Structure-property relationships in renewable composites of poly(lactic acid) reinforced by low amounts of micro- and nano-kraft-lignin.

We investigate the direct and indirect effects of micro- and nano-kraft lignin, kL and NkL, respectively, at a quite low amount of 0.5 wt%, in poly(lactic acid) (PLA)-based composites. These renewable composites were prepared via two routes, either simple melt compounding or in situ reactive extrusion. The materials are selected and prepared using targeted methods in order to vary two variables, i.e., the size of kL and the synthetic method, while maintaining constant polymer chain lengths, L-/D-lactide isomer ratio and filler amounts. The direct/indirect effects were respectively investigated in the amorphous/semicrystalline state, as crystallinity plays in general a dominant role in polymers. The investigation involves structural, thermal and molecular mobility aspects. Non-extensive polymer-lignin interactions were recorded here, whereas the presence of the fillers led to both enhancements and suppressions of properties, e.g., glass transition, crystallization, melting temperatures, etc. The local and segmental molecular dynamics map of the said systems was constructed and is shown here for the first time, demonstrating both expected and unexpected trends. An interesting discrepancy between the trends in the calorimetric measurement against the dielectric Tg is revealed, providing indications for 'dynamical heterogeneities' in the composites as compared to neat PLA. The reactive extrusion as compared to compounding-based systems was found to exhibit stronger effects on crystallizability and mobility, most, probably due to the severe enhancement of the chains' diffusion. In general, the effects are more pronounced when employing nano-lignin compared to micro-lignin, which is the expected beneficial behaviour of nanocomposites vs. conventional composites. Interestingly, the variety of these effects can be easily manipulated by the proper selection of the preparation method and/or the thermal treatment under relatively mild conditions. The latter capability is actually desirable for processing and targeted applications and is proved here, once again, as an advantage of biobased polyesters such as PLA.

3D-Printed Chitosan-Based Hydrogels Loaded with Levofloxacin for Tissue Engineering Applications.

Herein, we demonstrate the feasibility of a three-dimensional printed chitosan (CS)-poly(vinyl alcohol) (PVA)-gelatin (Gel) hydrogel incorporating the antimicrobial drug levofloxacin (LEV) as a potential tissue engineering scaffold. Hydrogels were prepared by physically cross-linking the polymers, and the printability of the prepared hydrogels was determined. The hydrogel with 3% w/v of CS, 3% w/v of PVA, and 2% w/v of Gel presented the best printability, producing smooth and uniform scaffolds. The integrity of 3D-printed scaffolds was improved via a neutralization process since after testing three different neutralized agents, i.e., NH3 vapors, EtOH/NaOH, and KOH solutions. It was proved that the CS/PVA/Gel hydrogel was formed by hydrogen bonds and remained amorphous in the 3D-printed structures. Drug loading studies confirmed the successful incorporation of LEV, and its in vitro release continued for 48 h. The cytotoxicity/cytocompatibility tests showed that all prepared scaffolds were cytocompatible.

Segmental mobility in sustainable copolymers based on poly(lactic acid) blocks built onto poly(butylene succinate) in situ.

Two series of newly synthesized sustainable block copolymers based on poly(butylene succinate) (PBSu) and polylactide (PLA) were studied. The copolymers were synthesized by a ring-opening polymerization of PLA in the presence of two initial PBSu of low molar mass. We focused on the effects of the PBSu/PLA ratio (1/99 up to 15/85), chain length and initial PBSu length on the final thermal transitions in the copolymers with an emphasis on molecular mobility/dynamics and subsequently on crystallization. Both aspects are considered relevant to the final materials performance, as well as facilitation of polymer renewability. Calorimetry and dielectric spectroscopy were the main investigation tools. In the amorphous state (i.e., in which the direct effects of copolymer structure are assessable), the segmental mobility of neat PLA was significantly faster in the copolymers. Segmental mobility was monitored via the decrease in the calorimetric and dielectric (α relaxation) glass-transition temperatures, Tg and Tg,diel, respectively. The effect was systematic with an increase in the PBSu/PLA ratio, and was rationalized through the plasticizing role of PBSu (low-Tg component) and facilitated also by the simultaneous lowering of the chain length in the copolymers. Dielectric spectroscopy allowed evaluation of the dynamical fragility (cooperativity) of chains, which was strongly suppressed in the copolymers. This finding suggested an increase in free volume or a gradual increase of interchain distances. This phenomenon could favor the natural enzymatic degradation of the systems (compostability), which is limited in neat PLA. We recorded enhancement of nucleation and the crystalline fraction in the copolymers that was likely connected with faster chain diffusion. Further lowering of the Tg with the implementation of crystallization was noted (which seemed a controversial effect) but which indicated crystallization-induced phase separation.

