Search Results (511)

Small-molecule blending is an effective strategy for improving the mechanical properties of poly(vinyl alcohol) (PVA). However, the influence of structural differences among phenolics on the toughening mechanism remains unclear. In this study, we systematically investigated the reinforcing effects of three trihydroxy-phenolics (apigenin, galangin, and baicalein) on PVA hydrogels by combining molecular simulations with experimental validation. Molecular simulations predicted that H-bonding crosslinking between phenolics and PVA chains is the central reinforcement mechanism, and that the spatial arrangement of hydroxyl groups and the competition between intermolecular H-bonding ultimately determine the performance. Structural characterization and experimental validation showed that apigenin, owing to the dispersed spatial distribution of its three hydroxyl groups, exhibits stronger H-bonding crosslinking ability and achieves the most significant reinforcement. After a single freeze–thaw cycle, all trihydroxy-phenolics/PVA composite hydrogels exhibited markedly better mechanical properties than pure PVA hydrogels, with the following strength order: apigenin/PVA > galangin/PVA ≈ baicalein/PVA. This study provides a rapid and efficient theoretical model and a reference case for small-molecule toughened PVA hydrogels. Full article

Increased corrosivity of biodiesel toward metallic components has motivated the search for environmentally friendly corrosion inhibitors. However, studies investigating plant extracts as inhibitors in biodiesel systems remain limited, particularly for babassu biodiesel. In this work, the ethanolic extract of Myracrodruon urundeuva (“Aroeira-do-Sertão”) leaves was investigated for the first time as a green corrosion inhibitor for AISI 4340 carbon steel exposed to babassu biodiesel. Static immersion tests were conducted for 2592 h (108 days) at 45 °C, and the inhibitory performance was compared with that of the commercial antioxidant Trolox™. Corrosion behavior was evaluated by gravimetric weight loss measurements and surface morphology analysis using scanning electron microscopy. Phytochemical screening, FTIR, and ¹H NMR spectroscopy revealed the presence of phenolic compounds, flavonoids, and tannins containing hydroxyl functional groups and conjugated aromatic systems. The ¹H NMR spectrum exhibited characteristic signals in the δ 6.6–6.4 ppm region, which were attributed to aromatic protons of phenolic compounds and flavonoids, while signals between δ 5.4 and 4.9 ppm indicated vinyl and olefinic protons associated with unsaturated secondary metabolites. These findings are consistent with FTIR results, confirming the presence of hydroxyl-rich phenolic structures and conjugated systems capable of promoting adsorption onto the metal surface. The extract exhibited a corrosion inhibition efficiency of 89%, significantly higher than that obtained with Trolox™ (27.9%). SEM analysis confirmed a substantial reduction in surface degradation in the presence of the extract. These results demonstrate the strong potential of Myracrodruon urundeuva leaf extract as a sustainable corrosion inhibitor for metallic materials in biodiesel environments. Full article

Poly(methyl vinyl ether-alt-maleic anhydride) (PMVEMA) is a versatile synthetic copolymer that has gained considerable attention in biomedical and pharmaceutical applications due to its biocompatibility, biodegradability, bioadhesive properties and chemical reactivity. This review summarizes the current knowledge regarding the derivatives, physicochemical properties, functionalization and crosslinking strategies of PMVEMA, with particular emphasis on their relevance to biomedical applications. A comprehensive literature analysis was performed using major scientific databases, combined with artificial intelligence-assisted text mining, to identify the principal research trends associated with PMVEMA. The reviewed studies demonstrate that the reactive anhydride groups of PMVEMA enable the formation of a wide variety of derivatives, including hydrogels, nanoparticles and nanofibers with tunable properties. These characteristics have facilitated its application in different fields, including immunology, drug delivery, dentistry and dermatology. In particular, PMVEMA-based systems exhibit enhanced mucosal adhesion, controlled drug release, immunoadjuvant activity and biocompatibility in vitro and in vivo. Despite its broad applicability, further studies are still needed to fully elucidate its biodegradation mechanisms in vivo and optimize its clinical translation. Full article

