Search Results (364)

Silica spicules provide a natural transdermal conduit but require a linker that binds strongly under physiological conditions and releases payloads selectively in response to biological cues. Existing silane chemistries or polydopamine coatings lack enzyme responsiveness and show limited control over release. We created a 180-member peptide library with the motif L–X1–X2–[Y–F–Y]–A–L–G–P–H–C and screened for silica binding. Biophysical assays (circular dichroism, ζ-potential, quartz crystal microbalance, atomic force microscopy) and molecular dynamics identified high-affinity binders. The lead, P176, was tested for matrix metalloprotease (MMP)-responsive cleavage. Conjugation and release of Vitamin C and Stigmasterol were analyzed by HPLC and Franz diffusion cells. P176 showed high silica affinity (~55 µg mg⁻¹), robust biophysical signals (Δf −35 to −38 Hz; rupture force ~154 pN; ζ shift −22 to−11.5 mV), and favorable adsorption energy (−48.5 kcal mol⁻¹, contact 4.5 nm², 8.5 H-bonds). The MMP gate displayed efficient kinetics (Vmax 117.9 RFU·min⁻¹, Km 5.0 µM) with >90% cleavage at 60 min, reduced to 26% by inhibitor. Conjugation yields reached 87% (Vitamin C) and 77% (Stigmasterol). Franz diffusion showed MMP-dependent release (24 h: Vitamin C 90–96%, Stigmasterol 80–85%) with minimal basal leakage. Released Vitamin C enhanced collagen I to ~250% in fibroblasts, while Stigmasterol attenuated LPS-induced macrophage morphology; keratinocytes retained normal marker expression. This study demonstrates that a single amphipathic, sequence-programmed peptide can couple strong silica anchoring with protease-responsive release and broad payload compatibility, establishing a versatile platform for spicule-based transdermal and regenerative delivery. Full article

Antibiotics have become an integral part of human life and production. The presence of sulfachloropyridazine (SCP), one of the most ubiquitous antibiotics, in water has been a growing concern owing to its long persistence and the difficulty in removing it by conventional water treatment processes. This study introduced ozone (O₃)-activated sodium percarbonate (SPC) as an innovative technique of advanced oxidation processes (AOPs), and the degradation of SCP from water by this method was thoroughly investigated. The impact of a variety of parameters, such as the dosage of SPC, the dosage of O₃, the pH value, and water matrix constituents, on the removal of SCP was evaluated with regard to the pseudo-first-order kinetic model. It was found that the removal effectiveness of SCP improved initially and then decreased with the rising dosage of SPC, with an optimal SPC dose achieved at 20 mg/L. Moreover, •OH, ${\mathrm{O}}_2^{•-}$ and ¹O₂ played important roles during SCP degradation based on radical quenching tests and electron paramagnetic resonance (EPR) tests. The SCP degradation pathways were predicted using density functional theory (DFT), which primarily involves the cleavage of S-C or S-N bonds and Smiles-type rearrangements, accompanied by hydroxylation. Furthermore, the toxicity of degradation intermediates was evaluated by the ECOSAR 1.1 software in terms of acute toxicity and chronic toxicity, and most of them exhibited lower levels of toxicity. The results can expand the research scope of SPC and reveal significant insights for SPC’s application in controlling antibiotic contamination. Full article

Haloketoesters are synthetic intermediates in various cyclization reactions that facilitate the production of biologically active compounds. Nonetheless, the selective synthesis of dihaloketoesters and trihaloketoesters, which are expected to be highly versatile, presents significant challenges. In this study, we designed a new synthetic approach that selectively and efficiently produces haloketoesters through the halogenative C–C bond cleavage and ring-opening reactions of cyclic 1,3-diketones. This convenient method enables the direct synthesis of di- and trichloro-functionalized ketoesters from 1,3-cyclohexadiones under mild conditions. Na₂HPO₄, employed as a buffer salt, proved to be effective in facilitating the alcoholytic ring-opening reaction of 2,2-dichloro-1,3-cyclohexadiones, which were generated as synthetic intermediates. Full article

In this work, the one-pot catalytic reductive fractionation of C-lignin in castor shell powders to efficiently provide catechyl monomers was achieved by tandem metal triflate and Pd/C catalysis. The optimized Pd/C + In(OTf)₃ combination performed best and provided a 66.9 mg·g⁻¹ yield of corresponding aromatic monomers with the catechol selectivity as high as 95.4%. For the promotion effect of the Lewis acid species, the mechanism studied indicated that the introduction of In³⁺ could significantly promote the C–O bond cleavage in the LCC to release the C-lignin fragments from the solid lignocellulose and simultaneously accelerate the cleavage of the critical C_α/β–OAr linkage bond in C-lignin to release catechol monomers. In addition, performance differences highlight the cooperation and function-matching effect between the hydrogenation metals and the Lewis ion species, which can promote the high-value utilization of forestry and agricultural residues in chemical synthesis. Full article

