Bioactivity and Antibacterial Analysis of Plasticized PLA Electrospun Fibers Reinforced with MgO and Mg(OH)2 Nanoparticles.

In this work, we focused on the bioactivity and antibacterial behavior of PLA-based electrospun fibers, efibers, reinforced with both MgO and Mg(OH)2 nanoparticles, NPs. The evolution of PLA-based efibers was followed in terms of morphology, FTIR, XRD, and visual appearance. The bioactivity was discussed in terms of hydroxyapatite growth after 28 days, considered as T28, of immersion in simulated body fluid, SBF. In particular, the biomineralization process evidenced after immersion in SBF started at T14 in both systems. The number of precipitated crystals increased by increasing the amount of both NPs. The chemical composition of the precipitated crystals was also characterized in terms of the Ca/P molar ratio after T28 of immersion in SBF, indicating the presence of hydroxyapatite on the surface of both reinforced efibers. Moreover, a reduction in the average diameter of the PLA-based efibers was observed, reaching a maximum reduction of 46 and 60% in the average diameter of neat PLA and PLA:OLA efibers, respectively, after 28 days of immersion in SBF. The antibacterial behavior of the MgO and Mg(OH)2 NPs in the PLA-based electrospun fibers was tested against Escherichia coli, E. coli, as the Gram-negative bacteria, and Staphylococcus aureus, S. aureus, as the Gram-positive bacteria, obtaining the best antibacterial activity against the Gram-negative bacteria E. coli of 21 ± 2% and 34 ± 6% for the highest concentration of MgO and Mg(OH)2 NPs, respectively.

A Comparison of Three-Layer and Single-Layer Small Vascular Grafts Manufactured via the Roto-Evaporation Method.

This study used the roto-evaporation technique to engineer a 6 mm three-layer polyurethane vascular graft (TVG) that mimics the architecture of human coronary artery native vessels. Two segmented polyurethanes were synthesized using lysine (SPUUK) and ascorbic acid (SPUAA), and the resulting materials were used to create the intima and adventitia layers, respectively. In contrast, the media layer of the TVG was composed of a commercially available polyurethane, Pearlbond 703 EXP. For comparison purposes, single-layer vascular grafts (SVGs) from individual polyurethanes and a polyurethane blend (MVG) were made and tested similarly and evaluated according to the ISO 7198 standard. The TVG exhibited the highest circumferential tensile strength and longitudinal forces compared to single-layer vascular grafts of lower thicknesses made from the same polyurethanes. The TVG also showed higher suture and burst strength values than native vessels. The TVG withstood up to 2087 ± 139 mmHg and exhibited a compliance of 0.15 ± 0.1%/100 mmHg, while SPUUK SVGs showed a compliance of 5.21 ± 1.29%/100 mmHg, akin to coronary arteries but superior to the saphenous vein. An indirect cytocompatibility test using the MDA-MB-231 cell line showed 90 to 100% viability for all polyurethanes, surpassing the minimum 70% threshold needed for biomaterials deemed cytocompatibility. Despite the non-cytotoxic nature of the polyurethane extracts when grown directly on the surface, they displayed poor fibroblast adhesion, except for SPUUK. All vascular grafts showed hemolysis values under the permissible limit of 5% and longer coagulation times.

Thermally-Activated Shape Memory Behavior of Biodegradable Blends Based on Plasticized PLA and Thermoplastic Starch.

