Search Results (187)

Phosphorus-modified poly(vinyl alcohol) (PVA) has recently gained increasing attention as a functional polymeric matrix suitable for gel-based systems, owing to its biocompatibility, film-forming ability, and capacity to develop semi-interpenetrating networks. In this work, PVA was chemically modified through the nucleophilic substitution of its hydroxyl groups with the chloride groups of phenyl dichlorophosphate, following a literature-reported method carried out in N,N-dimethylformamide (DMF) as reaction medium, resulting in phosphorus-containing PVA networks (PVA-OP3). Hybrid gel-like films were then prepared by incorporating titanium dioxide nanoparticles (TiO₂ NPs), known for their antimicrobial activity, low toxicity, and high stability. The resulting composites were structurally, morphologically, and thermally characterized using FTIR, SEM, and thermogravimetric analysis. The incorporation of TiO₂ NPs significantly improved the thermal stability, with T₅% increasing from 240 °C for neat PVA-OP3 to 288 °C for the optimal composite, increased the char residue from 4.5% for the neat polymer to 30.1% for PVA-OP3/TiO₂-4, and enhanced antimicrobial activity against both Gram-positive and Gram-negative bacteria. These findings demonstrate that PVA-OP3/TiO₂ hybrid films possess promising potential as advanced biomaterials for biomedical, protective, and environmental applications. Full article

Personal protective equipment (PPE) like single-use face masks is discarded after a single use and poses a significant danger to the environment, resulting in plastic pollution. Most of the face masks are made from synthetic polymers and are non-biodegradable to the environment; hence, concerns are being raised about polymers’ environmental impact. Most of the previous studies so far focus on polypropylene (PP) disposable masks and limited data related to environmental abiotic degradation behavior. There is a lack of studies aiming to understand the degradation behavior of different masks and the influence of physical-chemical factors. In this paper, we report on the environmental abiotic degradation of cloth, surgical and respirator filter facepiece 1 (FFP1) masks by accelerated artificial weathering. Furthermore, physical-chemical properties of masks were characterized by Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC) and Thermo Gravimetric Analysis (TGA). The cloth and FFP1 masks are made from polyethylene terephthalate (PET) and surgical masks were made from polypropylene (PP). Masks were exposed to an accelerated weathering test, which simulates the effects of natural sunlight and reproduces the damage caused by weathering elements such as sunlight, rain and dew. Masks were exposed to Ultraviolet radiation (UV) for 120, 240 and 360 h followed by condensation at 50 °C for 4 h. The FTIR results show that PET cloth and FFP1 PET masks are not degrading with the 360 h maximum exposure duration, which is equivalent to ±180 days. The FTIR scan of the PP surgical mask after 120 h of exposure time shows that it was degraded and broken down into fragments. For the PET cloth mask, a 58% reduction in crystallinity and heat of enthalpy was observed after 120 h of exposure. UV exposure causes a chain scission reaction, breaking down the ester bond in the case of the PET cloth mask. In the case of the PET FFP1 mask exposed to UV for 120, 240 and 360 h, a drastic reduction in crystallinity was observed as compared to the neat (original) PET FFP1 mask. Neat PET cloth and FFP1 masks have higher onset and maximum degradation temperatures as compared to the 120, 240 and 360 h UV exposed masks. Neat PET cloth and FFP1 masks have better resistance to thermal degradation. Full article

The Gould–Jacobs reaction for the synthesis of ethyl 4-quinolone-3-carboxylate derivatives is described. Thus, the condensation of 4-subtituted anilines and EMME to give the corresponding diethyl anilinomethylene malonate was carried out via neat MW irradiation or refluxing ethanol. These intermediates underwent Eaton’s reagent-catalyzed cyclisation with good to excellent yields. For the first step, the MW reaction took only 7 min compared with the two hours required for conventional heating, yet the yields were comparable in almost all cases. A series of eight 4-quinolone derivatives was obtained with good yields under mild conditions and with short reaction times. Full article

