Search Results (2,503)

In this study, we evaluated various density functional theory (DFT) methods to obtain thermodynamic parameters, such as enthalpy and Gibbs free energy, and compared them with experimental values obtained from conductometric analysis. As a model system, we chose the heptakis(2,6-di-O-methyl)-β-cyclodextrin (DIMEB) complex with the recently synthesized fluorinated compound, butane-1,4-diyl bis(2,2,2-trifluoroethane-1-sulfonate) (BFS). The analysis was carried out in the temperature range of 293.15–313.15 K. A conformational search was performed to identify the most stable complexes. The final stage of optimization was conducted at the ωB97X-D4/6-31G(d,p) level of theory in the presence of water, modeled using the conductor-like polarizable continuum model (CPCM). The thermodynamic analysis indicates that almost all theoretical methods overestimate the enthalpy and Gibbs free energy. This also applies to Minnesota functionals, which are commonly recommended for thermochemistry studies. The best agreement with experimental results was obtained for the composite methods r²SCAN-3c and PBEh-3c, with the coefficient of determination (R² = 0.9972) indicating excellent correlation between r²SCAN-3c and experiment. Full article

A novel amorphous Hf-MOFs precursor was successfully synthesized and converted into HfC nanoparticles via one-step pyrolysis. The effects of metal/ligand molar ratios, solvent types, and pyrolysis temperature were systematically studied. High-purity spherical HfC nanoparticles (44.30 ± 9.63 nm) were obtained at 1500 °C using a 1.5:1 metal/ligand molar ratio with mixed anhydrous ethanol/deionized water solvents. At a pyrolysis temperature of 1700 °C, the as-synthesized HfC nanoparticles possessed an exceptionally low oxygen content of 0.76%, alongside a carbon content of 6.42% that almost perfectly matches the theoretical value of stoichiometric HfC. The formation mechanism involving Hf-O-C coordination and carbothermal reduction was clarified. Additive-free HfC ceramics were fabricated using the as-synthesized HfC nanoparticles via spark plasma sintering (1950 °C, 30 MPa, 20 min). The resulting ceramics exhibited a relative density of 96.7% and a Vickers hardness of 20.2 GPa, both of which are significantly superior to those of ceramics sintered from commercial HfC powders under identical conditions (95.8% and 17.8 GPa, respectively). This work provides a promising and feasible pathway for the preparation of other high-quality ultra-high temperature hafnium-based carbide powders and ceramics. Full article

The widespread presence of ciprofloxacin (CIP) in aquatic environments threatens ecological and public health, yet conventional treatment processes fail to remove such persistent contaminants. Conventional solvothermal synthesis of Bi-doped g-C₃N₄ photocatalysts involves complicated procedures and low productivity. Herein, we employ a single-step, template-free and solvent-free green calcination method to construct Bi³⁺-modified g-C₃N₄ with strong Bi-N coordination interactions. A series of Bi/g-C₃N₄ photocatalysts with Bi-doping mass ratios of 0.09–0.34 wt% was prepared, and the structure–performance relationship as well as the surface–interface reaction mechanism for ciprofloxacin (CIP) degradation were systematically elucidated. Experimental results confirm that Bi³⁺ incorporates into the lattice via Bi-N coordination bonds with nitrogen in the g-C₃N₄ framework, which narrows the band gap, suppresses photogenerated carrier recombination, and constructs a loose porous morphology beneficial for increasing specific surface area and active sites. Under optimal conditions, 15Bi/g-C₃N₄ achieves 97.6% degradation of 15 mg L⁻¹ CIP within 90 min, which is 13.7% higher than that of pristine g-C₃N₄. The effects of catalyst dosage, initial pH, CIP concentration, common coexisting ions, and different real water matrices on the degradation performance were systematically investigated. Radical quenching experiments combined with ESR characterization confirm that h⁺ is the dominant reactive species responsible for CIP degradation. This green, simple and scalable method yields uniform products, and the resulting materials exhibit high efficiency, economic feasibility and environmental safety, demonstrating promising potential for antibiotic wastewater treatment. Full article