Biodegradable blends based on plasticized poly(lactic acid) PLA and thermoplastic starch (TPS) have been obtained. The influence of the PLA plasticizer as a compatibility agent has been studied by using two different plasticizers such as neat oligomeric lactic acid (OLA) and functionalized with maleic acid (mOLA). In particular, the morphological, thermal, and mechanical properties have been studied as well as the shape memory ability of the melt-processed materials. Therefore, the influence of the interaction between different plasticizers and the PLA matrix as well as the compatibility between the two polymeric phases on the thermally-activated shape memory properties have been studied. It is very interesting to use the same additive able to act as both plasticizer and compatibilizer, decreasing the glass transition temperature of PLA to a temperature close to the physiological one, obtaining a material suitable for potential biomedical applications. In particular, we obtain that OLA-plasticized blend (oPLA/TPS) show very good thermally-activated capability at 45 °C and 50% deformation, while the blend obtained by using maleic OLA (moPLA/TPS) did not show shape memory behavior at 45 °C and 50% deformation. This fact is due to their morphological changes and the loss of two well-distinguished phases, one acting as fixed phase and the other one acting as switching phase to typically obtain shape memory response. Therefore, the thermally-activated shape memory results show that it is very important to make a balance between plasticizer and compatibilizer, considering the need of two well-established phases to obtain shape memory response.

An Analysis of the Self-Healing and Mechanical Properties as well as Shape Memory of 3D-Printed Surlyn® Nanocomposites Reinforced with Multiwall Carbon Nanotubes.

This research work studies the self-healing ability, mechanical properties, and shape memory of the polymer Surlyn® 8940 with and without multiwall carbon nanotubes (MWCNTs) as a nanoreinforcement. This polymer comes from a partially neutralized poly(ethylene-co-methacrylic acid) (EMAA) ionomer copolymer. MWCNTs and the polymer went through a mixing process aimed at achieving an excellent dispersion. Later, an optimized extrusion method was used to produce a uniform reinforced filament, which was the input for the 3D-printing process that was used to create the final test samples. Various concentrations of MWCNTs (0.0, 0.1, 0.5, and 1.0 wt.%) were used to evaluate and compare the mechanical properties, self-healing ability, and shape memory of unreinforced and nanoreinforced materials. Results show an enhancement of the mechanical properties and self-healing ability through the addition of MWCNTs to the matrix of polymer, and the specimens showed shape memory events.

Study on the Tensile Behavior of Woven Non-Woven PLA/OLA/MgO Electrospun Fibers.

The present work deeply studied the mechanical behavior of woven non-woven PLA/OLA/MgO electrospun fibers, efibers, by using Box-Wilson surface response methodology. This work follows up a previous one where both the diameters and the thermal response of such efibers were discussed in terms of both the different amounts of magnesium oxide nanoparticles, MgO, as well as of the oligomer (lactic acid), OLA, used as plasticizer. The results of both works, in term of diameters, degree of crystallinity, and mechanical response, can be strongly correlated to each other, as reported here. In particular, the strain mechanism of PLA/OLA/MgO efibers was studied, showing an orientation of efibers parallel to the applied stress and identifying the mechanically weakest points that yielded the start of the breakage of efibers. Moreover, we identified 1.5 wt% as the critical amount of MgO, above which the plasticizing effect of OLA was weaker as the amount of both components increased. Moreover, the minimum elastic modulus value took place at 15 wt% of OLA, in agreement with the previously reported convergence point in the evolution of the degree of crystallinity. Regarding the yield point, a concentration of OLA between 20 and 30 wt% led to a slight improvement in the yielding capability in terms of tensile strength in comparison with neat PLA efibers. Therefore, the approach presented here permits the design of tailor-made electrospun nanocomposites with specific mechanical requirements.

Preparation and characterization of novel poly (lactic acid)/calcium oxide nanocomposites by electrospinning as a potential bone tissue scaffold.

