New insights into polylactide biodegradation from molecular ecological techniques

Molecular ecological techniques for direct identification of microbes involved in PLA degradation under aerobic composting conditions are described. Gene sequences from genera Paecilomyces, Thermomonospora, and Thermopolyspora were most abundant in the compost samples. Members of these phylogenetic lineages are therefore likely to play an important role in PLA degradation. The use of molecular ecological techniques to design cultivation strategies may also provide a new tool for identification and investigation of biodegradation mechanisms and for future development of efficient biological treatment or recycling processes for PLA and other biodegradable polymers.     

Mechanism of inhibition of human secretory phospholipase A2 by flavonoids: rationale for lead design

The human secretory phospholipase A2 group IIA (PLA2-IIA) is a lipolytic enzyme. Its inhibition leads to a decrease in eicosanoids levels and, thereby, to reduced inflammation. Therefore, PLA2-IIA is of high pharmacological interest in treatment of chronic diseases such as asthma and rheumatoid arthritis. Quercetin and naringenin, amongst other flavonoids, are known for their anti-inflammatory activity by modulation of enzymes of the arachidonic acid cascade. However, the mechanism by which flavonoids inhibit Phospholipase A2 (PLA2) remained unclear so far. Flavonoids are widely produced in plant tissues and, thereby, suitable targets for pharmaceutical extractions and chemical syntheses. Our work focuses on understanding the binding modes of flavonoids to PLA2, their inhibition mechanism and the rationale to modify them to obtain potent and specific inhibitors. Our computational and experimental studies focused on a set of 24 compounds including natural flavonoids and naringenin-based derivatives. Experimental results on PLA2-inhibition showed good inhibitory activity for quercetin, kaempferol, and galangin, but relatively poor for naringenin. Several naringenin derivatives were synthesized and tested for affinity and inhibitory activity improvement. 6-(1,1-dimethylallyl)naringenin revealed comparable PLA2 inhibition to quercetin-like compounds. We characterized the binding mode of these compounds and the determinants for their affinity, selectivity, and inhibitory potency. Based on our results, we suggest C(6) as the most promising position of the flavonoid scaffold to introduce chemical modifications to improve affinity, selectivity, and inhibition of PLA2-IIA by flavonoids.     

Morphology and properties of biodegradable poly (lactic acid)/poly (butylene adipate-co-terephthalate) blends with different viscosity ratio

Phase morphology exerts a tremendous influence on the properties of polymer blends. The development of the blend morphology depends not only on the intrinsic structure of the component polymers but also on extrinsic factors such as viscosity ratio, shearing force and temperature in the melt processing. In this study, various poly (butylene adipate-co-terephthalate) (PBAT) materials with different melt viscosity were prepared, and then poly (lactic acid) (PLA)/PBAT blends with different viscosity ratio were prepared in a counter-rotating twin-screw extruder under constant processing conditions. The influence of viscosity ratio on the morphology, mechanical, thermal and rheological properties of PLA/PBAT (70/30 w/w) blends was investigated. The experimental results showed that the morphology and properties of PLA/PBAT blends strongly depended on the viscosity ratio. Finer size PBAT phase were observed for viscosity ratio less than 1 (λ < 1) compared to samples with λ > 1. It was found that the interfacial tensions of PLA and PBAT were significantly different when the viscosity ratio was changed, the lowest interfacial tensions (0.12 mN/m) was obtained when the viscosity was 0.77. Additionally, the maximal tensile strength in PLA/PBAT blends were obtained when the viscosity ratio was 0.44, while the maximal impact properties were obtained when the viscosity ratio was 1.95.     

