Search Results (137)

In the context of critical challenges in curcumin-modified polyurethane synthesis—including limited curcumin bioavailability and suboptimal biodegradability/biocompatibility—a novel polyurethane material (Cur-PU) with good mechanical, shape memory, pH-responsive, and biocompatibility was synthesized via a one-pot, two-step synthetic protocol in which HO-PCL-OH served as the soft segment and curcumin was employed as the chain extender. The experimental results demonstrate that with the increase in Cur units, the crystallinity of the Cur-PU material decreases from 32.6% to 5.3% and that the intensities of the diffraction peaks at 2θ = 21.36°, 21.97°, and 23.72° in the XRD pattern gradually diminish. Concomitantly, tensile strength decreased from 35.5 MPa to 19.3 MPa, and Shore A hardness declined from 88 HA to 65 HA. These observations indicate that the sterically hindered benzene ring structure of Cur imposes restrictions on HO-PCL-OH crystallization, leading to lower crystallinity and retarded crystallization kinetics in Cur-PU. As a consequence, the material’s tensile strength and hardness are diminished. Except for the Cur-PU-3 sample, all other variants exhibited exceptional shape-memory functionality, with R_f and R_r exceeding 95%, as determined by three-point bending method. Analogous to pure curcumin solutions, Cur-PU solutions demonstrated pH-responsive chromatic transitions: upon addition of hydroxide ion (OH⁻) solutions at increasing concentrations, the solutions shifted from yellow-green to dark green and finally to orange-yellow, enabling sensitive pH detection across alkaline gradients. Hydrolytic degradation studies conducted over 15 weeks in air, UPW, and pH 6.0/8.0 phosphate buffer solutions revealed mass loss <2% for Cur-PU films. Surface morphological analysis showed progressive etching with the formation of micro-to-nano-scale pores, indicative of a surface-erosion degradation mechanism consistent with pure PCL. Biocompatibility assessments via L929 mouse fibroblast co-culture experiments demonstrated ≥90% cell viability after 72 h, while relative red blood cell hemolysis rates remained below 5%. Collectively, these findings establish Cur-PU as a biocompatible material with tunable mechanical properties, and pH responsiveness, underscoring its translational potential for biomedical applications such as drug delivery systems and tissue engineering scaffolds. Full article

Structural regulation is of great significance for improving the comprehensive performance of energetic materials (EMs). The structural regulation and properties of EMs were summarized. For single-component EMs, particle size control focuses on quality consistency and industrial scalability, morphology modification mainly improves sphericity through monomers or aggregates and explores the possibility of layered energetic materials in improving mechanical properties, and polycrystalline regulation suppresses metastable phases and explores novel crystalline forms using simulation-guided design. Composite EMs (CEMs) employ core–shell structures to balance safety with performance via advanced coating materials, cocrystal engineering to tailor energy release through intermolecular interactions, and lattice strain modulation, and mixing structures integrates component advantages while enhancing the reaction efficiency. Future directions emphasize computational simulations and novel fabrication methods to guide the rational design and precise preparation of next-generation EMs with specific functions. Full article

Boronic acids are an important class of molecules diversely used in organic synthesis, catalysis, medicinal chemistry, and for the design of functional materials. Particularly, aryl boronic acids in the solid state are known to exhibit pharmaceutical and photoluminescent properties for antimicrobial, sensing, and drug delivery applications. Furthermore, the phenazine molecule is known for its diverse pharmacological properties, including antibiotic activity. In the case of molecular crystalline solids, it is well established that understanding noncovalent interactions remains key to designing or engineering their functional properties. While both aryl boronic acids and phenazine molecules individually represent an important class of compounds, their co-assembly in the crystalline state is of interest within the context of supramolecular chemistry and crystal engineering. Herein, we report the supramolecular features of two newly synthesized cocrystals, which are composed of para-F/CF₃-substituted phenylboronic acids, respectively, and phenazine, as demonstrated by structure analysis by single-crystal X-ray diffraction. Full article

