Performance of polyester-based electrospun scaffolds under in vitro hydrolytic conditions: From short-term to long-term applications
The evaluation of the performance of polyesters under in vitro physiologic conditions is essential to design scaffolds with an adequate lifespan for a given application. In this line, the degradation-durability patterns of poly(lactide-co-glycolide) (PLGA), polydioxanone (PDO), polycaprolactone (PCL) and polyhydroxybutyrate (PHB) scaffolds were monitored and compared giving, as a result, a basis for the specific design of scaffolds from short-term to long-term applications. For this purpose, they were immersed in ultra-pure water and phosphate buffer solution (PBS) at 37 °
Polycaprolactone/gelatin-based scaffolds with tailored performance: in vitro and in vivo validation
Abstract Nanofibrous scaffolds composed of polycaprolactone (PCL) and gelatin (Ge) were obtained through a hydrolytic assisted electrospinning process. The PCL-to-Ge proportion (100/0 to 20/80), as well as the dissolution time (24, 48, 72, 96, 120 h) into a 1:1 formic/acetic acid solvent before electrospinning were modified to obtain the different samples. A strong influence of these factors on the physicochemical properties of the scaffolds was observed. Higher Ge percentage reduced crystallinity, allowed a uniform morphology and increased water contact angle. The increase in the dissolution time considerably reduced the molar mass and, subsequently, fibre diameter and crystallinity were a…
The Role of Eucalyptus Species on the Structural and Thermal Performance of Cellulose Nanocrystals (CNCs) Isolated by Acid Hydrolysis
Cellulose nanocrystals (CNCs) are attractive materials due to their renewable nature, high surface-to-volume ratio, crystallinity, biodegradability, anisotropic performance, or available hydroxyl groups. However, their source and obtaining pathway determine their subsequent performance. This work evaluates cellulose nanocrystals (CNCs) obtained from four different eucalyptus species by acid hydrolysis, i.e., E. benthamii, E. globulus, E. smithii, and the hybrid En × Eg. During preparation, CNCs incorporated sulphate groups to their structures, which highlighted dissimilar reactivities, as given by the calculated sulphate index (0.21, 0.97, 0.73 and 0.85, respectively). Although the impact o…
Conductive polycaprolactone/gelatin/polyaniline nanofibres as functional scaffolds for cardiac tissue regeneration
Abstract The endorsement of functional features such as biocompatibility, mechanical integrity, or electrical conductivity to tissue engineering (TE) scaffolds is essential to stimulate cell adhesion and proliferation. In this study, electrospun nanofibers based on polycaprolactone (PCL) and gelatin (Ge) (ratios 60/40, 50/50, and 40/60), and polyaniline (PAni) particles (0.25, 0.50, and 1.00%wt) were prepared. The time of dissolution in an acid solvent mixture before electrospinning allowed for obtaining nanofibers with controlled features. Changes in the molar mass (Mn from 90·103 to 15·103 g·mol−1), in the crystalline microstructure (Xc from 60 to 25%) and the surface morphology (diameter…
Spray-Drying Performance and Thermal Stability of L-Ascorbic Acid Microencapsulated with Sodium Alginate and Gum Arabic
[EN] The potential of sodium alginate (ALG) and gum arabic (GA) as wall polymers for Lascorbic acid (AA) encapsulation as a tool for their preservation against the thermo-oxidative degradation was investigated. The influence of such polymers used as wall material on the AAcontent, size, encapsulation efficiency, encapsulation yield and thermo-oxidative stability were evaluated. The AA-microparticles were obtained using the spray-drying technique. An experimental Taguchi design was employed to assess the influence of the variables in the encapsulation process. The microparticles morphology and size distribution were characterized by scanning electron microscopy and laser diffraction. The the…
Tailored electrospun nanofibrous polycaprolactone/gelatin scaffolds into an acid hydrolytic solvent system
[EN] Blended nanofibrous scaffolds based on polycaprolactone (PCL) and gelatin (Ge) were successfully prepared. A formic/acetic acid (1:1) mixture was used to dissolve PCL/Ge blends from 100/0 to 20/80 %wt in steps of 10 %wt. The hydrolysis of the PCL diluted in the formic/acetic acid mixture was considered as a method for tailoring the surface morphology and physicochemical features of the nanofibrous PCL/Ge scaffolds as a function of the dissolution time. The fibre diameter remained in the nanoscale range for all the studied scaffolds, which is crucial to mimic the extra-cellular matrix size. The reduction of the intrinsic viscosity, molar mass and hydrodynamic radius found for the PCL mo…
