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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.
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Deferoxamine (DFO) is a water-soluble iron chelator used pharmacologically for the management of patients with transfusional iron overload. However, DFO is not cell-permeable and has a short plasma half-life, which necessitates lengthy parenteral administration with an infusion pump. We previously reported the synthesis of chitosan (CS) nanoparticles for sustained slow release of DFO. In the present study, we developed solid dispersions and nanoparticles of a carboxymethyl water-soluble chitosan derivative (CMCS) for improved DFO encapsulation and release. CS dispersions and nanoparticles with DFO have been prepared by ironical gelation using sodium triphosphate (TPP) and were examined for comparison purposes. The successful presence of DFO in CMCS polymeric dispersions and nanoparticles was confirmed through FTIR measurements. Furthermore, the formation of CMCS nanoparticles led to inclusion of DFO in an amorphous state, while dispersion of DFO in the polymeric matrix led to a decrease in its crystallinity according to X-ray diffraction (XRD) and differential scanning calorimetry (DSC) results. An in vitro release assay indicated sustained release of DFO from CS and CMCS nanoparticles over 48 h and 24 h, respectively. Application of CMCS-DFO dispersions to murine RAW 264.7 macrophages or human HeLa cervical carcinoma cells triggered cellular responses to iron deficiency. These were exemplified in the induction of the mRNA encoding transferrin receptor 1, the major iron uptake protein, and the suppression of ferritin, the iron storage protein. Our data indicate that CMCS-DFO nanoparticles release bioactive DFO that causes effective iron chelation in cultured cells.
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Quitosana , Humanos , Animais , Camundongos , Desferroxamina/farmacologia , Quelantes , Transporte Biológico , FerroRESUMO
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.
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Quitosana , Engenharia Tecidual , Levofloxacino/farmacologia , Gelatina , Hidrogéis , Impressão TridimensionalRESUMO
Chitosan is a polysaccharide vastly examined in polymer science for its unique structure. In the present study, CS was derivatized with 2-methoxy-4vinylphenol (MVP) in four different ratios through a free radical reaction. The CS-MVP derivatives were characterized through FTIR, 1H-NMR, XRD, swelling, and solubility measurements. Owing to the enhanced antioxidant character of the MVP monomer, the antioxidant activity of the CS-MVP derivatives was assessed. In the optimum CS-MVP ratio, blends between CS and CS-MVP were prepared in ratios of 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80, and 10:90 w/w, and their miscibility was examined by scanning electron microscopy (SEM) and viscosity measurements. In the optimum ratios, highly concentrated inks were prepared, and their viscosity measurements revealed the successful formation of highly viscous gels with shear thinning behavior. These inks could be appropriate candidates for biomedical and drug delivery applications.
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Quitosana , Quitosana/química , Antioxidantes/farmacologia , Polímeros/química , Sistemas de Liberação de Medicamentos , Impressão Tridimensional , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
This work presents the successful preparation and characterization of polylactide/poly(propylene 2,5-furandicarboxylate) (PLA/PPF) and polylactide/poly(butylene 2,5-furandicarboxylate) (PLA/PBF) blends in form of bulk and fiber samples and investigates the influence of poly(alkylene furanoate) (PAF) concentration (0 to 20 wt%) and compatibilization on the physical, thermal, and mechanical properties. Both blend types, although immiscible, are successfully compatibilized by Joncryl (J), which improves the interfacial adhesion and reduces the size of PPF and PBF domains. Mechanical tests on bulk samples show that only PBF is able to effectively toughen PLA, as PLA/PBF blends with 5-10 wt% PBF showed a distinct yield point, remarkable necking propagation, and increased strain at break (up to 55%), while PPF did not show significant plasticizing effects. The toughening ability of PBF is attributed to its lower glass transition temperature and greater toughness than PPF. For fiber samples, increasing the PPF and PBF amount improves the elastic modulus and mechanical strength, particularly for PBF-containing fibers collected at higher take-up speeds. Remarkably, in fiber samples, plasticizing effects are observed for both PPF and PBF, with significantly higher strain at break values compared to neat PLA (up to 455%), likely due to a further microstructural homogenization, enhanced compatibility, and load transfer between PLA and PAF phases following the fiber spinning process. SEM analysis confirms the deformation of PPF domains, which is probably due to a "plastic-rubber" transition during tensile testing. The orientation and possible crystallization of PPF and PBF domains contribute to increased tensile strength and elastic modulus. This work showcases the potential of PPF and PBF in tailoring the thermo-mechanical properties of PLA in both bulk and fiber forms, expanding their applications in the packaging and textile industry.
