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This study explores, for the first time, the application of electrospun biobased poly(butylene 2,5-furanoate) (PBF) and poly(pentamethylene 2,5-furanoate) (PPeF) mats in biomedical and drug delivery fields, through a careful investigation of their structure–property relationship. PBF mats, with a glass transition temperature (Tg) of 25–30 °C and an as-spun crystallinity of 18.8%, maintained their fibrous structure (fiber diameter ~1.3 µm) and mechanical properties (stiffness ~100 MPa, strength ~4.5 MPa, strain at break ~200%) under treatment in physiological conditions (37 °C, pH 7.5). In contrast, PPeF mats, being amorphous with a Tg of 14 °C, underwent significant densification, with geometrical density increasing from 0.68 g/cm³ to 1.07 g/cm³, which depressed the specific (i.e., normalized by density) mechanical properties. DSC analysis revealed that the treatment promoted crystallization in PBF (reaching 45.9% crystallinity), while PPeF showed limited, but interestingly not negligible, structural reorganization. Both materials promoted good cell adhesion and were biocompatible, with lactate dehydrogenase release not exceeding 20% after 48 h. The potential of PBF mats for drug delivery was evaluated using dexamethasone. The mats exhibited a controlled drug release profile, with ~10% drug release in 4 h and ~50% in 20 h. This study demonstrates the versatility of these biopolyesters in biomedical applications and highlights the impact of polymer structure on material performance.

In recent years, the unsustainable consumption of fossil resources has been causing major ecological concerns, especially for the production of polymeric materials. 2,5-furandicarboxylic acid (FDCA) is one of the most appealing biobased chemical building blocks, because of its potential to replace the industrially widespread petrochemical, terephthalic acid. Camphoric acid (CA) is also an interesting biobased chemical derived from camphor, one of the most widespread fragrances. This work had the objective of combining CA, FDCA and biobased 1,6-hexanediol to synthesize random copolymers for sustainable food packaging applications by means of a solvent-free polycondensation process, obtaining poly(hexamethylene furanoate-co-camphorate)s (PHFC). The optimization of the synthesis made it possible to obtain high molecular weight polyesters with a percentage of camphoric acid up to 17 mol%, which could be compression-molded into films. They were subjected to molecular, structural, thermal and functional characterization via NMR, GPC, WAXS, DSC, and TGA analyses, as well as mechanical and gas permeability tests. Compared to the homopolymer of reference, it was possible to obtain higher flexibility, 430% higher elongation at break, and 223% higher toughness, with comparable, excellent gas permeability properties. Calorimetric evidence suggested that camphoric acid might have enhanced the formation of a partially ordered mesomorph phase in the copolymers under study.

High molecular weight, fully biobased random copolymers of 2,5-furandicarboxylic acid (2,5-FDCA) containing different amounts of (1R, 3S)-(+)-Camphoric Acid (CA) have been successfully synthesized by two-stage melt polycondensation and compression molding in the form of films. The synthesized copolyesters have been first subjected to molecular characterization by nuclear magnetic resonance spectroscopy and gel-permeation chromatography. Afterward, the samples have been characterized from a thermal and structural point of view by means of differential scanning calorimetry, thermogravimetric analysis, and wide-angle X-ray scattering, respectively. Mechanical and barrier properties to oxygen and carbon dioxide were also tested. The results obtained revealed that chemical modification permitted a modulation of the abovementioned properties depending on the amount of camphoric co-units present in the copolymers. The outstanding functional properties promoted by camphor moieties addition could be associated with improved interchain interactions (π-π ring stacking and hydrogen bonds).

Both academia and industry are currently devoting many efforts to develop high gas barrier bioplastics as substitutes of traditional fossil-based polymers. In this view, this contribution presents a new biobased aromatic polyester, i.e., poly(propylene 2,5-thiophenedicarboxylate) (PPTF), which has been compared with the furan-based counterpart (PPF). Both biopolyesters have been characterized from the molecular, thermo-mechanical and structural points of view. Gas permeability behavior has been evaluated with respect to 100% oxygen, carbon dioxide and nitrogen at 23 °C. In case of CO2 gas test, gas transmission rate has been also measured at different temperatures. The permeability behavior at different relative humidity has been investigated for both biopolyesters, the thiophen-containing sample demonstrating to be better than the furan-containing counterpart. PPF’s permeability behavior became worse than PPTF’s with increasing RH, due to the more polar nature of the furan ring. Both biopolyesters under study are characterized by superior gas barrier performances with respect to PEF and PET. With the simple synthetic strategy adopted, the exceptional barrier properties render these new biobased polyesters interesting alternatives in the world of green and sustainable packaging materials. The different polarity and stability of heterocyclic rings was revealed to be an efficient tool to tailor the ability of crystallization, which in turn affects mechanical and barrier performances.