To understand glycan–protein interactions at biological interfaces, designing surfaces modified with structurally controlled glycans is highly important. In particular, naturally occurring glycosaminoglycans (GAGs) possess periodic sugar arrangements that play important roles in protein recognition, highlighting the need for the development of periodic glycopolymer model systems that can serve as GAG mimics for quantitative interaction analysis. In this study, sequence-controlled periodic glycopolymers were synthesized by reversible addition–fragmentation chain-transfer (RAFT) polymerization and immobilized onto gold surfaces to construct glycan-modified interfaces. The synthesized material was a terminally functionalized periodic glycopolymer with the most basic structure, consisting of alternating maltose-containing vinyl ether (MalVE) units and ethyl maleimide (EtMI) units, with a trithiocarbonate group at the ω-terminal. This trithiocarbonate group was converted to a thiol group for immobilization through Au–S bond formation. Structural characterization by ¹H NMR spectroscopy, size exclusion chromatography (SEC), MALDI-TOF mass spectrometry, and UV–vis spectroscopy confirmed the structure as designed. Quartz crystal microbalance (QCM) measurements verified the stable immobilization of thiol-terminated periodic glycopolymers on the gold surface, and allowed for estimation of graft density and quantitative analysis of glycan-protein interactions at the modified interface. The periodic glycopolymer-modified surfaces exhibited selective binding behavior toward concanavalin A (ConA) compared to bovine serum albumin (BSA), with apparent binding constants on the order of 10⁶–10⁷ L mol⁻¹. This enhanced binding behavior indicated that specific and multivalent interactions with proteins also occurred at periodic pendant maltose residues along the main chain. These results demonstrate that the gold surface modified with end-functional periodic glycopolymers synthesized by RAFT polymerization provides a versatile platform for quantitative analysis of glycan-protein interactions and suggests potential applications for periodic glycopolymers as functional materials. Full article

Silicone rubber is an important external insulating material for composite bushings, composite insulators, and other power equipment. During long-term service, it is inevitably exposed to coupled environmental and electrical stresses, such as elevated temperature, moisture ingress, strong electric fields, and partial discharge, which may lead to hydrophobicity loss, surface chalking, crack propagation, and particle shedding. To reveal the microscopic degradation mechanism of silicone rubber under complex operating conditions, a molecular model of methyl vinyl silicone rubber was constructed using Materials Studio. A stable silicone rubber molecular structure was obtained through crosslinking, geometry optimization, and ensemble relaxation. Subsequently, a reactive molecular dynamics simulation system under coupled temperature–humidity–electric field conditions was established using LAMMPS and the ReaxFF reactive force field. Different temperature gradients, electric field intensities, and aging–recovery stages were designed to investigate the degradation behavior of silicone rubber. The evolution of the maximum carbon content, maximum silicon content, carbon-containing decomposition products, and typical small-molecule products, including H₂, H₂O, CH₄, C₂H₂, C₂H₄, and C₂H₆, was statistically analyzed. In addition, atomic trajectory tracking was performed to clarify the processes of methyl group detachment, Si-O bond cleavage, water molecule participation, and molecular chain reconstruction. The results show that high temperature mainly promotes methyl group detachment from side chains and fracture of the siloxane main chain, while a strong electric field accelerates the decomposition process and induces the transformation of long siloxane chains into shorter chains. Water molecules can react with broken siloxane chains to form hydroxyl-containing structures, making the structural degradation partially irreversible. The degradation process of silicone rubber under coupled temperature–humidity–electric field stress can be summarized as side-chain detachment, main-chain scission, water-assisted reactions, free-radical recombination, and local molecular aggregation. This study provides a molecular-level theoretical basis for aging mechanism analysis, condition assessment, and lifetime prediction of composite external insulating materials. Full article

