Poly L-lactide Research Articles

Employing Synchrotron X-ray Scattering and Microscopy to Explore Microstructural Mysteries in Bioresorbable Vascular Scaffolds

Crystal structure and morphology dictate the mechanical, thermal, and degradation properties of poly l-lactide (PLLA), the structural polymer of the first clinically approved bioresorbable vascular scaffolds (BVS). New experimental methods are developed to reveal the underlying mechanisms governing structure formation during the crimping step of the BVS manufacturing process. Our research specifically examines the “U-bends” – the region where the curvature is highest and stress is maximised during crimping, which can potentially lead to failure of the device with dramatic consequences on patient life. A custom-made crimping rig operated at a synchrotron beamline enabled collection of wide- and small-angle X-ray scattering (WAXS/SAXS) to probe local variations of the polymer morphology as a function of position in the crest of multiple U-bends with 5 μm resolution in situ after crimping and expansion. Additionally, polarised light microscopy (PLM) images of these deformed U-bends revealed areas with varying stress distribution developed during crimping and expansion. These variations were dependant on the initial biaxial stretching processing step. The integrated X-ray scattering-microscopy approach offered a comprehensive work-flow for uncovering the intricate relationship between processing conditions and the corresponding spatially-resolved semicrystalline morphology of a BVS. Statement of SignificanceThis research introduces a new method for gaining critical insights into the structural changes that occur during the manufacturing process of bioresorbable vascular scaffolds (BVS). The crimping and expansion of poly l-lactide (PLLA) – the structural material of BVS – are sequential manufacturing steps characterised by highly non-linear deformations at temperature conditions that remain unexplored.By utilising synchrotron X-ray scattering techniques alongside polarised light microscopy, we have developed new experimental methods to uncover the mechanisms governing structure formation during processing. This innovative approach not only deepens our understanding of the relationship between processing conditions and polymer morphology but also establishes the foundation for real-time observation methods during crimping and expansion. By improving the design and performance of BVS, this study has the potential to advance cardiovascular treatments and improve patient safety, making it highly relevant and impactful to both scientific research and clinical applications.

In Vitro Corrosion of Polyester-Coated Magnesium Alloy under pH-Static Conditions.

The resorption rate of bioresorbable implants requires tuning to match the desired field of application. The use of Mg as implant material is highly advantageous, as it provides sufficient mechanical strength combined with its biodegradability. Consequently, the implant vanishes after it has served its intended purpose, allowing the complete restoration of natural tissue and organ function. However, a biodegradable Mg implant requires a biodegradable coating to slow the rate of Mg corrosion, as a permanent coating would negate the benefits of using Mg as an implant material. Therefore, degradable polymers are the materials of choice, especially polyester-based coatings, such as PLLA, as they have been proven in clinical practice over the long term. Within this work, the degradation retarding effect of a physical barrier in form of four clinically relevant polyester-based coatings, poly-l-lactide (PLLA), poly-l-lactide-co-glycolide (PLGA), poly(l-lactide-co-PEG) triblock copolymer (PLLA-co-PEG), and polydioxanone (PDO), is investigated in vitro under pH-static conditions using CO2 gas to compensate pH changes due to Mg corrosion. Coating thicknesses of 7.5 to 8.3 μm were comparable to commercially available stent systems. Quantitative analysis of magnesium concentration in buffered test medium by a photometric assay allows real-time monitoring. Shielding effect of different polyesters through polymer coating and formation of a protective passivation layer beneath the polymer coating was observed and characterized using SEM and EDX techniques. Our finding was that even imperfect polymer layers provide a considerable protective effect, and the used in vitro setup matches reported in vivo observations regarding elemental composition of corrosion products.

