Search Results (534)

4,4′-substituted-2,2′-((hexahydro-1H-benzo[d]imidazole-1,3(2H)-diyl)bis(methylene))bisphenols (1a–d) and 2,6-bis{[3-(2-hydroxy-5-substitutedbenzyl)octahydro-1H-benzimidazol-1-yl]methyl}-4-substitutedphenols (2a–b) were synthesized via microwave (MW) irradiation of aminal (2R,7R,11S,16S)-1,8,10,17-tetraazapentacyclo[8.8.1.1.^8,170.^2,70.^11,16]icosane 2 with p-substituted phenols. Microwave (MW) irradiation improved reaction rates and yields at 80 °C. Compounds 1a–d were racemic, and 2a–b were diastereomeric. NMR spectra revealed key signals for the perhydrobenzimidazole fragment, aromatic rings, and aminal carbons. Differences in the ¹³C NMR spectra highlighted structural variations, such as distinct carbonyl and methoxyl signals in 2d. MW irradiation at higher temperatures (100–120 °C) reduced yields of 1, especially for phenols with methyl (Me) and methoxy (OMe) groups, suggesting a shift toward the formation of compound 2. Additionally, higher temperatures led to polymerization byproducts, emphasizing the impact of MW energy on reaction pathways. These results provide valuable insights for designing molecules with potential applications in materials science and medicinal chemistry. Full article

This study investigates the influence of photoinitiating systems on the degree of methacrylate group conversion and the rate of polymerization in UV/LED-curable nail gel formulations. Camphorquinone and Eosin Y, commonly used in medical and dental applications, were evaluated in bimolecular systems with onium and iodonium salts, thiols, and amines as co-initiators. Real-time FT-IR spectroscopy was employed to monitor polymerization under dual-LED irradiation (365 nm and 405 nm). The results demonstrate that the tested systems, inspired by photocurable medical products, exhibit significant potential for application in highly pigmented nail gels, achieving efficient curing with low residual monomer content. Full article

In this study, a highly stable light-responsive superhydrophobic paper was successfully fabricated. The process involved polymerizing the synthesized light-responsive monomer PAPAE with the hydrophilic monomer 2-hydroxyethyl methacrylate(HEMA), the fluorine-containing monomer hexafluorobutyl methacrylate(HFMA),and 3-trimethoxysilyl-propyl methacrylate(TSPM), followed by grafting (3-Aminopropyl) triethoxysilane (APTES)-modified SiO₂ nanoparticles onto the polymer to enhance surface roughness, and subsequently applying this composite to the paper surface. When the monomer ratio in the polymer was HFMA:TSPM:PAPAE:HEMA = 0.2:0.2:0.4:0.2, the resulting coating exhibited good water solubility, enabling the modified paper to achieve reversible wettability transitions under light irradiation. At a SiO₂-to-polymer ratio of 0.3, the contact angle variation range reached its maximum (96–156.8°). The proposed method for fabricating superhydrophobic paper not only offers relative simplicity, low cost, and strong versatility but also imparts the paper with excellent weather resistance, abrasion resistance, and ultrasonic durability, highlighting its great potential for practical applications. Full article

Novel universal bulk-fill composites with reversible addition–fragmentation chain-transfer (RAFT)-modulated polymerization continue the trend towards increasing simplification of the restoration process to facilitate the reconstruction of deep posterior restorations in 4 mm increments as well as anterior restorations through improved aesthetics. This study aims to assess the suitability of such materials for rapid curing (3 s) with high-radiant emittance in terms of degree of conversion (DC) and polymerization kinetics at relevant depths (2 mm vs. 4 mm). For this purpose, two newly introduced bulk-fill universal composites (Tetric^® plus Flow and Tetric^® plus Fill) were compared with already established fast-curing composites (Tetric^® Power Flow and Tetric^® Power Fill). DC was measured in real time over 300 s using ATR-FTIR spectroscopy. The temporal DC evolution was modelled using an exponential sum function. Novel bulk-fill composites showed DC results that were independent of the measured sample depth or curing mode. The polymerization kinetics of all composites are somewhat slower in the gel phase at moderate irradiance or when measured at deeper layers, but compensate for the differences in the glass phase, finally reaching equivalent DC values by the end of the 300-s observation period. These novel composites are therefore suitable for rapid curing (3 s) at high irradiance. Full article

