Search Results (1,418)

This work evaluated the effect of coffee oil epoxide (COE), produced from coffee waste, on thermal, mechanical, barrier, and exudation resistance properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/natural rubber (PHBV/NR) blends. Building upon previously published 0.3% COE results, this study examined 0.4% and 0.75% concentrations to optimize performance. Thermal analysis revealed that COE incorporation significantly enhanced chain mobility, with glass transition temperature depressions of 6.1 °C and 7.4 °C for 0.4% and 0.75% COE formulations, respectively, compared to unplasticized PHBV/NR blends. Crystallinity decreased from 54.5% (PHBV/NR) to 52.6% and 51.9% with increasing plasticizer concentration, while melting temperatures decreased by 3.9% and 4.9%, confirming improved polymer chain mobility. Mechanical properties demonstrated COE’s plasticizing effectiveness, with tensile strength decreasing by 13.3% (0.4% COE) and 16.2% (0.75% COE) compared to PHBV/NR blends. Young’s modulus similarly decreased by 21.0% and 24.0%, while elongation at break improved slightly with increasing COE content. Barrier properties improved substantially across all concentrations: water vapor transmission rates decreased from 4.05 g/m²·h (PHBV/NR) to 1.55 g/m²·h (0.3% COE) and 0.67 g/m²·h for 0.4% and 0.75% COE, attributed to COE’s hydrophobic nature. SEM morphological analysis confirmed improved phase compatibility at 0.40% COE, with reduced rubber droplet size and homogeneous surface morphology. Exudation testing revealed excellent retention (0.21–0.53 wt% loss over 63 days). Results indicate 0.40% COE as optimal, achieving superior barrier properties while maintaining mechanical performance for sustainable packaging applications. Full article

Background and Objectives: The vitamin K epoxide reductase complex subunit 1 (VKORC1) plays a central role in the vitamin K cycle, which is essential for γ-carboxylation of multiple bone-related proteins. Genetic variants in VKORC1 may influence bone mineral density (BMD) and osteoporosis risk. Materials and Methods: A systematic review and meta-analysis were conducted to evaluate the association between VKORC1 polymorphisms and osteopenia and osteoporosis. Relevant studies were identified through PubMed, Scopus, and Web of Science databases. Data on study characteristics, genotypes, BMD measurement, ethnicity, sex, and menopausal status were extracted. Results: Six studies comprising 7335 participants were included. All studies assessed BMD using dual-energy X-ray absorptiometry (DXA). The mean participant age ranged from 41.9 to 63.7 years. The VKORC1 variants most frequently studied, which were included in the meta-analysis, were rs9923231 and rs9934438. The overall effect of VKORC1 risk alleles on osteopenia/osteoporosis was significant with a p = 0.041 (fixed effects OR = 1.16, 95% CI = 1.01–1.35). Heterogeneity among studies was insignificant (I² = 0%, p = 0.893). Conclusions: A modest association was observed for the VKORC1 variants. The current body of evidence requires further studies to elucidate whether VKORC1 polymorphisms have a clinically meaningful role in bone health. Full article

Hexahydrocannabinol (HHC), a hydrogenated derivative of Δ⁹-tetrahydrocannabinol (Δ⁹-THC), is a semi-synthetic cannabinoid marketed as an alternative to Δ⁹-THC. Its hydroxylated metabolite, 8-hydroxyhexahydrocannabinol (8-OH-HHC), exists as four stereoisomers: (6aR,8R,9R,10aR), (6aR,8S,9S,10aR), (6aR,8S,9R,10aR), and (6aR,8R,9S,10aR). However, the lack of reference standards has hindered pharmacokinetic and forensic studies. This work reports the first stereoselective synthesis and structural confirmation of all four 8-OH-HHC stereoisomers. Two strategies were employed: hydroboration–oxidation and epoxidation–reduction. Hydroboration of Δ⁸-THC with BH₃·THF followed by oxidation predominantly produced anti-isomers (6aR,8R,9R,10aR) and (6aR,8S,9S,10aR) in moderate yields, along with small amounts of syn-isomer (6aR,8S,9R,10aR), suggesting an atypical mechanistic pathway. In contrast, syn-isomers (6aR,8S,9R,10aR) and (6aR,8R,9S,10aR) were accessed via epoxidation of Δ⁸-THC acetate using mCPBA and subsequent reduction with NaBH₃CN/BF₃·OEt₂, affording the desired products with moderate selectivity. Absolute configurations were confirmed by nuclear Overhauser effect spectroscopy (NOESY). These methods will facilitate future pharmacokinetic and forensic research and support the development of improved detection strategies. Full article