Safe and sustainable by design Ag nanomaterials: A case study to evaluate the bio-reactivity in the environment using a soil model invertebrate

Safe-and-sustainable-by-design (SSbD) nanomaterials (NMs) or NM-containing products are a priority. Silver (Ag) NMs have a vast array of applications, including biomedical and other products, even as nanopesticides. Thus, their release to the environment is expected to increase. The aim of the present study was to assess the ecotoxicity of the SSbD Ag NM to the soil model species Enchytraeus crypticus (Oligochaeta). The Ag NM tested consists in a SSbD Ag with biomedical applications, a hydroxyethyl cellulose (HEC) coated Ag NMs (AgHEC) and its toxicity was compared to the naked Ag NMs (Ag-Sigma), an Ag-based biomedical product (PLLA-Ag: Poly l-Lactide microfibers doped with Ag), and AgNO3. Effects were assessed both in soil and aqueous media, following the standard OECD guideline in soil (28 days) and the OECD extension (56 days), and short-term pulse (5 days) in aqueous media: reconstituted water (ISO water) and soil:water (S:W) extracts, followed by a 21-days recovery period in soil. Ag materials were thoroughly characterized as synthesized and during the test in media and animals. Results in S:W showed AgHEC was more toxic than Ag-Sigma (ca. 150 times) and PLLA-Ag (ca. 2.5 times), associated with a higher Ag uptake. Higher toxicity was related to a smaller hydrodynamic size and higher suspension stability, which in turn resulted in a higher bioavailability of Ag NMs and released ions, particularly in S:W. Toxicity was correlated with the main physicochemical features, providing useful prediction of AgNMs bioactivity. The ability to test E. crypticus in a range of media with different and/or increasing complexity (water, S:W extracts, soil) provided an excellent source to interpret results and is here recommended.

Fixation devices made of poly-L-lactide composite for rib reconstruction after thoracotomy

GRAND FIX mesh-type plates and pins (Gunze, Kyoto, Japan) are thin, bioabsorbable fixation devices made of poly-L-lactide (PLLA) composite. These devices are new, and how best to use them in clinical practice remains to be determined. Thus, we describe our approach to rib fixation after thoracotomy in an aortic surgery using GRAND FIX mesh-type plates and pins. The advantage of our approach is that it is easy to perform, but careful attention should be paid to fix the ribs appropriately.

Research on theoretical and experimental investigations of burr formation mechanism in micro-milling process of medical ploy-l-lactide

Medical grade poly-l-lactide (PLLA) has been widely applied for medical devices and consumables, e.g. biodegradable cardiovascular stents and surgical thread, due to its excellent biocompatibility. High-speed micro-milling technology shows great potential in high-precision and high-quality manufacturing of material PLLA, while it usually produces problems such as material burrs and defects. There is few research and analysis on the material removal mechanism and theory in the micro-milling process of polymers, and thus this paper aims to investigate the burr formation mechanism and processing quality in micro-milling process of medical PLLA. Firstly, a novel thermal-mechanical coupled theoretical model was proposed by considering the minimum cutting thickness and cutting-edge radius size effects, which can reveal the plastic flow law during micro-milling process of polymer material. This model was used to calculate the burr width at up and down milling sides of cutting area. Then material characterization and micro-milling experiments on two types of PLLA with different molecular weights were carried out to validate the established theoretical model, and further the micro-milling parameters were optimized to achieve the control of material burr formation and growth. As a result, a cardiovascular stent was fabricated by micro-milling with the optimized parameters (spindle speed of 25,000 rpm, feed rate of 100 mm/min and axial depth of cut of 5 μm), and the stents obtained significantly high surface quality. These results suggest that the proposed theoretical model has great advantages in the high-quality micro-milling of medical material PLLA. This work provides a potential stent manufacture technique in the development and clinical application of bioresorbable polymeric stents.

The Effect of Stereocomplexation and Crystallinity on the Degradation of Polylactide Nanoparticles.

Polymeric nanoparticles (PNPs) are frequently researched and used in drug delivery. The degradation of PNPs is highly dependent on various properties, such as polymer chemical structure, size, crystallinity, and melting temperature. Hence, a precise understanding of PNP degradation behavior is essential for optimizing the system. This study focused on enzymatic hydrolysis as a degradation mechanism by investigation of the degradation of PNP with various crystallinities. The aliphatic polyester polylactide ([C3H4O2]n, PLA) was used as two chiral forms, poly l-lactide (PlLA) and poly d-lactide (PdLA), and formed a unique crystalline stereocomplex (SC). PNPs were prepared via a nanoprecipitation method. In order to further control the crystallinity and melting temperatures of the SC, the polymer poly(3-ethylglycolide) [C6H8O4]n (PEtGly) was synthesized. Our investigation shows that the PNP degradation can be controlled by various chemical structures, crystallinity and stereocomplexation. The influence of proteinase K on PNP degradation was also discussed in this research. AFM did not reveal any changes within the first 24 h but indicated accelerated degradation after 7 days when higher EtGly content was present, implying that lower crystallinity renders the particles more susceptible to hydrolysis. QCM-D exhibited reduced enzyme adsorption and a slower degradation rate in SC-PNPs with lower EtGly contents and higher crystallinities. A more in-depth analysis of the degradation process unveiled that QCM-D detected rapid degradation from the outset, whereas AFM exhibited delayed changes of degradation. The knowledge gained in this work is useful for the design and creation of advanced PNPs with enhanced structures and properties.