Physical blends of PLA with high vinyl acetate containing EVA and their rheological,thermo-mechanical and morphological responses

Rheological, morphological and thermo-mechanical responses of poly(lactic acid) (PLA)/ethylene-co-vinyl-acetate copolymer (EVA) blends at EVA volume fractions varying in the range of 0–0.35 were evaluated. The micro-structural analysis demonstrated dispersive mixing at low content and co-continuous morphology at 30 wt % of EVA in PLA. Dynamic rheology demonstrated enhanced storage modulus and complex viscosity (η*) with increase in frequency of the blends indicated strong phase interaction. Cole-Cole and Han plots indicated partial miscibility and incompatibility between the polymer matrix and the dispersed phase. Dynamic mechanical analysis (DMA) revealed slight increase in damping parameters which indicated interaction or reinforcement in the blends. Additionally, the thermogravimetric analysis (TGA) of the blends showed two step degradation and enhanced thermal stability.     

In-situ changes of thermo-mechanical properties of poly(lactic acid) film immersed in alcohol solutions

Poly (lactic acid) (PLA) has properties suitable for many applications. However, PLA's properties are affected by environmental conditions. In this study, the glass-rubber transition temperatures (T_g) of PLA films were measured during immersion (i.e., in-situ) in pure alcohols and alcohol aqueous solutions using a dynamic mechanical analysis technique. The T_g of PLA decreased when immersed in alcohols. For pure aliphatic alcohols, the T_g reduction became smaller as the number of carbons (C1–C10) in the alcohol main chains increased. The Fox equation and the Hansen solubility parameters (HSP)/Flory-Huggins (FH) model were used to explain the T_g reduction. The relationships explained the interactions between PLA and pure alcohols with small molecules (C1–C8), but bigger pure alcohols (C9–C10) did not fit the prediction. The chemical isomerism in pure propanol (i.e., propan-1-ol and propan-2-ol) did not affect the T_g reduction. The T_g reduction in propan-2-ol aqueous solutions was concentration dependent although the partition coefficients based on the HSP and the FH parameters did not fit this relationship. The in-situ immersion of PLA in alcohol solutions could be used to evaluate the change in T_g from the T_g of dry PLA.     

Synergistic effect of polylactic acid(PLA) and Poly(butylene succinate-co-adipate) (PBSA) based sustainable,reactive, super toughened eco-composite blown films for flexible packaging applications

Polylactic acid (PLA)/poly (butylene succinate-co-adipate) (PBSA) based blend films at variable compositions and fixed weight percentage of Epoxy functionalized styrene acrylate (ESA) were prepared using a single step blending process, followed by blown film extrusion process. The morphological studies revealed proper interaction between polymers by the interaction of chain extender (ESA) subsequently improved the mechanical properties of the prepared blown films. Similarly, the blend films showed a decrease in oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) in the order of 60% and 14% as compared with VPLA film. The optical and antislip properties of the blend films also increased considerably. The thermal analysis of the blend films depicted marginal enhancement in the stability of PLA along with heterogeneous nucleation effect in PLA matrix due to the presence of ESA and PBSA.     

Microanalysis of hybrid characterization of PLA/cHA polymer scaffolds for bone regeneration

Tissue engineering uses some engineering strategies for the reconstruction and repair of the compromised tissues, among which the use of biomaterials as an alternative to conventional transplants is significant. However, not many research has been developed on the use of biopolymer nanostructure microanalysis and calcium phosphate composites of carbon apatite in PLA as scaffolds for tissue regeneration. In this work, poly (lactic acid) filaments with 5% and 20%, carbon apatite (cHA) were microanalysis to produce a 3D printing scaffold. The scaffolds were characterised by the Scanning Electron Microscope (SEM) and Energy Dispersive X-Ray (EDX) techniques, thereby making it possible to notice a good load dispersion. The microstructural analysis of the scaffolds was carried out by computerised micro-tomography to determine the roughness, morphological parameters of pore size distribution, porosity, as well as better visualisation of the distribution of particles. A computational in vitro and microanalysis tests to assess the biocompatibility viability of the PLA/cHA structure with a variation of scaffold geometry to evaluate their effects on morphological, physicochemical and mechanical properties were also carried out. The characterisation of Ca and P release assays were observed for longer incubation times and the dynamic condition control to simulate the stresses suffered by the biomaterial exerted by the flow of fluids was achieved. The results obtained indicated that the micrographs of the cross-sections of the scaffolds showed a flatness in the loaded material when compared to the 100/0 PLA. Furthermore, the apparent porosity of 5% and 20% of cHA scaffolds gave a porosity percentage of approximately 62% and 41% respectively. The reduced summit height, reduced valley depth and the percentage upper and lower bearing area difference of the samples are 16.33 nm, 9.62 nm and 75.07% respectively. The morphological characterisation surface roughness analysis and tolerance insertion gave a favourable reduced porosity result for the composite scaffolds with 5% of cHA. Hence, this work will assist biomaterial industries in the development of biomaterials which have been engineered with biological systems to meet medical purposes.     