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In the present study, poly(butylene succinate) (PBSu) and its bionanocomposites containing 1, 2.5, and 5 wt.% biochar (MSP700) were prepared via in situ melt polycondensation in order to investigate the thermal stability and decomposition mechanism of the materials. X-ray photoelectron spectroscopy (XPS) measurements were carried out to analyze the surface area of a biochar sample and PBSu/biochar nanocomposites. From XPS, it was found that only physical interactions were taking place between PBSu matrix and biochar nanoadditive. Thermal stability, decomposition kinetics, and the decomposition mechanism of the pristine PBSu and PBSu/biochar nanocomposites were thoroughly studied by thermogravimetric analysis (TGA) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). TGA thermograms depicted that all materials had high thermal stability, since their decomposition started at around 300 °C. However, results indicated a slight reduction in the thermal stability of the PBSu biochar nanocomposites because of the potential catalytic impact of biochar. Py-GC/MS analysis was employed to examine, in more detail, the thermal degradation mechanism of PBSu nanocomposites filled with biochar. From the decomposition products identified by Py-GC/MS after pyrolysis at 450 °C, it was found that the decomposition pathway of the PBSu/biochar nanocomposites took place mainly via ß-hydrogen bond scission, which is similar to that which took place for neat PBSu. However, at higher biochar content (5 wt.%), some localized differences in the intensity of the peaks of some specific thermal degradation products could be recognized, indicating that α-hydrogen bond scission was also taking place. A study of the thermal stability and decomposition pathway of PBSu/biochar bionanocomposites is crucial to examine if the new materials fulfill the requirements for further investigation for mulch films in agriculture or in electronics as possible applications.
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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.
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Materiais Biocompatíveis , Engenharia Tecidual , Polímeros , Impressão Tridimensional , Medicina Regenerativa , Engenharia Tecidual/métodos , Alicerces TeciduaisRESUMO
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 â¼75 to â¼30 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.
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Limitations associated with the use of linear biodegradable polyesters in the preparation of anticancer nano-based drug delivery systems (nanoDDS) have turned scientific attention to the utilization of branched-chain (co-)polymers. In this context, the present study evaluates the use of novel branched poly(ε-caprolactone) (PCL)-based copolymers of different architectures for the preparation of anticancer nanoparticle (NP)-based formulations, using paclitaxel (PTX) as a model drug. Specifically, three PCL-polyol branched polyesters, namely, a three-arm copolymer based on glycerol (PCL-GLY), a four-arm copolymer based on pentaerythritol (PCL-PE), and a five-arm copolymer based on xylitol (PCL-XYL), were synthesized via ring-opening polymerization and characterized by proton nuclear magnetic resonance (1H-NMR), gel permeation chromatography (GPC), intrinsic viscosity, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and Fourier-transform infrared (FT-IR) spectroscopy and cytotoxicity. Then, PTX-loaded NPs were prepared by an oil-in-water emulsion. The size of the obtained NPs varied from 200 to 300 nm, while the drug was dispersed in crystalline form in all formulations. High encapsulation efficiency and high yields were obtained in all cases, while FTIR analysis showed no molecular drug polymer. Finally, in vitro drug release studies showed that the studied nanocarriers significantly enhanced the dissolution rate and extent of the drug.