Biocompatible Synthetic Polymers for Tissue Engineering Purposes.

Synthetic polymers have been an integral part of modern society since the early 1960s. Besides their most well-known applications to the public, such as packaging, construction, textiles and electronics, synthetic polymers have also revolutionized the field of medicine. Starting with the first plastic syringe developed in 1955 to the complex polymeric materials used in the regeneration of tissues, their contributions have never been more prominent. Decades of research on polymeric materials, stem cells, and three-dimensional printing contributed to the rapid progress of tissue engineering and regenerative medicine that envisages the potential future of organ transplantations. This perspective discusses the role of synthetic polymers in tissue engineering, their design and properties in relation to each type of application. Additionally, selected recent achievements of tissue engineering using synthetic polymers are outlined to provide insight into how they will contribute to the advancement of the field in the near future. In this way, we aim to provide a guide that will help scientists with synthetic polymer design and selection for different tissue engineering applications.

Direct and indirect effects on molecular mobility in renewable polylactide-poly(propylene adipate) block copolymers as studied via dielectric spectroscopy and calorimetry.

In this work, we study a series of sustainable block copolymers based on polylactide, PLA, and poly(propylene adipate), PPAd, both polymers being prepared from renewable resources. Envisaging a wide range of future applications in the frame of a green and circular economy, e.g., packaging materials replacing conventional petrochemicals, the employment of PPAd aims at lowering the glass transition and melting temperatures of PLA and, finally, facilitation of the enzymatic degradation and compostability. The copolymers have been synthesized via ring opening polymerization of lactides in the presence of propylene adipate oligomers (5, 15 and 25%). The direct effects on the molecular mobility by the structure/composition are assessed in the amorphous state employing broadband dielectric spectroscopy (BDS) and calorimetry. BDS allowed the recording of local PLA and PPAd dynamics in all cases. The effects on local relaxations suggest favoring of interchain interactions, both PLA-PPAd and PPAd-PPAd. Regarding the more important segmental dynamics, the presence of PPAd leads to faster polymer chain diffusion, as monitored by the significant lowering of the dielectric and calorimetric glass transition temperature, Tg. This suggests the plasticizing role of PPAd on PLA (majority) in combination with the lowering of the average molar mass, Mn, in the copolymers from ∼75 to ∼30 kg mol-1, which is the actual scope for the synthesis of these materials. Interestingly, a strong suppression in fragility (chain cooperativity) is additionally recorded. In contrast to calorimetry and due to the high resolving power of BDS, for the higher PPAd fraction, the weak segmental relaxation of PPAd was additionally recorded. Overall, the recordings suggest a strong increase in free volume and two individual dynamic states, one for 0 and 5% PPAd and another for 15 and 25% PPAd. Within the latter, we gained indications for partial phase nano-separation of PPAd. Regarding indirect effects, these were followed via crystallization. Independent of the method of crystallization, namely, melt or cold, the presence of PPAd led to the systematic lowering of crystallization and melting temperatures and enthalpies. The effects reflect the decrease of crystalline nuclei, which is confirmed by optical microscopy as in the copolymers fewer although larger crystals are formed.

Synthesis and Characterization of Poly(lactic acid) Composites with Organosolv Lignin.