The substituent effects on crystal stacking topology and stability of the 5,5-dinitro-2H,2H-3,3-bi-1,2,4-triazole (DNBT) and its three energetic cocrystals with 1,3,5-trinitrobenzene (TNB), 2,4,6-trinitrotoluene (TNT), and picric acid (PA) were systematically investigated through combined density functional theory (DFT) calculations and classical molecular dynamics (MD) simulations. The interaction mechanism and detonation performance of the three energetic cocrystals were implemented to the electrostatic potential (ESP), Hirshfeld surface analysis, radial distribution function (RDF), binding energy, and detonation parameters. In contrast to N-H⋯O interactions in DNBT, three cocrystals exhibited more distinctly weak C-H⋯O intermolecular hydrogen bonds and NO₂-π stacking interactions to stabilize the lattice. Notably, the highest binding energy of PA/DNBT shows the largest stability and lowest impact sensitivity is related to the more intermolecular interactions. Although the introduction of substituents slightly affects the crystal density of DNBT crystals, it significantly reduces the impact sensitivity. Moreover, the balanced detonation performance and impact sensitivity of DNBT-based cocrystals make it a candidate to expand the applications of DNBT crystals. These findings contribute to a broadened understanding of construction and design strategies for the energy release mechanisms of energetic compounds with the azoles ring family. Full article

Addressing the limitations of poor piezoelectric photocatalytic activity and insufficient magnetic recovery in pure BiFeO₃ nanoparticles, Gd and Zr co-doped BiFeO₃ nanoparticles were synthesized via the sol-gel method. The structural characterization revealed a rhombohedral-to-orthorhombic phase transition with reduced grain size (~35 nm) and lattice distortion due to dopant incorporation. An XPS analysis confirmed Fe³⁺ dominance and oxygen vacancy enrichment, while optimized BGFZ9 exhibited enhanced remanent magnetization (0.1753 emu/g, 14.14 increase) compared to undoped BFO. The synergistic piezo-photocatalytic system achieved 81.08% Ofloxacin degradation within 120 min (rate constant: 0.0136 min⁻¹, 1.26 higher than BFO) through stress-induced piezoelectric fields that promoted electron transfer for ·O₂⁻/·OH radical generation via O₂ reduction. The Ofloxacin degradation efficiency decreased to 24.36% after four cycles, with structural integrity confirmed by XRD phase stability. This work demonstrates a triple-optimization mechanism (crystal phase engineering, defect modulation, and magnetic enhancement) for designing magnetically recoverable multiferroic catalysts in pharmaceutical wastewater treatment. Full article

Soil stabilizers are environmentally friendly engineering materials that enable efficient utilization of local soil-water resources. The application of nano-modified stabilizers to reinforce loess can effectively enhance the microscopic interfacial structure and improve the macroscopic mechanical properties of soil. This study employed nano-SiO₂ and nano-CaCO₃ to modify cement-based soil stabilizers, investigating the enhancement mechanisms of nanomaterials on stabilizer performance through compressive and flexural strength tests combined with microscopic analyses, including SEM, XRD, and FT-IR. The key findings are as follows: (1) Comparative analysis of mortar specimen strength under identical conditions revealed that nano-SiO₂ generally demonstrated superior mechanical enhancement compared to nano-CaCO₃ across various curing ages (1–3% dosage). At 1% dosage, the compressive strength of both modified stabilizers increased with curing duration. Early-stage strength differences (3 days) remained below 3% but showed a significant divergence with prolonged curing: nano-SiO₂ groups exhibited 10.3%, 11.3%, and 7.2% higher compressive strengths than nano-CaCO₃ at 7, 14, and 28 days, respectively. (2) The strength enhancement effect of nano-SiO₂ on MBER soil stabilizer followed a parabolic trend within 1–3% dosage range, peaking at 2.5% with over 15% strength improvement. (3) The exceptional performance of nano-SiO₂ originates from its high reactivity and ultrafine particle characteristics, which induce nano-catalytic hydration effects and demonstrate strong pozzolanic activity. These properties accelerate hydration processes while promoting the formation of interlocking C-S-H gels and hexagonal prismatic AFt crystals, ultimately creating a robust three-dimensional network that optimizes interfacial structure and significantly enhances strength characteristics across curing periods. These findings provide scientific support for the performance optimization of soil stabilizers and their sustainable applications in eco-construction practices. Full article