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Antineoplásicos , Nanopartículas , Polietilenoglicóis/química , Espectroscopia de Infravermelho com Transformada de Fourier , Poliésteres/química , Nanopartículas/química , Antineoplásicos/química , Paclitaxel/química , Portadores de Fármacos/químicaRESUMO
The massive accumulation of plastics over the decades in the aquatic environment has led to the dispersion of plastic components in aquatic ecosystems, invading the food webs. Plastics fragmented into microplastics can be bioaccumulated by fishes via different exposure routes, causing several adverse effects. In the present study, the dose-dependent cytotoxicity of 8−10 µm polypropylene microplastics (PP-MPs), at concentrations of 1 mg/g (low dose) and 10 mg/g dry food (high dose), was evaluated in the liver and gill tissues of two fish species, the zebrafish (Danio rerio) and the freshwater perch (Perca fluviatilis). According to our results, the inclusion of PP-MPs in the feed of D. rerio and P. fluviatilis hampered the cellular function of the gills and hepatic cells by lipid peroxidation, DNA damage, protein ubiquitination, apoptosis, autophagy, and changes in metabolite concentration, providing evidence that the toxicity of PP-MPs is dose dependent. With regard to the individual assays tested in the present study, the biggest impact was observed in DNA damage, which exhibited a maximum increase of 18.34-fold in the liver of D. rerio. The sensitivity of the two fish species studied differed, while no clear tissue specificity in both fish species was observed. The metabolome of both tissues was altered in both treatments, while tryptophan and nicotinic acid exhibited the greatest decrease among all metabolites in all treatments in comparison to the control. The battery of biomarkers used in the present study as well as metabolomic changes could be suggested as early-warning signals for the assessment of the aquatic environment quality against MPs. In addition, our results contribute to the elucidation of the mechanism induced by nanomaterials on tissues of aquatic organisms, since comprehending the magnitude of their impact on aquatic ecosystems is of great importance.
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Microplásticos , Poluentes Químicos da Água , Animais , Microplásticos/toxicidade , Plásticos/metabolismo , Peixe-Zebra/metabolismo , Polipropilenos , Ecossistema , Poluentes Químicos da Água/análise , Água DoceRESUMO
Poly(ethylene 2,5-furandicarboxylate) (PEF) nanocomposites reinforced with various content of graphene nanoplatelets (GNPs) were synthesized in situ in this work. PEF is a widely known biobased polyester with promising physical properties and is considered as the sustainable counterpart of PET. Despite its exceptional gas barrier and mechanical properties, PEF presents with a low crystallization rate. In this context, a small number of GNPs were incorporated into the material to facilitate the nucleation and overall crystallization of the matrix. Kinetic analysis of both the cold and melt crystallization processes of the prepared materials was achieved by means of differential scanning calorimetry (DSC). The prepared materials' isothermal crystallization from the glass and melt states was studied using the Avrami and Hoffman-Lauritzen theories. The Dobreva method was applied for the non-isothermal DSC measurements to calculate the nucleation efficiency of the GNPs on the PEF matrix. Furthermore, Vyazovkin's isoconversional method was employed to estimate the effective activation energy values of the amorphous materials' glass transition. Finally, the nanomechanical properties of the amorphous and semicrystalline PEF materials were evaluated via nanoindentation measurements. It is shown that the GNPs facilitate the crystallization process through heterogeneous nucleation and, at the same time, improve the nanomechanical behavior of PEF, with the semicrystalline samples presenting with the larger enhancements.
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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%.