Triblock SEBS/DVB crosslinked and sulfonated membranes: Fuel cell performance and conductivity
[EN] A set of styrene-ethylene-butylene-styrene triblock copolymer (SEBS) membranes with 10 or 25 wt.% divinyl-benzene (DVB) as a crosslinking agent were prepared and validated. Physicochemical characterization revealed suitable hydrolytic and thermal stability of photo-crosslinked membranes containing 25%wt. DVB and post-sulfonated. These compositions were evaluated in H2/O2 single cells, and electrical and proton conductivities were furtherly assessed. The membranes with the milder post-sulfonation showed greater proton conductivity than those with excessive sulfonation. In terms of electrical conductivity, a universal power law was applied, and the values obtained were low enough for bei…
Long-term properties and end-of-life of polymers from renewable resources
[EN] The long-term properties and end-of-life of polymers are not antagonist issues. They actually are inherently linked by the duality between durability and degradation. The control of the service-todisposal pathway at useful performance, along with low-impact disposal represents an added-value. Therefore, the routes of design, production, and discarding of bio-based polymers must be carefully strategized. In this sense, the combination of proper valorisation techniques, i.e. material, energetic and/ or biological at the most appropriate stage should be targeted. Thus, the consideration of the end-of-life of a material for a specific application, instead of the end-of-life of a material s…
Polylactide-based self-reinforced composites biodegradation: Individual and combined influence of temperature, water and compost
[EN] Self-reinforced polymer composites (SRCs) are proposed as a suitable alternative for composite development, based in the combination of a polymeric matrix and a polymeric fibre made of the same polymer. SRCs based in polylactide (PLA) could be fully biodegradable and their valorisation routes could presumably be assimilated to those for neat PEA. In this sense, the aim of this study was to develop new self-reinforced PLA-based composites and ascertain their biodegradability. For this purpose, PLA-based SRCs were obtained through a thermo-compression procedure and their biodegradability corroborated under standard conditions (ISO 20200). Moreover, a deep study of the effect of the diffe…
In vitro validation of biomedical polyester-based scaffolds: Poly(lactide-co-glycolide) as model-case
[EN] Monitoring and understanding the in vitro behaviour of polyester based scaffolds both comprising the study of the hydrolytic degradation and the cell seeding viability is essential to ensure the desired functionality, according to a given biomedical purpose. As a model case to compare the performance of techniques to monitor the in vitro behaviour, poly(lactide-co-glycolide) (PLGA) scaffolds were chosen. The in vitro hydrolytic degradation of PLGA scaffolds was carried out in water and phosphate buffered saline (PBS). The evolution of the mass loss, the molar mass, the thermal properties and the surface morphology were monitored. The hydrolytic degradation media was correspondingly eva…
Dielectric spectroscopy of novel thiol-ene/epoxy thermosets obtained from allyl-modified hyperbranched poly (ethyleneimine) and diglycidylether of bisphenol A
[EN] Dielectric Thermal Analysis (DETA) of a series of new thermoset obtained by click chemistry was performed. The new thermosets were obtained by a dual-curing process consisting in a first photochemical thiol-ene, followed by a thermal thiol-epoxy starting from an allyl-terminated hyperbranched poly(ethyleneimine) (HBPEI) and different proportions of diglycidylether of bisphenol A (DGEBA) and the corresponding stoichiometric proportions of pentaerythritol tetrakis (3-mercaptopropionate, PETMP). The dielectric behaviour was obtained experimentally supressing the conductive effects. Two sub-Tg intramolecular non-cooperative gamma and beta relaxations and an intermolecular cooperative alpha…
Poly (lactic acid)/D-limonene/ZnO bio-nanocomposites with antimicrobial properties
