好力学性能的骨修复复合材料.结果显示:改性MgO纳米颗粒(g-MgO-NPs)在PLLA基体中的分散效果及界面结合性比未改性的好.4%(质量比)g-MgO-NPs的添加量使薄膜的拉伸强度从10.6 MPa增大到30.1 MPa,断裂伸长率从71%减小为59%,并使薄膜降解后的pH值趋于稳定,基本接近生理盐水的pH值.由此表明:g-MgO-NPs在一定程度上能改善聚乳酸复合膜的降解性及其力学性能.     

Fabrication of porous poly(L-lactide) (PLLA) scaffolds for tissue engineering using liquid–liquid phase separation and freeze extraction

PLLA scaffolds were successfully fabricated using liquid–liquid phase separation with freeze extraction techniques. The effects of different processing conditions, such as method of cooling (direct quenching and pre-quenching), freezing temperature (−80°C and −196°C) and polymer concentration (3, 5 and 7 wt%) were investigated in relations to the scaffold morphology. SEM micrographs of scaffolds showed interconnected porous network with pore size ranging from 20 to 60 μm. The scaffolds had porosity values ranging from 80 to 90%. Changes to the interconnected network, porosity and pore size were observed when the method of cooling and polymer concentration was changed. Direct quenching to −80°C gave a more porous interconnected microstructure with uniform pore size compared to samples prepared using pre-quenching method. Larger pores were observed for samples quenched at −80°C compared to −196°C. Scaffolds prepared using direct quenching to −196°C had higher elastic modulus and compressive stress compared to those quenched to −80°C. The compressive elastic modulus ranged from 4 to 7 MPa and compressive stress at 10% strain was from 0.13 to 0.18 MPa.     

单轴拉伸PLLA/PBS共混薄膜的包装特性研究

目的提高聚乳酸(PLLA)的韧性、强度及阻氧性能。方法采用双螺杆挤出流延线制备单轴拉伸PLLA/聚丁二酸丁二醇酯(PLLA/PBS)共混薄膜,用万能拉伸试验机、差示扫描量热分析仪(DSC)和透氧仪,对不同拉伸比例的PLLA/PBS共混薄膜的力学性能、热学性能和阻氧性进行了评估。结果随着拉伸比例的增大,PLLA/PBS共混薄膜屈服强度和弹性模量增大,断裂伸长率呈先增大后降低的趋势。随拉伸比例的增大,PLLA/PBS共混薄膜结晶速率明显提高,其阻氧性也得到一定的改善。结论通过单轴拉伸和与PBS共混提高了PLLA的韧性和强度,中等拉伸比例的PLLA/PBS共混薄膜的阻氧性相对较好。     

PLLA纳米纤维编织缝合线的制备及生物相容性研究

以PLLA为原料,采用静电纺丝和圆盘定向收集得到具有有序排列的纳米纤维束,并将其编织成线,得到PLLA纳米纤维缝合线.对新型可吸收PLLA缝线的微观形貌、血液相容性、细胞毒性进行了性能表征,并测试了其力学性能.结果表明,纳米纤维在一定的圆盘转速下表现出较好的定向性,力学性能良好.缝线在溶血试验中溶血率＜5%,符合医用材料的溶血要求.MTT实验结果表明缝线材料无细胞毒性,且显示出较高的增殖率,说明新型可吸收PLLA纳米纤维缝线具有良好的生物相容性和安全性.     