Lignin, being one of the main structural components of lignocellulosic biomass, is considered the most abundant natural source of phenolics and aromatics. Efforts for its valorisation were recently explored as it is mostly treated as waste from heat/energy production via combustion. Among them, polymer-based lignin composites are a promising approach to both valorise lignin and to fine tune the properties of polymers. In this work, organosolv lignin, from beech wood, was used as fillers in a poly (lactic acid) (PLA) matrix. The PLA/lignin composites were prepared using melt mixing of masterbatches with neat PLA in three different lignin contents: 0.5, 1.0 and 2.5 wt%. Lignin was used as-isolated, via the organosolv biomass pretreatment/fractionation process and after 8 h of ball milling. The composites were characterised with Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy, X-ray Diffraction (XRD), and Differential Scanning Calorimetry (DSC). Additionally, their antioxidant activity was assessed with the 2,2-Diphenyil-1-picrylhydrazyl (DPPH) method, the colour was measured with a colorimeter and the mechanical properties were evaluated with tensile testing. Ball milling, at least under the conditions applied in this study, did not induce a further substantial decrease in the already relatively small organosolv lignin primary particles of ~1 µm. All the produced PLA/lignin composites had a uniform dispersion of lignin. Compression-moulded films were successfully prepared, and they were coloured brown, with ball-milled lignin, giving a slightly lighter colour in comparison with the as-received lignin. Hydrogen bonding was detected between the components of the composites, and crystallization of the PLA was suppressed by both lignin, with the suppression being less pronounced by the ball-milled lignin. All composites showed a significantly improved antioxidant activity, and their mechanical properties were maintained for filler content 1 wt%.

Revisiting Non-Conventional Crystallinity-Induced Effects on Molecular Mobility in Sustainable Diblock Copolymers of Poly(propylene adipate) and Polylactide.

This work deals with molecular mobility in renewable block copolymers based on polylactide (PLA) and poly(propylene adipate) (PPAd). In particular, we assess non-trivial effects on the mobility arising from the implementation of crystallization. Differential scanning calorimetry, polarized light microscopy and broadband dielectric spectroscopy were employed in combination for this study. The materials were subjected to various thermal treatments aiming at the manipulation of crystallization, namely, fast and slow cooling, isothermal melt- and cold-crystallization. Subsequently, we evaluated the changes recorded in the overall thermal behavior, semicrystalline morphology and molecular mobility (segmental and local). The molecular dynamics map for neat PPAd is presented here for the first time. Unexpectedly, the glass transition temperature, Tg, in the amorphous state drops upon crystallization by 8-50 K. The drop becomes stronger with the increase in the PPAd fraction. Compared to the amorphous state, crystallization leads to significantly faster segmental dynamics with severely suppressed cooperativity. For the PLA/PPAd copolymers, the effects are systematically stronger in the cold- as compared to the melt-crystallization, whereas the opposite happens for neat PLA. The local ßPLA relaxation of PLA was, interestingly, recorded to almost vanish upon crystallization. This suggests that the corresponding molecular groups (carbonyl) are strongly involved and immobilized within the semicrystalline regions. The overall results suggest the involvement of either spatial nanoconfinement imposed on the mobile chains within the inter-crystal amorphous areas and/or a crystallization-driven effect of nanophase separation. The latter phase separation seems to be at the origins of the significant discrepancy recorded between the calorimetric and dielectric recordings on Tg in the copolymers. Once again, compared to more conventional techniques such as calorimetry, dielectric spectroscopy was proved a powerful and quite sensitive tool in recording such effects as well as in providing indirect indications for the polymer chains' topology.

Composite Membranes of Poly(ε-caprolactone) with Bisphosphonate-Loaded Bioactive Glasses for Potential Bone Tissue Engineering Applications.

Poly(ε-caprolactone) (PCL) is a bioresorbable synthetic polyester with numerous biomedical applications. PCL membranes show great potential in guided tissue regeneration because they are biocompatible, occlusive and space maintaining, but lack osteoconductivity. Therefore, two different types of mesoporous bioactive glasses (SiO2-CaO-P2O5 and SiO2-SrO-P2O5) were synthesized and incorporated in PCL thin membranes by spin coating. To enhance the osteogenic effect of resulting membranes, the bioglasses were loaded with the bisphosphonate drug ibandronate prior to their incorporation in the polymeric matrix. The effect of the composition of the bioglasses as well as the presence of absorbed ibandronate on the physicochemical, cell attachment and differentiation properties of the PCL membranes was evaluated. Both fillers led to a decrease of the crystallinity of PCL, along with an increase in its hydrophilicity and a noticeable increase in its bioactivity. Bioactivity was further increased in the presence of a Sr substituted bioglass loaded with ibandronate. The membranes exhibited excellent biocompatibility upon estimation of their cytotoxicity on Wharton's Jelly Mesenchymal Stromal Cells (WJ-SCs), while they presented higher osteogenic potential in comparison with neat PCL after WJ-SCs induced differentiation towards bone cells, which was enhanced by a possible synergistic effect of Sr and ibandronate.

