Search Results (377)

This study investigates the influence of cellulose nanofibrils (CNFs) on the polymerization kinetics of methyl methacrylate (MMA) during in situ suspension polymerization at 70 °C (343.15 K). Four CNF concentrations were evaluated and compared to a reference system without CNFs. Polymerizations were carried out in a thermostatted flask immersed in an ethylene glycol bath and covered to ensure thermal stability. The temperature profiles of both the reaction medium and the surrounding bath were continuously recorded, allowing for the calculation of heat flow, polymerization rate (R_p), and monomer conversion. The incorporation of CNFs led to a significant increase in R_p and faster MMA conversion. This effect was attributed to the presence of nanocellulose within the polymerizing medium, which restricted diffusion and contributed to the onset of the phenomenon of autoacceleration. Additionally, CNFs promoted a higher total heat release, underscoring the need for thermal control during scale-up. The resulting material qualifies as a biocomposite, as biobased nanofibrils became integrated into the polymer matrix. These findings demonstrate that CNFs act as effective kinetic promoters in MMA polymerizations and may serve as functional additives to enhance both reaction performance and sustainability. However, safety considerations remain critical when transferring this approach to industrial processes. Full article

Glucose-responsive insulin delivery systems that effectively regulate insulin retention and release in response to real-time fluctuation of glucose levels are highly desirable for diabetes care with minimized risk of hypoglycemia. Herein, we report a class of glucose-sensitive copolymer microgels, prepared from a simple one-pot precipitation copolymerization of 4-vinylphenylboronic acid (VPBA), 2-(dimethylamino) ethyl acrylate (DMAEA), and oligo(ethylene glycol) methyl ether methacrylate (M_w = 300, MEO₅MA), for gated glucose-responsive insulin release within the physiologically desirable glucose level range. The composition of the p(VPBA-DMAEA-MEO₅MA) copolymer microgels were analyzed using NMR and FTIR spectra. The cis-diols of glucose can reversibly bind with the −B(OH)₂ groups of the VPBA component in the microgels, resulting in the formation of negatively charged boronate esters that induce the volume phase transition of the microgels. The DMAEA component is incorporated to reduce the pK_a of VPBA, thus improving the glucose sensitivity of the microgels at physiological pH. The neutral hydrophilic MEO₅MA component is used to tune the onset of the glucose responsiveness of the microgels to the physiologically desirable levels. The more the MEO₅MA component copolymerized in the microgels, the greater the glucose concentration required to initiate the swelling of the microgels to trigger the release of insulin. When the onset of the glucose response was tuned to 4−5 mM, the copolymer microgels retained insulin effectively in the hypo-/normo-glycemic range but also released insulin efficiently in response to the elevation of glucose levels in the hyperglycemic range, which is essential for diabetes management. The copolymer microgels display no cytotoxicity in vitro. Full article

New stable three-dimensional hydrogels were obtained in an inert gas atmosphere in light in an aqueous dispersion of the main components: cod collagen, methyl methacrylate, polyethylene glycol, RbTe_1.5W_0.5O₆ complex oxide, and modifying additives. The analysis of the new hydrogels’ cytotoxicity using the MTT assay showed that the cytotoxicity of the sample extracts was observed in a number of examples, but was decreased with increasing dilution of the extracts. The decrease in cell viability at high concentrations of the extract is likely caused by a decrease in the number of specific components of the complete culture medium used to produce extracts. It is related to the well-known adsorption of medium proteins by the gel component, high-molecular compounds included in the matrix. The stimulating effect of the substances included in its composition was observed with a significant dilution of the extract, i.e., the proliferative activity of the cells increased. The extract of the hydrogel hydrolysate sample and all its dilutions did not show cytotoxicity in the MTT assay examples. It determines the prospect of its use on the wound surface, since hydrogel destruction occurs under the action of body enzymes. The new hydrogel is a promising material for creating wound coverings or scaffolds. Full article