The development of efficient, low-cost electrocatalysts for the oxygen evolution reaction (OER) is crucial for advancing sustainable hydrogen production through water splitting. This study presents a dual-engineering strategy to enhance the OER performance of Co₃O₄ by synthesizing hollow microspheres assembled from nanosheets (HMNs) with abundant oxygen vacancies and highly active crystal facet exposure. Through a modified one-step hydrothermal process, Co₃O₄ HMNs with exposed (111) and (100) crystal facets were successfully fabricated, demonstrating superior OER activity compared to Co₃O₄ nanocubes (NCs) with only (100) facet exposure. The optimized Co₃O₄-5% HMNs exhibited a low overpotential of 330 mV at 10 mA cm⁻² and a Tafel slope of 69 mV dec⁻¹. The enhanced performance was attributed to the synergistic effects of crystal facet engineering and defect engineering, which optimized the Co-O bond energy, increased the number of active sites, and improved conductivity. The unique hollow structure further facilitated mass transport and prevented nanosheet stacking, exposing more edge sites for catalytic reactions. This work highlights the potential of geometric and electronic structure modulation in designing high-performance OER catalysts for sustainable energy applications. Full article

Addressing the critical challenges of interfacial defects and insufficient stability in perovskite solar cells, this work introduces a co-solvent engineering strategy to dynamically regulate the phenethylammonium chloride (PEACl) passivation layer. The effect of isopropyl alcohol (IPA) and a DMSO: IPA (1:100) mixture as solvent for forming the PEACl 2D passivation layer is systematically explored, and the synergistic interplay between solvent coordination strength and crystallization kinetics is systematically investigated. The DMSO: IPA (1:100) blend balances Pb-O coordination (via DMSO) and rapid phase separation (via IPA), enabling the oriented growth of a dense, ultrathin 2D perovskite overlayer. This suppresses defect density (electron traps reduced to 1.68 × 10¹⁵ cm⁻³) and extends carrier lifetime, yielding a champion power conversion efficiency (PCE) of 24.27%—a significant improvement over the control (22.73%). For the first time, we establish a dual-parameter “solvent coordination-crystallization kinetics” model, providing a universal framework for designing environmentally benign solvent systems and advancing the industrial scalability of high-performance perovskite solar cells (PSCs). Full article

Boron phosphide (BP), an emerging III–V semiconductor, has garnered significant interest because of its exceptional structural stability, wide bandgap, high thermal conductivity, and tunable electronic properties. This review provides a comprehensive analysis of BP, commencing with its distinctive structural characteristics and proceeding with a detailed examination of its exceptional physicochemical properties. Recent progress in BP synthesis is critically examined, with a focus on key fabrication strategies such as chemical vapor deposition, high-pressure co-crystal melting, and molten salt methods. These approaches have enabled the controlled growth of high-quality BP nanostructures, including bulk crystals, nanoparticles, nanowires, and thin films. Furthermore, the review highlights the broad application spectrum of BP, spanning photodetectors, sensors, thermal management, energy conversion, and storage. Despite these advances, precise control over the growth, morphology, and phase purity of BP’s low-dimensional structures remains a critical challenge. Addressing these limitations requires innovative strategies in defect engineering, heterostructure design, and scalable manufacturing techniques. This review concludes by outlining future research directions that are essential for unlocking BP’s potential in next-generation electronics, sustainable energy technologies, and multifunctional materials. Full article