[EN] Antimicrobial films of poly (lactic acid) (PLA)/D-limonene/zinc oxide (ZnO)-based bio-nanocomposites were prepared via melt compounding and subsequent thermocompression. D-limonene was incorporated at concentrations of 10 or 20 wt%, and ZnO pure nanoparticles and those organically modified with oleic acid (O-ZnO), with an average diameter of 13.5 nm, were included at concentrations of 3, 5, and 8 wt%. The plasticizing effect of D-Limonene was corroborated by a decrease in the glass transition temperature compared to pure PLA. The presence of ZnO and O-ZnO in the PLA matrix promoted a slight increase in the degree of crystallinity due to its nucleant performance. Although ZnO and O-ZnO …
Crosslinked Sulfonated Poly(vinyl alcohol)/Graphene Oxide Electrospun Nanofibers as Polyelectrolytes
[EN] Taking advantage of the high functionalization capacity of poly(vinyl alcohol) (PVA), bead-free homogeneous nanofibrous mats were produced. The addition of functional groups by means of grafting strategies such as the sulfonation and the addition of nanoparticles such as graphene oxide (GO) were considered to bring new features to PVA. Two series of sulfonated and nonsulfonated composite nanofibers, with different compositions of GO, were prepared by electrospinning. The use of sulfosuccinic acid (SSA) allowed crosslinked and functionalized mats with controlled size and morphology to be obtained. The functionalization of the main chain of the PVA and the determination of the optimum co…
Impact of hydrothermal ageing on the thermal stability, morphology and viscoelastic performance of PLA/sisal biocomposites
The influence of the combined exposure to water and temperature on the behaviour of polylactide/sisal biocomposites coupled with maleic acid anhydride was assessed through accelerated hydrothermal ageing. The biocomposites were immersed in water at temperatures from 65 to 85 °C, between the glass transition and cold crystallisation of the PLA matrix. The results showed that the most influent factor for water absorption was the percentage of fibres, followed by the presence of coupling agent, whereas the effect of the temperature was not significant. Deep assessment was devoted to biocomposites subjected to hydrothermal ageing at 85 °C, since it represents the extreme degrading condition. Th…
Effect of the dissolution time into an acid hydrolytic solvent to tailor electrospun nanofibrous polycaprolactone scaffolds
[EN] The hydrolysis of the polycaprolactone (PCL) as a function of the dissolution time in a formic/acetic acid mixture was considered as a method for tailoring the morphology of nanofibrous PCL scaffolds. Hence the aim of this research was to establish a correlation between the dissolution time of the polymer in the acid solvent with the physicochemical properties of the electrospun nanofibrous scaffolds and their further service life behaviour. The physico-chemical properties of the scaffolds were assessed in terms of fibre morphology molar mass and thermal behaviour. A reduction of the molar mass and the lamellar thickness as well as an increase of the crystallinity degree were observed …
Hydrothermal ageing of polylactide/sisal biocomposites. Studies of water absorption behaviour and Physico-Chemical performance
An accelerated hydrothermal degrading test was designed in order to analyse the synergic effect of water and temperature on PLA/sisal biocomposites with and without coupling agent. As well, the physicochemical properties of biocomposites were monitored along the hydrothermal test by means of Scanning Electron Microscopy, Size Exclusion Chromatography and Differential Scanning Calorimetry. The addition of fibre induced higher water absorption capability and promoted physical degradation, as observed in the surface topography. During the processing of biocomposites and throughout the hydrothermal ageing, a reduction of molecular weight due to chain scission was found. As a consequence, a fast…
Novel silicon microparticles to improve sunlight stability of raw polypropylene
Oxidation of polyolefins by ultraviolet/visible irradiation is a significant limitation for their use in several technological applications. The use of high-tech additives such as silicon microparticles becomes a compositing strategy that can improve the performance of these materials at long-term service conditions. Silicon particles were added to non-additivated raw polypropylene (PP) prepared by hot melt extrusion and subjected to accelerated sunlight irradiation tests. The stability of thermal properties, mechanical performance and thermal decomposition behaviour of composites was evaluated by differential scanning calorimetry, dynamic mechanical thermal analysis and thermogravimetry. T…