In this study, syntactic composite foams were developed by incorporating cenosphere (CS) particles recovered from recycled fly ash into a one-component polyurethane (PU) foam system. During production, CS was added to the spray-applied PU foam at specific ratios, and the foaming reaction was simultaneously initiated via manual mixing. This approach minimized particle settling caused by the filler–matrix density difference and promoted a more homogeneous structure. Two types of CS, with mean sizes of approximately 70 µm and 130 µm, were incorporated at five loadings ranging from 5 wt% to 15 wt%. The resulting composites were evaluated for their acoustic, mechanical, and thermal performance. Thermal analyses revealed that CS addition increased the glass-transition temperature (Tg) by ≈12 °C and delayed the 5% mass-loss temperature (T₅%) by ≈30–35 °C compared with the neat N2 foam, confirming the stabilizing role of cenospheres. The refoaming process with manual mixing promoted finer cell diameters and thicker walls, enhancing the sound absorption coefficient (α), particularly at medium and high frequencies. Moreover, increasing the filler content improved both the sound transmission loss (STL) and compressive strength, alongside density, although further gains in α and STL were limited beyond a 10 wt% filler content. Significant enhancements in compressive strength were achieved at filler ratios above 12.5 wt%. Unlike conventional two-component PU foams, this study demonstrates a sustainable one-component PU system reinforced with recycled cenospheres that simultaneously achieves acoustic, mechanical, and thermal multifunctionality. To the best of our knowledge, this is the first report on incorporating recycled cenospheres into a one-component PU foam system, overcoming dispersion challenges of conventional two-component formulations and presenting an environmentally responsible route for developing versatile insulation materials. Full article

Studies have shown that the iron concentration in the peritoneal fluid of women is associated with the severity of endometriosis. Therefore, investigation of iron metabolism-related genes (IM-RGs) in endometriosis holds significant implications for both prevention and therapeutic strategies in affected patients. Differentially expressed IM-RGs (DEIM-RGs) were identified by intersecting IM-RGs with differentially expressed genes derived from GSE86534. Mendelian randomization analysis was employed to determine DEIM-RGs causally associated with endometriosis, with subsequent verification through sensitivity analyses and the Steiger test. Biomarkers associated with IM-RGs in endometriosis were validated using expression data from GSE86534 and GSE105764. Functional annotation, regulatory network construction, and immunological profiling were conducted for these biomarkers. Single-cell RNA sequencing (scRNA-seq) (GSE213216) was utilized to identify distinctively expressed cellular subsets between endometriosis and controls. Experimental validation of biomarker expression was performed via reverse transcription–quantitative polymerase chain reaction (RT-qPCR). BMP6 and SLC48A1, biomarkers indicative of cellular BMP response, were influenced by a medicus variant mutation that inactivated PINK1 in complex I, concurrently enriched by both biomarkers. The lncRNA NEAT1 regulated BMP6 through hsa-mir-22-3p and hsa-mir-124-3p, while SLC48A1 was modulated by hsa-mir-423-5p, hsa-mir-19a-3p, and hsa-mir-19b-3p. Immune profiling revealed a negative correlation between BMP6 and monocytes, whereas SLC48A1 displayed a positive correlation with activated natural killer cells. scRNA-seq analysis identified macrophages and stromal stem cells as pivotal cellular components in endometriosis, exhibiting altered self-communication networks. RT-qPCR confirmed elevated expression of BMP6 and SLC48A1 in endometriosis samples relative to controls. Both BMP6 and SLC48A1 were consistently overexpressed in endometriosis, reinforcing their potential as biomarkers. Moreover, macrophages and stromal stem cells were delineated as key contributors. These findings provide novel insights into therapeutic and preventive approaches for patients with endometriosis. Full article