Alternating glycopolymers bearing periodically arranged pendant carbohydrate residues were synthesized by reversible addition–fragmentation chain transfer (RAFT) copolymerization of maltose-containing vinyl ether (MalVE) and ethyl maleimide (EtMI). The resulting trithiocarbonate-terminated polymers were subsequently converted into thiol-terminated glycopolymers through post-polymerization end-group transformation. These structurally well-defined alternating glycopolymers were immobilized onto gold nanoparticles (AuNPs) via Au–S interactions to construct glycopolymer-functionalized glycointerfaces. Surface functionalization of the AuNPs was confirmed by an increase in hydrodynamic diameter from approximately 42 to 59 nm after polymer immobilization. The resulting glycopolymer-functionalized AuNPs exhibited concentration-dependent lectin-mediated aggregation behavior in the presence of concanavalin A, accompanied by characteristic red shifts and broadening of the localized surface plasmon resonance (LSPR) band arising from multivalent carbohydrate–lectin interactions at the nanoparticle interface. Although the apparent association constants obtained for free alternating glycopolymers using fluorescently labeled lectin cannot be directly compared with those obtained from LSPR-based aggregation assays of AuNP-immobilized glycopolymers, the values increased from the order of 10⁵ L mol⁻¹ in solution to the order of 10⁷ L mol⁻¹ at the nanoparticle interface. This trend suggests that immobilization onto AuNPs enhances multivalent carbohydrate–lectin interactions through multivalent presentation of the glycopolymer chains at the nanoparticle interface. As a control experiment, peanut agglutinin (PNA), which does not recognize maltose residues, was added to the glycopolymer-functionalized AuNPs. No significant LSPR shift or spectral broadening was observed, indicating that nanoparticle aggregation was not induced by nonspecific lectin addition but arose from specific interactions between maltose residues and Con A. Quantitative analysis suggested that polymer chain length may influence the aggregation behavior. These results demonstrate that alternating glycopolymers provide a useful platform for constructing sequence-regulated glycointerfaces and for investigating multivalent biomolecular interactions at nanoparticle surfaces. Full article

The application of silk sericin as a polymeric biomaterial has recently gained interest, although its film was found to be fragile, exhibiting brittleness when subjected to relatively slight stress, and it also displayed higher water solubility. This study focused on the enhanced physico-mechanical properties of the three films obtained by the crosslinking of sericin protein from three silkworm cocoons with poly (vinyl alcohol) (PVA) to reduce phase separation and solubilization of the films by promoting miscibility between sericin and PVA. The findings demonstrated how crosslinking with glutaraldehyde enhanced thermal stability and tensile strength and controlled the solubility of the three sericin–PVA films. The sericin from G. postica, G. rufobrunnea, and Argema mimosae is composed of serine, aspartic acid, and glutamic acid, which make up 80% of the total polar amino acids. X-ray diffraction (XRD) patterns showed that sericin–PVA films have semicrystalline features, representing amorphous and crystalline regions. The XRD results also indicated that the Saturniidae sericin–PVA film (Sat-SPF), Gonometa postica sericin–PVA film (GP-SPF), and Gonometa rufobrunnea sericin–PVA film (GR-SPF) have crystallinity percentages of 66.4%, 55.9%, and 17.7%, respectively. The moisture vapor transmission rate (MVTR) values observed in this study ranged from 991.2 to 5160 g/m²/24 h, indicating that these films can effectively regulate moisture levels in wounds. The swelling capacity of the three sericin–PVA composite films depends on the crosslinking density of their structures and was also found to be sensitive to the pH of the aqueous media, demonstrating their hydrophilic nature and potential use in drug delivery systems. The water vapor permeability of sericin–PVA films increased with higher environmental relative humidity (RH) and moisture content within the films. The elongation at break for GP-SPF (107.2% ± 3.1) and Sat-SPF (73.0% ± 4.1) was significantly higher than in GR-SPF (29.3% ± 2.3). However, their tensile strength and elastic modulus were lower than those of GR-SPF. These results show that the number of polar groups (amino and hydroxyl groups) from both sericin and PVA influences all the properties of the sericin–PVA composite films. The three sericin–PVA solutions were found to have antibacterial efficacy against three Gram-positive and one Gram-negative bacteria over 24 h. Scanning electron microscopy (SEM) images revealed a rough surface with a granular network pattern, which supports the potential use of sericin–PVA films for cell adhesion and proliferation, which are essential for biomedical wound dressing applications. Full article