The development of a metalloenzyme-like catalytic system for the efficient oxidation of olefins under a dioxygen (O₂) atmosphere at room temperature is of significant interest in the field of catalysis. Herein, we present a highly active and selective aerobic epoxidation of olefins using metalloenzyme-like catalysts based on a non-heme ligand, tris(2-pyridylmethyl)amine (TPA). Notably, manganese chloride complexed with TPA (Mn(TPA)Cl₂) demonstrated excellent activity for the epoxidation of trans-stilbene using O₂ as the oxidant in the presence of a co-reductant at 30 °C. A quantitative conversion of 99% and high yield of 98%, as determined by gas chromatography using an external standard method, were achieved under optimum reaction conditions. Furthermore, Mn(TPA)Cl₂ exhibited a good substrate tolerance to styrene derivatives with electron-withdrawing or electron-donating groups, cyclic olefins with different substituents and substitution degrees, as well as long-chain olefins. Coupled with a high turnover frequency (TOF) of up to 30,720 h⁻¹, these results underscore the potential of Mn(TPA)Cl₂ as a promising metalloenzyme-like catalytic platform for the aerobic synthesis of diverse epoxides from olefins under ambient conditions. Full article

This work presents an approach to water-dispersible polylactide (PLA) particle fabrication and their application in low-temperature film formation using a combination of mechanical dispersion and ultrasonication techniques. Stable PLA dispersions were obtained after removal of surfactant and allowed for thin-film preparation, exhibiting a significantly reduced minimum film formation temperature (MFFT) from 128 °C to 80 °C after reducing the characteristic particle size from ~2.2 µm to ~140 nm. To tailor the interfacial behavior and mechanical flexibility of the resulting coatings, a set of conventional and bio-based plasticizers was evaluated, including epoxidized fatty acids, PEG-400, and several hydrophobic deep eutectic solvents (HDESs) synthesized from menthol and carboxylic acids. Compatibility between PLA and each plasticizer was predicted using Hansen solubility parameters. The efficiency of plasticization was assessed through glass transition temperature suppression in solvent-cast films. The combination of submicron PLA particles and selected plasticizers enabled film formation at temperatures as low as 48 °C, confirming the potential of these systems for energy-efficient coating technologies. Furthermore, composite coatings incorporating micro-sized cellulose fibers (L/D ≈ 10.5–11.5) regenerated from agricultural residues were successfully obtained, demonstrating the feasibility of integrating bio-derived fillers into waterborne PLA formulations. In this study, the use of water-insoluble deep eutectic solvents type plasticizers for PLA coatings from water dispersions was reported for the first time. This establishes a foundation for developing sustainable, low-VOC, and low film formation temperature PLA-based coating materials. Full article

Vicia faba L. is a widely cultivated legume known to contain numerous specialised metabolites. In this study, the seed coats and cotyledons of two ancient V. faba L. varieties, historically consumed in southern Italy and distinguished by black and purple seed coats, were extracted using 80% methanol and 80% ethanol. Extracts were analysed for total polyphenol, flavonoid and proanthocyanidin contents, and antioxidant activity using DPPH, ABTS, and FRAP assays. The purple seed coats exhibited the highest levels of phenolics and antioxidant capacity, exceeding those of black seed coats. Next, liquid chromatography coupled with high-resolution mass spectrometry (LC-ESI-HR-MS) was used to characterise the bioactive metabolites in both seed coats and cotyledons. The purple variety showed a higher phytochemical content, with a greater level of flavonoids and proanthocyanidins in methanolic extract. Furthermore, the purple seed coat exhibited in vitro anti-inflammatory activity by inhibiting soluble epoxide hydrolase (sEH), a key enzyme in the arachidonic acid cascade, with an IC₅₀ of 31.51 ± 1.16 µg/µL. Elemental analysis was performed for both varieties to assess their nutritional value. Specifically, the purple seed coats were found to represent a valuable source of bioactive compounds and micronutrients, highlighting their potential applications in nutraceutical, cosmetic, and food supplement sectors. Full article

