RESUMEN
Silk sericin (SS)-based hydrogels show promise for wound healing due to their biocompatibility, moisture regulation, and cell proliferation properties. However, there is still a need to develop green crosslinking methods to obtain non-toxic, absorbent, and mechanically strong SS hydrogels. This study investigated the effects of three green crosslinking methods, annealing treatment (T), exposure to an absolute ethanol vapor atmosphere (V.E), and water vapor (V.A), on the physicochemical and mechanical properties of SS and poly (vinyl alcohol) (PVA) biohydrogels. X-ray diffraction and Fourier-transform infrared spectroscopy were used to determine chemical structures. Thermal properties and morphological changes were studied through thermogravimetric analysis and scanning electron microscopy, respectively. The water absorption capacity, mass loss, sericin release in phosphate-buffered saline (PBS), and compressive strength were also evaluated. The results showed that physical crosslinking methods induced different structural transitions in the biohydrogels, impacting their mechanical properties. In particular, V.A hydrogen presented the highest compressive strength at 80% deformation owing to its compact and porous structure with crystallization and bonding sites. Moreover, both the V.A and T hydrogels exhibited improved absorption capacity, stability, and slow SS release in PBS. These results demonstrate the potential of green physical crosslinking techniques for producing SS/PVA biomaterials for wound healing applications.
RESUMEN
Superhydrophobic poly(vinylidene fluoride) (PVDF) membranes were obtained by a surface treatment consisting of oxygen plasma activation followed by functionalisation with a mixture of silica precursor (SiP) (tetraethyl-orthosilicate [TEOS] or 3-(triethoxysilyl)-propylamine [APTES]) and a fluoroalkylsilane (1H,1H,2H,2H-perfluorooctyltriethoxysilane), and were benchmarked with coated membranes without plasma activation. The modifications acted mainly on the surface, and the bulk properties remained stable. From a statistical design of experiments on surface hydrophobicity, the type of SiP was the most relevant factor, achieving the highest water contact angles (WCA) with the use of APTES, with a maximum WCA higher than 155° for membranes activated at a plasma power discharge of 15 W during 15 min, without membrane degradation. Morphological changes were observed on the membrane surfaces treated under these plasma conditions, showing a pillar-like structure with higher surface porosity. In long-term stability tests under moderate water flux conditions, the WCA of coated membranes which were not activated by oxygen plasma decreased to approximately 120° after the first 24 h (similar to the pristine membrane), whilst the WCA of plasma-treated membranes was maintained around 130° after 160 h. Thus, plasma pre-treatment led to membranes with a superhydrophobic performance and kept a higher hydrophobicity after long-term operations.
RESUMEN
A three-step surface modification consisting of activation with NaOH, functionalisation with a silica precursor and organofluorosilane mixture (FSiT), and curing was applied to a poly(vinylidene fluoride) (PVDF) membrane for the recovery of dissolved methane (D-CH4) from aqueous streams. Based on the results of a statistical experimental design, the main variables affecting the water contact angle (WCA) were the NaOH concentration and the FSiT ratio and concentration used. The maximum WCA of the modified PVDF (mPVDFmax) was >140° at a NaOH concentration of 5%, an FSiT ratio of 0.55 and an FSiT concentration of 7.2%. The presence of clusters and a lower surface porosity of mPVDF was detected by FESEM analysis. In long-term stability tests with deionised water at 21 L h−1, the WCA of the mPVDF decreased rapidly to around 105°, similar to that of pristine nmPVDF. In contrast, the WCA of the mPVDF was always higher than that of nmPVDF in long-term operation with an anaerobic effluent at 3.5 L h−1 and showed greater mechanical stability, since water breakthrough was detected only with the nmPVDF membrane. D-CH4 degassing tests showed that the increase in hydrophobicity induced by the modification procedure increased the D-CH4 removal efficiency but seemed to promote fouling.
RESUMEN
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 of the incorporation of sulphate groups on the crystalline structure was committed, changes in the hydrophilicity and water retention ability or thermal stability were observed. These effects were also corroborated by the apparent activation energy during thermal decomposition obtained through kinetic analysis. Low-sulphated CNCs (E. benthamii) involved hints of a more crystalline structure along with less water retention ability, higher thermal stability, and greater average apparent activation energy (233 kJ·mol-1) during decomposition. Conversely, the high-sulphated species (E. globulus) involved higher reactivity during preparation that endorsed a little greater water retention ability and lower thermal stability, with subsequently less average apparent activation energy (185 kJ·mol-1). The E. smithii (212 kJ·mol-1) and En × Eg (196 kJ·mol-1) showed an intermediate behavior according to their sulphate index.
RESUMEN
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 °C. The scaffolds for short-time applications were PLGA and PDO, in which the molar mass diminished down to 20% in a 20-30 days lifespan. While PDO developed crystallinity that prevented the geometry of the fibres, those of PLGA coalesced and collapsed. The scaffolds for long-term applications were PCL and PHB, in which the molar mass followed a progressive decrease, reaching values of 10% for PCL and almost 50% for PHB after 650 days of immersion. This resistant pattern was mainly ascribed to the stability of the crystalline domains of the fibres, in which the diameters remained almost unaffected. From the perspective of an adequate balance between the durability and degradation, this study may serve technologists as a reference point to design polyester-based scaffolds for biomedical applications.
RESUMEN
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 composition of GO were analyzed in terms of the nanofibrous morphology, the chemical structure, the thermal properties, and conductivity. The crosslinking and the sulfonation treatment decreased the average fiber diameter of the nanofibers, which were electrical insulators regardless of the composition. The addition of small amounts of GO contributed to the retention of humidity, which significantly increased the proton conductivity. Although the single sulfonation of the polymer matrix produced a decrease in the proton conductivity, the combination of the sulfonation, the crosslinking, and the addition of GO enhanced the proton conductivity. The proposed nanofibers can be considered as good candidates for being exploited as valuable components for ionic polyelectrolyte membranes.