Background/Objectives: Fenbendazole is a potential cancer treatment and a proven antiparasitic in veterinary applications. However, its poor water solubility limits its application. In this study, potential fenbendazole solubility enhancement was investigated through size reduction methods. The effect of the presence of Soluplus^® on solubility was investigated as well. Methods: Solubility enhancement was explored using microfluidization and ultrasonication techniques. These techniques were applied to fenbendazole alone and in combination with Soluplus^®. UV–Vis spectroscopy was used to determine solubility. Possible chemical reactions were checked using Fourier transform infrared spectroscopy (FT-IR). Differential scanning calorimetry (DSC) was conducted to analyze the physical structure and crystallinity of the samples. Scanning electron microscopy (SEM) was also utilized for characterization of the effect of the treated formulations and the size reduction method on morphology. The elements present in samples were identified with energy-dispersive X-ray spectroscopy (EDX) combined with SEM. A comparison of crystalline structure between the products was performed via X-ray powder diffraction (XRPD). Dynamic light scattering (DLS) was also used to measure the samples’ average particle size at different stages. Results: Both ultrasonication and microfluidization led to marginal increases in the solubility of neat fenbendazole. In contrast, formulations processed in the presence of Soluplus^® demonstrated a greater enhancement in solubility. However, solubility improvement was not retained in the dried samples. The post-drying samples, irrespective of the presence of Soluplus^®, showed nearly the same solubility as neat fenbendazole. Conclusions: Size-reduction methods, particularly when combined with Soluplus^®, improved the solubility of fenbendazole. However, drying appeared to reverse these gains, regardless of the method used. Full article

Athletic performance is modulated by a complex interaction of physiological, environmental, and genetic factors, with regular exercise triggering molecular changes that influence gene expression and tissue adaptation. Despite growing knowledge, the underlying molecular mechanisms remain only partially understood, highlighting the need for precise biomarkers to monitor training-induced physiological adaptations. Long non-coding RNAs (lncRNAs) regulate cellular processes, including adaptation to physical exercise. Twelve healthy elite female volleyball players (mean age 27 ± 5.4 years) participated in the study. This study evaluated the expression of selected lncRNAs (SNHG4, SNHG5, PACERR, NEAT1, HIX003209, and HOTTIP) during a 10-week training program and evaluated their potential as biomarkers of training adaptation. Blood samples were collected before and after the training period. LncRNA expression was measured by quantitative polymerase chain reaction. HOTTIP exhibited an increase in expression after training (over sixfold change, p = 0.009, adjusted p = 0.024) and demonstrated high diagnostic accuracy (AUC = 0.917), which improved to 0.97 when combined with creatine kinase. Other lncRNAs showed no significant changes, although a correlation between HOTTIP and SNHG4 was noted. HOTTIP is markedly upregulated following chronic exercise and, especially when combined with creatine kinase, shows promise as a molecular biomarker for monitoring training adaptation in elite female volleyball players. Full article

Flame-retardant poly (ethylene terephthalate) composites (FR PET) have been developed with the potential to be used as substrates in applications where flexibility and transparency are required. Several phosphorous-based flame retardants of a different nature were selected here for compounding by melt blending with a low-molecular-weight PET polymer. The fire reaction, transparency, and mechanical properties were analyzed. TGA and cone calorimetry were used to elucidate the gas-phase and condensed-phase actions of flame retardants and their effectivity. Cone calorimeters showed an improved performance with the addition of flame retardants, particularly a reduction in generated heat, improving the FGI (fire growth index) value. However, a V0 classification (following the UL94 standard) was achieved only with the addition of an organic phosphonate, Aflammit PCO900, to the PET matrix. This behavior was linked to the early reaction of this flame retardant in the gas phase, in addition to a plastification effect that causes the removal of the polymer from the incident flame. The presence of flame retardants reduced the transparency of composites over the neat PET, but, nevertheless, a good optical performance remained. No special effect was observed on the crystallization parameters. Therefore, the increase in opacity can be attributed to the poor miscibility of flame retardants and/or differences in the diffraction index of the polymer and FR additives. Full article