PLLA/PVP共混静电纺丝形貌表征及性能研究

采用静电纺丝法制备了PLLA/PVP共混纤维膜,通过SEM、接触角表征了纤维膜的形貌以及亲水性能,同时测定了纤维膜的力学性能,探讨了共混液中PVP的比例对纤维膜形貌、亲水性能及力学性能的影响。结果表明:随着共混液中PVP比例的增大,PLLA的亲水性得到改善,但纤维的强力却迅速下降。当PVP的比例为40%和50%时,接触角接近零。SEM分析结果显示:纤维丝上孔的孔径和密度随着PVP比例的增大而发生改变。     

成核剂对PLLA/PDLA共混纤维结构和性能的影响

将取代芳基磷酸酯盐类化合物(TMP-5)、多酰胺类化合物(TMC-328)、水滑石(HT)等不同类型的成核剂添加到聚L-乳酸(PLLA)与聚D-乳酸(PDLA)中共混熔融纺丝,初步研究了成核剂对纤维结构和性能的影响。结果表明,PDLA与PLLA共混熔融纺丝可以形成立构复合型PLA(sc-PLA)晶体,成核剂的加入,更加促进了聚乳酸纤维中sc-PLA晶体的形成;而且,成核剂TMP-5的加入,既可以改善纤维的耐热性能,又有助于纤维断裂强度和拉伸模量的增大,提高了纤维的力学性能。     

PGS/PLLA静电纺丝复合纳米纤维支架的性能研究

基于聚癸二酸丙三醇酯(PGS)优异的亲水性能,左旋聚乳酸(PLLA)良好的力学性能,以六氟异丙醇(HFIP)为溶剂,将PGS与PLLA按质量比1∶3、1∶1、3∶1配制成25%的纺丝液,采用静电纺丝技术制备了不同比例的新型三维纳米支架。通过扫描电镜、傅里叶红外光谱仪(FT-IR)、X射线衍射仪、热重分析仪、Instron微力试验机、接触角测量仪对共纺膜片进行表征。结果表明共纺膜片分布均匀,交织成网状;共纺膜片中加入PLLA对PGS聚合物结构几乎没有影响;随着PGS含量增加,结晶度呈增强趋势;伴随PLLA质量增加,热稳定性也趋于稳定;加入PGS,PGS/PLLA共纺膜片获得较好的亲水性,支架力学性能也得到改善;PGS/PLLA三维支架和山羊颞下颌关节盘细胞共培养,结果表明关节盘细胞在不同比例支架上粘附、铺展均良好,且在PGS/PLLA(1/3)膜片上生长较好。     

静电纺制备的PLLA/PCL复合支架性能及细胞相容性

利用静电纺丝技术制备了一系列不同比例的左旋聚乳酸/聚己内酯(PLLA/PCL)复合纳米纤维支架。通过扫描电镜、差热分析、宽角X射线衍射和接触角测试手段对支架结构与形态、结晶性能及亲水性进行了表征;采用在缓冲溶液中加酶的方式,研究了复合材料的降解性能;将体外培养的真皮成纤细胞接种至材料表面,用扫描电镜观察了成纤细胞在材料表面的生长情况。研究结果表明,电纺丝得到的复合支架纤维直径均一,且呈相互连通的多孔网状结构;脂肪酶的存在加速了支架材料的降解速度;成纤细胞在复合支架上具有良好的生长状态。     

取向TSF/PLLA静电纺纳米纤维毡的制备及其生物相容性

利用静电纺丝技术制备了取向的柞蚕丝素/左旋聚乳酸(TSF/PLLA)纳米纤维毡。通过扫描电子显微镜(SEM)、X射线衍射分析(XRD)和拉伸测试分别对TSF/PLLA纳米纤维的形貌、结晶结构及力学性能进行了研究。将人成骨肉瘤细胞(MG-63)种植在TSF/PLLA纳米纤维上,通过荧光显微镜分析和MTT(四甲基偶氮噻唑蓝比色法),观察细胞在材料表面的生长情况,评价纳米纤维的生物学性能。结果表明,TSF含量为10%时,纤维直径分布均匀,结晶度高。但是,TSF含量超过10%后,纤维直径粗细不匀明显,纤维的力学性能下降。与无规纤维毡相比,取向的纳米纤维毡力学性能优异,初始模量高,更能够促进细胞增殖,对细胞的生长行为影响大。