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Antioxidantes , Lignina , Lignina/química , Antioxidantes/farmacologia , Poliésteres/química , Varredura Diferencial de Calorimetria , Polímeros/químicaRESUMO
Despite the advantages of polylactide (PLA), its inadequate UV-shielding and gas-barrier properties undermine its wide application as a flexible packaging film for perishable items. These issues are addressed in this work by investigating the properties of melt-mixed, fully bioderived blends of polylactide (PLA) and poly(ethylene furanoate) (PEF), as a function of the PEF weight fraction (1-30 wt %) and the amount of the commercial compatibilizer/chain extender Joncryl ADR 4468 (J, 0.25-1 phr). J mitigates the immiscibility of the two polymer phases by decreasing and homogenizing the PEF domain size; for the blend containing 10 wt % of PEF, the PEF domain size drops from 0.67 ± 0.46 µm of the uncompatibilized blend to 0.26 ± 0.14 with 1 phr of J. Moreover, the increase in the complex viscosity of PLA and PLA/PEF blends with the J content evidences the effectiveness of J as a chain extender. This dual positive contribution of J is reflected in the mechanical properties of PLA/PEF blends. Whereas the uncompatibilized blend with 10 wt % of PEF shows lower mechanical performance than neat PLA, all the compatibilized blends show higher tensile strength and strain at break, while retaining their high elastic moduli. The effects of PEF on the UV- and oxygen-barrier properties of PLA are also remarkable. Adding only 1 wt % of PEF makes the blend an excellent barrier for UV rays, with the transmittance at 320 nm dropping from 52.8% of neat PLA to 0.4% of the sample with 1 wt % PEF, while keeping good transparency in the visible region. PEF is also responsible for a sensible decrease in the oxygen transmission rate, which decreases from 189 cc/m2·day for neat PLA to 144 cc/m2·day with only 1 wt % of PEF. This work emphasizes the synergistic effects of PEF and J in enhancing the thermal, mechanical, UV-shielding, and gas-barrier properties of PLA, which results in bioderived blends that are very promising for packaging applications.
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Poliésteres , Polietileno , Etilenos , Oxigênio , PolímerosRESUMO
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.
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Poliésteres , Temperatura de Transição , Cristalização/métodosRESUMO
This article takes a step forward in understanding the mechanisms involved during the preparation and performance of cross-linked high-drug-loading (HDL) amorphous solid dispersions (ASDs). Specifically, ASDs, having 90 wt % poorly water-soluble drug indomethacin (IND), were prepared via in situ thermal cross-linking of poly(acrylic acid) (PAA) and poly(vinyl alcohol) (PVA) and thoroughly evaluated in terms of physical stability and in vitro supersaturation. Results showed that HDL ASDs having excellent active pharmaceutical ingredient (API) amorphous stability and prolonged in vitro supersaturation were prepared by fine tuning the cross-linking procedure. Unraveling of the processes involved during ASD's formation shed light on the significant role of the cross-linking conditions (i.e., temperature and time), the physicochemical properties of the API, and the hydrolysis level of the cross-linker as key factors in modulating ASD's stability. In-depth analysis of the prepared systems revealed the (1) reduction of API's molecular motions within the cross-linked polymeric networks (through API's strong spatial confinement), (2) the structural changes in the prepared cross-linked matrices (induced by the high API drug loading), and (3) the tuning of the cross-linking density via utilization of low-hydrolyzed PVA as the major mechanisms responsible for ASD's exceptional performance. Complementary analysis by means of molecular dynamics simulations also highlighted the vital role of strong drug-polymer intermolecular interactions evolving among the ASD components. Overall, the impression of the complexity of in situ cross-linked ASDs has been reinforced with the excessive variation of parameters investigated in the current study, offering thus insights up to the submolecular level to lay the groundwork and foundations for the comprehensive assessment of a new emerging class of HDL amorphous API formulations.