Oral solid drug delivery continues to be the gold standard in pharmaceutical formulations, owing to its cost-effectiveness, ease of administration, and high patient compliance. Tablets, the most widely used dosage form, are favored for their precise dosing, simplicity, and economic advantages. Among these, controlled release (CR) tablets stand out for their ability to maintain consistent drug levels, enhance therapeutic efficacy, and reduce dosing frequency, thereby improving patient adherence and treatment outcomes. A well-designed CR system ensures a sustained and targeted drug supply, optimizing therapeutic performance while minimizing side effects. This review delves into the latest advancements in CR formulations, with a particular focus on hydrophilic matrix systems, which regulate drug release through mechanisms such as swelling, diffusion, and erosion. These systems rely on a variety of polymers as drug-retarding agents to achieve tailored release profiles. Recent breakthroughs in crystal engineering and polymer science have further enhanced drug solubility and bioavailability, addressing critical challenges associated with poorly soluble drugs. In terms of manufacturing, direct compression has emerged as the most efficient method for producing CR tablets, streamlining production while ensuring consistent drug release. The integration of the Quality by Design framework has been instrumental in optimizing product performance by systematically linking formulation and process variables to patient-centric quality attributes. The advent of cutting-edge technologies such as artificial intelligence and 3D printing is revolutionizing the field of CR formulations. AI enables predictive modeling and data-driven optimization of drug release profiles, while 3D printing facilitates the development of personalized medicines with highly customizable release kinetics. These innovations are paving the way for more precise and patient-specific therapies. However, challenges such as regulatory hurdles, patent constraints, and the need for robust in vivo validation remain significant barriers to the widespread adoption of these advanced technologies. This succinct review underscores the synergistic integration of traditional and emerging strategies in the development of CR matrix tablets. It highlights the potential of hydrophilic and co-crystal matrix systems, particularly those produced via direct compression, to enhance drug bioavailability, improve patient adherence, and deliver superior therapeutic outcomes. By bridging the gap between established practices and innovative approaches, this field is poised to address unmet clinical needs and advance the future of oral drug delivery. Full article

Modern tissue engineering requires not only degradable materials promoting cell growth and differentiation, but also vascularization of the engineered tissue. Porous polylactide/polycaprolactone (PLA/PCL, ratio 3/5) foam scaffolds were prepared by a combined porogen leaching and freeze-drying technique using NaCl (crystal size 250–500 µm) and a water-soluble cellulose derivative (Klucel^TM E; 10–100% w/w relative to the total PLA/PCL concentration) as porogens. Scanning electron microscopy, micro-CT, and Brunauer–Emmett–Teller analysis showed that all scaffolds contained a trimodal range of pore sizes, i.e., macropores (average diameter 298–539 μm), micropores (100 nm to 10 μm), and nanopores (mostly around 3.0 nm). All scaffolds had an open porosity of about 90%, and the pores were interconnected. The size of the macropores and the nanoporosity were higher in the scaffolds prepared with Klucel. Nanoporosity increased water uptake by the scaffolds, while macroporosity promoted cell ingrowth, which was most evident in scaffolds prepared with 25% Klucel. Human adipose-derived stem cells co-cultured with endothelial cells formed pre-vascular structures in the scaffolds, which was further enhanced in a dynamic cell culture system. The scaffolds are promising for the engineering of pre-vascularized soft tissues (relatively pliable 10% Klucel scaffolds) and hard tissues (mechanically stronger 25% and 50% Klucel scaffolds). Full article

This work aims to explore the influence of crystal phase engineering on the photocatalytic hydrogen evolution activity of Ru/C₃N₄ systems. By precisely tuning the combination of Ru precursors and reducing solvents, we successfully synthesized Ru co-catalysts with distinct crystal phases (hcp and fcc) and integrated them with C₃N₄. The photocatalytic hydrogen evolution experiments demonstrated that hcp-Ru/C₃N₄ achieved a significantly higher hydrogen evolution rate (24.23 μmol h⁻¹) compared to fcc-Ru/C₃N₄ (7.44 μmol h⁻¹), with activity reaching approximately 42% of Pt/C₃N₄ under the same conditions. Photocurrent and electrochemical impedance spectroscopy analyses revealed that hcp-Ru/C₃N₄ exhibited superior charge separation and transfer efficiency. Moreover, Gibbs free energy calculations indicated that the hydrogen adsorption energy of hcp-Ru (ΔG_H* = −0.14 eV) was closer to optimal compared to fcc-Ru (−0.32 eV), enhancing the hydrogen generation process. These findings highlight that crystal-phase engineering plays a critical role in tuning the electronic structure and catalytic properties of Ru-based systems, offering insights for the design of highly efficient noble metal catalysts for photocatalysis. Full article

