Search Results (19)

Poly(ethylene furanoate) (PEF) has been identified as a bio-based alternative or supplement to poly(ethylene terephthalate) (PET) for various applications such as food packaging and bottles as well as technical- and high-performance fibers and yarns. In this study, the processing of PEF nonwovens in the meltblow process is successfully demonstrated and reported for the first time, according to our best knowledge The resulting fabrics achieved median fiber diameters of 2.04 µm, comparable to PET. The filtration efficiency of 25 g m⁻² fabrics exceeded 50% comparable to PET and PBT of the same grammage and was raised to over 90% with post-process electrostatic charging, maintaining stability. As for other aromatic polymers, applying infrared heating modules into the process indicated the potential to minimize heat shrinkage. However, the suppressed ring rotation and slower crystallization kinetics of PEF showed the need for longer post-treatment times as the heat shrinkage remained between 20% and 40% at 10 °C. Overcoming this, PEF can be a viable, bio-based alternative to PET, particularly for such high-temperature nonwoven applications that require thin layers. Full article

PEA 46 is a biobased polymer with promising properties for sustainable packaging applications, which can be obtained via polymerization of a furan 2,5-dicarboxylic acid (2,5-FDCA) derivative and a diol monomer containing internal amide bonds (46 amido diol). In the literature, PEA 46 showed a complex series of thermal transitions during DSC scans. For this reason, in this initial exploratory study PEA 46 was subjected to compression molding and the melting behavior of film samples was investigated with parallel DSC and WAXS analyses. At room temperature, a mesomorph phase was the only one observed. Subjecting the samples to heating scans led to the formation of phase α, caused by a sequence of partially overlapping melting and recrystallization phenomena. An additional melting and recrystallization phenomenon resulted in the development of a phase β, which melted at approximately 173 °C, the temperature after which the material was completely amorphous and isotropic. Phase α could be enhanced via thermal annealing, whereas phase β could be enhanced via a melt crystallization treatment. Full article

In recent years, bio-based poly(ethylene furanoate) has gained the attention of packaging industries owing to its remarkable properties as a promising alternative to fossil-based polymers. It is necessary to synthesize high-molecular-weight polymers using effective and straightforward techniques for their commercialization. In this present work, poly(ethylene 2,5-furan dicarboxylate) (PEF) was produced with a high molecular weight of 0.43 dL/g using 2,5-furan dicarboxylic acid (FDCA) or its derivative Dimethyl-2,5-Furan dicarboxylate (DMFD), followed by solid-state polymerization (SSP) conducted at different temperatures and reaction times. The intrinsic viscosity ([η]), carboxyl end-group concentration (–COOH), and thermal properties of the produced polyesters were evaluated using differential scanning calorimetry (DSC). The results indicated that the SSP process improved the melting temperature and crystallinity of both the PEF samples as the reaction times and temperatures increased, as corroborated by DSC and X-ray diffraction (XRD) analyses. Additionally, both intrinsic viscosity and number-average molecular weight saw an increase with longer SSP durations and higher temperatures, while the concentration of carboxyl end groups decreased, aligning with expectations. The overall results indicate that PEF (DMFD) samples exhibited a significant increase in crystallization and molecular weight, attributed to their lower degree of crystallinity and their monomer’s high purity. Full article

Garcinia gummi-gutta, commonly known as Garcinia cambogia (syn.), is a popular traditional herbal medicine known for its role in treating obesity, and has been incorporated into several nutraceuticals globally for this purpose. The fruit rind is also used as a food preservative and a condiment because of its high content of hydroxycitric acid, which imparts a sharp, sour flavour. This review highlights the major bioactive compounds present in the tree Garcinia gummi-gutta, with particular emphasis on (2S, 3S)-tetrahydro-3-hydroxy-5-oxo-2,3-furan dicarboxylic acid, commonly referred to as garcinia acid. This acid can be isolated in large amounts through a simple procedure. Additionally, it explores the synthetic transformations of garcinia acid into biologically potent and functionally useful enantiopure compounds, a relatively under-documented area in the literature. This acid, with its six-carbon skeleton, a γ-butyrolactone moiety, and two chiral centres bearing chemically amenable functional groups, offers a versatile framework as a chiron for the construction of diverse molecules of both natural and synthetic origin. The synthesis of chiral 3-substituted and 3,4-disubstituted pyrrolidine-2,5-diones, analogues of the Quararibea metabolite—a chiral enolic-γ-lactone; the concave bislactone skeletons of fungal metabolites (+)-avenaciolide and (−)-canadensolide; the structural skeletons of the furo[2,3-b]furanol part of the anti-HIV drug Darunavir; (−)-tetrahydropyrrolo[2,1-a]isoquinolinones, an analogue of (−)-crispine A; (−)-hexahydroindolizino[8,7-b]indolones, an analogue of the naturally occurring (−)-harmicine; and furo[2,3-b]pyrroles are presented here. Full article

