Effect of TiO2 nanoparticle loading on Poly(l-lactic acid) porous scaffolds fabricated by TIPS

Porous nanocomposite scaffolds of poly(l-lactic acid) (PLA), loaded with TiO₂ nanoparticles, were prepared by thermally induced phase-separation (TIPS). The preparation procedure induced crystalline polymer structures (with degree of crystallinity up to 51%) with no evidence of residual solvent, as confirmed by thermal analysis. Scaffold porosity, distribution of the nanofiller and shape of the pores were investigated by X-ray micro computed tomography (μ-CT) and scanning electron microscopy (SEM). The produced scaffolds with porosity of 86 ± 2% have interconnected open tubular pores with diameter and length in the ranges 40–80 μm and 200–400 μm respectively. The inorganic TiO₂ nano-additive is well dispersed in the scaffold walls, with only a small fraction of micrometric aggregates observable. All investigated polymer scaffolds display similar compressive moduli (between 2.1 and 2.8 MPa). Thermogravimetry (TGA), wide angle X-ray diffraction (XRD) and SEM analyses run on scaffolds subjected to in vitro mineralization tests showed that PLA scaffolds loaded with TiO₂ develop an amount of hydroxyapatite four times higher than that of plain PLA, thus assessing that titania nanoparticles confer improved bioactivity to the scaffolds.     

Poly(l-lactic acid)/alkali lignin composites: properties,biocompatibility, cytotoxicity and antimicrobial behavior

In this study, poly(L-lactic acid) (PLA)/low molar mass alkali lignin (aL) (1%, 5% and 10% w/w) composites were prepared primarily for a comprehensive understanding of the effect of aL on their antimicrobial properties, biocompatibility and cytotoxic behavior. The properties were evaluated by Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, thermogravimetry and X-ray diffraction. The mechanical, water vapor barrier properties and photodegradability were analyzed as well. The results showed a significant inhibiting effect of aL on the crystallization behavior of PLA, increased water barrier properties (up to 73%) and photodegradability. PLA/aL composites showed a tenfold reduction in Gram-positive bacteria viability, very good cellular response and very low cytotoxicity levels, thus validating these materials as non-cytotoxic and with high potential to be used as food packaging.

Graphical abstract

     

生物可降解塑料PBS与天然可降解高分子材料共混改性研究进展

介绍了当前可生物降解塑料PBS与各种天然可降解高分子材料共混改性的方法和加工工艺,以及改性后材料的力学性能、热学性能以及降解性能的变化。     

Plasma surface treatments of poly(l-lactic acid) (PLLA) and poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV)

The surfaces of poly(l-lactic acid) (PLLA) and poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) were modified by oxygen and nitrogen plasma treatments. The physical and chemical surface characteristics were evaluated by contact angle tests, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The plasma treatments caused an increase in both contact angle and roughening, altered the surface morphology, inserted polar groups, and, consequently, enhanced the hydrophilicity for both PLLA and PHBV polymers.     

Mineralization of poly(l-lactic acid)-based foams induced by cellulose nanofibrils

Cellulose nanofibrils (CNFs) were blended with poly(l-lactic acid) (PLLA) to produce CNFs/PLLA composite solid foams. The dispersed CNFs’ phase was partially embedded in the PLLA matrix. The CNFs not only reduced the water contact angle of the composite, but also induced the formation of hydroxyapatite (HA) on the walls of its inner pores. After incubation for 7 days in 3× simulated body fluid, a large number of HA particles were formed throughout the CNFs/PLLA composite foams. HA particles have diameters ranging from 200 nm to 2 μm and a Ca/P ratio of 1.42. The spatial distribution of calcium and phosphorus elements was uniform. A porosity of approximately 92 % was achieved after mineralization of the CNFs/PLLA composite foams. The mass of HA grown over CNFs/PLLA foams increased faster than in the case of PLLA foams. The ternary polymeric foams have potential applications in tissue engineering.     

