Search Results (20)

Poly(hydroxyalkanoates) (PHAs) have garnered significant attention due to their biodegradable and biocompatible properties, making them promising alternatives to conventional petroleum-based plastics. As microbial-derived polyesters, PHAs offer a sustainable solution to plastic waste accumulation and microplastics because they can be produced from renewable resources, including food-related waste. Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), a copolymer in the PHA family, exhibits improved mechanical flexibility and thermal properties compared to poly(3-hydroxybutyrate), thereby broadening its potential applications. In this work, eight samples of PHBV, including those made from food waste and municipal waste streams, were studied by solid-state NMR. Information obtained includes the copolymer composition, chemical shifts due to crystalline lattices, crystallinity, and polymer chain mobility. The composition matches the results from the fatty acid feed and solution NMR analysis. The samples appear to be about 62–70% crystalline. No significant differences in mobility are observed from NMR relaxation data. These results indicate that PHBV materials generated from different food-related waste sources, despite their compositional differences, possess similar crystallinity and molecular mobility, suggesting their suitability as biobased semi-crystalline plastics. Full article

The depletion of fossil fuels and environmental concerns have driven the development of sustainable materials, including bio-based and biodegradable plastics, as alternatives to conventional plastics. Although these plastics aid in waste management and climate change mitigation, their vulnerability to oxidative degradation impacts their longevity, durability, and performance. Natural antioxidants such as tocopherols, flavonoids, and tannins, extracted from plants or agri-food waste, present a sustainable alternative to synthetic stabilizers by enhancing the oxidative thermal stability of polymers like poly(lactic acid) (PLA), poly(butylene succinate) (PBS), poly(butylene succinate-adipate) (PBSA), poly(butylene adipate-co-terephthalate) (PBAT), poly(hydroxyalkanoate) (PHA), and starch-based materials. This review highlights recent advances in bio-based plastics stabilized with natural antioxidants, their mechanisms of action, and their role in improving material properties for applications like packaging. Additionally, it explores their impact on recycling processes, advancements in composite production techniques, and future research directions. Bioplastics can achieve enhanced performance, reduce waste, and support a circular economy by incorporating natural antioxidants. Full article

In line with environmental awareness movements and social concerns, the textile industry is prioritizing sustainability in its strategic planning, product decisions, and brand initiatives. The use of non-biodegradable materials, obtained from non-renewable sources, contributes heavily to environmental pollution throughout the textile production chain. As sustainable alternatives, considerable efforts are being made to incorporate biodegradable biopolymers derived from residual biomass, with reasonable production costs, to replace or reduce the use of synthetic petrochemical-based polymers. However, the commercial deployment of these biopolymers is dependent on high biomass availability and a cost-effective supply. Residual forest biomass, with lignocellulosic composition and seasonably available at low cost, constitutes an attractive renewable resource that might be used as raw material. Thus, this review aims at carrying out a comprehensive analysis of the existing literature on the use of residual forest biomass as a source of new biomaterials for the textile industry, identifying current gaps or problems. Three specific biopolymers are considered: lignin that is recovered from forest biomass, and the bacterial biopolymers poly(hydroxyalkanoates) (PHAs) and bacterial cellulose (BC), which can be produced from sugar-rich hydrolysates derived from the polysaccharide fractions of forest biomass. Lignin, PHA, and BC can find use in textile applications, for example, to develop fibers or technical textiles, thus replacing the currently used synthetic materials. This approach will considerably contribute to improving the sustainability of the textile industry by reducing the amount of non-biodegradable materials upon disposal of textiles, reducing their environmental impact. Moreover, the integration of residual forest biomass as renewable raw material to produce advanced biomaterials for the textile industry is consistent with the principles of the circular economy and the bioeconomy and offers potential for the development of innovative materials for this industry. Full article