Biobased Poly(ethylene furanoate) Polyester/TiO2 Supported Nanocomposites as Effective Photocatalysts for Anti-inflammatory/Analgesic Drugs.

In the present study, polymer supported nanocomposites, consisting of bio-based poly(ethylene furanoate) polyester and TiO2 nanoparticles, were prepared and evaluated as effective photocatalysts for anti-inflammatory/analgesic drug removal. Nanocomposites were prepared by the solvent evaporation method containing 5, 10, 15, and 20 wt% TiO2 and characterized using Fourier Transform Infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Thin films of them have been prepared by the melt press and optimization of the photocatalytic procedure was conducted for the most efficient synthesized photocatalyst. Finally, mineralization was evaluated by means of Total organic carbon (TOC) reduction and ion release, while the transformation products (TPs) generated during the photocatalytic procedure were identified by high-resolution mass spectrometry.

Thermal Decomposition Kinetics and Mechanism of In-Situ Prepared Bio-based Poly(propylene 2,5-furan dicarboxylate)/Graphene Nanocomposites.

Bio-based polyesters are a new class of materials that are expected to replace their fossil-based homologues in the near future. In this work, poly(propylene 2,5-furandicarboxylate) (PPF) nanocomposites with graphene nanoplatelets were prepared via the in-situ melt polycondensation method. The chemical structure of the resulting polymers was confirmed by 1H-NMR spectroscopy. Thermal stability, decomposition kinetics and the decomposition mechanism of the PPF nanocomposites were studied in detail. According to thermogravimetric analysis results, graphene nanoplatelets did nοt affect the thermal stability of PPF at levels of 0.5, 1.0 and 2.5 wt.%, but caused a slight increase in the activation energy values. Pyrolysis combined with gas chromatography and mass spectroscopy revealed that the decomposition mechanism of the polymer was not altered by the presence of graphene nanoplatelets but the extent of secondary homolytic degradation reactions was increased.

Optimization of chitosan-gelatin-based 3D-printed scaffolds for tissue engineering and drug delivery applications.

The combination of biocompatible materials and advanced three-dimensional (3D) additive manufacturing technologies holds great potential in the development of finely tuned complex scaffolds with reproducible macro- and micro-structural characteristics for biomedical applications, such as tissue engineering and drug delivery. In this study, biocompatible printable inks based on chitosan, collagen and gelatin were developed and 3D-printed with a pneumatic-based extrusion printer. The printability of various chitosan-gelatin (CS-Gel) hydrogel inks was assessed by evaluating the quality of the printed constructs. The inks required an extrusion pressure of 150 ± 40 MPa with G22 and G25 nozzles for optimal printing. Inks with low chitosan concentrations (<4% w/v) exhibited poor printability, while inks with 4 % w/v chitosan and 1 % w/v gelatin (CG) demonstrated satisfactory extrusion and printing quality. The addition of collagen (0.1 % w/v) to the optimized ink (CGC) did not compromise printability. Post-printing stabilization using KOH produced self-supporting scaffolds with consistent morphological integrity, while weaker bases like NaOH/EtOH and ammonia vapors resulted in lower pore sizes and reduced structural stability. Water evaporation studies showed that neutralized samples had slower evaporation rates due to the strong intermolecular interactions formed during the neutralization process, contributing to a stable crosslinked network. FTIR spectra confirmed the formation of polyelectrolyte complexes in the CS-Gel and CS-Gel-Collagen blends, further enhancing structural stability. Swelling tests indicated that neutralized constructs maintained stability in different pH environments, with KOH-treated samples exhibiting the lowest swelling ratios and the highest structural stability. After optimizing the ink composition, 10 wt% Levofloxacin was loaded in the constructs as a model antibiotic and it's in vitro release rate was quantified. Drug loading was approximately 4 % for both ink compositions GC and CGC. CG Levo released over 80 % of levofloxacin within the first hour, reaching full release in 24 h, indicating inadequate control, while CGK Levo exhibited slower initial release (55 % in 15 min) followed by stabilized release after 4 h, likely due to controlled diffusion from expanded constructs. These findings demonstrate that the developed hydrogel inks and optimized printing parameters can produce scaffolds suitable for tissue engineering applications. Finally, the cell compatibility of the 3D-printed constructs was confirmed with MTT assay on fibroblasts and the antimicrobial activity of the drug-loaded constructs was tested against E. coli and S. aureus, showing an increase of the bacteria free zone from 8 ± 0.4 mm of the control against E. coli up to 16.4 ± 0.37 mm in the presence of the KOH-treated CG Levo printed construct.