Bi-layered constructs based on poly(l-lactic acid) and starch for tissue engineering of osteochondral defects

Articular cartilage has a limited capacity to repair itself, and conventional therapeutic approaches have shown to have limited success as they are deficient and inconsistent in long-term repair. Tissue engineering has shown to be an alternative route to regenerate articular defects. In this work, new bi-layered scaffolds are developed in order to enhance the integration between the engineered cartilage tissue and the corresponding subchondral bone. The concept includes the use of a common polymer in both sides, poly(l-lactic acid), PLLA, to increase the bonding between them, and the use of compression moulding followed by particle leaching to process porous scaffolds with controllable porosities. A compact layer could be observed between the two layers that could be useful for independent cell culturing of the developed osteochondral constructs. A blend of starch and PLLA was used in the cartilage side, which was found to possess adequate hydration capability. For the bone region, where more stiffness and strength was required, PLLA reinforced with hydroxyapatite was used. Preliminary bioactivity tests demonstrated that the bone-layer could induce the formation of a calcium–phosphate layer in vitro, whereas the cartilage layer does not exhibit the ability for calcification.     

Modulation of poly (d,l-lactic acid) with amniotic fluid for improvement of the cell affinity

The objective of this study was to investigate the effects of naturally occurring amniotic fluid modified poly(d,l-lactic acid) (PDLLA) film on the culture of rat calvaria osteoblast. The characteristics of surfaces (both modified and control) were examined by contact angle measurement and electron spectroscopy for chemical analysis (XPS). Cell adhesion and proliferation were used to assess the cell behavior on modified films and control one. MTT assay was used to determine cell viability and alkaline phosphatase (ALP) activity was taken to evaluate differentiated cell function. Compared with the untreated films, cell adhesion of osteoblast was significantly higher (P < 0.05) than that found on control, and osteoblast proliferation was also greater than control one (P < 0.01) at the time interval of 4 and 7 days. Moreover, the alkaline phosphatase (ALP) activity exhibited statistic difference (P < 0.05) and cell viability demonstrated significant difference (P < 0.01) between amniotic fluid modified PDLLA films and control one. These results suggested that amniotic fluid was a suitable material when used to modify PDLLA in order to improve its biocompatibility.     

Evaluation of poly (L-lactic acid) monofilaments with high mechanical performance in vitro degradation

Journal of Materials Science - Nowadays, the degradation properties of poly (L-lactic acid) (PLLA) braided stents are still not well understood. The main challenge relies on the unknown degradation...     

新型生物降解材料聚乳酸的微孔发泡技术研究进展

介绍了新型生物可降解材料聚乳酸(PLA)微孔塑料的最新研究进展,并详细介绍了PLA微孔塑料的泡孔形态和力学性能的影响因素.     

A review on biodegradable materials for cardiovascular stent application

A stent is a medical device designed to serve as a temporary or permanent internal scaffold to maintain or increase the lumen of a body conduit. The researchers and engineers diverted to investigate biodegradable materials due to the limitation of metallic materials in stent application such as stent restenosis which requires prolonged anti platelet therapy, often result in smaller lumen after implantation and obstruct re-stenting treatments. Biomedical implants with temporary function for the vascular intervention are extensively studied in recent years. The rationale for biodegradable stent is to provide the support for the vessel in predicted period of time and then degrading into biocompatible constituent. The degradation of stent makes the re-stenting possible after several months and also ameliorates the vessel wall quality. The present article focuses on the biodegradable materials for the cardiovascular stent. The objective of this review is to describe the possible biodegradable materials for stent and their properties such as design criteria, degradation behavior, drawbacks and advantages with their recent clinical and preclinical trials.     

Fabrication of Mg alloy tubes for biodegradable stent application

Though Mg alloys are promising candidates for biodegradable stents, it is very difficult to fabricate stent tubes with high dimensional accuracy using Mg alloys because of their low deformability. This study aimed to develop thin-walled, high-quality Mg alloy tubes with good performance in stent applications. Cold drawing with a fixed mandrel was carried out for extruded Mg-0.8%Ca and AZ61 alloy tubes using optimized drawing parameters and lubrication, and stent tubes with 1.5–1.8 mm outer diameter and 150 μm thickness were fabricated. A dimensional evaluation showed that the tube dimensional errors were within 0.02–2.5%. Also, an immersion test of pure Mg with different crystal orientations showed that the crystal orientation affected the corrosion properties, results that are the same with other Mg alloys. The crystal orientation of the stent tube could be controlled by changing the deformation amount and direction in the drawing, showing that it is possible to further improve the biodegradability of stents by approaching their fabrication from a processing aspect.     