The oxidative dehydrogenation of propane (ODHP) catalyzed by oxygen offers several advantages, including resistance to carbon deposition and low energy consumption. However, achieving high propylene selectivity at industrially relevant conversions remains challenging, as existing catalysts typically require temperatures exceeding 500 °C, promoting over-oxidation to CO_x. In this study, we developed a NiO nanoparticle-decorated graphitic carbon nitride catalyst (NiO@CN-600) via thermal polymerization–oxidation for photo-thermal synergistic ODHP. At 430 °C, thermal catalysis achieved a propane conversion of 14%. Remarkably, introducing light irradiation boosted conversion to 24%, a 10% increase. Further experimental results reveal that the photo-thermal synergistic catalysis can be described by the following mechanism: initial thermal energy provides sufficient activation energy, enabling the reaction to overcome the energy barrier and proceed smoothly. Simultaneously, the introduction of light energy enhances the activity of lattice oxygen, making it more likely to detach from the lattice and form oxygen vacancies, which in turn boosts the efficiency of the oxidation reaction on the catalyst surface. Full article

The impact of encapsulating gemcitabine (GEM) into nanoparticles on its delivery remains underexplored, with the potential benefits of targeted drug delivery and stimuli-responsive release yet to be fully clarified. Herein, we designed a near-infrared (NIR) light-responsive polymeric nanoparticle, ZnPc@P(PEG-CMA-TKGEM), which integrates reactive oxygen species (ROS) generation and cell imaging capabilities. The self-assembled polymeric micelles exhibit a hydrodynamic size of ~134 nm. Under NIR irradiation, the cumulative drug release rate reaches 51% within 48 h, which is three times higher than that of the non-irradiated control group. In cytotoxicity assays, the cell viability of the NIR-irradiated drug-loaded group is approximately 17%, while that of the NIR-irradiated blank group (without drug loading) remains above 80%. These results confirm that the nanocarriers successfully deliver GEM to target cells and achieve controlled drug release via NIR stimulation. Full article

This article examines the influence of micro- and nanoscale calcium carbonate (CaCO₃) fillers on the dielectric behavior and aging resistance of polyvinyl chloride (PVC)-based composites. PVC films containing varying CaCO₃ contents (0%, 2.5%, 5%, and 7.5% by weight) were subjected to accelerated aging through prolonged ultraviolet (UV) exposure and thermal stress for up to 1248 h. The evolution of dielectric properties was characterized by impedance spectroscopy, while structural modifications were analyzed using Fourier-transform infrared (FTIR) spectroscopy. Additionally, changes in surface morphology, internal homogeneity (related to particle size, shape, and distribution), and chemical composition were investigated using scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (SEM-EDX), to evaluate the effects of irradiation and variations in the material’s surface composition and morphology. The results reveal a significant correlation between filler concentration and dielectric stability, highlighting the potential of CaCO₃ reinforcement to improve the long-term reliability of polymeric insulating materials. The results further highlight that beyond the amount of filler used, the fine-scale feature of CaCO₃, particularly its particle size and how well it is dispersed, has a significant impact on how the material responds to aging and maintains its dielectric properties. Full article

In this study, a shape-changeable 3D scaffold with photothermal effects was developed to address the clinical challenges of complex bone defects. The multifunctional construct was fabricated via in situ polymerization combined with a gas foaming technique, creating hierarchical porous architectures that mimic the native bone extracellular matrix. By incorporating polydopamine (PDA)-modified amorphous calcium phosphate (CA) into poly(propylene glycol) (PPG)- and poly(ԑ-caprolactone) (PCL)-based polyurethane (PU). The obtained scaffolds achieved osteoinductive potential for bone tissue engineering. The surface PDA modification of CA enabled efficient photothermal shape conversion under near-infrared (NIR) irradiation, facilitating non-invasive remote control of localized hyperthermia. The optimized scaffolds exhibited interconnected porosity (approximately 70%) with osteoconductive pore channels (200–500 μm), resulting in good osteoinduction in cell culture, and precise shape-memory recovery at physiological temperatures (~40 °C) under NIR for minimally invasive delivery. The synergistic effect of osteogenesis promotion and photothermal transition demonstrated this programmable scaffold as a promising solution for integrated minimally invasive bone repair and defect reconstruction. Full article