Fascinated by the influence of fluorine atom substitution in liquid crystal mesogens and building on our previous research on the influence of fluorination in liquid crystal mesogens, a novel project was undertaken where racemates and enantiomers of alkoxycyanobiphenyls with two adjacent fluorine atoms, one on each of two terminal carbon atoms, were synthesized to study their phase properties. The compounds were synthesized via Mitsunobu reaction, alkylation, epoxidation, hydrolytic kinetic resolution, fluoride opening, and deoxyfluorination. Racemates showed a monotropic nematic phase, while enantiomers showed a monotropic cholesteric phase. The dipole moments of the final difluorinated mesogens were also evaluated. The phase behavior of all the epoxy and fluorohydrin intermediates was also measured. This article provides data on the phase behavior of a handful of racemic compounds and their enantiomers. Additionally, the phase behavior of the enantiomerically impure and enantiomerically pure compounds is compared. Full article

Hydroxyl-terminated polybutadiene (HTPB) is widely used in polyurethane binders, adhesives, and elastomers, but its low polarity and unsaturated backbone limit adhesion and long-term stability. Epoxidation presents a promising approach to addressing these limitations. However, most prior studies have focused on high-cis polybutadiene (PB), and systematic tuning of epoxidation in industrial low-cis HTPB has not been thoroughly examined. In this work, the epoxidation conversion of low-cis HTPB was systematically controlled by varying the equivalent amount of 3-chloroperbenzoic acid (m-CPBA). Conversion was governed solely by oxidant stoichiometry, while reaction time, concentration, and temperature had minimal effect, consistent with rapid, mixing-controlled epoxidation. Selective modification of 1,4-cis and 1,4-trans units enabled direct evaluation of how epoxidation degree influences polyurethane network formation and performance. Polyurethanes derived from epoxidized HTPB (EHTPB-PU) exhibited a clear correlation between epoxidation degree and network formation. Mechanical, adhesion, and chemical-resistance measurements revealed optimal performance at 10% epoxidation, where polarity and network compactness are effectively balanced. At this level, polyurethanes showed enhanced tensile strength, broad substrate adhesion, and increased resistance to acidic, basic, polar, and nonpolar environments, along with reduced water uptake. These results identify moderate epoxidation as a practical and efficient strategy for improving HTPB-based polyurethane materials. Full article

This review surveys literature from 2010 to 2025 on Aspergillus-derived enzymes for kinetic resolution (KR), using conventional databases and AI-assisted platforms. Among over 340 species, A. niger, A. oryzae, and A. terreus are widely recognized as safe and industrially relevant. Lipases from these fungi exhibit high stability, broad substrate specificity, and enantioselectivity, enabling efficient resolution of racemic mixtures. Advances in enzyme immobilization, protein engineering, and reaction medium optimization have enhanced catalytic performance under diverse conditions. Complementary enzymes, including esterases and epoxide hydrolases, further expand biocatalytic applications. Despite increasing demand for enantiopure compounds, challenges in yield, scalability, and enzyme discovery call for integrated molecular and process strategies. Aspergillus spp. emerge as a promising system for high-level enzyme expression, offering robust secretion capacity, efficient post-translational processing, and strong adaptability for industrial biocatalysis. Full article