Cotton fabrics are widely used due to their comfort and biodegradability; however, their intrinsic hydrophilicity limits their performance in advanced applications. In this work, a fluorine-free approach for imparting durable hydrophobicity to cotton was developed based on thiol-ene crosslinking of polysiloxane networks formed on the fiber surface. Two thiol-functional polysiloxanes differing in –SH group content were combined with four vinyl-functional organosilicon crosslinkers under UV (2,2-dimethoxy-2-phenylacetophenone (DMPA)) and thermal (2,2′-azobis(2-methylpropionitrile) (AIBN)) initiation. FT-IR analysis confirmed the presence of siloxane structures, while SEM-EDS revealed stable silicon- and sulfur-containing layers. SEM observations showed continuous coatings without blocking the textile structure. Water contact angle (WCA) measurements demonstrated that hydrophobic performance strongly depends on thiol content and crosslinker structure, with the highest values obtained for the thiol-rich polysiloxane and tetrafunctional vinyl crosslinker. All modified fabrics exhibited high durability, with minimal changes in WCA and complete droplet stability (1800 s) after washing. In the case of the lower-functionality polysiloxane, an increase in hydrophobicity after washing was observed, attributed to the reorganization of siloxane chains. These results demonstrate that thiol-ene crosslinking provides an effective strategy for designing durable, fluorine-free hydrophobic coatings on cotton. Full article

A major limitation for the wider use of membrane-based technologies is the presence of biofouling, which is related to the decline of permeate flux, as well as the associated energy and economic costs for the necessary cleaning. In this work, the interactions and compatibility of 28 common polymeric materials with 36 potential biofoulants (categorized in six groups) is examined, based on Hansen Solubility Parameters (HSPs). Also, a simple methodology is proposed for polymer screening and comparing the suitability of 28 polymers to be used as fabrication materials or coatings, aiming to produce membranes with lower biofouling potential. The methodology gives a score to each polymer based on its interaction with water and various foulants. The screening among the commonly used polymers showed that poly (vinyl alcohol) (PVOH) is a good selection for the manufacturing of membranes, or for effective surface coating to limit biofouling, when compared to the other candidate polymers. The case of PVOH material received the highest score (11.6), while other polymers ranked with lower scores (less than 10). Its physically cross-linked nature that arises from a strong self-association pattern may also be beneficial for biofouling mitigation, since it limits the available sites for interactions (e.g., through hydrogen bonds) with the potential foulant agents. Swelling experiments on the PVOH gels with real wastewater (produced after anaerobic digestion) support the predictions for lowering the biofouling potential. Full article

m-Aminostyrene (MAS) is a key molecular scaffold with an electron-donating amino group and a conjugating vinyl group, exhibiting significant potential in photonic materials and biological applications due to its rotamerism and photoinduced behavior. Despite its importance, a comprehensive, rotamer-resolved investigation of its vibronic and cationic spectroscopic properties is lacking. Here, we report a high-resolution study on the cis and trans rotamers of jet-cooled MAS using two-color resonant enhanced multi-photon ionization (2C-REMPI), UV-UV hole-burning (HB), and mass-analyzed threshold ionization (MATI) spectroscopies, combined with density functional theory (DFT) calculations. The HB technique unambiguously resolves the vibronic spectra of each rotamer, overcoming the limitations of previous one-color REMPI studies. The excitation energies (S₁ ← S₀) are determined to be 30,416 cm⁻¹ (cis) and 30,932 cm⁻¹ (trans). The MATI spectra yield precise adiabatic ionization energies (AIEs) of 61,569 cm⁻¹ (cis) and 61,274 cm⁻¹ (trans). A comprehensive assignment of vibrational modes in both the S₁ and D₀ states is provided, revealing distinct mode activities and frequency shifts between the two rotamers. A propensity for Δν = 0 upon ionization is observed, indicating high geometrical similarity between the S₁ and D₀ states. This work provides a crucial spectroscopic blueprint for understanding the electronic and vibrational structure of MAS rotamers, with implications for the design of functionalized styrene-based molecular systems. Full article