熔融缩聚合成聚乳酸-聚乙二醇共聚物及其性能研究

采用羧基封端乳酸预聚物与聚乙二醇熔融缩聚合成了聚乳酸-聚乙二醇共聚物,并用GPC、FTIR、1H-NMR等方法表征了预聚物与共聚物,结果表明,预聚物的羧基封端率高于95%,预聚物的相对分子质量可由投料比(物质的量比)控制.热分析结果表明,共聚物中聚乳酸链段呈无规分布,而聚乙二醇链段能够形成结晶微区.力学性能测试结果表明,共聚物的断裂伸长率达371%,有望在聚乳酸韧性改性方面得到应用.     

Effect of additives on the interfacial strength of poly(l-lactic acid) and poly(3-hydroxy butyric acid)-flax fibre composites

The interfacial shear strength (IFSS), evaluated by single fibre pull-out tests was quantified for various biopolymer-flax fibre composites that were modified with additives. The additives included a plasticiser (glycerol triacetate) (GTA) absorbed onto/into the fibres, 4,4′-thiodiphenol (TDP) that is capable of forming hydrogen bonds between the matrix and cellulose from the fibres, and a hyperbranched polyester (HBP) to impart improved fracture toughness. Fibres were washed with acetone to remove the surface impurities and dried under vacuum before absorption of plasticiser and adsorption of thiodiphenol. It was found that the different additives significantly influenced the IFSS for the biopolymer-flax fibre systems while extraction with acetone had a no effect on the IFSS compared with the untreated fibres. The use of TDP imparted the most significant increase in IFSS whilst the HBP had an opposing effect. The use of ESEM corroborated with the findings of the single fibre pull-out tests.     

Elaboration and surface modification of structured poly(l-lactic acid) thin film on various substrates

Biosourced or biodegradable polymers like poly(lactic acid) (PLA) are often base-material for tissue-engineered scaffolds. However, in most of the cases, their bioadhesion properties are not satisfactory. Since the adhesion is controlled both by roughness and surface chemistry, PLA films were textured by applying the breath figure procedure and, then, plasma-treated. Depending on physicochemical characteristics of the breath figure technique, nice hexagonal structures were obtained. Their surface properties, i.e. hydrophobic–hydrophilic balance were controlled by plasma modification. However, their surface decoration could be only preserved with some specific plasma parameters depending on the applied energy and also on the induced surface chemistry.     

Poly(l-lactide-co-glycolide) biodegradable microfibers and electrospun nanofibers for nerve tissue engineering: an in vitro study

For tissue engineering applications, the distribution and growth of cells on a scaffold are key requirements. The potential of biodegradable poly(l-lactide-co-glycolide) (PLGA) polymer with different microstructures, as scaffolds for nerve tissue engineering was investigated. In this study, an attempt was made to develop porous nanofibrous scaffolds by the electrospinning method. In this process, polymer fibers with diameters in the nanometer range are formed by subjecting a polymer fluid jet to a high electric field. Attempt was also made to develop microbraided and aligned microfiber scaffolds. A polymer film scaffold was made by solvent casting method. C17.2 nerve stem cells were seeded and cultured on all the four different types of scaffolds under static conditions for 3 days. Scanning electron micrographs showed that the nerve stem cells adhered and differentiated on all the scaffolds and supported neurite outgrowth. Interesting observation was seen in the aligned microfiber scaffolds, where the C17.2 nerve stem cells attached and differentiated along the direction of the fibers. The size and shape of the cell-polymer constructs remained intact. The present study suggests that PLGA is a potential scaffold for nerve tissue engineering and predicts the orientation and growth of nerve stem cells on the scaffold.     