Resol phenol–formaldehyde (PF) resin was modified with 2.5 and 5.0 wt% polymethylhydrosiloxane (PMHS). This study characterizes the modified resin and its subsequently fabricated glass fiber (GF)-reinforced composites (30–60 wt% GF). Formation of an organic–inorganic hybrid network, via reaction between Si-H groups of PMHS and hydroxyl (-OH) groups of the resol resin, was confirmed by FTIR and ¹H NMR. DSC and TGA/DTG revealed enhanced thermal stability for PMHS-modified resin: the decomposition temperature of Resol–PMHS 5.0% increased to 483 °C (neat resin: 438 °C), and char yield at 800 °C rose to 57% (neat resin: 38%). The 60 wt% GF-reinforced Resol–PMHS 5.0% composite exhibited tensile, flexural, and impact strengths of 145 ± 7 MPa, 160 ± 7 MPa, and 71 ± 5 kJ/m², respectively, superior to the unmodified resin composite (136 ± 6 MPa, 112 ± 6 MPa, and 51 ± 5 kJ/m²). SEM observations indicated improved fiber–matrix interfacial adhesion and reduced delamination. These results demonstrate that PMHS modification effectively enhances the thermo-mechanical properties of the PF resin and its composites, highlighting potential for industrial applications. Full article

1,3-Dipolar cycloadditions on nitrone dipoles are key reactions to access five-membered heterocycles, which are useful intermediates in the synthesis of biologically relevant glycomimetics. The good atomic balance and high stereoselectivity characteristic of such reactions make them good candidates for the development of green protocols. In the present work, these features were maximized by avoiding the use of organic solvents and considering starting materials derived from biomass. Reactions involving (acyclic and cyclic) carbohydrate-derived nitrones as dipoles and levoglucosenone as dipolarophile were considered. Performing selected 1,3-dipolar cycloadditions in neat conditions showed reduced reaction times, maintaining similar selectivity and yields with respect to the classical protocols. The use of microwave irradiation and orbital shaking were also exploited to increase the sustainability of the synthetic protocols. The collected results highlight the potential of solvent-free 1,3-dipolar cycloadditions in the design of efficient synthetic routes according to green chemistry principles, such as prevention, atom economy, safer solvents and auxiliaries, and use of renewable feedstocks. Full article

LDPE was crosslinked with novel dynamic or conventional crosslinking agents during melt processing. Both crosslinkers were synthesized by the esterification of Thiele’s acid or adipic acid with 4-hydroxy-TEMPO. ¹H-NMR showed that a temperature of 170 °C and a reaction time of 24 min are required for a successful crosslinking. The concentrations of crosslinking agents were 1.45, 2.9, and 5.8 mol%. Conventionally crosslinked LDPEs show a decrease in soluble content in hot xylene with increased crosslinker concentrations, while dynamically crosslinked LDPEs show no change after thermal treatment, indicating the scission of dynamic crosslinks. The rheology of both crosslinked LDPEs at 130 °C shows that the stress release is slower than that of neat LDPE, confirming crosslinking, while at 170 °C a shift in the stress release and also a shift in the flow properties of dynamically crosslinked LDPE towards those of neat LDPE are observed, both indicating the cleavage of dynamic crosslinks. Compared to neat LDPE, the mechanical properties of both crosslinked LDPEs show an increase in Young’s modulus and tensile strength and a decrease in elongation and creep when the concentration of both crosslinkers is increased. By increasing the processing temperature to 170 °C, the crystallinity index decreases, leading to a rather small improvement in the mechanical properties. Full article

In this study, novel biodegradable polycaprolactone (PCL)-based composites for sustainable packaging applications were developed by adding surface-treated wood fibers (WFs). Specifically, the WFs were treated with citric acid (CA) to improve the fiber/matrix adhesion and then melt compounded with a PCL matrix. The presence of an absorption peak at 1720 cm⁻¹ in the Fourier transform infrared (FTIR) spectra of CA-treated WFs, coupled with the increase in the storage modulus and complex viscosity in the rheological analysis, confirmed the occurrence of an esterification reaction between CA and WFs, with a consequent increase in interfacial interactions with the PCL matrix. Scanning electron microscopy (SEM) of the cryo-fractured surface of the composites highlighted that PCL was able to efficiently wet the fibers after the CA treatment, with limited fiber pull-out. Quasi-static tensile tests showed that the composites reinforced with CA-treated wood fibers exhibited a significant increase in yield strength (about 30% with a WF amount of 10% at 0 °C) and also a slight improvement in the VICAT softening temperature (about 6 °C with respect to neat PCL). Water absorption tests showed reduced water uptake in CA-treated composites, consistent with the reduced hydrophilicity confirmed by higher water contact angle values. Therefore, the results obtained in this work highlighted the potential of CA-treated WFs as reinforcement for PCL composites, contributing to the development of eco-sustainable and high-performance packaging materials. Full article