Plasma polymerization offers a solvent-free route to functional polymer materials, but the structural integrity and accessibility of functional groups in plasma-derived networks remain insufficiently validated. Herein, N-vinylimidazole (NVI) was polymerized using atmospheric-pressure dielectric barrier discharge (DBD) plasma in a liquid-film configuration to generate a chemically heterogeneous poly(N-vinylimidazole)-like material that could be recovered and evaluated in aqueous solution. ATR–FTIR and ¹H NMR spectroscopy indicate substantial vinyl-group consumption with retention of imidazole functionality. Functional behavior was probed using chromium(III) (Cr³⁺) as a model metal ion. UV–Vis spectroscopy revealed systematic changes in the Cr³⁺ d–d transition region (~580–600 nm) with increasing polymer concentration, consistent with ligand-field perturbation arising from interactions with imidazole donor sites. A monotonic increase in absorbance with an increasing ligand-to-metal ratio was observed, followed by plateau behavior at higher ratios, indicating saturation of accessible coordination environments. These results demonstrate that plasma-polymerized material retains chemically accessible imidazole functionalities capable of coordinating transition-metal ions in solution, establishing atmospheric-pressure plasma polymerization as a viable route to functional imidazole-containing materials. Full article

Fluorine-18 is often considered an ideal positron emitter owing to its excellent chemical, physiological, and nuclear properties. Consequently, the development of rapid, simple, and reliable ¹⁸F-labeling strategies remains critically important for synthesizing new radiopharmaceuticals for PET molecular imaging. A common approach involves the synthesis of ¹⁸F-labeled prosthetic groups that subsequently undergo bioconjugation with peptides or other biomolecules to generate ¹⁸F-labeled imaging probes. However, conventional synthetic methods for these prosthetic groups are often lengthy, require large quantities of precursor and solvent, and typically rely on elevated reaction temperatures. Herein, we report a droplet-based microscale synthetic methodology for the preparation of the [¹⁸F]FVSB prosthetic group that minimizes precursor and solvent usage, proceeds rapidly, and operates at relatively low temperatures. Conditions were optimized using a platform for performing droplet reactions in parallel, enabling high-throughput study of multiple reaction parameters within a short period of time. Additionally, we introduce a simple micro-cartridge purification technique that affords purified [¹⁸F]FVSB in small volumes. Furthermore, we describe an efficient bioconjugation that requires substantially lower reagent amounts than the previously reported macroscale method. The microscale process we report could facilitate wider use of this ¹⁸F-labeling strategy and can be extended to label other thiol-bearing peptides or biomolecules. Full article

Branched poly(vinyl alcohol) (PVA) was synthesized via chemical modification of linear PVA with epichlorohydrin in an alkaline aqueous medium under conditions preventing crosslinking. Branching was confirmed by IR and Heteronuclear Single Quantum Coherence (HSQC) spectroscopy, as well as by viscometric analysis. An iterative procedure is proposed for refining the branching factor (g) and the viscosity-average molecular weight of the branched macromolecules. Coil diameters determined by viscometry and dynamic light scattering showed satisfactory agreement. While an increase in the viscosity-average molecular weight of branched PVA enhances its surface activity in the low-adsorption region, the branched geometry itself hinders subsequent adsorption due to steric shielding of the interface. This correlates with wetting behavior on Teflon: lightly branched PVA requires a higher concentration to induce wetting inversion than its linear counterpart but further increase in molecular weight shifts the inversion point to lower concentrations due to a higher density of hydroxyl groups. Concurrently, the concentration dependence of the work of adhesion degenerates with increasing molecular weight. Despite their reduced adsorption capacity, the specific geometry of branched PVA macromolecules provides effective steric stabilization of micrometer-sized particles during styrene suspension polymerization. These results demonstrate that chain branching in PVA is a powerful tool for tuning its adsorption properties, stabilizing ability, and interfacial activity. Full article