Melt blending of poly(lactic acid) with biomedically relevant polyurethanes to improve mechanical performance

Minimally invasive surgery procedures are of utmost relevance in clinical practice. However, the associated mechanical stress on the material poses a challenge for new implant developments. In particular PLLA, one of the most widely used polymeric biomaterials, is limited in its application due to its high brittleness and low elasticity. In this context, blending is a conventional method of improving the performance of polymer materials. However, in implant applications and development, material selection is usually limited to the use of medical grade polymers. The focus of this work was to investigate the extent to which blending poly-l-lactide (PLLA) with low contents of a selection of five commercially available medical grade polyurethanes leads to enhanced material properties. The materials obtained by melt blending were characterized in terms of their morphology and thermal properties, and the mechanical performance of the blends was evaluated taking into account physiological conditions. From these data, we found that mixing PLLA with Pellethane 80A is a promising approach to improve the material's performance, particularly for stent applications. It was found that PLLA/Pellethane blend with 10% polyurethane exhibits considerable plastic deformation before fracture, while pure PLLA fractures with almost no deformation. Furthermore, the addition of Pellethane only leads to a moderate reduction in elongation at yield and yield stress. In addition, dynamic mechanical analysis for three different PLLA/Pellethane ratios was performed to investigate thermally induced shape retention and shape recovery of the blends.

Nanostructured Poly-l-lactide and Polyglycerol Adipate Carriers for the Encapsulation of Usnic Acid: A Promising Approach for Hepatoprotection.

The present study investigates the utilization of nanoparticles based on poly-l-lactide (PLLA) and polyglycerol adipate (PGA), alone and blended, for the encapsulation of usnic acid (UA), a potent natural compound with various therapeutic properties including antimicrobial and anticancer activities. The development of these carriers offers an innovative approach to overcome the challenges associated with usnic acid's limited aqueous solubility, bioavailability, and hepatotoxicity. The nanosystems were characterized according to their physicochemical properties (among others, size, zeta potential, thermal properties), apparent aqueous solubility, and in vitro cytotoxicity. Interestingly, the nanocarrier obtained with the PLLA-PGA 50/50 weight ratio blend showed both the lowest size and the highest UA apparent solubility as well as the ability to decrease UA cytotoxicity towards human hepatocytes (HepG2 cells). This research opens new avenues for the effective utilization of these highly degradable and biocompatible PLLA-PGA blends as nanocarriers for reducing the cytotoxicity of usnic acid.

An integrated mechanical degradation model to explore the mechanical response of a bioresorbable polymeric scaffold

Simulation of bioresorbable medical devices is hindered by the limitations of current material models. Useful simulations require that both the short- and long-term response must be considered; existing models are not physically-based and provide limited insight to guide performance improvements. This study presents an integrated degradation framework which couples a physically-based degradation model, which predicts changes in both crystallinity (Xc) and molecular weight (Mn), with the results of a micromechanical model, which predicts the effective properties of the semicrystalline polymer. This degradation framework is used to simulate the deployment of a bioresorbable PLLA (Poly (L-lactide) stent into a mock vessel and the subsequent mechanical response during degradation under different diffusion boundary conditions representing neointimal growth. A workflow is established in a commercial finite element code that couples both the immediate and long-term responses. Clinically relevant lumen loss is reported and used to compare different responses and the effect of neo-intimal tissue regrowth post-implantation on degradation and on the mechanical response is assessed. In addition, the effects of possible changes in Xc, which could occur during processing and stent deployment, are explored.