This paper demonstrates the successful synthesis of novel hybrid heterogeneous catalysts for the sustainable conversion of CO₂ into cyclic organic carbonates (COCs). The nanocat-alysts have been fabricated by encapsulating pre-formed ultra-small gold nanostructures into a nascent zinc-coordination polymer (ZnCP) framework formed from two organic building blocks, 2,4-naphthalenedicarboxylic acid (1,4-NDC) and 5-amino-1H-tetrazole (5-Atz), which serves as a nitrogen-rich ligand. Applying the fabricated catalysts in the synthesis of COCs yields high yields (up to 97%) and high selectivity (up to 100%), with exceptionally high turnover frequencies (TOFs) (up to 408 h⁻¹). The catalytic process can be carried out under mild conditions (80 °C, 1.5 MPa CO₂) and without the use of solvents. Nitrogen-rich ligand molecules in the structure of ZnCPs enhance catalytic performance thanks to additional nucleophilic centres, which are effective in the epoxides’ ring-opening process. The hybrid catalysts with encapsulated gold nanostructures, which modify the liquid–gas interface between epoxide and CO₂, give significantly higher yields and TOFs for less active epoxides. The designed hybrid nanocatalysts exhibit superior stability under the studied reaction conditions and can be reused without loss of activity. The developed coordination polymers are constructed from green components, and green chemistry principles are applied to prepare these catalytic materials. Full article

The metabolism of polyunsaturated fatty acids (PUFAs) is a broad research field, and the products identified so far offer potential medical and industrial applications. Epoxy fatty acids (EpFAs) act as lipid mediators that modulate renal function, angiogenesis, vascular dilatation and inflammation; moreover, they regulate monocyte aggregation and are involved in cardiovascular and metabolic diseases. On the other hand, EpFAs are precursors of environmentally friendly products for the plastics industry, in which the grade of epoxidation of the compounds gives the polymeric material different advantageous characteristics. The controlled chemical synthesis of poly epoxidized PUFAs is challenging as the reactions are non-selective. In contrast, the biosynthetic route based on cytochrome P450 monooxygenases and lipoxygenases is highly selective but ineffective due to the instability of the enzymes in cell-free systems. Fungal unspecific peroxygenases (UPOs, EC 1.11.2.1) with P450-like activity offer a suitable alternative for the selective synthesis of EpFAs from PUFAs. Here we demonstrate that a recombinant unspecific peroxygenase from Aspergillus niger (rAniUPO) is able to sequentially epoxidize eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) to 14,15-17,18 diepoxyeicosatrienoic acid (14,15-17,18 diEpETrE) and 16,17-19,20-diepoxydocosatetraenoic acid (16,17-19,20 diEpDTE), respectively, while arachidonic acid is transformed into 13-hydroxy-14,15-epoxyeicosatrienoic acid (14,15-hepoxilin B₃). Optimal production for these oxygenated derivatives (up to 15 mg) was achieved using 2 mM hydrogen peroxide as the co-substrate. The obtained molecules were identified using high-resolution mass spectrometry and their structure was verified by NMR. Our results demonstrate the suitability of UPOs for the synthesis of EpFAs that can be used in medical research and industrial applications. Full article

Non-isocyanate polyurethanes (NIPUs) represent a sustainable alternative to conventional isocyanate-based systems, eliminating toxic reagents while maintaining good performance. In this study, bio-based NIPU coatings were synthesized from carbonated soybean oil (CSBO) via the carbonation of epoxidized soybean oil (ESBO) using carbon dioxide (CO₂), followed by polymerization with ethylenediamine (EDA) and varying concentrations of 3-aminopropyltriethoxysilane (APTES) (0–20 wt%). The amine groups of EDA and APTES participate in the ring-opening of cyclic carbonates to form β-hydroxyurethane linkages, while the triethoxysilane moieties of APTES may undergo hydrolysis–condensation to produce Si–O–Si domains, resulting in a β-hydroxyurethane–siloxane hybrid network. The optimized formulation CEA-5 exhibited the best, including a tensile strength of 3.3 MPa, elongation at break of ~150%, glass transition temperature (T_g) of ~7 °C, and thermal stability up to ~350 °C, where major thermal degradation happens. The synthesized coating material also shows adhesion (3.6 MPa on oak for CEA-10), hydrophobic behavior (water contact angle (WCA) ~102° for CEA-5), good chemical and ultraviolet (UV) resistance, and shape memory. The synergistic effect of urethane hydrogen bonding and siloxane crosslinking imparted enhanced toughness, flexibility, and durability. These findings express a scalable, eco-friendly strategy for producing silane-modified NIPU coatings with good mechanical, thermal, and coating performance suitable for sustainable industrial coating and adhesive applications. Full article