聚丙烯酸-聚乳酸接枝共聚物涂膜的制备及性能

采用溶液聚合法合成了生物降解材料聚丙烯酸-聚乳酸接枝共聚物(PAA-g-PLLA),通过红外、核磁和凝胶渗透色谱对其结构进行了表征,测定了涂膜的附着力、黏度和硬度等基本性能。正交实验结果表明最佳的合成工艺条件为:硬软单体的质量比为55∶35,过氧化苯甲酰(BPO)的用量为3%,反应温度为85℃,甲基丙烯酸羟乙酯-聚乳酸大单体(HEMA-PLLA)与软硬单体的质量比为1∶2,单体与溶剂的质量比为2∶2。对比聚丙烯酸涂膜和PAA-g-PLLA涂膜的接触角,以及PLLA降解性能看出,PAA-g-PLLA涂膜具有降低表面能和自抛光的双重特性。     

原位反应挤出制备聚乳酸与聚醚酯嵌段共聚物合金的性能研究

以0.35%(质量分数)的过氧化二异丙苯(DCP)为引发剂和2%(质量分数)的马来酸酐(MAH)为增容剂,通过原位反应挤出的方法制备了聚乳酸(PLLA)/聚醚酯嵌段共聚物(TPEE)合金。利用TG、差示扫描量热(DSC)、SEM等研究了其热性能和相形态,并测试了合金的力学性能和熔体流动速率。结果表明,在引发剂DCP的存在下,MAH的添加使得反应挤出制备的合金中PLLA与TPEE之间产生部分共价键连接而增加了相容性。合金的热稳定性、韧性随TPEE含量的增加而升高,但模量和强度下降。另外,不同TPEE含量的合金的熔体流动速率均高于纯PLLA和TPEE,表明在原位反应挤出过程中PLLA与TPEE均发生了一定程度的降解反应。同时,对合金的流变性能也进行了研究。     

Poly(L-lactic acid) nanocylinders as nanofibrous structures for macroporous gelatin scaffolds

Electrospun Nanofiber sheets have been shown to mimic the structure of extracellular matrix (ECM). Although these nanofibers have shown great potential for use as tissue engineering scaffolds, it is difficult for the electrospun nanofiber based sheets to be shaped into the desired three-dimensional structure. In this study, poly(L-lactic acid) (PLLA), a biodegradable and biocompatible polyester, was electrospun to produce nanofibers that were treated with an amino group containing base in order to fabricate polymeric nanocylinders. The aspect ratio of the PLLA nanocylinders was tunable by varying the aminolysis time and density of the amino group containing base. The effects of changes in nanofibrous morphology of the PLLA nanocylinders/macro-porous gelatin scaffolds on cell adhesion and proliferation were evaluated. The results revealed different cell morphology, adhesion, and proliferation in the nanocylinders composite gelatin scaffold versus gelatin scaffold alone. Confocal laser scanning microscopy observation showed more spreading and a more flattened cell morphology after NIH3T3 cells were cultured on PLLA nanocylinders/gelatin scaffolds for 10 hours and 4 days. These results indicate that the gelatin/PLLA nanocylinder composite is a promising way to fabricate 3D nanofibrous scaffolds that accelerates cell adhesion and proliferation for tissue engineering.     

Poly(ethylene-co-acrylic acid) stationary phases for the separation of shape-constrained isomers

A new approach for the synthesis of long alkyl chain length stationary phases for use in reversed-phase liquid chromatography is described. Poly(ethylene-co-acrylic acid) copolymers (i.e., (-CH2CH2-)x[CH2CH(CO2H)-]y) with different levels of acrylic acid were covalently bonded to silica via glycidoxypropyl or aminopropyl linkages. 13C cross polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) spectroscopy was used to characterize the new reversed-phase materials. Aspects of shape selectivity were evaluated for six different columns with Standard Reference Material (SRM) 869a, Column Selectivity Test Mixture for Liquid Chromatography. Selectivity for isomer separations was enhanced for stationary phases prepared with poly(ethylene-co-acrylic acid) containing a mass fraction of 5% acrylic acid. The relationship between alkyl conformation and chromatographic properties was studied by 13C magic angle spinning (MAS) NMR measurements, and correlations were made with the composition of the polymer. Finally, the effectiveness of this phase is demonstrated by the separation of several beta-carotene isomers.