Conventional lithium-ion battery separators made from petroleum-based polymers pose environmental concerns due to their non-renewable origin and energy-intensive production. Novel bio-based alternatives, such as poly(alkylene 2,5-furanoate)s (PAFs), offer improved sustainability and favorable thermomechanical properties. This work investigated electrospun mats of poly(butylene 2,5-furandicarboxylate) (PBF) and poly(pentamethylene 2,5-furandicarboxylate) (PPeF), which, despite structural similarity, exhibit distinct behaviors. PBF mats demonstrated superior performance with fiber diameters of about 1.0 µm and porosity of 53.6% with high thermal stability (Tg = 25 °C, Tm = 170 °C, 18.8% crystallinity). The semicrystalline PBF showed higher electrolyte uptake (531–658 wt%) and had a lower MacMullin number (NM = 3–10) than commercial Celgard separators (NM = 15), indicating enhanced ionic conductivity. Electrochemical testing revealed stability up to 5 V and successful cycling performance with specific capacity of 135 mAh/g after 100 cycles and coulombic efficiency near 100%. In contrast, PPeF’s amorphous nature (Tg = 14 °C) resulted in temperature-sensitive pore closure that enhanced safety by reducing short-circuit risk, although its solubility in carbonate electrolytes limited its application to aqueous systems. These findings highlight the potential of PAF-based separators to improve both the environmental impact and performance of batteries, supporting the development of safer and more sustainable energy storage systems.

The rapid development of ophthalmic surgery in recent years has made big steps forward, making interventions such as penetrating and lamellar keratoplasty or trabeculectomy widely practiced. However, the use of non-absorbable sutures in these procedures poses significant challenges. Indeed, unequal tension between the various stitches can lead to deformations of the cornea or lens and consequently to problems such as post-operative astigmatism or anisometropia. To overcome these problems, sutures with improved closure via a highly stretchable behaviour together with an excellent elastic return are a credible solution. Accordingly, to widen the plethora of superelastic polymeric materials, in the present study a novel solution deriving from two furan-based polyesters, poly(pentamethylene furanoate), PPeF, and poly(hexamethylene furanoate), PHF, was successfully obtained. Of note, these homopolymers are also entirely derived from sustainable sources. The two homopolymers were physically and chemically mixed to obtain copolymers with different block lengths, which were characterised from molecular, thermal, mechanical, and surface wettability points of view, showing interesting properties which were easily modulated as a function of block length. Lastly, all the materials showed good stability over time and cell viability and, for some of them, a great mechanical recovery upon deformation was also observed.

Cardiovascular diseases are responsible for a large number of severe disability cases and deaths worldwide. Strong research in this field has been extensively carried out, in particular for the associated complications, such as the occlusion of small-diameter (<6 mm) vessels. Accordingly, in the present research, two random copolyesters of poly(butylene 2,5-furandicarboxylate) (PBF) and poly(butylene isophthalate) (PBI), were successfully synthesized via two-step melt polycondensation and were thoroughly characterized from molecular, thermal, and mechanical perspectives. The copolymeric films displayed a peculiar thermal behavior, being easily processable in the form of films, although amorphous, with Tg close to room temperature. Their thermal stability was high in all cases, and from the mechanical point of view, the materials exhibited a high ultimate strength, together with values of elastic moduli tunable with the chemical composition. The long-term stability of these materials under physiological conditions was also demonstrated. Cytotoxicity was assessed using a direct contact assay with human umbilical vein endothelial cells (HUVECs). In addition, hemocompatibility was tested by evaluating the adhesion of blood components (such as the adsorption of human platelets and fibrinogen). As a result, a proper chemical design and, in turn, both the solid-state and functional properties, are pivotal in regulating cell behavior and opening new frontiers in the tissue engineering of soft tissues, including vascular tissues.