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Estabilidade de Medicamentos , Indometacina/química , Reagentes de Ligações Cruzadas , Composição de Medicamentos , Liberação Controlada de Fármacos , Simulação de Dinâmica MolecularRESUMO
We investigate the thermal transitions and molecular mobility in new nanocomposites of biobased poly(ethylene furanoate) (PEF), by calorimetry and dielectric spectroscopy, supplemented by X-ray diffraction, Fourier transform infra-red spectroscopy and polarized light microscopy. The emphasis is placed on the facilitation of the crystallization of PEF, which is in general low and slow due to structural limitations that result in poor nucleation. Tuning of the crystalline fraction (CF) and semicrystalline morphology are important for optimization of the mechanical performance and manipulation of the permeation of small molecules (e.g., in packaging applications). The nucleation and CF are successfully improved here by the in situ filling of PEF with 0.5-2.5 wt% of carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs). The improvements are discussed in connection with weak or absent interfacial polymer-filler interactions. CNTs were found to be more effective in facilitating crystallization, as compared with GNPs, possibly due to their larger aspect ratio. The segmental dynamics of PEF are both accelerated and decelerated by the addition of GNP and CNT, respectively, with complex phenomena contributing to the effects, namely, nucleation, changes in molar mass and changes in the free volume. The molecular mobility of PEF is moderately affected 'directly' by the particles, whereas stronger effects are induced by crystallization (an indirect effect) and, furthermore, by the increase in the length of alkylene sequences on the chain. Local dynamics exhibit time scale disturbances when the temperature approaches that of the glass transition, which is proposed here to be a common characteristic in the case of mobilities originating from the polymer backbone for these as well as different polyesters. Despite the weak effects on molecular mobility, the role of the fillers as nucleating agents seems to be further exploitable in the frame of envisaged applications, as the use of such fillers in combination with thermal treatment offer possibilities for manipulating the semicrystalline morphology, ion transport and, subsequently, permeation of small molecules.
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This work describes the synthesis of poly(butylene adipate) (PBAd), by melt polycondensation, poly(l-lactic acid) (PLLA), by ring opening polymerization, and the new block copolymer PLLA/PBAd in ratios 90/10, 95/5, 75/25 and 50/50. Due to the biocompatibility and low toxicity of neat PBAd and PLLA, these copolymers are suitable to be used in biomedical applications. The 1H and 13C nuclear magnetic resonance spectroscopy techniques were employed for structural characterization. The thermal transitions, with an emphasis on crystallization, were assessed by differential scanning calorimetry, supplemented by X-ray diffraction and polarized optical microscopy. Molecular mobility studies were conducted using two advanced techniques, broadband dielectric spectroscopy and thermally stimulated depolarization currents. The results from the structural techniques, in combination with each other, provided proof of the presence of PLLA and PBAd blocks and, moreover, the successful copolymer synthesis. The overall data showed that the different co-polymer compositions result directly in severe changes in the polymer crystal distribution and, indirectly, the formation of PBAd micro/nano domains surrounded by PLLA. Furthermore, it was demonstrated that both the continuity of the two polymers throughout the copolymer volume and the semicrystalline morphology can be tuned to a wide extent. The latter makes these systems quite promising envisaging biomedical applications, including the encapsulation of small molecules, e.g. drug solutions. The molecular mobility map was constructed for these systems for the first time, revealing the local (short scale) and segmental (larger nm scale) mobility of PBAd and PLLA, as well as intermediate behaviors of the copolymers.
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Poliésteres , Polímeros , Butileno Glicóis , Ácido Láctico , Difração de Raios XRESUMO
In the present study, chitosan (CS) and pectin (PEC) were utilized for the preparation of 3D printable inks through pneumatic extrusion for biomedical applications. CS is a polysaccharide with beneficial properties; however, its printing behavior is not satisfying, rendering the addition of a thickening agent necessary, i.e., PEC. The influence of PEC in the prepared inks was assessed through rheological measurements, altering the viscosity of the inks to be suitable for 3D printing. 3D printing conditions were optimized and the effect of different drying procedures, along with the presence or absence of a gelating agent on the CS-PEC printed scaffolds were assessed. The mean pore size along with the average filament diameter were measured through SEM micrographs. Interactions among the characteristic groups of the two polymers were evident through FTIR spectra. Swelling and hydrolysis measurements confirmed the influence of gelation and drying procedure on the subsequent behavior of the scaffolds. Ascribed to the beneficial pore size and swelling behavior, fibroblasts were able to survive upon exposure to the ungelated scaffolds.