Conductive hydrogels are attractive for flexible electronics, but their practical use is often limited by resistance drift during repeated deformation and performance degradation at low temperatures. Here, core–shell polyaniline-coated polyacrylonitrile (PANi@PAN) electrospun nanofibers were incorporated into a polyacrylamide/hydroxypropyl cellulose (PAM/HPC) hydrogel matrix to construct a hybrid conductive network. The PANi shell serves as an electronic pathway alongside ionic conduction in the hydrated polymer network, leading to markedly improved electromechanical stability. The resistance drift is about 11% after 2000 stretching–relaxation cycles at 0–100% strain, about 12 times lower than that of the nanofiber-free hydrogel. Stable electrical responses are maintained under large deformation, with a resistance drift as low as 3.3% over a strain range of 0–400%. The hydrogels show a conductivity of 0.32 S m⁻¹ while retaining high stretchability (>600%). An ethylene glycol/water binary solvent is used to suppress ice formation and improve moisture retention, allowing stable electromechanical performance at −15 °C over 500 cycles. The hydrogel also adheres reliably to human skin (about 10.25 kPa) and functions as a conformal strain sensor without extra fixation. Full article

High-sensitivity rapid detection of ammonia (NH₃) in environmental monitoring, industrial safety, early diagnosis, and other fields is of great significance. Covalent organic frameworks (COFs) have shown great potential in the field of gas sensing due to their designable porous structure and active sites. However, the traditional solvothermal synthesis method of COFs has problems such as cumbersome steps, high energy consumption and serious environmental pollution. Therefore, it is of great significance to invent a new method for COF synthesis that is green and efficient and makes it easy to conduct flexible ammonia gas sensing. This study first reported a solvent-free synthesis of imine connection 1,3,5-Triformylbenzene (TFB) and p-Phenylenediamine (PDA)—a new strategy for COF. This method innovatively employs zinc trifluoromethyl sulfonate (Zn(OTf)₂) as a bifunctional catalyst. This catalyst not only efficiently catalyzes para-phenylenediamine, but its zinc ions also play a unique structural guiding role, guiding the reactants to be arranged in a directional manner, thereby constructing a highly ordered porous crystal structure. A series of characterizations confirmed that the obtained TFB-PDA-COF had good crystallinity and a high proportion of imine bonds (C=N). The powder material was coated onto a flexible polyimide (PI) substrate, successfully constructing a resistive ammonia gas sensor that operates at room temperature. The test results show that this sensor has a high response value, rapid response/recovery capability, and good selectivity for ammonia gas. More importantly, based on a flexible PI substrate, the device can maintain stable sensing performance even under repeated bending conditions, demonstrating its great potential in practical flexible electronic applications. This work not only provides a brand-new “zinc ion-guided” paradigm for the green and controllable synthesis of COF but also lays a material foundation for their application in the next-generation flexible sensing field. Full article

To address the trade-off between storage stability and curing reactivity in NCO-terminated waterborne polyurethane (WPU) systems, a solvent-free WPU emulsion with dual-curing characteristics was developed using vanillin (VAN) and 2-hydroxyethyl acrylate/pentaerythritol triacrylate (HEA/PETA). Hexamethylene diisocyanate (HDI) and 2,2-bis(hydroxymethyl)butyric acid (DMBA) were used as the isocyanate component and internal hydrophilic moiety, respectively, to prepare a self-dispersible polyurethane prepolymer. VAN was introduced as a latent isocyanate-related component, while HEA/PETA served as acrylate-bearing reactive modifiers, followed by self-emulsification to form a stable aqueous dispersion. The prepolymer structure, curing behavior, and adhesive performance on bamboo substrates were systematically investigated. The results supported the successful introduction of VAN-derived structures into the polyurethane chains and the retention of polymerizable C=C bonds from HEA/PETA. Thermal analysis suggested dual-curing behavior with two distinguishable thermal events, involving lower-temperature polymerization of unsaturated groups and a VAN-related higher-temperature reaction. The resulting WPU exhibited dry and wet shear strengths above 23 MPa and 9 MPa, respectively. These findings demonstrate a feasible strategy for integrating emulsion stability, staged curing, and adhesive performance in solvent-free WPU systems. Full article