Drought is a serious environmental problem that limits the yield of wheat around the world. Using biochemical and microscopy methods, it was shown that methyl jasmonate (MeJA) has the ability to induce the oxidative stress tolerance in roots of wheat plants due to the regulation of antioxidant enzymes activity, proline (Pro), and wheat germ agglutinin (WGA) accumulation. During the first hours of 12% polyethylene glycol (PEG) exposure, stress increased the superoxide radical (O₂^•−) and the hydrogen peroxide (H₂O₂) accumulation, the activity of superoxide dismutase (SOD), total peroxidase (POD), ascorbate peroxidase (APX), catalase (CAT), the percent of dead cells (PDC), malondialdehyde accumulation (MDA), and electrolyte leakage (EL) of wheat roots as compared to the control. Stress enhanced proline (Pro) and wheat germ agglutinin (WGA) contents in roots and the plant’s nutrient medium, as well as decreased the mitotic index (MI) of cells of root tips in comparison to the control. During PEG exposure, 10⁻⁷ M MeJA pretreatment increased the parameter of MI, declined O₂^•− and H₂O₂ generation, PDC, MDA, and EL parameters as compared to MeJA-untreated stressed seedlings. During 1 day of drought, MeJA pretreatment additionally increased the activity of SOD, total POD, APX, CAT, Pro, and WGA accumulation in wheat roots in comparison to MeJA-untreated stressed plants. During stress, MeJA pretreatment caused a decrease in Pro exudation into the growth medium, while WGA content in the medium was at the control level. Full article

Star polymers—macromolecules featuring multiple arms radiating from a central core—offer unique potential for biomedical applications due to their tunable architecture, multifunctionality and ability to incorporate stimuli-responsive and biocompatible components. In this study, functional star polymers with oligo (ethylene glycol) methyl ether methacrylate (OEOMA) arms and 2-(dimethylamino)ethyl methacrylate (DMAEMA) core units were synthesized via atom transfer radical polymerization (ATRP) using the “arm-first” strategy. The star polymers were used as nanoreactors for the in situ reduction of silver nitrate to form silver nanoparticles (AgNPs) without additional reducing agents. UV–Vis spectroscopy confirmed the formation of spherical AgNPs with absorption maxima around 430 nm, and transmission electron microscopy revealed uniform particle morphology. These hybrid nanomaterials (STR-AgNPs) were incorporated into polymethyl methacrylate (PMMA)-based bone cement to impart antibacterial properties. Mechanical testing showed that the compressive strength remained within acceptable limits, while antibacterial assays against E. coli demonstrated a significant inhibition of bacterial growth. These findings suggest that STR-AgNPs serve as promising candidates for infection-resistant bone implants, providing localized antibacterial effects while maintaining mechanical integrity and biocompatibility. Full article

A catalyst with the active component Cu loaded onto the carrier activated carbon was prepared, and metal Ca was introduced into the catalyst to modify it. This catalyst was used in the hydrogenation reaction of dimethyl oxalate, and the reaction kinetics was studied. The kinetic experiments were carried out in a fixed bed reactor with a reaction temperature varying from 483 K to 513 K, reaction pressure varying from 1.5 Mpa to 2.5 Mpa, and the weight hourly space velocity of dimethyl oxalate varying from 0.435 h⁻¹ to 0.726 h⁻¹. Eight possible dynamic models were proposed, the optimal model was selected, and the parameters of the optimal model were calculated using MATLAB. The results showed that dimethyl oxalate adsorbed on the active site by dissociation adsorption, and the dissociation adsorption of ester was the rate-controlling step. The parameters of the model were consistent with thermodynamics and statistical analysis, further proving that the model has good forecasting performance. Full article