Cardiovascular disease (CVD), the leading cause of death globally, affects the heart and arteries with a variety of clinical manifestations, the most dramatic of which are myocardial infarction (MI), abdominal aortic aneurysm (AAA), and intracranial aneurysm (IA) rupture. In MI, necrosis of the myocardium, scar formation, and loss of cardiomyocytes result from insufficient blood supply due to coronary artery occlusion. Beyond stenosis, the arteries that are structurally and functionally connected to the cardiac tissue can undergo pathological dilation, i.e., aneurysmal dilation, with high risk of rupture. Aneurysms of the intracranial arteries (IAs) are more commonly seen in young adults, whereas those of the abdominal aorta (AAA) are predominantly seen in the elderly. IAs, unpredictably, can undergo rupture and cause life-threatening hemorrhage, while AAAs can result in rupture, internal bleeding and high mortality rate. In this clinical context, hydrogels, three-dimensional networks of water-seizing polymers, have emerged as promising biomaterials for cardiovascular tissue repair or protection due to their biocompatibility, tunable properties, and ability to encapsulate and release bioactive molecules. This review provides an overview of the current state of research on the use of hydrogels as an innovative platform to promote cardiovascular-specific tissue repair in MI and functional recovery or protection in aneurysmal dilation.

In recent years there has been a growing interest in the use of proteins as biocompatible and environmentally friendly biomolecules for the design of wound healing and drug delivery systems. Keratin is a fascinating protein, obtainable from several keratinous biomasses such as wool, hair or nails, with intrinsic bioactive properties including stimulatory effects on wound repair and excellent carrier capability. In this work keratin/poly(butylene succinate) blend solutions with functional properties tunable by manipulating the polymer blending ratios were prepared by using 1,1,1,3,3,3-hexafluoroisopropanol as common solvent. Afterwards, these solutions doped with rhodamine B (RhB), were electrospun into blend mats and the drug release mechanism and kinetics as a function of blend composition was studied, in order to understand the potential of such membranes as drug delivery systems. The electrophoresis analysis carried out on keratin revealed that the solvent used does not degrade the protein. Moreover, all the blend solutions showed a non-Newtonian behavior, among which the Keratin/PBS 70/30 and 30/70 ones showed an amplified orientation ability of the polymer chains when subjected to a shear stress. Therefore, the resulting nanofibers showed thinner mean diameters and narrower diameter distributions compared to the Keratin/PBS 50/50 blend solution. The thermal stability and the mechanical properties of the blend electrospun mats improved by increasing the PBS content. Finally, the RhB release rate increased by increasing the keratin content of the mats and the drug diffused as drug-protein complex.

Mechanotransduction is a molecular process by which cells translate physical stimuli exerted by the external environment into biochemical pathways to orchestrate the cellular shape and function. Even with the advancements in the field, the molecular events leading to the signal cascade are still unclear. The current biotechnology of tissue engineering offers the opportunity to study in vitro the effect of the physical stimuli exerted by biomaterial on stem cells and the mechanotransduction pathway involved in the process. Here, we cultured multipotent human mesenchymal/stromal cells (hMSCs) isolated from bone marrow (hBM-MSCs) and adipose tissue (hASCs) on films of poly(butylene 1,4-cyclohexane dicarboxylate) (PBCE) and a PBCE-based copolymer containing 50 mol% of butylene diglycolate co-units (BDG50), to intentionally tune the surface hydrophilicity and the stiffness (PBCE = 560 Mpa; BDG50 = 94 MPa). We demonstrated the activated distinctive mechanotransduction pathways, resulting in the acquisition of an elongated shape in hBM-MSCs on the BDG50 film and in maintaining the canonical morphology on the PBCE film. Notably, hASCs acquired a new, elongated morphology on both the PBCE and BDG50 films. We found that these events were mainly due to the differences in the expression of Cofilin1, Vimentin, Filamin A, and Talin, which established highly sensitive machinery by which, rather than hASCs, hBM-MSCs distinguished PBCE from BDG50 films.