Calcium oxide nanoparticles (n-CaO) ca. 22 nm were obtained from eggshell waste. The n-CaO was incorporated into the PLA matrix in 10 and 20 wt% of filler content by electrospinning process to get PLA/n-CaO fibers with homogenous morphology and diameter as a potential use in scaffold for bone tissue regeneration. The incorporation of n-CaO into PLA modifies the mechanical properties, having a reinforcement effect on the matrix. The Young modulus for PLA/n-CaO nanocomposites increased between 122 and 138 % concerning neat PLA fibers, showing a more rigid behavior. The PLA/n-CaO nanocomposite fibers showed in vitro bioactivity, capable of inducing the precipitation of hydroxyapatite (HA) layer in the fiber surface after seven days in SBF solution. The biocidal and biological properties of PLA/n-Cao with 20 wt% showed a 30 % reduction in bacterial viability against S. aureus and 11 % against E. coli after 6 h of bacterial exposure. Furthermore, the fibers did not show a cytotoxic effect on the bone marrow ST-2 cell line, allowing cell adhesion and proliferation in the RPMI medium. The PLA/n-CaO with 20 wt% of nanoparticles showed a higher capacity to promote osteogenic differentiation, significantly increasing the alkaline phosphatase (ALP) expression after seven days compared to PLA and cell control. The in vivo analysis corroborated the biocompatibility of the prepared scaffolds; the presence of n-CaO in PLA reduced the formation of fibrous encapsulation of the material, improving the healing process. These results validated using n-CaO to enhance the functionality of polymer matrices as a PLA, bringing bioactive, biocide, and biocompatible properties, opening a new and interesting route to develop new biomaterials as a scaffold for bone tissue engineering.

Fabrication of PLA-Based Electrospun Nanofibers Reinforced with ZnO Nanoparticles and In Vitro Degradation Study.

In this work, electrospun nanofibers based on polylactic acid, PLA, reinforced with ZnO nanoparticles have been studied, considering the growing importance of electrospun mats based on biopolymers for their applications in different fields. Specifically, electrospun nanofibers based on PLA have been prepared by adding ZnO nanoparticles at different concentrations, such as 0.5, 1, 3, 5, 10 and 20 wt%, with respect to the polymer matrix. The materials have been characterized in terms of their morphological, mechanical, and thermal properties, finding 3 wt% as the best concentration to produce PLA nanofibers reinforced with ZnO nanoparticles. In addition, hydrolytic degradation in phosphate buffer solution (PBS) was carried out to study the effect of ZnO nanoparticles on the degradation behavior of PLA-based electrospun nanofiber mats, obtaining an acceleration in the degradation of the PLA electrospun mat.

A Review on Reinforcements and Additives in Starch-Based Composites for Food Packaging.

The research of starch as a matrix material for manufacturing biodegradable films has been gaining popularity in recent years, indicating its potential and possible limitations. To compete with conventional petroleum-based plastics, an enhancement of their low resistance to water and limited mechanical properties is essential. This review aims to discuss the various types of nanofillers and additives that have been used in plasticized starch films including nanoclays (montmorillonite, halloysite, kaolinite, etc.), poly-saccharide nanofillers (cellulose, starch, chitin, and chitosan nanomaterials), metal oxides (titanium dioxide, zinc oxide, zirconium oxide, etc.), and essential oils (carvacrol, eugenol, cinnamic acid). These reinforcements are frequently used to enhance several physical characteristics including mechanical properties, thermal stability, moisture resistance, oxygen barrier capabilities, and biodegradation rate, providing antimicrobial and antioxidant properties. This paper will provide an overview of the development of starch-based nanocomposite films and coatings applied in food packaging systems through the application of reinforcements and additives.

Thermal Properties and In Vitro Biodegradation of PLA-Mg Filaments for Fused Deposition Modeling.

Additive manufacturing, in particular the fused deposition method, is a quite new interesting technique used to obtain specific 3D objects by depositing layer after layer of material. Generally, commercial filaments can be used in 3D printing. However, the obtention of functional filaments is not so easy to reach. In this work, we obtain filaments based on poly(lactic acid), PLA, reinforced with different amounts of magnesium, Mg, microparticles, using a two-step extrusion process, in order to study how processing can affect the thermal degradation of the filaments; we additionally study their in vitro degradation, with a complete release of Mg microparticles after 84 days in phosphate buffer saline media. Therefore, considering that we want to obtain a functional filament for further 3D printing, the simpler the processing, the better the result in terms of a scalable approach. In our case, we obtain micro-composites via the double-extrusion process without degrading the materials, with good dispersion of the microparticles into the PLA matrix without any chemical or physical modification of the microparticles.