Tissue scaffolds are one of the main components of the tissue engineering triad, playing a vital role in tissue engineering. However, their production procedures heavily rely on solvent-intensive and energy-demanding methods. This raises serious questions about industrial-scale manufacturability, residual solvent toxicity to living health, and sustainability for nature and the environment. Therefore, the main aim of this study is to identify robust scaffolds that provide a suitable microenvironment for resident cells and promote tissue regeneration, while reducing waste through environmentally friendly production methods. In this context, the scalable and ecologically friendly production methods emerge as necessary alternatives as biodegradable polymer scaffolds are used in more therapeutic settings. Clinically applicable and green synthesis-based supercritical carbon dioxide (scCO₂) technologies, melt electrowriting (MEW), and solvent-free processing techniques are the main topics of this study for a critical analysis of biodegradable polymer scaffold production techniques. Scaffold structure–property correlations, polymer selection and interactions, production procedures, the benefits and drawbacks of existing fabrication technologies, and sustainability issues are discussed in detail. It aims to contribute a novel perspective and approach to literature by presenting and comparing production-oriented approaches as sustainable and green methods. The challenges in the development of biodegradable tissue scaffolds, along with the significance of green manufacturing techniques, are also revealed. The approach is designed to connect processing factors to scaffold features in addition to evaluating current technologies. This review tries to offer a framework for producing biodegradable polymer scaffolds in a sustainable and clinically implementable context. Full article

This paper provides a comprehensive overview of research findings concerning the acid catalytic effect (ACE) of hot compressed water and water–alcohol mixtures, along with the applications of these solvents. The ACE observed during reactions can be categorized into three types: inherent, associated, and interfering. These ACE types originate from the solvent, solutes, and reactor, respectively. Distinguishing and evaluating these ACEs is crucial for elucidating reaction mechanisms and developing reaction models. Water exhibits inherent ACE in both its dissociated and undissociated forms under hot compressed conditions. Hot compressed water–alcohol mixtures possess the capability to tune the characteristics of solvents, including ACE, through their composition. The application of hot compressed water and water–alcohol is prevalent in a variety of fields, including the conversion of biomass and biomass-derived materials, extraction, biodiesel production, organic synthesis reactions, recycling via the decomposition of polymers, and inorganic material synthesis. In these applications, the utilization of water–alcohol mixtures resulted in a higher yield of target products and/or superior properties of products compared to the use of pure solvents, such as water alone or alcohol alone. The observed results can be attributed to the optimization of the roles of water and alcohol in the reaction through mixing them. Full article

Background/Objectives: Paracetamol is a widely analgesic and antipyretic drug; however, its limited anti-inflammatory efficacy and safety concerns motivate the search for novel non-opioid alternatives. In this study, a series of 4-hydroxyphenylamino-naphthoquinones were designed as paracetamol-inspired analogs and synthesized via a solvent-free, silica-assisted Michael addition, providing a sustainable and efficient synthetic route. Methods: The compounds were evaluated using an integrated strategy combining in silico prediction, density functional theory calculations, molecular docking, ADMET profiling, and in vivo phenotypic pharmacological assays. Results: In vivo evaluation revealed pronounced peripheral antinociceptive activity in the acetic acid-induced writhing model and robust anti-inflammatory effects in carrageenan-induced paw edema, comparable to those of naproxen. These findings suggest a predominantly peripheral mechanism consistent with anti-inflammatory and antinociceptive profiles linked to cyclooxygenase inhibition. A normalization-based multi-criteria analysis integrating peripheral, anti-inflammatory, central, and antipyretic endpoints enabled transparent phenotypic prioritization within the series. Under this framework, compound 7 emerged as the most balanced peripheral–anti-inflammatory candidate, whereas compound 8, evaluated experimentally as a regioisomeric mixture, showed comparatively stronger central antinociceptive activity in the hot plate test. Antipyretic activity in an LPS-induced fever model was limited and not sustained. Conclusions: Overall, these findings indicated that the 4-hydroxyphenylamino-naphthoquinone scaffold emerges as a promising non-opioid platform for peripheral inflammatory pain, supporting further investigation of its pharmacological and mechanistic properties. Full article