Cement stabilized macadam (CSM) bases are prone to cracking and void damage under long-term traffic loading and environmental actions, which accelerates structural deterioration. Although grouting is an effective method for treating such concealed defects, laboratory-based evaluation of repair effectiveness remains limited. In this study, field-cored CSM specimens were recombined in a cylindrical mold to simulate four void conditions (1/4, 2/4, 3/4, and 4/4), and repaired using an inorganic cementitious composite grouting material based on ultra-fine cement and high-belite sulphoaluminate cement (HBSAC), and modified with ethylene-vinyl acetate (EVA) latex, wollastonite (WO) whiskers, and polyvinyl alcohol (PVA) fibers. The repair effectiveness was evaluated through ultrasonic testing, capacitance measurement, uniaxial compression with acoustic emission (AE) monitoring, and computed tomography (CT). The results show that the longitudinal wave velocity of all repaired groups increases continuously with curing time, with a maximum increase of 21.98% at 28 days. The normalized capacitance response exhibits clear time- and layer-dependent variation, with the 4/4 group showing the most pronounced spatial heterogeneity. In the uniaxial compression tests, the peak load increases from 181 kN in the control group to 201–286 kN in the repaired groups, while the tensile-related AE event proportion increases from 77.35% in the 1/4 group to 89.38% in the 4/4 group. CT analysis shows that the proportion of micropores smaller than 1 mm³ increases from 66.3% to 82.7%, whereas the proportion of pores larger than 100 mm³ decreases from 46.5% to 21.6% after repair. These results demonstrate that the composite grouting material provides effective filling, structural reconstruction, and mechanical enhancement for void-damaged CSM, and that the proposed multi-source characterization framework is suitable for evaluating grouting repair performance. Full article

Poly(vinyl alcohol)/chitosan (PVA/CS) biodegradable films reinforced with acid-functionalized multi-walled carbon nanotubes (f-MWCNTs) were fabricated via solution casting to investigate the effects of nanotube incorporation on structural, mechanical, thermal, dielectric, and physicochemical properties. Unlike conventional CNT-reinforced systems, this study focuses on the role of acid functionalization in improving nanotube dispersion and interfacial interactions, enabling simultaneous enhancement of multiple performance characteristics. Fourier transform infrared spectroscopy (FTIR) analysis confirmed strong intermolecular interactions between PVA/CS functional groups and carboxyl groups on f-MWCNTs, while scanning electron microscopy (SEM) revealed homogeneous nanotube dispersion at low loadings and partial aggregation at higher contents. X-ray diffraction (XRD) indicated that crystallinity was modified in a non-monotonic manner with increasing nanotube concentration due to competing nucleation and chain-restriction effects, while dielectric measurements showed an increase in dielectric constant from 3.78 to 4.27 as a result of enhanced interfacial polarization. The thermal conductivity improved from 0.195 to 0.247 W·m⁻¹·K⁻¹, and tensile strength increased from 19.8 to 24.5 MPa at 0.2 wt.% f-MWCNT, with elongation at break decreasing from 37.9% to 25.1%, reflecting increased stiffness. The degree of swelling and water solubility decreased with higher nanotube content, indicating reduced hydrophilicity and enhanced structural compactness. The results provide new insights into how surface-functionalized nanofillers can be used to tailor the multifunctional performance of biodegradable polymer nanocomposite films, highlighting their potential in advanced applications such as sustainable packaging, flexible electronics, sensors, and membrane technologies. Full article