The aim of this study was to evaluate (a) the degree of conversion (DC%), (b) film thickness, and (c) the effect of film thickness on DC% in modern light-cured resin composite restoratives [Filtek Universal (F), Clearfil Majesty ES 2 Universal (M), Tetric EvoCeram (T) and Viscalor (V)] used for luting composite onlays before/after preheating. For (a), the luting composites placed at 150 μm film thickness under the onlays (4 mm thickness, 2.9% transmittance) were light-cured for 120 s (3 × 40 s top, buccal, lingual sites) before and after preheating (54 °C/5 min-F,M,T and 65 °C/30 s-V). The DC% was measured at central, middle and side locations along the median in-length axis by ATR-FTIR spectroscopy. Specimens polymerized without onlays (40 s, top) served as controls. For (b), film thickness was measured employing a modified ISO 4049 standard (37 °C plate temperature, 5 N load) before and after preheating, using a dual-cured resin luting agent as control. For (c), onlays were luted with preheated T at 150 and 350 μm film thickness and light-cured for 2 × (3 × 40) s and 3 × (3 × 40) s, employing directly irradiated specimens (60 s, 120 s) as controls. For (a), significant differences were found in F and T before and after preheating. Before preheating, significant differences were registered between F–T, F–M, F–V and V–T, whereas after they were registered between F–M, F–T and F–V. All these values were significantly lower than the controls. For (b), significantly lower film thickness was recorded after preheating (−16.1–−33.3%, highest in V), with a ranking of F, M > V > T (before) and F, M > T, V (after). All values were significantly higher than the control. For (c), increased exposure improved DC% in the greater spacer group, with the controls providing superior values. It can be concluded that the use of modern highly filled composites as luting agents for low translucency onlays may result in suboptimal polymerization and film thickness, warranting caution. Full article

Over efficient photocatalysts, CO₂ photoreduction typically converts CO₂ into low-carbon chemicals, which serve as raw materials for downstream synthesis processes. Here, an efficient composite photocatalyst heterojunction (Cu₂O-u/g-C₃N₄) has been fabricated to reduce CO₂. Graphitic carbon nitride (g-C₃N₄) was synthesized via thermal polymerization of urea at 550 °C, while pre-dispersed Cu₂O derived from urea pyrolysis (Cu₂O-u) was prepared by thermal reduction of urea and CuCl₂·2H₂O at 180 °C. The heterojunction Cu₂O-u/g-C₃N₄ was subsequently constructed through hydrothermal treatment at 180 °C. This heterojunction exhibited a bandgap of 2.10 eV, with dual optical absorption edges at 485 nm and above 800 nm, enabling efficient harvesting of solar light. Under 175 W mercury lamp irradiation, the heterojunction catalyzed liquid-phase CO₂ photoreduction to formic acid, acetic acid, and methanol. Its formic acid production activity surpassed that of pristine g-C₃N₄ by 3.14-fold and TiO₂ by 8.72-fold. Reaction media, hole scavengers, and reaction duration modulated product selectivity. In acetonitrile/isopropanol systems, formic acid and acetic acid production reached 579.4 and 582.8 μmol·h⁻¹·g_cat⁻¹. Conversely, in water/triethanolamine systems, methanol production reached 3061.6 μmol·h⁻¹·g_cat⁻¹, with 94.79% of the initial conversion retained after three cycles. Finally, this work ends with the conclusions of the CO₂ photocatalytic reduction to formic acid, acetic acid, and methanol, and recommends prospects for future research. Full article

It is widely recognized that fine surface structures found in nature contribute to surface functionality, and studies on the design of functional materials based on biomimetics have been actively conducted. In this study, polymer thin films with hierarchically ordered surface structure were prepared by combining both nanoimprinting using anodically oxidized porous alumina (AAO) as a template and surface-initiated atom transfer radical polymerization (SI-ATRP). To prepare such polymer films, we designed a new copolymer (poly{[2-(4-methyl-2-oxo-2H-chromen-7-yloxy)ethyl methacrylate]-co-[2-(2-bromo-2-methylpropionyloxy)ethyl methacrylate]}; poly(MCMA-co-HEMABr)) with coumarin moieties and α-haloester moieties in the pendants. The MCMA repeating units function to fix the pillar structure by photodimerization, and the HEMABr ones act as the polymerization initiation sites for SI-ATRP on the pillar surfaces. Surface structures consisting of vertically oriented multiple pillars were fabricated on the spin-coated poly(MCMA-co-HEMABr) thin films by nanoimprinting using an AAO template. Then, the coumarin moieties inside each pillar were crosslinked by UV light irradiation to fix the pillar structure. SEM observation confirmed that the internally crosslinked pillar structures were maintained even when immersed in organic solvents such as 1,2-dichloroethane and anisole, which are employed as solvents under SI-ATRP conditions. Finally, poly(2,2,2-trifluoroethyl methacrylate) and poly(N-isopropylacrylamide) chains were grafted onto the thin film by SI-ATRP, respectively, to prepare the hierarchically ordered surface structure. Furthermore, in this study, the surface properties as well as the thermoresponsive hydrophilic/hydrophobic switching of the obtained polymer films were investigated. The surface morphology and chemistry of the films with and without pillar structures were compared, especially the interfacial properties expressed as wettability. Grafting poly(TFEMA) increased the static contact angle for both flat and pillar films, and the con-tact angle of the pillar film surface increased from 104° for the flat film sample to 112°, suggesting the contribution of the pillar structure. Meanwhile, the pillar film surface grafted with poly(NIPAM) brought about a significant change in wettability when changing the temperature between 22 °C and 38 °C. Full article