Furanoate polyesters are an extremely promising new class of materials for packaging applications, particularly furanoate-based nanocomposites, which have gained a high interest level in research and development in both academia and industries. The monomers utilised for the synthesis of furanoate-based polyesters were derived from lignocellulosic biomass, which is essential for both eco-friendliness and sustainability. Also, these polyesters have a lower carbon footprint compared to fossil-based plastics, contributing to greenhouse gas reduction. The furanoate-based nanocomposites exhibit enhanced performance characteristics, such as high thermal stability, excellent mechanical strength, superior barrier resistance, and good bacteriostatic rate, making them suitable for a wide range of industrial applications, especially for food-packaging applications. This paper reviews the recent trends in the synthesis routes of monomers, such as the various catalytic activities involved in the oxidation of 5(hydroxymethyl)furfural (HMF) into 2,5-furandicarboxylic acid (FDCA) and its ester, dimethyl furan-2,5-dicarboxylate (DMFD). In addition, this review explores the fabrication of different furanoate-based nanocomposites prepared by in situ polymerization, by melt mixing or solvent evaporation methods, and by using different types of nanoparticles to enhance the overall material properties of the resulting nanocomposites. Emphasis was given to presenting the effect of these nanoparticles on the furanoate polyester’s properties. Full article

One-step oxidative esterification of 2,5-furandiformaldehyde (DFF) derived from biomass to prepare Dimethyl Furan-2,5-dicarboxylate (FDMC) not only simplifies the catalytic process and increases the purity of the product, but also avoids the polymerization of 5-hydroxymethylfurfural (HMF) at high-temperature conditions. Gold supported on a series of acidic oxide, alkaline oxide, and hydrotalcite was prepared using colloidal deposition to explore the effect of support on the catalytic activities. The Au/Mg₃Al-HT exhibited the best catalytic activity, with 97.8% selectivity of FDMC at 99.9% conversion of DFF. This catalyst is also suitable for oxidative esterification of benzaldehyde and furfural. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and CO₂ temperature programmed desorption (CO₂-TPD) were performed to characterize the catalysts. The results indicated that the medium and strong basic sites in the catalysts benefited for the absorption of intermediate agents and facilitated the oxidative esterification of aldehyde groups, while neutral or acidic supports tended to produce an acetal reaction. It is worth noting that basicity on the support surface reduced the electronic state of the Au nanoparticle (Au^δ−) and, thus, enhanced the catalytic selectivity of oxidative esterification. This finding demonstrated that the support plays a crucial role in oxidative esterification. Full article

This work aimed to produce bio-based poly(ethylene furanoate) (PEF) with a high molecular weight using 2,5-furan dicarboxylic acid (FDCA) or its derivative dimethyl 2,5-furan dicarboxylate (DMFD), targeting food packaging applications. The effect of monomer type, molar ratios, catalyst, polycondensation time, and temperature on synthesized samples’ intrinsic viscosities and color intensity was evaluated. It was found that FDCA is more effective than DMFD in producing PEF with higher molecular weight. A sum of complementary techniques was employed to study the structure–properties relationships of the prepared PEF samples, both in amorphous and semicrystalline states. The amorphous samples exhibited an increase in glass transition temperature of 82–87 °C, and annealed samples displayed a decrease in crystallinity with increasing intrinsic viscosity, as analyzed by differential scanning calorimetry and X-ray diffraction. Dielectric spectroscopy showed moderate local and segmental dynamics and high ionic conductivity for the 2,5-FDCA-based samples. The spherulite size and nuclei density of samples improved with increased melt crystallization and viscosity, respectively. The hydrophilicity and oxygen permeability of the samples were reduced with increased rigidity and molecular weight. The nanoindentation test showed that the hardness and elastic modulus of amorphous and annealed samples is higher at low viscosities due to high intermolecular interactions and degree of crystallinity. Full article