A method for simultaneously improving the flame retardancy and toughness of PLA

In order to modify the brittleness and flame retardant properties of poly(lactic acid) (PLA), a series of flame retardant toughened PLA composites were prepared using poly(ethylene glycol) 6000 (PEG6000) as a toughening and charring agent together with ammonium polyphosphate (APP) as an acid source and blowing agent. The fire and thermal behavior of PLA/PEG/APP composites was evaluated by limiting oxygen index (LOI), UL‐94, cone calorimeter, and thermogravimetric analysis (TGA). The results showed that the PLA/PEG/APP system had good charring ability and could improve the flame retardancy of PLA. When the content of APP in the composites was more than 5 wt%, all samples could reach UL‐94 V‐0 rating. The results of mechanical property tests demonstrated that the brittleness of PLA was also improved after blended with PEG6000. All the PLA/PEG/APP composites with an APP content of less than 10 wt% showed an obvious neck and fracture behavior, that is, the tensile behavior of PLA was changed from brittle to ductile. Copyright © 2010 John Wiley & Sons, Ltd.     

聚乳酸/聚氨酯共混体系相容性研究

采用热塑性聚氨酯弹性体(TPU)作为改性剂来增韧聚乳酸(PLA),通过溶度参数法、聚合物混合焓变法预测了TPU和PLA的相容性,并且通过稀溶液粘度法、动态热机械分析(DMA)及扫描电镜(SEM)对两者相容性进行表征,结果显示PLA和TPU为部分相容体系.共混溶液的粘度与组成含量的变化呈非线性关系;PLA/TPU共混膜的...     

Biodegradation of sequentially surface treated lignocellulose reinforced polylactic acid composites: Carbon dioxide evolution and morphology

Maple fibres were treated with a variety of sequential treatments, namely sodium hydroxide (NaOH), NaOH followed by acetylation, or NaOH followed by silanation. These fibres were incorporated into a polylactic acid (PLA) composite and the biodegradation effects were investigated. After 124 days, all composites had exceeded 90% biodegradation with most close to 100%. The PLA composite with the NaOH-treated fibres had the quickest onset of degradation (4.9 days) and highest peak rate of degradation (1.77% biodegradation/day) of all composites studied. Neat PLA had a similarly high peak rate of degradation at 1.85% biodegradation/day, but had a later onset of 11 days. Gel permeation chromatography (GPC) analysis showed the earlier onset of degradation of the composites was caused by increased hydrolysis during composite fabrication as well as composting. GPC showed the formation of up to three molecular weight bands in the PLA during composting which were hypothesised to be occurring by surface hydrolysis, bulk hydrolysis and hydrolysis at the fibre interface. Analysing the remaining composite revealed the NaOH treatment not only caused an increased rate of degradation in the PLA through increase fibre porosity, but also caused an increased rate of degradation in the fibre from the lack of surface waxes and hemicellulose. Similar, yet slower, behaviours were also seen in the NaOH followed by acetylation and NaOH followed by silane treated composites with all composites degrading more rapidly than the neat PLA and neat maple fibre samples.