Valorization of Tomato Agricultural Waste for 3D-Printed Polymer Composites Based on Poly(lactic acid).

Agricultural waste is a renewable source of lignocellulosic components, which can be processed in a variety of ways to yield added-value materials for various applications, e.g., polymer composites. However, most lignocellulosic biomass is incinerated for energy. Typically, agricultural waste is left to decompose in the fields, causing problems such as greenhouse gas release, attracting insects and rodents, and impacting soil fertility. This study aims to valorise nonedible tomato waste with no commercial value in Additive Manufacturing (AM) to create sustainable, cost-effective and added-value PLA composites. Fused Filament Fabrication (FFF) filaments with 5 and 10 wt.% tomato stem powder (TSP) were developed, and 3D-printed specimens were tested. Mechanical testing showed consistent tensile properties with 5% TSP addition, while flexural strength decreased, possibly due to void formation. Dynamic mechanical analysis (DMA) indicated changes in storage modulus and damping factor with TSP addition. Notably, the composites exhibited antioxidant activity, increasing with higher TSP content. These findings underscore the potential of agricultural waste utilization in FFF, offering insights into greener waste management practices and addressing challenges in mechanical performance and material compatibility. This research highlights the viability of integrating agricultural waste into filament-based AM, contributing to sustainable agricultural practices and promoting circular economy initiatives.

Exploration of Methodologies for Developing Antimicrobial Fused Filament Fabrication Parts.

Composite 3D printing filaments integrating antimicrobial nanoparticles offer inherent microbial resistance, mitigating contamination and infections. Developing antimicrobial 3D-printed plastics is crucial for tailoring medical solutions, such as implants, and cutting costs when compared with metal options. Furthermore, hospital sustainability can be enhanced via on-demand 3D printing of medical tools. A PLA-based filament incorporating 5% TiO2 nanoparticles and 2% Joncryl as a chain extender was formulated to offer antimicrobial properties. Comparative analysis encompassed PLA 2% Joncryl filament and a TiO2 coating for 3D-printed specimens, evaluating mechanical and thermal properties, as well as wettability and antimicrobial characteristics. The antibacterial capability of the filaments was explored after 3D printing against Gram-positive Staphylococcus aureus (S. aureus, ATCC 25923), as well as Gram-negative Escherichia coli (E. coli, ATCC 25922), and the filaments with 5 wt.% embedded TiO2 were found to reduce the viability of both bacteria. This research aims to provide the optimal approach for antimicrobial and medical 3D printing outcomes.

Poly(Lactic Acid) Composites with Lignin and Nanolignin Synthesized by In Situ Reactive Processing.