Centrifugal Force-Spinning to Obtain Multifunctional Fibers of PLA Reinforced with Functionalized Silver Nanoparticles.

The design and development of multifunctional fibers awakened great interest in biomaterials and food packaging materials. One way to achieve these materials is by incorporating functionalized nanoparticles into matrices obtained by spinning techniques. Here, a procedure for obtaining functionalized silver nanoparticles through a green protocol, using chitosan as a reducing agent, was implemented. These nanoparticles were incorporated into PLA solutions to study the production of multifunctional polymeric fibers by centrifugal force-spinning. Multifunctional PLA-based microfibers were obtained with nanoparticle concentrations varying from 0 to 3.5 wt%. The effect of the incorporation of nanoparticles and the method of preparation of the fibers on the morphology, thermomechanical properties, biodisintegration, and antimicrobial behavior, was investigated. The best balance in terms of thermomechanical behavior was obtained for the lowest amount of nanoparticles, that is 1 wt%. Furthermore, functionalized silver nanoparticles confer antibacterial activity to the PLA fibers, with a percentage of killing bacteria between 65 and 90%. All the samples turned out to be disintegrable under composting conditions. Additionally, the suitability of the centrifugal force-spinning technique for producing shape-memory fiber mats was tested. Results demonstrate that with 2 wt% of nanoparticles a good thermally activated shape-memory effect, with high values of fixity and recovery ratios, is obtained. The results obtained show interesting properties of the nanocomposites to be applied as biomaterials.

Hydrolytic Degradation and Bioactivity of Electrospun PCL-Mg-NPs Fibrous Mats.

In this work, the in vitro degradation behavior of nanofibers was investigated in phosphate buffer solution (PBS) and simulated body fluid (SBF) to study their degradation behavior, as well as their bioactivity. The degradation was studied at different immersion times in order to evaluate how the presence of Mg-based nanoparticles can affect the degradation in terms of morphology, crystallinity, degradation rate and pH changes, and finally to evaluate the bioactivity of PCL-based electrospun nanofibers. We found that the degradation of the materials takes more than 3 months; however, the presence of nanoparticles seems to have an accelerating effect on the degradation of the electrospun nanofibers based on PCL. In fact, a reduction in diameter of almost 50% was observed with the highest content of both types of nanoparticles and an increase in crystallinity after 296 days of immersion in PBS. Moreover, the carbonyl index was calculated from an FTIR analysis, and a reduction of 20-30% was observed due to the degradation effect. Additionally, the bioactivity of PCL-based electrospun nanofibers was studied and the formation of crystals on the nanofibers surface was detected, except for neat electrospun PCL related to the formation of NaCl and apatites, depending on the amount and type of nanoparticles. The presence of apatites was confirmed by an XRD analysis and FT-IR analysis observing the characteristic peaks; furthermore, the EDX analysis demonstrated the formation of apatites than can be reconducted to the presence of HA when 20 wt% of nanoparticles is added to the PCL electrospun fibers.

Fabrication and assessment of bifunctional electrospun poly(l-lactic acid) scaffolds with bioglass and zinc oxide nanoparticles for bone tissue engineering.

Electrospun scaffolds based on poly(l-lactic acid) (PLLA) with bioglass (n-BG) and zinc oxide (n-ZnO), and mixture of both, were developed to design bifunctional biomaterials with enhanced bioactive and biocidal properties. The presence of n-BG increased the fiber diameter of the pure PLA from 1.5 ± 0.3 µm to 3.0 ± 0.8 µm for 20 wt%. ZnO and the mixed nanoparticles did not significantly affect the morphology. The mechanical properties decreased with the presence of nanoparticles. Scaffolds based on PLA/n-BG promoted hydroxyapatite (HA) formation in simulated body fluid (SBF) that was inhibited with the presence of ZnO. Notably, mixed particles produced bioactivity although at longer times. The incorporation of n-ZnO produced a biocidal capacity against S. aureus in the polymeric scaffold, reaching a viability reduction of 60 % after 6 h of exposure. When both types of nanoparticles were combined, the bacterial viability reduction was 30 %. Pure PLA scaffolds and the composites with n-BG showed good ST-2 bone marrow-derived cell line viability, scaffolds with n-BG (pure or mixture) presented lower viability. Results validated the use of both n-BG and n-ZnO fillers for the development of novel bifunctional PLA-based scaffolds with both bioactive and biocidal properties for bone tissue engineering applications.