In this study, a solvent-free, slow-curing, inherently flame-retardant polyurea coating was successfully developed through an optimized formulation. The novel polyurea was synthesized using mixed Schiff base latent curing agents derived from terminal polyether amines with different-number average molecular weights (D2000 and D400), methyl isobutyl ketone, and polyethyl phosphate glycol ester (OP550). Subsequently, polyurea/meta-aramid (PUA/AF) composite fabrics were fabricated via a scraping coating technique. Thermogravimetric analysis revealed enhanced char formation and reduced decomposition temperatures due to the incorporation of OP550. Comprehensive flame retardant performance was demonstrated through vertical flame testing, limiting oxygen index, and micro-scale combustion calorimetry, with results showing significantly reduced heat release rates, lower total heat release, and increased residual char. Mechanical evaluations indicated marked improvements in tearing, tensile, single-yarn tensile, and bursting forces, attributed to strong fiber–polyurea interfacial interactions, as confirmed by detailed SEM morphological analyses. Moreover, the PUA/AF composites exhibited excellent static puncture resistance and effective self-healing capability. Collectively, these advancements highlight the potential of PUA/AF composite fabrics as promising candidates for advanced protective textiles, integrating superior flame retardancy, mechanical strength, puncture resistance, and self-repairing functionality. Full article

Cultural Heritage is a vital socioeconomic driver that must contend with works of art continuously exposed to degradation processes, which are further exacerbated by climate change. Aged coatings, varnishes, and soil can compromise the appearance of artworks, preventing their preservation and valorization. In response, soft matter and colloidal systems, such as nanostructured cleaning fluids (NCFs), have proved to be valuable solutions for safely and effectively cleaning works of art. Here, a novel cleaning system is proposed, for the first time employing microgels of poly(N-isopropylacrylamide) (PNIPAM) with surface chains of oligoethylene glycol methyl ether methacrylate (OEGMA) to favor shear deformation by lubrication. These microgels are loaded with NCFs featuring “green” solvents and different kinds of bio-derived or petroleum-based surfactants (non-ionic, zwitterionic). Rheological characterization of the combined systems highlighted a sharp transition from solid to liquid-like state in the 21–24 °C range when the zwitterionic surfactant dodecyldimethylamine oxide was used; the system displays a solid-like behavior at rest but flows easily at intermediate strains. At slightly higher temperature (>24 °C), an inversion of the G′, G″ values was observed, leading to a system that behaves as a liquid. Such control of rheological behavior is significant for feasible and complete removal of soiled polymer coatings from textured ceramic surfaces, which are difficult to clean with conventional gels, without leaving residues. These results position the PNIPAM-OEGMA microgels as promising cleaning materials for the conservation of Cultural Heritage, with possible applications also in fields where gelled systems are of interest (pharmaceutics, cosmetics, detergency, etc.). Full article

Cryptic sites, which are transient binding sites that emerge through protein conformational changes upon ligand binding, are valuable targets for drug discovery, particularly for allosteric modulators. However, identifying these sites remains challenging because they are often discovered serendipitously when both ligand-binding (holo) and ligand-free (apo) states are experimentally determined. Here, we introduce CrypTothML, a novel framework that integrates mixed-solvent molecular dynamics (MSMD) simulations and machine learning to predict cryptic sites accurately. CrypTothML first identifies hotspots through MSMD simulations using six chemically diverse probes (benzene, dimethyl-ether, phenol, methyl-imidazole, acetonitrile, and ethylene glycol). A machine learning model then ranks these hotspots based on their likelihood of being cryptic sites, incorporating both hotspot-derived and protein-specific features. Evaluation on a curated dataset demonstrated that CrypTothML outperforms recent machine learning-based methods, achieving an AUC-ROC of 0.88 and successfully identifying cryptic sites missed by other methods. Additionally, CrypTothML ranked cryptic sites as the top prediction more frequently than existing methods. This approach provides a powerful strategy for accelerating drug discovery and designing allosteric drugs. Full article

