The study presented herein concerns the mechanical properties of two common polymers for potential biomedical applications, PLA and PETG, processed through fused filament fabrication (FFF)—Material Extrusion (ME). For the uniaxial tension tests carried out, two printing orientations—XY (Horizontal, H) and YZ (Vertical, V)—were considered according to the general principles for part positioning, coordinates, and orientation typically used in additive manufacturing (AM). In addition, six specimens were tested for each printing orientation and material, providing insights into mechanical properties such as Tensile Strength, Young’s Modulus, and Ultimate Strain, suggesting the materials’ potential for biomedical applications. The experimental results were then compared with correspondent mechanical properties obtained from the literature for other polymers like ASA, PC, PP, ULTEM 9085, Copolyester, and Nylon. Thereafter, fatigue resistance curves (S-N curves) for PLA and PETG, printed along 45°, were determined at room temperature for a load ratio, R, of 0.2. Scanning electron microscope observations revealed fibre arrangements, compression/adhesion between layers, and fracture zones, shedding light on the failure mechanisms involved in the fatigue crack propagation of such materials and giving design reference values for future applications. In addition, fractographic analyses of the fatigue fracture surfaces were carried out, as well as X-ray Computed Tomography (XCT) and Thermogravimetric (TGA)/Differential Scanning Calorimetric (DSC) tests.

This work assessed the film-forming capacity of exopolysaccharides (EPS) produced by six Alteromonas strains recently isolated from different marine environments in French Polynesia atolls. The films were transparent and resulted in small colour alterations when applied over a coloured surface (ΔEab below 12.6 in the five different colours tested). Moreover, scanning electron microscopy showed that the EPS films were dense and compact, with a smooth surface. High water vapour permeabilities were observed (2.7–6.1 × 10−11 mol m−1 s−1 Pa−1), which are characteristic of hydrophilic polysaccharide films. The films were also characterised in terms of barrier properties to oxygen and carbon dioxide. Interestingly, different behaviours in terms of their mechanical properties under tensile tests were observed: three of the EPS films were ductile with high elongation at break (ε) (35.6–47.0%), low tensile strength at break (Ꞇ) (4.55–11.7 MPa) and low Young’s modulus (εm) (10–93 MPa), whereas the other three were stiffer and more resistant with a higher Ꞇ (16.6–23.6 MPa), lower ε (2.80–5.58%), and higher εm (597–1100 MPa). These properties demonstrate the potential of Alteromonas sp. EPS films to be applied in different areas such as biomedicine, pharmaceuticals, or food packaging.

Superparamagnetic iron oxide nanoparticles (SPIONs) are widely used in magnetic hyperthermia, where their therapeutic efficacy depends on efficient heat generation. However, intracellular uptake of SPIONs has been shown to reduce their heat dissipation capacity, limiting hyperthermia performance. To address this challenge, we explored the use of small-molecule endocytosis inhibitors to block SPIONs’ uptake in vitro. SPIONs stabilized with 3-aminopropyl triethoxysilane (APTES) were evaluated in an advanced cutaneous melanoma cell line treated with a small library of endocytosis inhibitors. Among these, methyl-β-cyclodextrin significantly reduced SPIONs’ uptake compared to untreated cells. Importantly, uptake inhibition restored SPIONs’ heat dissipation capacity from specific absorption rates of 63 to 91 W g−1 and improved the temperature increase by 2.6 °C, under magnetic hyperthermia conditions. These findings demonstrate that targeting nanoparticle internalization with small-molecule inhibitors, particularly methyl-β-cyclodextrin, enhances the efficiency of magnetic hyperthermia in melanoma cells. This strategy offers a promising approach to optimize magnetic hyperthermia for melanoma treatment.

Gelatin is a popular biopolymer for biomedical applications due to its harmless impact with a negligible inflammatory response in the host organism. Gelatin interacts with soluble molecules in aqueous media as ionic counterparts such as ionic liquids (ILs) to be used as cosolvents to generate the so-called Ionogels. The perfluorinated IL (FIL), 1-ethyl-3-methylpyridinium perfluorobutanesulfonate, has been selected as co-hydrosolvent for fish gelatin due to its low cytotoxicity and hydrophobicity aprotic polar structure to improve the drug aqueous solubility. A series of FIL/water emulsions with different FIL content and their corresponding shark gelatin/FIL Ionogel has been designed to enhance the drug solubility whilst retaining the mechanical structure and their nanostructure was probed by simultaneous SAXS/WAXS, FTIR and Raman spectroscopy, DSC and rheological experiments. Likewise, the FIL assisted the solubility of the antitumoural Doxorubicin whilst retaining the performing mechanical properties of the drug delivery system network for the drug storage as well as the local administration by a syringe. In addition, the different controlled release mechanisms of two different antitumoral such as Doxorubicin and Mithramycin from two different Ionogels formulations were compared to previous gelatin hydrogels which proved the key structure correlation required to attain specific therapeutic dosages.