Poly(lactic acid) (PLA) composites with 0.5 wt% lignin or nanolignin were prepared with two different techniques: (a) conventional melt-mixing and (b) in situ Ring Opening Polymerization (ROP) by reactive processing. The ROP process was monitored by measuring the torque. The composites were synthesized rapidly using reactive processing that took under 20 min. When the catalyst amount was doubled, the reaction time was reduced to under 15 min. The dispersion, thermal transitions, mechanical properties, antioxidant activity, and optical properties of the resulting PLA-based composites were evaluated with SEM, DSC, nanoindentation, DPPH assay, and DRS spectroscopy. All reactive processing-prepared composites were characterized by means of SEM, GPC, and NMR to assess their morphology, molecular weight, and free lactide content. The benefits of the size reduction of lignin and the use of in situ ROP by reactive processing were demonstrated, as the reactive processing-produced nanolignin-containing composites had superior crystallization, mechanical, and antioxidant properties. These improvements were attributed to the participation of nanolignin in the ROP of lactide as a macroinitiator, resulting in PLA-grafted nanolignin particles that improved its dispersion.

Effect of Monomer Type on the Synthesis and Properties of Poly(Ethylene Furanoate).

This work aimed to produce bio-based poly(ethylene furanoate) (PEF) with a high molecular weight using 2,5-furan dicarboxylic acid (FDCA) or its derivative dimethyl 2,5-furan dicarboxylate (DMFD), targeting food packaging applications. The effect of monomer type, molar ratios, catalyst, polycondensation time, and temperature on synthesized samples' intrinsic viscosities and color intensity was evaluated. It was found that FDCA is more effective than DMFD in producing PEF with higher molecular weight. A sum of complementary techniques was employed to study the structure-properties relationships of the prepared PEF samples, both in amorphous and semicrystalline states. The amorphous samples exhibited an increase in glass transition temperature of 82-87 °C, and annealed samples displayed a decrease in crystallinity with increasing intrinsic viscosity, as analyzed by differential scanning calorimetry and X-ray diffraction. Dielectric spectroscopy showed moderate local and segmental dynamics and high ionic conductivity for the 2,5-FDCA-based samples. The spherulite size and nuclei density of samples improved with increased melt crystallization and viscosity, respectively. The hydrophilicity and oxygen permeability of the samples were reduced with increased rigidity and molecular weight. The nanoindentation test showed that the hardness and elastic modulus of amorphous and annealed samples is higher at low viscosities due to high intermolecular interactions and degree of crystallinity.

Blending PLA with Polyesters Based on 2,5-Furan Dicarboxylic Acid: Evaluation of Physicochemical and Nanomechanical Properties.

Poly(lactic acid) (PLA) is a readily available, compostable biobased polyester with high strength and toughness, and it is excellent for 3D printing applications. Polymer blending is an economic and easy way to improve its properties, such as its slow degradation and crystallization rates and its small elongation, and thus, make it more versatile. In this work, the effects of different 2,5-furan dicarboxylic acid (FDCA)-based polyesters on the physicochemical and mechanical properties of PLA were studied. Poly(butylene furan 2,5-dicarboxylate) (PBF) and its copolymers with poly(butylene adipate) (PBAd) were synthesized in various comonomer ratios and were blended with 70 wt% PLA using melt compounding. The thermal, morphological and mechanical properties of the blends are investigated. All blends were immiscible, and the presence of the dispersed phases improved the crystallization ability of PLA. Mechanical testing revealed the plasticization of PLA after blending, and a small but measurable mass loss after burying in soil for 7 months. Reactive blending was evaluated as a compatibilizer-free method to improve miscibility, and it was found that when the thermal stability of the blend components allowed it, some transesterification reactions occurred between the PLA matrix and the FDCA-based dispersed phase after 20 min at 250 °C.

Benefit of coupling heparin to crosslinked collagen I/III scaffolds for human dermal fibroblast subpopulations' tissue growth.

Currently, there is a lack of models representing the skin dermal heterogeneity for relevant research and skin engineering applications. This is the first study reporting production of dermal equivalents reproducing features of papillary and reticular dermal compartments. Inspired from our current knowledge on the architecture and composition differences between the papillary and reticular dermis, we evaluated different collagen-based porous materials to serve as scaffolds for the three-dimensional expansion of freshly isolated papillary and/or reticular fibroblasts. The scaffolds, composed of either collagen I or collagen I and III mixtures, were prepared by lyophilization. Pore size and hydrolytic stability were controlled by crosslinking with 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDC) and N-hydroxysuccinimide (NHS) or EDC/NHS with covalently bound heparin. The evaluation of the resultant "papillary" and "reticular" dermal equivalents was based on the analysis of characteristic features of each dermal compartment, such as cell density and deposition of newly synthetized extracellular matrix components in histological sections. Crosslinking supported cell growth during dermal tissue formation independent on the fibroblast subpopulation. The presence of collagen III seemed to have some positive but non-specific effect only on the maintenance of the mechanical strength of the scaffolds during dermal formation. Histological analyses demonstrated a significant and specific effect of heparin on generating dermal equivalents reproducing the respective higher papillary than reticular cell densities and supporting distinct extracellular matrix components deposition (three to five times more carbohydrate material deposited by papillary fibroblasts in all scaffolds containing heparin, while higher collagen production was observed only in the presence of heparin).