Bio-Catalysis for the Functionalization of Cellulose Nanocrystals.

In this work, the chemical modification of cellulose nanocrystals (NCs) using an enzyme as a catalyst has been performed by a "grafting from" reaction, in order to covalently functionalize the external surface of NCs with both poly(L-lactic acid) (PLLA) and poly(ε-caprolactone) (PCL) by ring-opening polymerization. Firstly, cellulose nanocrystals were prepared from commercial cellulose microcrystals by acid hydrolysis and then functionalized by using Yarrowia lipolytica lipase immobilized on Lewatit resin as a catalyst. To confirm the success of the grafting reactions, 1H-NMR has been performed as well as FT-IR and Raman spectroscopy. Moreover, thermogravimetric analysis has been used to determine the amount of polymeric chains grafted onto the surface of cellulose nanocrystals. Furthermore, the crystalline nature of the polymeric chains grafted onto the cellulose surface has been studied by DSC, X-ray scattering, as well as SAXS analysis. To our knowledge, it is the first time that a biocatalyst approach has been used to obtain biopolymeric functionalized cellulose nanocrystals.

Supramolecular Polycaprolactone-Based Polyurethanes with Thermally Activated Shape-Memory Behavior.

In this work, using supramolecular polyurethanes theories, two polycaprolactone-based polyurethanes with 2-ureido-4-[1H]-pyrimidinone (UPy) motifs capable of forming quadruple hydrogen bonds were synthetized and characterized, focusing our attention on their capability to show thermally activated shape-memory response. In particular, 1H NMR analyses confirmed the chemical structure of the supramolecular polyurethanes, while DSC showed their totally amorphous morphology. DMTA in tensile mode was used to study their thermally activated shape-memory properties. In our case, the UPy units are the switching domains while the network formed by the segregated hard segments is the permanent domain obtained materials with excellent shape-memory response at both 100 and 85 °C. These materials are promising for multi-responsive materials where bio-based and potentially recyclable polymers with excellent shape-memory properties are needed.

Effect of the Addition of MgO Nanoparticles on the Thermally-Activated Shape Memory Behavior of Plasticized PLA Electrospun Fibers.

In this work, the thermally-activated shape memory behavior of poly(lactic acid)-based electrospun fibers (PLA-based efibers) reinforced with different amounts of magnesium oxide (MgO) nanoparticles (NPs) was studied at different temperatures. In particular, MgO NPs were added at different concentrations, such as 0.1, 0.5, 1 and 3 wt%, with respect to the PLA matrix. The glass-transition temperature of PLA-based efibers was modulated by adding a 20 wt% of oligomer lactic acid as plasticizer. Once the plasticized PLA-based efibers were obtained and basically characterized in term of morphology as well as thermal and mechanical properties, thermo-mechanical cycles were carried out at 60 °C and 45 °C in order to study their thermally-activated shape memory response, demonstrating that their crystalline nature strongly affects their shape memory behavior. Importantly, we found that the plastificant effect in the mechanical response of the reinforced plasticized PLA efibers is balanced with the reinforcing effect of the MgO NPs, obtaining the same mechanical response of neat PLA fibers. Finally, both the strain recovery and strain fixity ratios of each of the plasticized PLA-based efibers were calculated, obtaining excellent thermally-activated shape memory response at 45 °C, demonstrating that 1 wt% MgO nanoparticles was the best concentration for the plasticized system.

Compositional Influence on the Morphology and Thermal Properties of Woven Non-Woven Mats of PLA/OLA/MgO Electrospun Fibers.