Poor drug entrapment, burst release, and variable drug release profiles are the most critical challenges associated with biodegradable-polymer-based microspheres. In this study, biodegradable-polymer-based microspheres were used to entrap an antiplatelet drug, eptifibatide, using a single-emulsion solvent evaporation method. Critical challenges associated with biodegradable-polymer-based microspheres were addressed by incorporating different additives in the drug or polymer phase. Additives such as hydroxy propyl beta cyclodextrins (HPβCD), carboxy methyl cellulose sodium (Na CMC), and trehalose were added to the drug phase to evaluate their impact on the entrapment and stability of eptifibatide. The effect of the addition of additives such as polyvinyl alcohol (PVA), polyethylene glycol-400 (PEG-400), and methoxy polyethylene glycol phospholipid dimyristoyl phosphatidylethanolamine (mPEG-2000-DMPE, Na) to the polymer phase on the release profile of eptifibatide was evaluated. The inclusion of HPβCD resulted in good drug entrapment and helped control the initial unwanted burst release. Including Na CMC increased eptifibatide entrapment from 75% to 95%. Trehalose helped prevent the degradation of eptifibatide during lyophilization, and including PVA and PEG-400 reduced the lag phase and led to a controlled-release profile. Thus, including additives in the formulation can effectively improve the drug load and address issues associated with biodegradable-polymer-based microspheres. Full article

The optical characteristics of semiconductor’s particles are strongly dependent on physicochemical properties and the reduced size of the system. Decreasing the size of the material causes an increase in the ratio between the number of atoms on the surface and the number of atoms inside the particle, that is, the increase in specific surface area and surface defects. Due to their high surface-area-to-volume ratio and increased number of active sites on the surface, the nanostructured materials with altered optical properties compared to the bulk material are preferable for catalytic reactions. In this study, an ultra-small and very crystalline zircon-nanostructured bismuth vanadate (BiVO₄) semiconductor was prepared by ethylene glycol-assisted synthesis. The nanoparticles have a radius between 2 and 8 nm, as shown by TEM images, and a high Brunauer–Emmett–Teller (BET) specific surface area. The optical, structural, microstructural, and photocatalytic properties were examined in detail. X-ray photoelectron spectroscopy (XPS) technique confirmed the occurrence of Bi, V, and O elements and also found that Bi and V exist in +3 and +5 oxidation states, respectively. The photocatalytic activity of the samples was checked using methyl orange (MO) under UV-Vis lighting. The photocatalytic performance was compared to commercial TiO₂ powder. The results showed tetragonal zircon-type nanostructured BiVO₄ as a promising catalyst for rapid removal of pollutants from wastewater. Full article

This study investigates the hydrothermal gasification (HTG) of apricot tree resin, focusing on the yield and chemical composition of the resulting gas and aqueous phases. K₂CO₃ and KOH were used as catalysts within a temperature range of 300–600 °C, with a constant reaction time of 60 min. The results show that temperature and catalyst choice significantly influence gas yield, liquid composition, and solid residue formation. Higher temperatures increased the gas yield while decreasing aqueous and solid residues. The catalytic effect of K₂CO₃ and KOH enhanced the gaseous product conversion, with KOH achieving the highest gas yield and lowest residue formation at 600 °C. Among the liquid-phase compounds, carboxylic acids and 5-methyl furfural were the most abundant, reaching peak concentrations at 300 °C in the presence of K₂CO₃. The addition of alkali catalysts reduced key acidic intermediates such as glycolic, acetic, and formic acids. The inverse relationship between temperature and liquid/solid product formation underscores the importance of optimizing reaction conditions for efficient biomass conversion. These findings contribute to the growing field of biomass valorization by highlighting the potential of underutilized tree resins in sustainable biofuel production, advancing knowledge in renewable hydrogen production, and supporting the broader development of bio-based energy solutions. Full article