Polymeric materials made from renewable sources that can biodegrade in the environment are attracting considerable attention as substitutes for petroleum-based polymers in many fields, including additive manufacturing and, in particular, Fused Deposition Modelling (FDM). Among the others, poly(hydroxyalkanoates) (PHAs) hold significant potential as candidates for FDM since they meet the sustainability and biodegradability standards mentioned above. However, the most utilised PHA, consisting of the poly(hydroxybutyrate) (PHB) homopolymer, has a high degree of crystallinity and low thermal stability near the melting point. As a result, its application in FDM has not yet attained mainstream adoption. Introducing a monomer with higher excluded volume, such as hydroxyvalerate, in the PHB primary structure, as in poly(hydroxybutyrate-co-valerate) (PHBV) copolymers, reduces the degree of crystallinity and the melting temperature, hence improving the PHA printability. Blending amorphous poly(lactic acid) (PLA) with PHBV enhances further PHA printability via FDM. In this work, we investigated the printability of two blends characterised by different PLA and PHBV weight ratios (25:75 and 50:50), revealing the close connection between blend microstructures, melt rheology and 3D printability. For instance, the relaxation time associated with die swelling upon extrusion determines the diameter of the extruded filament, while the viscoelastic properties the range of extrusion speed available. Through thoroughly screening printing parameters such as deposition speed, nozzle diameter, flow percentage and deposition platform temperature, we determined the optimal printing conditions for the two PLA/PHBV blends. It turned out that the blend with a 50:50 weight ratio could be printed faster and with higher accuracy. Such a conclusion was validated by replicating with remarkable fidelity high-complexity objects, such as a patient’s cancer-affected iliac crest model. Full article

Biopolymers obtained from renewable resources are an interesting alternative to conventional polymers obtained from fossil resources, as they are sustainable and environmentally friendly. Poly(lactic acid) (PLA) is a biodegradable aliphatic polyester produced from 100% renewable plant resources and plays a key role in the biopolymer market, and is experiencing ever-increasing use worldwide. Unfortunately, this biopolymer has some usage limitations when compared with traditional polymers; therefore, blending it with other biopolymers, such as poly(butylene succinate) (PBS), poly(butylene succinate-co-butylene adipate) (PBSA), poly(butylene adipate-co-butylene terephthalate) (PBAT) and different poly(hydroxyalkanoates) (PHA), is considered an interesting method to improve it significantly, customize its properties and extend the range of its applications. The following review highlights, in its first part, the physico-chemical and mechanical properties of PLA in comparison to the other biopolymers listed above, highlighting the various drawbacks of PLA. The second part of the review deals with recent developments, results, and perspectives in the field of PLA-based blends. Full article

Biocompatible gels based on poly(3-hydroxyalkanoate)s (PHAs) were developed by radical polymerization in the presence of poly(ethylene glycol) diacrylate (PEGDA). In order to elaborate cross-linked networks based on PEGDA and PHAs, several PHAs were tested; saturated PHAs, such as poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) or poly(3-hydroxyoctanoate) (PHO), and an unsaturated PHA, poly(3-hydroxyoctanoate-co-3-hydroxyundecenoate) PHOU. The PHA_xPEGDA_1−x networks obtained in this work were studied by FTIR, Raman spectroscopy, DSC, TGA and NMR. The microscopic structure varied according to the mass proportions between the two polymers. Time Domain ¹H DQ NMR measurements demonstrated that in the case of the unsaturated PHA, it was chemically crosslinked with PEGDA, due to the presence of double bonds in the lateral groups. The organogels were able to swell in organic solvents, such as THF, up to 2000% and in water up to 86%. It was observed by rheological analysis that the stiffness of the networks was dependent on the content of PHA and on the degree of cross-linking. The biocompatible characters of PHOU and PEGDA were not affected by the formation of the networks and these networks had the advantage of being non-cytotoxic to immortalized C2C12 myoblast cells. Full article