A simple and innovative synthesis strategy was established to produce polymer microspheres with a distinctive walnut-like morphology, incorporating Fe₃O₄ nanoparticles within their structure. This was achieved through γ-ray-initiated mini-emulsion polymerization. To ensure high encapsulation efficiency, the surface of the Fe₃O₄ nanoparticles was chemically altered to shift their wettability from hydrophilic to hydrophobic, enabling uniform dispersion within the monomer phase before polymerization. The formation of the walnut-like architecture was found to be significantly influenced by both the polymerization dynamics and phase separation, as well as the shrinkage of the crosslinked polymer network formed between the monomer and the resulting polymer. Divinylbenzene (DVB) was chosen as the monomer due to its ability to generate a mechanically stable polymer framework. The γ-ray irradiation effectively initiated polymerization while preserving structural coherence. A detailed analysis using FTIR, SEM, and TEM confirmed the successful fabrication of the Fe₃O₄-loaded polymer microspheres with their characteristic textured surface. Moreover, magnetic characterization via vibrating sample magnetometry (VSM) indicated pronounced superparamagnetic behavior and strong magnetic responsiveness, highlighting the potential of these microspheres for advanced biomedical applications. Full article

Visible-light-driven photocatalytic hydrogen production is one of the ideal green technologies for solar-to-chemical energy conversion. Carbon nitride (C₃N₄, CN) has been attracting extensive attention for its suitable band structure and stability, but the efficiency of photocatalytic hydrogen evolution is low due to insufficient visible-light absorption and rapid charge recombination. Herein, we develop a novel (F, K)-co-doped CN (FKCN) catalyst via a facile thermal polymerization approach using KOH-modified melamine and NH₄F as the dopant precursors. The FKCN catalyst demonstrates broadened light absorption, significantly enhanced charge separation, and excellent cyclic stability. And the optimal F_(0.15)K₍₆₎CN catalyst achieves a hydrogen evolution rate of as high as 3101.5 μmol g⁻¹ h⁻¹ (12-fold that of pristine CN) under visible-light irradiation (λ ≥ 420 nm), which is among the best element-doped CN photocatalysts. This work highlights the effectiveness of a multi-element doping strategy in designing CN-based photocatalysts for efficient hydrogen evolution. Full article

This study developed cholesteric liquid crystal broadband reflective films using zinc oxide nanoparticles (ZnO NPs) and homotriazine UV-absorbing dye (UV-1577) to enhance infrared shielding. Unlike benzotriazole-based UV absorber UV-327, which suffers from volatility and contamination, UV-1577 exhibits superior compatibility with liquid crystals, higher UV absorption efficiency, and enhanced processing stability due to its larger molecular structure. By synergizing UV-1577 with ZnO NPs, we achieved a gradient UV intensity distribution across the film thickness, inducing a pitch gradient that broadened the reflection bandwidth to 915 nm and surpassing the performance of previous systems using UV-327/ZnO NPs (<900 nm). We conducted a detailed examination of the factors influencing the reflective bandwidth. These included the UV-1577/ZnO NP ratio, the concentrations of the polymerizable monomer (RM257) and chiral dopant (R5011), along with polymerization temperature, UV irradiation intensity, and irradiation time. The resultant films demonstrated efficient ultraviolet shielding via the UV-1577/ZnO NPs collaboration and infrared shielding through the induced pitch gradient. This work presents a scalable strategy for energy-saving smart windows. Full article

The present work introduces a sustainable, low-carbon method to fabricate durable, non-toxic superhydrophobic surfaces using bamboo-derived cellulose. Uniform TEMPO-carboxylated cellulose particles (TOC-Ps), approximately 2 μm in diameter, were synthesized through thermal polymerization and spray drying. These particles, featuring a nano-scale convex structure formed by intertwined TOC nanofibers, were applied to substrates and modified with low-surface-energy materials to achieve superhydrophobicity. At an optimal TOC-P mass ratio of 6%, the surface displayed a water contact angle of 156.2° and a sliding angle of 7°. The coating maintained superhydrophobicity after extensive mechanical testing—120 cm of abrasion, 100 bending cycles, and continuous trampling—and exhibited robust chemical stability across harsh conditions, including subjection to high temperatures, UV irradiation, and corrosive solutions (pH 2–12). The hierarchical micro–nano structure was found to enhance both hydrophobicity and durability, offering an environmentally friendly alternative for self-cleaning surfaces, textiles, and building applications. Full article