A continuous phase-evolution model for cold and strain-induced crystallization in semi-crystalline polymers

The dynamic crystallization during extreme thermomechanical history under producing or service strongly influences the dimensional stability of the semi-crystalline thermoplastic polymers. To produce high-precision structural components, the proper thermomechanical history needs to be carefully designed to eliminate the crystallization-induced shrinkage. On the contrary, the rapidly developed four-dimensional (4D) printing technology tries to amplify the crystallization-induced shrinkage to directly produce the complex curvatures without supporting materials. However, the crystals formed at different deformation states might have different orientations, leading to an anisotropic residual deformation. Therefore, tracing of all crystals formed with different initial configurations is the key issue to ensure the geometric accuracy of both the high-precision and the deformable components. In this study, we developed a continuous phase-evolution model for both the cold and the strain-induced crystallization in semi-crystalline thermoplastics. The irreversible cold crystallization is analogized as the raindrop falling into the pool, and the reversible strain-induced crystallization is analogized as the nonequilibrium liquid-gas phase transformation. Using the continuous phase-evolution concept, the crystal growth is described by a series of continuously formed crystal phases sequentially added into the initial amorphous medium. Each newly formed crystal phase is in a stress-free state at the formation moment, and therefore the crystallization history coupled with the whole deformation history can be memorized. By introducing the oriented growth tensor representing the stress-free state of all formed crystals, the deformation-history dependent anisotropic crystallization and the corresponding residual deformation can be traced. The developed model is validated by comparing with the experimental data of the dynamic crystallization in amorphous poly l-lactide polymers under thermomechanical loading cycles. Finally, the predictive capability of the model is illustrated by several demonstrations, to show the influences of deformation-history dependent crystallization orientations and the corresponding anisotropic residual deformation.

Multi-layer antibacterial polyester fabrics for infection management and moisture wicking in a textile-based biomaterial wound dressing

Antibacterial woven polyester fabrics are drawing much attention in the medical and textile industries because they can provide many health-promoting properties that prevent infection while providing a barrier to the external environment. In this work, we developed and investigated two different polyester fabrics to demonstrate the antibacterial, non-adhesive, and moisture wicking properties of a multicomponent wound dressing. Vertical wicking of a braided layer composed of Poly-l-lactide (PLLA) yarn of 4-deep-grooved (4DG) fibers was tested using porcine blood serum to mimic wound exudate viscosity. Bacterial inhibition of Pseudomonas putida was measured after exposure to gentamicin sulfate (GS)-incorporated PLLA skin-contact layers of two different shaped yarns. Poly-ethylene glycol (PEG) was added to the GS PLLA contact layer to further prevent non-specific cellular attachment. Results indicated vertical wicking of moisture at 0.88 mm/s. While a specific wicking rate for adequate wound moisture regulation has not been indicated in the literature due to wound and patient variability, we assert that rapid removal of excess fluid from the wound bed, as demonstrated by our fabric is an essential component for a comprehensive wound dressing. Antibacterial experiments showed that GS exhibited both bactericidal and bacteriostatic trends by killing bacteria and further inhibiting growth, respectively. The surface treatment of PEG on PLLA contact layers showed less cellular attachment, promoting non-adhesion during dressing changes. Ultimately, using woven polyester medical textiles in wound care allows for optimizing parameters, such as antimicrobial uptake/release and moisture wicking for personalized healing. The construct studied here may serve as a tunable platform for development of wound dressings with specific antibacterial, moisture, and tissue adhesion requirements.

ФОТОДЕГРАДАЦИЯ ПОЛУКРИСТАЛЛИЧЕСКОГО ПОЛИЛАКТИДА ПОД ДЕЙСТВИЕМ УФ РАДИАЦИИ. I. ГЕТЕРОФАЗНЫЙ МЕХАНИЗМ РАЦЕМИЗАЦИИ МАКРОМОЛЕКУЛ