Bismaleimide–triazine (BT) resins are widely utilized in various applications, with ongoing efforts to enhance their performance. In this work, a partially epoxidized polyhedral oligomeric silsesquioxane (PEOVS) containing vinyl and epoxy groups was successfully synthesized, and BT/PEOVS nanocomposites were prepared by blending PEOVS with BT resin. The results revealed that the unique structure of PEOVS significantly improved its dispersion within the resin matrix and enhanced the overall properties of the BT resin. The curing mechanism and properties of BT/PEOVS nanocomposites, with weight ratios of 99.5/0.5, 99/1, 98.5/1.5, 98/2, and 96/4, were analyzed using Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), and dielectric measurements. The addition of PEOVS markedly improved the dielectric performance, with a 2% PEOVS content achieving a dielectric constant of 2.39 and a dielectric loss of 0.0036 at 1 MHz. Furthermore, the glass transition temperature and storage modulus were significantly enhanced, with a PEOVS content of 1.5% resulting in a glass transition temperature of 279 °C. The results demonstrate that incorporating PEOVS, featuring dual reactive functional groups, effectively enhances the comprehensive properties of BT resins, providing valuable insights into their modification and practical applications. Full article

A 3D printing filament was fabricated from poly(lactic acid) (PLA), cassava pulp (CP), and epoxy using a twin-screw extruder. Several bio-composites were synthesized by varying the amount of epoxy (0.5, 1.0, 3.0, 5.0, and 10.0 wt.%). The size of the CP fibers significantly affected the surface quality, filament diameter, and mechanical properties of the final product. The smallest fiber size (45 µm) provided a smooth surface and consistent diameter. Incorporating 1 wt.% of epoxy into PLA/CP enhanced the tensile strength (56.6 MPa), elongation at break (6.2%), and hydrophobicity of the composite. The composite mechanical properties deteriorated at epoxy contents above 1 wt.% due to the amplified plasticizer effect of excessive epoxy. The optimized PLA/CP/epoxy formulation was used to generate the 3D filament. The resultant filament displayed a tensile strength of 64.6 MPa and elongation at break of 9.8%, attributed to the fine morphology achieved via thorough mixing provided by the twin-screw extruder. Epoxide-mediated crosslinking between PLA and CP enabled the development of a novel 3D printing filament with excellent mechanical properties. This research illustrates how agricultural residues can be upcycled into high-performance biomaterials with innovation in sustainable manufacturing, inclusive economic growth, reducing reliance on petroleum-based plastics and thus providing benefits regarding human health, climate change mitigation, plastic in the ocean, and environmental impacts. Full article

Propylene oxide is the first and only chiral molecule to have been observed in the interstellar medium. Given the mechanisms for forming chiral species, which are important for astrobiology in understanding the origins of life, we report here an experimental and theoretical investigation into the electronic structure of propylene oxide and its evolution from the methylation and epoxidation of ethene. Here, electron momentum spectroscopy is used as an orbital-imaging technique to probe experimental orbital momentum distributions. These are directly compared with theoretical orbital momentum distributions calculated at the equilibrium geometry, and those calculated by considering the vibrational motion of the propylene oxide target. This allows us to identify which molecular orbitals are sensitive to specific vibrational normal modes, thereby facilitating understanding and controlling chemical reactivity. By extending our investigation to include intermediate species along the evolution of ethene through methylation and epoxidation, we can develop an understanding of how the orbital electronic structure evolves through this series of important chemicals. Full article