Nanoparticles have recently emerged as valuable tools in biomedical imaging techniques. Here PEGylated and fluorinated nanocapsules based on poly(3-hydroxyalkanoate) containing a liquid core of perfluorooctyl bromide PFOB were formulated by an emulsion-evaporation process as potential ¹⁹F MRI imaging agents. Unsaturated poly(hydroxyalkanoate), PHAU, was produced by marine bacteria using coprah oil and undecenoic acid as substrates. PHA-g-(F; PEG) was prepared by two successive controlled thiol-ene reactions from PHAU with firstly three fluorinated thiols having from 3 up to 17 fluorine atoms and secondly with PEG-SH. The resulting PHA-g-(F; PEG)-based PFOB nanocapsules, with a diameter close to 250–300 nm, are shown to be visible in ¹⁹F MRI with an acquisition time of 15 min. The results showed that PFOB-nanocapsules based on PHA-g-(F; PEG) have the potential to be used as novel contrast agents for ¹⁹F MRI. Full article

Poly(hydroxyalkanoates) (PHAs) with different material properties, namely, the homopolymer poly(3-hydroxybutyrate), P(3HB), and the copolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate, P(3HB-co-3HV), with a 3HV of 25 wt.%, were used for the preparation of porous biopolymeric scaffolds. Solvent casting with particulate leaching (SCPL) and emulsion templating were evaluated to process these biopolymers in porous scaffolds. SCPL scaffolds were highly hydrophilic (>170% swelling in water) but fragile, probably due to the increase of the polymer’s polydispersity index and its high porosity (>50%). In contrast, the emulsion templating technique resulted in scaffolds with a good compromise between porosity (27–49% porosity) and hydrophilicity (>30% water swelling) and without impairing their mechanical properties (3.18–3.35 MPa tensile strength and 0.07–0.11 MPa Young’s Modulus). These specifications are in the same range compared to other polymer-based scaffolds developed for tissue engineering. P(3HB-co-3HV) displayed the best overall properties, namely, lower crystallinity (11.3%) and higher flexibility (14.8% elongation at break. Our findings highlight the potency of our natural biopolyesters for the future development of novel porous scaffolds in tissue engineering, thanks also to their safety and biodegradability. Full article

Arctic bacteria employ various mechanisms to survive harsh conditions, one of which is to accumulate carbon and energy inside the cell in the form of polyhydroxyalkanoate (PHA). Whole-genome sequencing of a new Arctic soil bacterium Pseudomonas sp. B14-6 revealed two PHA-production-related gene clusters containing four PHA synthase genes (phaC). Pseudomonas sp. B14-6 produced poly(6% 3-hydroxybutyrate-co-94% 3-hydroxyalkanoate) from various carbon sources, containing short-chain-length PHA (scl-PHA) and medium-chain-length PHA (mcl-PHA) composed of various monomers analyzed by GC-MS, such as 3-hydroxybutyrate, 3-hydroxyhexanoate, 3-hydroxyoctanoate, 3-hydroxydecanoate, 3-hydroxydodecenoic acid, 3-hydroxydodecanoic acid, and 3-hydroxytetradecanoic acid. By optimizing the PHA production media, we achieved 34.6% PHA content using 5% fructose, and 23.7% PHA content using 5% fructose syrup. Differential scanning calorimetry of the scl-co-mcl PHA determined a glass transition temperature (T_g) of 15.3 °C, melting temperature of 112.8 °C, crystallization temperature of 86.8 °C, and 3.82% crystallinity. In addition, gel permeation chromatography revealed a number average molecular weight of 3.6 × 10⁴, weight average molecular weight of 9.1 × 10⁴, and polydispersity index value of 2.5. Overall, the novel Pseudomonas sp. B14-6 produced a polymer with high medium-chain-length content, low T_g, and low crystallinity, indicating its potential use in medical applications. Full article