The regularities of UV photodegradation of semi-crystalline films of poly-L-lactide (PLA) formed from solution in chloroform have been analyzed on the basis of IR spectroscopy and gel permeation chromatography. When analysing the experimental results, we took into account the fact that during the preparation of semi-crystalline films of poly-L-lactide, mechanical stresses accumulate in them. The presence of the latter is the reason why the acts of photodegradation proceeding according to the Norrish I mechanism prevail at the initial stage of the process in imperfect elements of the crystalline phase, in which enantiomerisation and racemisation of PLA macromolecules occur simultaneously with the rupture of polymer chains into radicals. In this work, the role of such important factors as the presence of interfacial stresses stabilising in films at the stage of their formation and the role of triplet energy migration through the system of carbonyl groups are considered for the first time. The imperfectly structured primary elements of the crystalline phase formed in the matrix of solid PLA represent ‘traps’ of triplet energy of photoexcitation migrating along the matrix C=O-groups. In such traps, C-C-bonds are broken on the inner walls of nanoscale slits of imperfect crystallites, and under such harsh conditions, either recombination with restoration of molecular chains or disproportionation of end radicals with fixation of chain fragmentation acts are realised. Acts of recombination of radicals with free valence on carbon atoms are preceded with a small probability by acts of enantiomerization of chiral carbon from the L state into the D state. These acts take place in the middle segments of polymer chains, resulting in the appearance of interchain bonding sites in the form of racemates. During the continuing photoprocess, the acts of macromolecule rupture propagate to the glassy phase of PLA. The observed peculiarities of photodegradation are explained by the heterophase mechanism of transfer of triplet excitation energy by carbonyl C=O-groups of the polymer from the glassy to the crystalline phase, in which C=O-groups not only accept the triplet energy migrating through the matrix, but also transform it into the energy of polymer chain scission.

Oriented polyaniline/poly-l-lactic acid/gelatin nanofiber scaffolds promote outgrowth of spiral ganglion neurons.

Sensorineural hearing loss (SNHL) is caused by the loss of sensory hair cells (HCs) and/or connected spiral ganglion neurons (SGNs). The current clinical conventional treatment for SNHL is cochlear implantation (CI). The principle of CI is to bypass degenerated auditory HCs and directly electrically stimulate SGNs to restore hearing. However, the effectiveness of CI is limited when SGNs are severely damaged. In the present study, oriented nanofiber scaffolds were fabricated using electrospinning technology to mimic the SGN spatial microenvironment in the inner ear. Meanwhile, different proportions of polyaniline (PANI), poly-l-lactide (PLLA), gelatin (Gel) were composited to mimic the composition and mechanical properties of auditory basement membrane. The effects of oriented PANI/PLLA/Gel biomimetic nanofiber scaffolds for neurite outgrowth were analyzed. The results showed the SGNs grew in an orientation along the fiber direction, and the length of the protrusions increased significantly on PANI/PLLA/Gel scaffold groups. The 2% PANI/PLLA/Gel group showed best effects for promoting SGN adhesion and nerve fiber extension. In conclusion, the biomimetic oriented nanofiber scaffolds can simulate the microenvironment of SGNs as well as promote neurite outgrowth in vitro, which may provide a feasible research idea for SGN regeneration and even therapeutic treatments of SNHL in future.

A CuS@g-C3N4 heterojunction endows scaffold with synergetic antibacterial effect.

Graphitic carbon nitride (g-C3N4) had aroused tremendous attention in photodynamic antibacterial therapy due to its excellent energy band structure and appealing optical performance. Nevertheless, the superfast electron-hole recombination and dense biofilm formation abated its photodynamic antibacterial effect. To this end, a nanoheterojunction was synthesized via in-situ growing copper sulfide (CuS) on g-C3N4 (CuS@g-C3N4). On the one hand, CuS could form Fermi level difference with g-C3N4 to accelerate carrier transfer and thus facilitate electron-hole separation. On the other hand, CuS could respond near-infrared light to generate localized thermal to disrupt biofilm. Then the CuS@g-C3N4 nanoparticle was introduced into the poly-l-lactide (PLLA) scaffold. The photoelectrochemistry results demonstrated that the electron-hole separation efficiency was apparently enhanced and thereby brought an approximate sevenfold increase in reactive oxygen species (ROS) production. The thermal imaging indicated that the scaffold possesses a superior photothermal effect, which effectively eradicated the biofilm by disrupting its extracellular DNA and thereby facilitated to the entry of ROS. The entered ROS could effectively kill the bacteria by causing protein, K+, and nucleic acid leakage and glutathione consumption. As a consequence, the scaffold displayed an antibacterial rate of 97.2% and 98.5% against E. coli and S. aureus, respectively.

Biomechanical Performance of Biodegradable Screw Fixation in Mandibular Distraction Osteogenesis.