The demand for bio–based products is increasing, but the development of efficient purification processes is lagging. However, typically these processes are expensive, non–specific and/or lack of efficiency. Molecularly imprinted polymers (MIPs) are synthetic affinity materials able to mimic the molecular recognition ability of natural molecules, offering a cost–effective alternative to replace the commercial affinity–driven materials based on proteins and antibodies. In this work, MIPs were developed using supercritical carbon dioxide (scCO2) technology using two approaches: i) one–templating (O–MIPs), using L–leucine (LEU) as template, and ii) a dual–templating (D–MIPs), using LEU and L–lysine (LYS) as templates, to evaluate their potential in the molecular recognition of amino acids in simple and complex aqueous solutions. MIPs produced in scCO2 have already shown good performances in organic and aqueous solutions, for small and non–polar template molecules. Herein, their applicability is extended to amino acids but also proteins. MIPs were produced using 2–vinylpyridine (VP) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as crosslinker under scCO2 conditions. Polymers were obtained as white, ready–to–use dry powders. Their affinity performance was assessed by Static Binding Tests (SBTs) and Solid Phase Extraction (SPE) assays using different amino acids and proteins. The best SBT results was obtained by D–MIP with Qmax = 216 mg LEU + LYS/g D–MIP, and IFmax = 8.3. D–MIP also presented higher binding capacities to adsorb their templated–molecules by a dynamic process (SPE) (Qmax = 79 mg LEU + LYS/g D–MIP), and selectively bind their templates in a solution containing a protein (IFmax = 6.8). The green D–MIP provides a robust, tailor–made and sustainable alternative for biopurification processes.

Eutectogels, obtained from the combination of deep eutectic systems (DESs) or natural deep eutectic systems (NADESs) with polymers, represent a new class of sustainable soft materials. Combining the tunable properties of DESs, such as low volatility, ionic conductivity, and biocompatibility, with the structural integrity of gels, these materials can be designed to have improved mechanical flexibility, self-healing ability, and environmental stability. Recent research focused on understanding how the composition of DESs, polymer type, or crosslinking mechanisms influence the physicochemical behavior and performance of eutectogels. Advances in this field enabled their use in diverse biotechnological applications, particularly in drug delivery, transdermal systems, wound healing, and tissue engineering, where they demonstrate improved biofunctionality and adaptability compared to traditional hydrogels. Nevertheless, challenges related to scalability, reproducibility, long-term stability, and toxicity must be addressed to reach their full potential. Progress in this area relies on multidisciplinary efforts between green chemistry, materials science, and bioengineering. Overcoming these hurdles could allow eutectogels to evolve from academic concepts into a new generation of sustainable, high-performance soft materials with broad applicability in the biotechnology field.

In the present study, three different newly developed copolymers of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with 20, 40, and 60 mol % contents in 3-hydroxyvalerate (3HV) were produced by the biotechnological process of mixed microbial cultures (MMCs) using cheese whey (CW), a by-product from the dairy industry, as feedstock. The CW-derived PHBV copolyesters were first purified and then processed by solution electrospinning, yielding fibers of approximately 2 μm in cross-section in all cases. The resultant electrospun PHBV mats were, thereafter, post-processed by annealing at different temperatures, below their maximum of melting, selected according to their 3HV content in order to obtain continuous films based on coalesced fibers, so-called biopapers. The resultant PHBV films were characterized in terms of their morphology, crystallinity, and mechanical and barrier properties to assess their potential application in food packaging. The CW-derived PHBV biopapers showed high contact transparency but a slightly yellow color. The fibers of the 20 mol % 3HV copolymer were seen to contain mostly poly(3-hydroxybutyrate) (PHB) crystals, the fibers of the 40 mol % 3HV copolymer a mixture of PHB and poly(3-hydroxyvalerate) (PHV) crystals and lowest crystallinity, and the fibers of the 60 mol % 3HV sample were mostly made of PHV crystals. To understand the interfiber coalesce process undergone by the materials during annealing, the crystalline morphology was also assessed by variable-temperature both combined small-angle and wide-angle X-ray scattering synchrotron and Fourier transform infrared experiments. From these experiments and, different from previously reported biopapers with lower 3HV contents, all samples were inferred to have a surface energy reduction mechanism for interfiber coalescence during annealing, which is thought to be activated by a temperature-induced decrease in molecular order. Due to their reduced crystallinity and molecular order, the CW-derived PHBV biopapers, especially the 40 mol % 3HV sample, were found to be more ductile and tougher. In terms of barrier properties, the three copolymers performed similarly to water and limonene, but to oxygen, the 40 mol % sample showed the highest relative permeability. Overall, the materials developed, which are compatible with the Circular Bioeconomy organic recycling strategy, can have an excellent potential as barrier interlayers or coatings of application interest in food packaging.