Synthesis, Properties, and Enzymatic Hydrolysis of Poly(lactic acid)-co-Poly(propylene adipate) Block Copolymers Prepared by Reactive Extrusion.

Poly(lactic acid) (PLA) is a biobased polyester with ever-growing applications in the fields of packaging and medicine. Despite its popularity, it suffers from inherent brittleness, a very slow degradation rate and a high production cost. To tune the properties of PLA, block copolymers with poly(propylene adipate) (PPAd) prepolymer were prepared by polymerizing L-lactide and PPAd oligomers via reactive extrusion (REX) in a torque rheometer. The effect of reaction temperature and composition on the molecular weight, chemical structure, and physicochemical properties of the copolymers was studied. The introduction of PPAd successfully increased the elongation and the biodegradation rate of PLA. REX is an efficient and economical alternative method for the fast and continuous synthesis of PLA-based copolymers with tunable properties.

Influence of Reactive Chain Extension on the Properties of 3D Printed Poly(Lactic Acid) Constructs.

Fused deposition modeling (FDM) is currently the most popular 3D printing method, where thermoplastic polymers are predominantly used. Among them, the biobased poly(lactic acid) (PLA) governs the FDM filament market, with demand higher than supply, since not all grades of PLA are suitable for FDM filament production. In this work, the effect of a food grade chain extender (Joncryl ADR® 4400) on the physicochemical properties and printability of PLA marketed for injection molding was examined. All samples were characterized in terms of their mechanical and thermal properties. The microstructure of the filaments and 3D-printed fractured surfaces following tensile testing were examined with optical and scanning electron microscopy, respectively. Molecular weight and complex viscosity increased, while the melt flow index decreased after the incorporation of Joncryl, which resulted in filaments of improved quality and 3D-printed constructs with enhanced mechanical properties. Dielectric spectroscopy revealed that the bulk properties of PLA with respect to molecular mobility, both local and segmental, were, interestingly, not affected by the modifier. Indirectly, this may suggest that the major effects of the extender are on chain length, without inducing chain branching, at least not to a significant extent.

Preparation and Evaluation of Collagen-Based Patches as Curcumin Carriers.

Patients with psoriasis are dissatisfied with the standard pharmacological treatments, whether systemic or topical, with many of them showing interest in complementary and alternative medicine. Curcumin (Cur), a natural polyphenol derived from turmeric, has recently gained attention for skin-related diseases because of its proven anti-inflammatory action. However, topical treatment with Cur would be inadequate because of its hydrophobicity, instability, and low bioavailability. In addition, hyperkeratosis and lack of moisture in psoriatic skin result in low penetration that would prevent actives from permeating the stratum corneum. In this work, a polymer-based formulation of Cur for the topical treatment of psoriasis is reported. To improve the physicochemical stability of Cur, it was first encapsulated in chitosan nanoparticles. The Cur-loaded nanoparticles were incorporated in a hydrophilic, biocompatible collagen-based patch. The nanoparticle-containing porous collagen patches were then chemically cross-linked. Morphology, chemical interactions, swelling ratio, enzymatic hydrolysis, and Cur release from the patches were evaluated. All patches showed excellent swelling ratio, up to ~1500%, and after cross-linking, the pore size decreased, and their hydrolysis rates decelerated. The in vitro release of Cur was sustained with an initial burst release, reaching 55% after 24 h. Cur within the scaffolds imparted a proliferation inhibitory effect on psoriatic human keratinocytes in vitro.