Internal distraction devices are commonly used in congenital micrognathia. The eventual need for device and screw removal can be challenging, requiring extensive dissection and disturbance of bone regenerate. Bioabsorbable poly-L-lactide (PLLA) screws, compared to traditional titanium screws, simplify device removal. Previous in vivo studies have found that the maximal compressive force generated by mandibular distraction is 69.4N. We hypothesized that PLLA screws could support these compressive/distraction forces. Ten mandibles were obtained from 5 canine cadavers. Paired mandibles from the same cadaver were each fixated to a mandibular distractor with eight screws (either titanium or PLLA). Devices were each set to 15 and 30 mm of distraction distance. Compression force of 80 N was then generated parallel to the axis of the distraction device. Distractor displacement was measured to detect any mechanical failure during this pre-set load. Finally, if no failure was observed at 80 N, a load-to-failure compression test was done in the PLLA group to determine the mechanical failure point. All distractors in both the titanium and PLLA screw groups withstood 80 N of compression without failure. When the load-to-failure test was performed in the PLLA group, the average device failure point was 172.8 N (range 148-196 N). Review of high-frame-rate video demonstrated that all failures occurred due to the PLLA screws breaking or falling out. Bioabsorbable PLLA screws can withstand compressive forces more than double that of the maximal in vivo forces needed during mandibular distraction. These screws may be an acceptable alternative for the fixation of internal mandibular distractors.

Ag sputter coating of PLLA nonwovens

Abstract Physical vapor deposition (PVD) sputtering is a promising technique for the generation of electrically conductive coatings on complex structured biomaterials, such as nonwovens, that can be used in implants. The ultra-thin coatings can fulfil a variety of purposes, such as drug depot or biosensor. The aim of our studies was to determine the feasibility of generating thin silver (Ag) coatings on complex structured poly-L-lactide (PLLA) nonwovens by sputtering and their morphological characterization. PVD sputter process was performed using a customized plasma chamber and a complex rotation of the tender electrospun PLLA nonwovens. Morphological analysis revealed a promising homogenous Ag coating, representing the structure of the nonwovens.

Multi-objective design optimization of bioresorbable braided stents

Background and objectivesBioresorbable braided stents, typically made of bioresorbable polymers such as poly-l-lactide (PLLA), have great potential in the treatment of critical limb ischemia, particularly in cases of long-segment occlusions and lesions with high angulation. However, the successful adoption of these devices is limited by their low radial stiffness and reduced elastic modulus of bioresorbable polymers. This study proposes a computational optimization procedure to enhance the mechanical performance of bioresorbable braided stents and consequently improve the treatment of critical limb ischemia. MethodsFinite element analyses were performed to replicate the radial crimping test and investigate the implantation procedure of PLLA braided stents. The stent geometry was characterized by four design parameters: number of wires, wire diameter, initial stent diameter, and braiding angle. Manufacturing constraints were considered to establish the design space. The mechanical performance of the stent was evaluated by defining the radial force, foreshortening, and peak maximum principal stress of the stent as objectives and constraint functions in the optimization problem. An approximate relationship between the objectives, constraint, and the design parameters was defined using design of experiment coupled with surrogate modelling. Surrogate models were then interrogated within the design space, and a multi-objective design optimization was conducted. ResultsThe simulation of radial crimping was successfully validated against experimental data. The radial force was found to be primarily influenced by the number of wires, wire diameter, and braiding angle, with the wire diameter having the most significant impact. Foreshortening was predominantly affected by the braiding angle. The peak maximum principal stress exhibited contrasting behaviour compared to the radial force for all parameters, with the exception of the number of wires. Among the Pareto-optimal design candidates, feasible peak maximum principal stress values were observed, with the braiding angle identified as the differentiating factor among these candidates. ConclusionsThe exploration of the design space enabled both the understanding of the impact of design parameters on the mechanical performance of bioresorbable braided stents and the successful identification of optimal design candidates. The optimization framework contributes to the advancement of innovative bioresorbable braided stents for the effective treatment of critical limb ischemia.

Investigation of biodegradability and cellular activity of PCL/PLA and PCL/PLLA electrospun webs for tissue engineering applications.