Colloidal crystals are periodic arrays of monodisperse particles that exhibit optical stopbands, which can be experimentally observed as a Bragg reflection characterized by a specific Bragg wavelength and width. Precise control of these characteristic parameters is essential for applications in structural color materials, sensors, and tunable photonic crystals. Although the Bragg reflection wavelength can be widely tuned by adjusting the lattice spacing via changes in particle size and concentration, controlling the width over a wide range—such as through expansion—is challenging because it is intrinsically determined by the refractive index contrast between the colloidal particles and their surrounding medium. In this study, the Bragg reflection width of non-close-packed colloidal crystals immobilized in an elastomer film was successfully expanded by adjusting the photoinitiator concentration and ultraviolet light intensity for photopolymerization. Expansion was attributed to the superposition of Bragg reflections at different wavelengths, resulting from spatial variations in the lattice spacings of the non-close-packed colloidal crystals formed during photopolymerization. Owing to the solvent-free and highly flexible nature of the elastomer-immobilized, non-close-packed colloidal crystal film, the Bragg reflection wavelength was readily tuned by mechanical compression while maintaining the expanded Bragg reflection width, thereby advancing the practical applications of structural color materials. Full article

Aflatoxin B1 (AFB1) poses a serious threat to global food and feed safety. Laccase-based enzymatic degradation represents a promising green strategy for AFB1 removal; however, its industrial application is severely limited by the rapid thermal inactivation of wild-type enzymes under high-temperature processing conditions (>70 °C). Here, we engineered the thermal stability of a laccase from Bacillus amyloliquefaciens B10 through an integrated strategy combining computational structural biology with semi-rational design. By coupling molecular dynamics (MD) simulations with folding free-energy (ΔΔG) calculations, we identified key flexible regions associated with thermal instability and subsequently implemented iterative saturation mutagenesis. The best single mutant, R196C, retained more than 96% relative activity after heat treatment at 80 °C for 10 min. Further iterative mutational stacking progressively enhanced thermostability: the R90E/R196C double mutant showed 1.25-fold higher activity at 80 °C than R196C, and the R90E/R196C/H54F triple mutant showed a further 1.16-fold increase over the double mutant. The final quadruple mutant, R90E/R196C/H54F/R253I, achieved 86.9% AFB1 degradation at 80 °C after 24 h. High-temperature MD simulations (100 ns at 353.15 K) indicated that the enhanced thermostability was associated with reduced conformational flexibility, lower radius of gyration (Rg) and solvent-accessible surface area (SASA), and a coil-to-β-sheet transition that contributed to stabilization of the protein core. In addition, efficient secretory expression of the engineered enzyme was achieved in Pichia pastoris, reaching 3.0 U/mL, while the crude enzyme maintained more than 70% activity at 80 °C. Collectively, these results provide a practical basis for the rational engineering and scalable production of thermostable biocatalysts for AFB1 detoxification-related applications of AFB1 control, and offer broader insights into the targeted enhancement of thermal stability in industrial enzymes. Full article

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) enters host cells when the spike receptor-binding domain (RBD) engages angiotensin-converting enzyme 2 (ACE2). Cannabinoid scaffolds have recently been reported to bind S1/RBD, block spike-mediated membrane fusion, and modulate host inflammatory pathways, making them attractive candidates for entry inhibition. Here, we applied an integrated computational pipeline to prioritize cannabis-derived compounds as interfacial blockers of the RBD–ACE2 complex across variants. Eleven phytocannabinoids were docked into the wild-type (WT) RBD–ACE2 interface, identifying three cavities, with ligands preferentially occupying pocket 1. Complexes were subjected to triplicate 200 ns all-atom molecular dynamics (MD) simulations for WT, Delta, and Omicron BA.1 RBD–ACE2. Binding energetics were quantified using molecular mechanics/generalized Born surface area (MM/GBSA) and solvated interaction energy (SIE), and per-residue contributions were analyzed together with solvent-accessible surface area (SASA) and residue interaction networks. Among all compounds, cannabidiol (CBD) and cannabinol (CBN) were the only ligands that remained stably bound in pocket 1 for all variants. CBN showed the most favorable ligand–complex binding in WT, whereas CBD preserved favorable binding in Omicron BA.1 despite reduced interface burial, indicating that van der Waals/electrostatic complementarity and solvation, rather than surface coverage alone, govern affinity. Both ligands weakened modeled RBD–ACE2 binding by perturbing hot-spot residues centered on Y505 or N501Y in RBD and E37, A387, and R393 in ACE2. Overall, our results highlight CBD and CBN as tractable, variant-spanning interface disruptors and illustrate how MD-based free-energy calculations can support computational drug discovery against evolving viral protein–protein interfaces. Full article