Almond peel extracts, containing 0.2–0.8% (w/w) phenolic compounds with notable antioxidant and antimicrobial activities, could be used as a natural source of active compounds for the development of active films for food preservation. In this study, almond peel extracts obtained by subcritical water extraction at 160 and 180 °C were incorporated into PLA films (PLA-E160 and PLA-E180). The films were characterized in terms of their microstructure, mechanical, barrier, optical and thermal properties. Furthermore, the release of phenolic compounds and hydroximethylfurfural (HFM) into food simulants with different polarity was evaluated, as well as the film’s potential antioxidant and antimicrobial activities. To validate their effectiveness as active packaging materials, shelf-life studies were conducted on fresh orange juice and sunflower oil packaged using PLA-160 films. The results show that the incorporation of the almond peel extracts led to significant changes in the films’ microstructure and mechanical properties, which became darker, mechanically less resistant, and stretchable (p < 0.05), with slightly lower thermal stability than neat PLA films. The release of phenolic compounds and HFM from extract-enriched films was promoted in the 95% ethanol simulant due to the matrix swelling and relaxation. Food products packaged with PLA-E160 exhibited slower oxidative degradation during storage, as indicated by the higher ascorbic acid content and hue color in orange juice and lower peroxide content in sunflower oil. Nevertheless, both in vivo and in vitro studies showed no antimicrobial effectiveness from the films, likely due to the limited release of active compounds to the surrounding medium. Thus, almond peel extract conferred valuable properties to PLA films, effectively reducing oxidative reactions in food products sensitive to these deterioration processes. Full article

In this work, we report the observation of uncatalyzed ene reactions between several phenylpropanoid compounds and diethyl azodicarboxylate (DEAD). For allylbenzene, the reaction produces the ene product at molar ratios of up to 1:2 of allylbenzene to DEAD. At higher levels of DEAD, more complex reactions are observed. For the reaction between methyl eugenol and DEAD, similar ene reaction products have been found. However, the reaction of eugenol with DEAD is more complex; in addition to the ene reaction, other reactions happen at the same time. Most of the structures of the resulting products have been elucidated using NMR spectroscopy (¹H, ¹³C, and 2D), and the findings have been further corroborated by FTIR analysis. Interestingly, these products appear to undergo molecular aggregation, which results in self-thickening in their neat form. However, the viscosity significantly decreases upon dilution with a solvent. This self-thickening property suggests their potential use as thickening agents in organic solvent formulations. Full article

Due to excellent chemical resistance and impermeability, high-density polyethylene (HDPE) is widely used in petrochemical transportation, product packaging, sports equipment, and marine applications. Yet, with the wide variety of service environments, its mechanical and thermal properties do not meet the demand. In the present study, a compounding cross-linker comprising di-tert-butyl peroxide (DTBP) and triallyl isocyanurate (TAIC) is employed by combining with a two-step preparation process. High-quality cross-linking reactions are achieved for HDPE. In this study, the cross-linking of DTBP is first examined separately. A peak cross-linking degree of 74.7% is achieved, and there is a large improvement in thermal resistance and mechanical properties. Subsequently, the composite cross-linking system of DTBP and TAIC is investigated. The peak cross-linking degree is 82.1% (10% increase compared to DTBP). The peak heat deformation temperature is 80.1 °C (22% increase compared to DTBP). The peak impact strength is 104.73 kJ/m² (207% increase compared to neat HDPE). The flexural strength is 33.6 MPa (22% increase compared to neat HDPE). The results show that this cross-linking system further improves the cross-linking degree, heat resistance, and mechanical properties of HDPE, indicating its potential application in engineering materials for high performance. Full article