Amphiphilic block copolymers are essential for developing advanced polymer nanomaterials with applications in bioimaging, drug delivery, and nanoreactors. In this study, we successfully synthesized functional block copolymer assemblies at high concentrations through redox-initiated reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of 2-(acetoacetoxy)ethyl methacrylate (AEMA), a β-ketoester functional monomer. Utilizing a redox initiation system at 50 °C, we produced poly(poly(ethylene glycol) methyl ether methacrylate)-b-PAEMA (PPEGMA_n-PAEMA_m). Kinetic studies demonstrated rapid monomer conversion exceeding 95% within 30 min, with distinct polymerization phases driven by micelle formation and monomer depletion. Transmission Electron Microscopy (TEM) and Dynamic Light Scattering (DLS) revealed the formation of diverse morphologies, including worm-like, vesicular structures, and spherical micelles, depending on the macro-CTA molecular weight and monomer concentration. Additionally, post-polymerization modification with aggregation-induced emission (AIE) luminogens, such as 1-(4-aminophenyl)-1,2,2-tristyrene (TPE-NH₂), resulted in AIE-active polymer assemblies exhibiting strong fluorescence in aqueous dispersions. These AIE-active polymer assemblies also exhibited good biocompatibility. These findings demonstrate the efficacy of redox-initiated RAFT emulsion polymerization in fabricating functional, scalable block copolymer assemblies with potential applications in the field of life sciences. Full article

The rational design of BiOBr photocatalysts with optimized surface properties and enhanced photooxidative capacities is crucial. This study proposes a synergistic strategy combining hydroxyl-rich solvents with polyvinylpyrrolidone (PVP) surfactants to modulate the structural and electronic properties of BiOBr through a solvothermal approach. The resulting self-assembled microspheres demonstrated exceptional efficiency in degrading ciprofloxacin (CIP), methyl orange (MO), and rhodamine B (RhB). Among the synthesized variants, BiOBr-EG-PVP (fabricated with ethylene glycol and PVP) exhibited the highest photocatalytic activity, achieving near-complete removal of 20 mg/L CIP and RhB within 10 min under visible light irradiation, with degradation rates 60.12–101.73 times higher than pristine BiOBr. The structural characterization revealed that ethylene glycol (EG) not only induced the formation of self-assembled microspheres but also introduced abundant surface hydroxyl groups, which simultaneously enhanced the hole-mediated oxidation capabilities. The incorporation of PVP further promoted the development of hierarchical honeycomb-like microspheres and synergistically enhanced both the hydroxyl group density and photooxidative potential through interfacial engineering. Density functional theory (DFT) calculations confirmed that the enhanced photooxidative performance originated from an increased surface oxygen content. This work elucidates the synergistic effects of hydroxyl-rich solvents and surfactant modification in the fabrication of advanced BiOBr-based photocatalysts, providing new insights for high-performance photocatalysis for environmental remediation. Full article

Amphiphilic statistical copolymers can be utilized for the formulation of nanocarriers for the drug delivery of insoluble substances. Oligoethylene glycol methylether methacrylate and methyl methacrylate are two biocompatible monomers that can be used for biological applications. In this work, the synthesis of linear poly(oligoethylene glycol methylether methacrylate-co-methyl methacrylate), P(OEGMA-co-MMA), and statistical copolymers via reversible addition fragmentation chain transfer (RAFT) polymerization is reported. P(OEGMA-co-MMA) copolymers with different comonomer compositions were synthesized and characterized by size exclusion chromatography (SEC), ¹H-NMR, and ATR-FTIR spectroscopy. Self-assembly studies were carried out by the dissolution of polymers in water and via the co-solvent protocol. For the characterization of the formed nanoaggregates, DLS, zeta potential, and fluorescence spectroscopy (FS) experiments were performed. Such measurements delineate the association of copolymers into aggregates with structural characteristics dependent on copolymer composition. In order to investigate the drug encapsulation properties of the formed nanoparticles, curcumin and quercetin were loaded into them. The co-solvent protocol was followed for the encapsulation of varying concentrations of the two drugs. Nanocarrier formulation properties were confirmed by DLS while UV–Vis and FS experiments revealed the encapsulation loading and the optical properties of the drug-loaded nanosystems in each case. The maximum encapsulation efficiency was found to be 54% for curcumin and 49% for quercetin. For all nanocarriers, preliminary qualitive biocompatibility studies were conducted by the addition of FBS medium in the copolymer aqueous solutions which resulted in no significant interactions between copolymer aggregates and serum proteins. Novel nanocarriers of curcumin and quercetin were fabricated as a first step for the utilization of these statistical copolymer nanosystems in nanomedicine. Full article