Synthesis of dicarboxymethyl cellulose (DCMC) under heterogeneous conditions was examined. Cellulose was etherified using sodium bromomalonate in isopropanol/water in the presence of NaOH. The reaction was performed with five different NaOH concentrations (5–30 w/v %) and the products were characterized by anion-exchange high-performance liquid chromatography (AE-HPLC), inductively coupled plasma atomic emission- (ICP-AES), Fourier transform infrared- (FTIR), and nuclear magnetic resonance (1D-/2D-NMR) spectroscopy. Adjusting the amount of NaOH resulted in increasing functionalization of the cellulose achieving an average degree of substitution (DS) between 0.05 and 0.51. Both ICP-AES and AE-HPLC gave comparable DS values. NMR spectroscopic analysis showed that etherification occurred preferably at O-6 and, to a certain extent, at the secondary positions depending on the reaction conditions. Graphic abstract: [Figure not available: see fulltext.].

Bioprinting approaches are of great promise for tissue engineering applications as they allow the fabrication of constructs able to mimic native tissues’ mechanical and topographical features. Additional control over cells fate can be enhanced using stimuli-responsive materials, requiring the development of novel bioinks for this purpose. In this study, bioinks comprising κ-carrageenan, collagen, and magnetic nanoparticles were designed for 3D bioprinting applications. The characterization of this material was performed, where mechanical compressive tests yielded Young’s moduli ranging from 8.25 to 18.4 kPa. Rheological assessments also revealed the shear-thinning behavior of the bioinks and a temperature-dependent gelation. The capability of these bioinks to produce 3D constructs by extrusion bioprinting was established through the printability evaluation and the development of complex structures, supporting the viability and proliferation of mesenchymal stromal cells (MSCs). Finally, as proof-of-concept, it was observed that the secretome of bioprinted MSCs stimulated with an external magnetic field of 80 mT was able to increase the number of tubes formed by human umbilical vein endothelial cells.

Vinyl emulsions started to be used by artists in paintings at least since the early 1960s, being now present in several artworks worldwide. However, different vinyl formulations can result in distinct behaviours over time, and if some artworks are currently showing a good condition, others already show damages due to the use of compositions more susceptible to degradation. For this reason, it is fundamental to identify the main components in the vinyl acetate-based (VAc-based) emulsion. This work focuses on the molecular study of VAc-based emulsions by infrared and Raman spectroscopies. It aims at deepening the knowledge on the variability of the composite formulation and on the identification of characteristic bands and spectral profiles (identified as spectral markers) for both polymer and additives. To this end, a broad set of vinyl emulsions was gathered, including reference materials, historical commercial brands in use by Portuguese artists, and commercial brands collected from industrial companies. The entire set includes vinyl homopolymers produced for the purpose of the study and known formulations of vinyl homopolymers and copolymers, with and without plasticisers, according to technical data sheets and previous studies. Furthermore, unknown formulations have been included to validate the usefulness of the identified spectral markers. This set has been studied in the form of solid films deposited in glass slides by infrared spectroscopy in attenuated total reflection mode (ATR-FTIR) and micro-Raman spectroscopy (µ-Raman), both conducted in situ. As conclusions, the combined use of ATR-FTIR and µ-Raman proved to be very useful as different spectral markers were detected by each technique, confirming their complementarity. Besides the clear identification of vinyl acetate-based emulsions by both techniques, it was also possible to suggest spectral markers for the copolymerisation of vinyl acetate with vinyl versatate by µ-Raman, the stabilisation of the emulsion with poly(vinyl alcohol) by ATR-FTIR, and the addition of phthalates or benzoates plasticisers by both ATR-FTIR and µ-Raman.