In the present work, a statistical study of the morphology and thermal behavior of poly(lactic acid) (PLA)/oligomer(lactic acid) (OLA)/magnesium oxide nanoparticles (MgO), electrospun fibers (efibers) has been carried out. The addition of both, OLA and MgO, is expected to modify the final properties of the electrospun PLA-based nanocomposites for their potential use in biomedical applications. Looking for the compositional optimization of these materials, a Box−Wilson design of experiment was used, taking as dependent variables the average fiber diameter as the representative of the fiber morphologies, as well as the glass transition temperature (Tg) and the degree of crystallinity (Xc) as their thermal response. The results show values of 73.76% (diameter), 88.59% (Tg) and 75.61% (Xc) for each polynomial fit, indicating a good correlation between both OLA and MgO, along with the morphological as well as the thermal behavior of the PLA-based efibers in the experimental space scanned.

Electrospun fibers of poly (lactic acid) containing bioactive glass and magnesium oxide nanoparticles for bone tissue regeneration.

Electrospun fibers of poly (lactic acid) (PLA) containing 10 and 20 wt% of bioactive glass (n-BG) and magnesium oxide (n-MgO) nanoparticles of ca. 27 and 23 nm respectively, were prepared toward to application in bone tissue engineering. The addition of both nanoparticles into the PLA will produce a synergic effect increasing its bioactivity and antimicrobial behavior. Neat PLA scaffold and the composites with MgO showed an average fiber diameter of 1.7 ± 0.6 µm, PLA/n-BG and PLA/n-BG/n-MgO fibers presented a significant diameter increase reaching values of ca. 3.1 ± 0.8 µm. Young's modulus of the electrospun scaffolds was affected by the direct presence of the particle and scaffold morphologies. All the composites having n-BG presented bioactivity through the precipitation of hydroxyapatite structures on the surface. Although n-MgO did not add bioactivity to the PLA fibers, they were able to render antimicrobial characteristics reducing the S. aureus viability around 30%, although an effect on E. coli strain was not observed. PLA/n-BG nanocomposites did not display any significant antimicrobial behavior. The different composites increased the alkaline phosphatase (ALP) expression as compared with pure PLA barely affecting the cell viability, meaning a good osteoblastic phenotype expression capacity, with PLA/n-BG presenting the highest osteoblastic expression.

Shape-Memory Materials via Electrospinning: A Review.

This review aims to point out the importance of the synergic effects of two relevant and appealing polymeric issues: electrospun fibers and shape-memory properties. The attention is focused specifically on the design and processing of electrospun polymeric fibers with shape-memory capabilities and their potential application fields. It is shown that this field needs to be explored more from both scientific and industrial points of view; however, very promising results have been obtained up to now in the biomedical field and also as sensors and actuators and in electronics.

PLA Electrospun Fibers Reinforced with Organic and Inorganic Nanoparticles: A Comparative Study.

In this work, different poly (lactic acid) (PLA)-based nanocomposite electrospun fibers, reinforced with both organic and inorganic nanoparticles, were obtained. As organic fibers, cellulose nanocrystals, CNC, both neat and functionalized by "grafting from" reaction, chitosan and graphene were used; meanwhile, hydroxyapatite and silver nanoparticles were used as inorganic fibers. All of the nanoparticles were added at 1 wt% with respect to the PLA matrix in order to be able to compare their effect. The main aim of this work was to study the morphological, thermal and mechanical properties of the different systems, looking for differences between the effects of the addition of organic or inorganic nanoparticles. No differences were found in either the glass transition temperature or the melting temperature between the different electrospun systems. However, systems reinforced with both neat and functionalized CNC exhibited an enhanced degree of crystallinity of the electrospun fibers, by up to 12.3%. From a mechanical point of view, both organic and inorganic nanoparticles exhibited a decreased elastic modulus and tensile strength in comparison to neat electrospun PLA fibers, improving their elongation at break. Furthermore, all of the organic and inorganic reinforced systems disintegrated under composting conditions after 35 days.