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Materiais Biocompatíveis/normas , Engenharia Biomédica/normas , Quitosana/normas , Pectinas/normas , Impressão Tridimensional/normas , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Engenharia Biomédica/métodos , Sobrevivência Celular/efeitos dos fármacos , Sobrevivência Celular/fisiologia , Células Cultivadas , Quitosana/química , Quitosana/farmacologia , Humanos , Pectinas/química , Pectinas/farmacologia , Reologia/métodos , Alicerces Teciduais/química , Alicerces Teciduais/normas , Viscosidade/efeitos dos fármacosRESUMO
Mesoporous silica-based nanoparticles (MSNs) are considered promising drug carriers because of their ordered pore structure, which permits high drug loading and release capacity. The dissolution of Si and Ca from MSNs can trigger osteogenic differentiation of stem cells towards extracellular matrix calcification, while Mg and Sr constitute key elements of bone biology and metabolism. The aim of this study was the synthesis and characterization of sol-gel-derived MSNs co-doped with Ca, Mg and Sr. Their physico-chemical properties were investigated by X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray analysis (SEM/EDX), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence spectroscopy (XRF), Brunauer Emmett Teller and Brunauer Joyner Halenda (BET/BJH), dynamic light scattering (DLS) and ζ-potential measurements. Moxifloxacin loading and release profiles were assessed with high performance liquid chromatography (HPLC) cell viability on human periodontal ligament fibroblasts and their hemolytic activity in contact with human red blood cells (RBCs) at various concentrations were also investigated. Doped MSNs generally retained their textural characteristics, while different compositions affected particle size, hemolytic activity and moxifloxacin loading/release profiles. All co-doped MSNs revealed the formation of hydroxycarbonate apatite on their surface after immersion in simulated body fluid (SBF) and promoted mitochondrial activity and cell proliferation.
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Sistemas de Liberação de Medicamentos , Moxifloxacina/farmacologia , Nanopartículas/química , Engenharia Tecidual , Proliferação de Células/efeitos dos fármacos , Difusão Dinâmica da Luz , Humanos , Magnésio/química , Microscopia Eletrônica de Varredura , Moxifloxacina/química , Osteogênese/efeitos dos fármacos , Porosidade , Dióxido de Silício/química , Difração de Raios XRESUMO
In this work, the modification process of poly(lactic acid) (PLA) with metal-based nanoparticle (NPs) additives (Ag, ZnO, TiO2) at different loading (0.5, 1.0, and 2.5 wt%) and by melt-mix extrusion method followed by film formation as one of the advantageous techniques for industrial application have been investigated. PLA nanoparticle composite films (PLA-NPs) of PLA-Ag, PLA-ZnO, PLA-TiO2 were fabricated, allowing convenient dispersion of NPs within the PLA matrix to further pursue the challenge of investigating the surface properties of PLA-NPs reinforced plastics (as films) for the final functional properties, such as antimicrobial activity and surface mechanical properties. The main objective was to clarify how the addition of NPs to the PLA during the melt extrusion process affects the chemistry, morphology, and wettability of the surface and its further influence on the antibacterial efficiency and mechanical properties of the PLA-NPs. Therefore, the effect of Ag, ZnO, and TiO2 NPs incorporation on the morphology (SEM), elemental mapping analysis (SEM-EDX), roughness, surface free energy (SFE) of PLA-NPs measured by goniometry and calculated by OWRK (Owens, Wendt, Rabel, and Kaelble) model was evaluated and correlated with the final functional properties such as antimicrobial activity and surface mechanical properties. The developed PLA-metal-based nanocomposites, with improved mechanical and antimicrobial surface properties, could be used as sustainable and biodegradable materials, offering desirable multifunctionalities not only for food packaging but also for cosmetics and hygiene products, as well as for broader plastic products where antimicrobial activity is desirable.