Cytochromes P450 are a superfamily of heme-containing monooxygenases involved in a variety of oxidative metabolic reactions, primarily catalyzing the insertion of an oxygen atom into a C-H bond. CYP102 represents the first example of a bacterial P450 that can be classified as a type II (eukaryotic-like) P450 and functions as a catalytically self-sufficient enzyme. These unique features have made CYP102 an attractive system for studying P450 structure and function. However, an overall picture of the specific amino acid residues that are crucial to the functioning of CYP102 and the effect of mutations on the P450 structure and catalysis is yet to be reported. Such an approach will aid protein engineering approaches used to improve this enzyme. To address this research knowledge gap, we have investigated 105 CYP102 crystal structures in this study. We demonstrate that the CYP102 active site is highly dynamic and flexible. Amino acid residues that play critical roles in substrate binding, orientation, and anchoring were identified. Mutational studies highlighted the roles of amino acids and provided possible bioengineering improvement strategies for CYP102. Decoy molecules are a promising agent for deceiving CYP102 and permitting non-native substrates into the active site. Ru(II)-diimine photosensitizers and zinc/cobalt (III) sepulchrate (Co(III)Sep) could be used as alternative electron sources. The present study serves as a reference for understanding the structure–functional analysis of CYP102 family members precisely and of P450 enzymes in general. Significantly, this work contributes to the effort to develop an improved CYP102 enzyme, thereby advancing the field of P450 research and potentially leading to new industrial applications. Full article

Cementitious Capillary Crystallization Waterproofing Material (CCCW), as an efficient self-healing agent, can effectively repair damage in concrete structures, thereby extending their service life. To address the various types of damage encountered in practical engineering applications, this study investigates the impact of different mixing methods for CCCW (including internal mixing, curing, and post-crack repair) on the multi-dimensional self-healing performance of concrete. The self-healing capacity of concrete was evaluated through water pressure damage self-healing tests, freeze–thaw damage self-healing tests, mechanical load damage self-healing tests, and crack damage self-healing tests. The results show that the curing-type CCCW mixing method exhibited the best self-healing effect in repairing water pressure, freeze–thaw, and load damages, with corresponding healing rates of 88.9%, 92.7%, and 90.5%, respectively. The internally mixed CCCW method was also effective for repairing load damage in concrete, while the repair-type CCCW mixing method demonstrated the weakest repair effect on these types of damage. For concrete with induced pre-existing cracks, the internally mixed CCCW method, after 28 days of water-immersion curing, exhibited a significantly higher crack self-healing ability, with a self-healing ratio of 333.8%. Optical microscopy observations revealed that the crack surfaces were almost fully sealed, with a substantial deposition of white crystalline material at the crack sites. Further analysis using scanning electron microscopy (SEM) and X-ray Diffraction (XRD) provided insights into the surface morphology and phase characteristics of the self-healed cracks, indicating that calcium carbonate (CaCO₃) and calcium silicate hydrate (C-S-H) were the main products responsible for crack healing. Full article

Development of cocrystals through crystal engineering is a viable strategy to formulate poorly water-soluble active pharmaceutical ingredients as stable crystalline solid forms with enhanced bioavailability. This study presents a controlled cocrystallization process by cooling for the 1:1 cocrystal of Ketoconazole, an antifungal class II drug with the Fumaric acid coformer. This was successfully set up following the meta-stable zone width determination in acetone–water 4:6 (V/V) and pure ethanol. Considering the optimal crystallization data, laboratory scale-up processes were carried out at 1 g batch size, efficiently delivering the cocrystal in high yields up to 90% pure and single phase as revealed by powder X-ray diffraction. Biological assays in vitro showed improved viability and oxidative damage of the cocrystal over Ketoconazole on human dermal fibroblasts and hepatocarcinoma cells; in vivo, on Wistar rats, the cocrystal increased oral Ketoconazole bioavailability with transient minor biochemical transaminases increases and without histological liver alterations. Locally on Balb C mice, it induced no epicutaneuous sensitization. A molecular docking study conducted on sterol 14α-demethylase (CYP51) enzyme from the pathogenic yeast Candida albicans revealed that the cocrystal interacts more efficiently with the enzyme compared to Ketoconazole, indicating that the coformer enhances the binding affinity of the active ingredient. Full article