Poly(lactic acid) (PLA) is a readily available, compostable biobased polyester with high strength and toughness, and it is excellent for 3D printing applications. Polymer blending is an economic and easy way to improve its properties, such as its slow degradation and crystallization rates and its small elongation, and thus, make it more versatile. In this work, the effects of different 2,5-furan dicarboxylic acid (FDCA)-based polyesters on the physicochemical and mechanical properties of PLA were studied. Poly(butylene furan 2,5-dicarboxylate) (PBF) and its copolymers with poly(butylene adipate) (PBAd) were synthesized in various comonomer ratios and were blended with 70 wt% PLA using melt compounding. The thermal, morphological and mechanical properties of the blends are investigated. All blends were immiscible, and the presence of the dispersed phases improved the crystallization ability of PLA. Mechanical testing revealed the plasticization of PLA after blending, and a small but measurable mass loss after burying in soil for 7 months. Reactive blending was evaluated as a compatibilizer-free method to improve miscibility, and it was found that when the thermal stability of the blend components allowed it, some transesterification reactions occurred between the PLA matrix and the FDCA-based dispersed phase after 20 min at 250 °C. Full article

What is known as Furan-2,5-dicarboxylic acid (FDCA) is an attractive compound since it has similar properties to terephthalic acid. Further, 5-hydroxymethylfurfural oxidase (HMFO) is an enzyme, which could convert HMF to FDCA directly. Most wild types of HMFO have low activity on the oxidation of HMF to FDCA. The variant of 8BxHFMO from Methylovorus sp. MP688 was the only reported enzyme that was able to perform FDCA production. However, the stabilization of 8BxHMFO is still not that satisfactory, and further improvement is necessary for the industrial application of the enzyme. In this work, stability-enhanced HMFO from 8BxHFMO was engineered through employing B-factor analysis. The mutation libraries were created based on the NNK degeneracy of residues with the top ten highest B-factor value, and two of the effective mutants were screened out through the high throughput selection with the horseradish peroxidase (HRP)-Tyr assay. The mutants Q319K and N44G show a significantly increased yield of FDCA in the reaction temperature range of 30 to 40 °C. The mutant Q319K shows the best performance at 35 °C with a FDCA yield of 98% (the original 8BxHMFO was only 85%), and a half-life exceeding 72 h. Moreover, molecular dynamic simulation indicates that more hydrogen bonds are formed in the mutants, which improves the stability of the protein structure. The method could enhance the design of more stable biocatalysts; and provides potential for the further optimization and utilization of HMFO in biotechnological processes. Full article

The electrochemical production of 2,5-furandicarboxylic acid (FDCA) from 5-(hydroxymethyl)furfural (HMF) is receiving growing attention. The FDCA-based polyethylene 2,5-furan dicarboxylate (PEF) polymer is a green candidate for substituting polyethylene terephthalate. This work demonstrated a highly efficient CoB/g-C₃N₄ nanosheet on the surface of the nickel foam as an electrode for the HMF electrooxidation reaction. Electrolysis at a constant potential combined with liquid chromatography showed the formation of FDCA with a yield of 97% with an excellent faradaic efficiency of near 95%. CoB/g-C₃N₄ achieved a current density of 20 mA cm⁻² for HMF oxidation in 1.0 M KOH with 10 mM HMF at 1.37 V vs. RHE before the competing oxygen evolution reaction. The electrocatalyst was effectively reused up to three times without compromising efficiency. This work demonstrates a cheap and active electrocatalyst material for the electrochemical formation of FDCA from HMF and gives perception into the reaction mechanism. Full article

We report on the pilot scale synthesis and melt spinning of poly(ethylene furanoate) (PEF), a promising bio-based fiber polymer that can heave mechanical properties in the range of commercial poly(ethylene terephthalate) (PET) fibers. Catalyst optimization and solid state polycondensation (SSP) allowed for intrinsic viscosities of PEF of up to 0.85 dL·g⁻¹. Melt-spun multifilament yarns reached a tensile strength of up to 65 cN·tex⁻¹ with an elongation of 6% and a modulus of 1370 cN·tex⁻¹. The crystallization behavior of PEF was investigated by differential scanning calorimetry (DSC) and XRD after each process step, i.e., after polymerization, SSP, melt spinning, drawing, and recycling. After SSP, the previously amorphous polymer showed a crystallinity of 47%, which was in accordance with literature. The corresponding XRD diffractograms showed signals attributable to α-PEF. Additional, clearly assignable signals at 2θ > 30° are discussed. A completely amorphous structure was observed by XRD for as-spun yarns, while a crystalline phase was detected on drawn yarns; however, it was less pronounced than for the granules and independent of the winding speed. Full article