Poly(hydroxyalkanoates) (PHAs) with differing material properties, namely, the homopolymer poly(3-hydroxybutyrate), P(3HB), the copolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate), P(3HB-co-3HV), with a 3HV content of 25 wt.% and a medium chain length PHA, and mcl-PHA, mainly composed of 3-hydroxydecanoate, were studied as scaffolding material for cell culture. P(3HB) and P(3HB-co-3HV) were individually spun into fibers, as well as blends of the mcl-PHA with each of the scl-PHAs. An overall biopolymer concentration of 4 wt.% was used to prepare the electrospinning solutions, using chloroform as the solvent. A stable electrospinning process and good quality fibers were obtained for a solution flow rate of 0.5 mL h⁻¹, a needle tip collector distance of 20 cm and a voltage of 12 kV for P(3HB) and P(3HB-co-3HV) solutions, while for the mcl-PHA the distance was increased to 25 cm and the voltage to 15 kV. The scaffolds’ hydrophilicity was significantly increased under exposure to oxygen plasma as a surface treatment. Complete wetting was obtained for the oxygen plasma treated scaffolds and the water uptake degree increased in all treated scaffolds. The biopolymers crystallinity was not affected by the electrospinning process, while their treatment with oxygen plasma decreased their crystalline fraction. Human dermal fibroblasts were able to adhere and proliferate within the electrospun PHA-based scaffolds. The P(3HB-co-3HV): mcl-PHA oxygen plasma treated scaffold highlighted the most promising results with a cell adhesion rate of 40 ± 8%, compared to 14 ± 4% for the commercial oxygen plasma treated polystyrene scaffold Alvetex^TM. Scaffolds based on P(3HB-co-3HV): mcl-PHA blends produced by electrospinning and submitted to oxygen plasma exposure are therefore promising biomaterials for the development of scaffolds for tissue engineering. Full article

A novel generation of gels based on medium chain length poly(3-hydroxyalkanoate)s, mcl-PHAs, were developed by using ionic interactions. First, water soluble mcl-PHAs containing sulfonate groups were obtained by thiol-ene reaction in the presence of sodium-3-mercapto-1-ethanesulfonate. Anionic PHAs were physically crosslinked by divalent inorganic cations Ca²⁺, Ba²⁺, Mg²⁺ or by ammonium derivatives of gallic acid GA-N(CH₃)₃⁺ or tannic acid TA-N(CH₃)₃⁺. The ammonium derivatives were designed through the chemical modification of gallic acid GA or tannic acid TA with glycidyl trimethyl ammonium chloride (GTMA). The results clearly demonstrated that the formation of the networks depends on the nature of the cations. A low viscoelastic network having an elastic around 40 Pa is formed in the presence of Ca²⁺. Although the gel formation is not possible in the presence of GA-N(CH₃)₃⁺, the mechanical properties increased in the presence of TA-N(CH₃)₃⁺ with an elastic modulus G’ around 4200 Pa. The PHOSO₃⁻/TA-N(CH₃)₃⁺ gels having antioxidant activity, due to the presence of tannic acid, remained stable for at least 5 months. Thus, the stability of these novel networks based on PHA encourage their use in the development of active biomaterials. Full article