Biodegradability and cellular activity are key performance indicators that should be prioritized for tissue engineering applications. Biopolymer selection, determination of necessary structural properties, and their synergistic interactions play an active role in obtaining the expected biodegradability and biological activity from scaffolds. In this study, it is aimed to produce electrospun webs with improved biocompatibility by blending polycaprolactone (PCL) with polylactic acid (PLA) and poly-l-lactide (PLLA), and examine the effect of biopolymer selection and blend ratio on the biodegradability and cellular activity of surfaces. In this context, fibrous webs are produced from PCL/PLA and PCL/PLLA blends with a weight ratio of 80/20 and 50/50 and pure polymers of PCL, PLA, and PLLA by electrospinning method and subjected to morphological and biological analyses. The biodegradation tests are carried out hydrolytically while the cell viability and cell proliferation analyses are performed with adult human primary dermal fibroblasts and human umbilical endothelial cells (HUVECs). The results show that the fiber diameters of the fabricated webs ranged from 0.747 to 1.685 μm. At the end of the 5th month, it is observed that the biodegradation rates of the webs blended 50% with PLA and PLLA, in comparison to PCL ones, increase from 3.7% to 13.33% and 7.69%, respectively. On the other hand, cell culture results highlight that the addition of 20% PLA and PLLA improves the cellular activity of both cell types, but increased PLA or PLLA ratio in PCL webs has a negative effect as it makes the structure stiff and brittle.

Eco-Friendly Blends of Recycled PET Copolymers with PLLA and Their Composites with Chopped Flax Fibres.

The structure and properties of blends of a novel polyethylene terephthalate copolymer (COPET) obtained by chemical recycling of commercial PET with high-molar-mass poly-L-lactide (PLLA) are investigated and compared to corresponding composites with chopped flax fibres. The focus is on the morphology at nano- and micro-scales, on the thermal characteristics and on the mechanical behaviour. The blends are immiscible, as evidenced by virtually unchanged glass transition temperatures of the blend components compared to the neat polymers (49 °C for COPET and 63 °C for PLLA by DSC). At low PLLA content, the blends display a sea-island morphology with sub-micron to micron droplet sizes. As the composition approaches 50/50, the morphology transitions to a coarser co-continuous elongated structure. The blends and composites show strongly improved stiffness compared to COPET above its glass transition temperature, e.g., from melt behaviour at 60 °C for COPET alone to almost 600 MPa for the 50/50 blend and 500 MPa for the 20% flax composite of the 80/20 COPET/PLLA blend. The flax fibres increase the crystallisation rate of PLLA in blends with dispersed PLLA morphology. The evidence of cavitation on the fracture surfaces of blends shows that despite the immiscibility of the components, the interfacial adhesion between the phases is excellent. This is attributed to the presence of aliphatic ester spacers in COPET. The tensile strength of the 80/20 blend is around 50 MPa with a Young's modulus of 2250 MPa. The corresponding 20% flax composite has similar tensile strength but a high Young's modulus equal to 6400 MPa, which results from the individual dispersion and strong adhesion of the flax fibres and leads close to the maximum possible reinforcement of the composite, as demonstrated by tensile tests and nano-indentation. The Ashby approach to eco-selection relying on the embodied energy (EE) further clarifies the eco-friendliness of the blends and their composites, which are even better positioned than PLLA in a stiffness versus EE chart.

Synergistic effect of GMA and TMPTA as co-agent to adjust the branching structure of PLLA during UV-induced reactive extrusion

Abstract In this work, glycidyl methacrylate (GMA) and trimethylol propanetriacrylate (TMPTA) are employed to adjust the branching structure of poly L-lactide acid (PLLA) during reactive extrusion induced by UV irradiation. The reaction of GMA epoxide with terminal carboxyl or hydroxyl groups at PLLA chain end can introduce C=C groups onto PLLA molecular chains. Chain branching reaction occurred via the free-radical grafting reaction of the vinyl group in TMPTA with both PLLA backbone and the C=C group terminated PLLA induced by UV irradiation. As a result, varied branching levels can be obtained by changing the ratio of GMA and TMPTA. The characterizations of rheological properties and size exclusive chromatograph correlated to the chain branches were performed to evaluate the chain branching extent. The increases in shear viscosity and storage modulus at terminal zone, and the reduced branching degree were observed in the branched PLLA samples. The results from 1H-NMR and FIRT indicate that the grafting reaction of GMA onto PLLA take place successfully. Thus, this study proposes a strategy to adjust LCB-PLA structure using GMA and TMPTA as co-agents, which is of great importance for the industrialization of PLA products.