In the era of polymers from renewable resources, polyesters derived from 2,5 furan dicarboxylic acid (FDCA) have received increasing attention due to their outstanding features. To commercialize them, it is necessary to synthesize high molecular weight polymers through efficient and simple methods. In this study, two furan-based polyesters, namely poly (propylene furanoate) (PPF) and poly(butylene furanoate) (PBF), were synthesized with the conventional two-step melt polycondensation, followed by solid-state polycondensation (SSP) conducted at different temperatures and reaction times. Molecular weight, structure and thermal properties were measured for all resultant polyesters. As expected, increasing SSP time and temperature results in polymers with increased intrinsic viscosity (IV), increased molecular weight and reduced carboxyl end-group content. Finally, those results were used to generate a simple mathematical model that prognosticates the time evolution of the materials’ IV and end groups concentration during SSP. Full article

Polyesters based on 2,5-furandicarboxylic acid (FDCA) are a new class of biobased polymers with enormous interest, both from a scientific and industrial perspective. The commercialization of these polymers is imminent as the pressure for a sustainable economy grows, and extensive worldwide research currently takes place on developing cost-competitive, renewable plastics. The most prevalent method for imparting these polymers with new properties is copolymerization, as many studies have been published over the last few years. This present review aims to summarize the trends in the synthesis of FDCA-based copolymers and to investigate the effectiveness of this approach in transforming them to a more versatile class of materials that could potentially be appropriate for a number of high-end and conventional applications. Full article

Deep eutectic solvents (DESs) have been applied as cosolvents in various biocatalytic processes during recent years. However, their use in combination with redox enzymes has been limited. In this study, we have explored the beneficial effects of several DES as cosolvents on the performance of 5-hydroxymethylfurfural oxidase (HMFO), a valuable oxidative enzyme for the preparation of furan-2,5-dicarboxylic acid (FDCA), and other compounds, such as carbonyl compounds and carboxylic acids. The use of natural DESs, based on glucose and fructose, was found to have a positive effect. Higher conversions are obtained for the synthesis of several oxidized compounds, including FDCA. Depending on the type of DES, the stability of HMFO could be significantly improved. As the use of DES increases the solubility of many substrates while they only mildly affect dioxygen solubility, this study demonstrates that biocatalysis based on HMFO and other redox biocatalysts can benefit from a carefully selected DES. Full article

Various ferulic acid (FA) dimers occurring in plant cell walls, such as 8-5-, 8-O-4-, 5-5-, and 8-8-coupled dimers, are effective antioxidants and potential antimicrobials. It is necessary to access these diferulates as reference compounds to validate those isolated from plants. 3,6-bis(4-hydroxy-3-methoxyphenyl)-tetrahydrofuro-[3,4-c]furan-1,4-dione, a 8-8-coupled FA dilactone generated from ferulic acid via radical coupling, has been used to synthesize 8-8-coupled FA dimers although few reports investigated the distribution of products and mechanisms involved in the transformation of FA dilactone. In this work, the FA dilactone, obtained from FA by a peroxidase-catalyzed radical coupling, was reacted under various base/acid conditions. Effects of reaction conditions and workup procedures on the distribution of products were investigated by GC-MS. The isolated products from such treatments of FA dilactone were characterized by NMR. New derivatives of FA dimer including 2-(4-hydroxy-3-methoxybenzylidene)-3-(hydroxyl-(4-hydroxy-3-methoxyphenyl)methyl)succinic acid and 2-(bis(4-hydroxy-3-methoxyphenyl)-methyl)-succinic acid were produced from NaOH treatment. Another novel 8-8-coupled cyclic FA dimer, diethyl 6-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-methoxy-1,2-dihydronaphthalene-2,3-dicarboxylate was identified in products from FA dilactone treated by dry HCl in absolute ethanol. Mechanisms involved in such transformations were proposed. Full article