In the last decade, the dairy industry underwent a rapid expansion due to the increasing demand of milk-based products, resulting in high quantity of wastewater, i.e., whey and ricotta cheese exhausted whey (RCEW). Although containing high content of nutritional compounds, dairy by-products are still disposed as waste rather being reintroduced in a new production chain, hence leading to environmental and economic issues. This study proposes a new biotechnological approach based on the combination of membrane filtration and fermentation to produce poly-hydroxyalkanoates (PHA), biodegradable bioplastics candidate as an alternative to petroleum-derived plastics. The protocol, exploiting the metabolic capability Haloferax mediterranei to synthesize PHA from RCEW carbon sources, was set up under laboratory and pilot scale conditions. A multi-step fractionation was used to recover a RCEW fraction containing 12.6% (w/v) of lactose, then subjected to an enzymatic treatment aimed at releasing glucose and galactose. Fermentation conditions (culture medium for the microorganism propagation, inoculum size, time, and temperature of incubation) were selected according to the maximization of polymer synthesis, under in-flasks experiments. The PHA production was then tested using a bioreactor system, under stable and monitored pH, temperature, and stirring conditions. The amount of the polymer recovered corresponded to 1.18 g/L. The differential scanning calorimetry (DSC) analysis revealed the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) as the polymer synthesized, with a relatively high presence of hydroxyvalerate (HV). Identity and purity of the polymer were confirmed by attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and X-ray photoelectron (XPS) spectroscopy analyses. By combining the fractionation of RCEW, one of the most abundant by-products from the agri-food industry, and the use of the halophile Hfx mediterranei, the production of PHBV with high purity and low crystallinity has successfully been optimized. The process, tested up to pilot scale conditions, may be further implemented (e.g., through fed-batch systems) and used for large-scale production of bioplastics, reducing the economical and environmental issues related the RCEW disposal. Full article

Welding technology may be considered as a promising processing method for the formation of packaging products from biopolymers. However, the welding processes used can change the properties of the polymer materials, especially in the region of the weld. In this contribution, the impact of the welding process on the structure and properties of biopolymer welds and their ability to undergo hydrolytic degradation will be discussed. Samples for the study were made from polylactide (PLA) and poly(3-hydroxyalkanoate) (PHA) biopolymers which were welded using two methods: ultrasonic and heated tool welding. Differential scanning calorimetry (DSC) analysis showed slight changes in the thermal properties of the samples resulting from the processing and welding method used. The results of hydrolytic degradation indicated that welds of selected biopolymers started to degrade faster than unwelded parts of the samples. The structure of degradation products at the molecular level was confirmed using mass spectrometry. It was found that hydrolysis of the PLA and PHA welds occurs via the random ester bond cleavage and leads to the formation of PLA and PHA oligomers terminated by hydroxyl and carboxyl end groups, similarly to as previously observed for unwelded PLA and PHA-based materials. Full article

In the cosmetic sector, natural and sustainable products with a high compatibility with skin, thus conjugating wellness with a green-oriented consumerism, are required by the market. Poly(hydroxyalkanoate) (PHA)/starch blends represent a promising alternative to prepare flexible films as support for innovative beauty masks, wearable after wetting and releasing starch and other selected molecules. Nevertheless, preparing these films by extrusion is difficult due to the high viscosity of the polymer melt at the temperature suitable for processing starch. The preparation of blends including poly(butylene succinate-co-adipate) (PBSA) or poly(butylene adipate-co-terephthalate) (PBAT) was investigated as a strategy to better modulate melt viscosity in view of a possible industrial production of beauty mask films. The release properties of films in water, connected to their morphology, was also investigated by extraction trials, infrared spectroscopy and stereo and electron microscopy. Then, the biocompatibility with cells was assessed by considering both mesenchymal stromal cells and keratinocytes. All the results were discussed considering the morphology of the films. This study evidenced the possibility of modulating thanks to the selection of composition and the materials processing of the properties necessary for producing films with tailored properties and processability for beauty masks. Full article

Biocompatible and biodegradable bacterial polyesters, poly(hydroxyalkanoates) (PHAs), were combined with linalool, a well-known monoterpene, extracted from spice plants to design novel antibacterial materials. Their chemical association by a photo-induced thiol-ene reaction provided materials having both high mechanical resistance and flexibility. The influence of the nature of the crosslinking agent and the weight ratio of linalool on the thermo-mechanical performances were carefully evaluated. The elongation at break increases from 7% for the native PHA to 40% for PHA–linalool co-networks using a tetrafunctional cross-linking agent. The materials highlighted tremendous anti-adherence properties against Escherichia coli and Staphylococcus aureus by increasing linalool ratios. A significant decrease in antibacterial adhesion of 63% and 82% was observed for E. coli and S. aureus, respectively. Full article