In this study, Paliperidone Palmitate (PP), a second-generation antipsychotic, commonly used for the treatment of schizophrenia, was encapsulated in bio-based non-isocyanate polyurethane (NIPU) nanoemulsions. NIPU was synthesized via an isocyanate-free polyaddition route, addressing safety and environmental concerns associated with conventional polyurethanes. The drug-loaded nanoparticles were produced utilizing oil-in-water (O/W) emulsions followed by solvent evaporation and lyophilization. NIPU concentrations of 0.3% and 0.5% w/v, as well as 0.5% w/v PVA were employed, while PP was incorporated at 0.2%, 0.5% and 1% w/v. The formulations were characterized by FTIR, DSC and XRD analyses, and the mechanical strength of neat sponges was evaluated. The nanoparticle formation and size were assessed by DLS and SEM analyses. The water contact angle, porosity measurements and aquatic and enzymatic hydrolysis were additionally performed. The resulting nanocarriers exhibited controlled particle size, increased drug-loading values, structural stability and biodegradability. Lastly, the in vitro dissolution studies revealed a system-specific burst release behavior, and a controlled and sustained overall drug-release profile for majority of the formulations, thereby indicating the potential of NIPU nanocarriers for drug delivery applications, particularly where sustained therapeutic effects are required. Full article

Polymer films and coatings play an increasingly critical role in extending material functionality across industrial, biomedical, and environmental applications. Recent advances in surface engineering have enabled precise control of interfacial properties, leading to enhanced durability, cleanliness, and protection. This review summarizes state-of-the-art strategies for modifying polymer surfaces, with an emphasis on plasma-based surface modification and plasma-induced polymerization as versatile, solvent-free methods for tailoring wettability, chemical functionality, and adhesion. Furthermore, it examines emerging classes of self-cleaning and self-sterilizing coatings that leverage photocatalytic, hydrophobic, or antimicrobial mechanisms to mitigate contamination, biofouling, and pathogen transmission. Additionally, developments in high-performance barrier films designed to protect food products and electronic devices through improved resistance to gases, moisture, and chemical agents are highlighted. By integrating insights from materials chemistry, surface physics, and nanostructured coating design, this review provides a comprehensive overview of current achievements and future directions in functional polymer films and coatings aimed at anti-pollution, antibacterial, and anti-corrosion performance. Full article

The burgeoning convenience food sector, particularly in China, has intensified demand for packaging that simultaneously delivers convenience, environmental sustainability, and functional performance. This study addresses this need by developing a novel self-sealing, rapidly soluble food packaging film. The film was prepared using solvent casting technology, with a konjac glucomannan (KGM) matrix as the base material and gelatin (Gel) and hydroxypropyl tapioca starch (HS) as reinforcing agents. Leveraging the thermoplastic effect of HS (its hydroxypropyl side chains disrupt the ordered hydrogen bond network of KGM and Gel, enhancing molecular chain mobility) characterization via FTIR and SEM confirmed successful heat-sealing upon HS incorporation, while dissolution testing validated enhanced dissolution kinetics. The optimal formulation (KGH₃) exhibited superior mechanical properties (tensile strength (TS): 17.54 MPa) and excellent barrier performance against both light and oxygen transmission compared to pristine KGM and KG control films. Self-sealed pouches fabricated from KGH films preserved edible oil for 65 days, maintaining peroxide values within acceptable limits and demonstrating 48.7% reduction in oxidation compared to KG films. These findings establish KGM–Gel–HS film as promising candidates for adhesive-free, biodegradable packaging of lipid-rich foods. Full article