Rice husk is a lignocellulosic biomass rich in silica, which, when disposed of inappropriately, represents an environmental hazard. This study investigated the application of deep eutectic solvents (DES) as a green and efficient approach to the rice husk fractionation, combining the selective dissolution of lignin and sugars with the purification of the silica-rich inorganic fraction. Six different DES were produced from choline chloride or betaine with different hydrogen bond donors and characterized for water content and pH. The DES based on carboxylic acids was more acidic, which favored the cleavage of ester and glycosidic bonds in the biomass. The TGA, XRF, SEM, and XRD analyses revealed that the lactic acid-based DES promoted better removal of lignin and mineral impurities, resulting in a purer silica with an amorphous morphology. The 110 °C condition was the most effective in preserving the thermal integrity of the organic (sugars and lignin) and inorganic (silica-rich ash) fractions. The results highlight the potential of DES as selective, sustainable, and tunable solvents for the valorization of agricultural waste, achieving biosilica with SiO₂ purity exceeding 80% and lignin removal above 70%, reinforcing the potential of DES as sustainable solvents for agricultural waste valorization. Full article

Azaoxyallyl cations, as novel and versatile three-atom components, have been widely utilized in cycloaddition reactions, with the competition between O- and N-cyclization pathways remaining a key research focus. This study investigates the mechanism and site selectivity of (3+2) cycloaddition between azaoxyallyl cations and 1,2-benzisoxazoles using density functional theory calculations. The results reveal a stepwise (3+2) addition to the C=N double bond, followed by base-assisted N-O bond cleavage and isoxazole ring-opening, leading to oxazoline (via O-cyclization) or imidazolone (via N-cyclization) derivatives. When unsubstituted 1,2-benzisoxazole is used as the substrate, O-cyclization dominates as a kinetically controlled process due to lower activation barriers, while N-cyclization, as a thermodynamically controlled process, is minor. The presence of a methyl group at the C(3) position in 1,2-benzisoxazoles completely blocks N-O bond cleavage, forcing exclusive (3+2) cycloaddition to yield less stable tricyclic products via N-cyclization rather than O-cyclization. These findings align with experimental observations and provide new mechanistic insights into the site selectivity of azaoxyallyl cation cycloadditions. Full article

The growing environmental and economic impacts of carbon-based fuels have accelerated the search for sustainable alternatives, with hydrogen (H₂) emerging as a clean and efficient energy carrier. Sodium borohydride (NaBH₄) is a promising hydrogen storage compound, due to its high hydrogen content (10.6 wt%) and stability under ambient conditions. However, its hydrolysis with water proceeds slowly without an effective catalyst. In this study, gold nanoparticle-decorated spherical carbon (AuSC) composites were synthesized and evaluated as catalysts for NaBH₄ hydrolysis. The spherical carbon support, prepared via a glucose-mediated route, provided a high-surface-area and conductive matrix that dispersed and stabilized Au nanoparticles, preventing agglomeration. Catalyst morphology and composition were characterized using XRD, TEM, SEM, and EDS analyses. The AuSC catalyst exhibited excellent catalytic activity, producing 21.8 mL of H₂ at pH 7, 303 K, and 835 μmol NaBH₄. The activation energy (E_a) was determined to be 51.6 kJ mol⁻¹, consistent with a heterolytic B–H bond cleavage mechanism at the Au–C interface. The TON (2.82 × 10⁴) and TOF (1.41 × 10⁴ h⁻¹) values confirmed high intrinsic catalytic efficiency. These results demonstrate that Au-decorated spherical carbon composites are efficient, stable, and promising catalysts for hydrogen generation from NaBH₄ hydrolysis under mild conditions. Full article

In this study, we investigate the catalytic degradation of polystyrene (PS) in water at low temperature (90–110 °C, 1 atm) using a multiphase carbide–alloy catalyst obtained by mechanosynthesis. X-ray diffraction and scanning electron microscopy confirm a mixture of Mo–W carbides and Fe/Ni alloys, consistent with multiple types of active sites. High-resolution mass spectrometry (MS) is used to assign products by oligomer-series spacing (styrene repeat mass, 104.15 Da) and the residual mass $\Delta m$ for end-group identification. At 90 °C without catalyst, the spectrum shows PS fragments between $m/z=888$–4618, consistent with thermal depolymerization. With catalyst at 90 °C, new lower-$m/z$ peaks emerge and long-chain signals diminish, indicating enhanced chain scission under mild conditions. Increasing the temperature to 100 and 110 °C yields even lighter ions (e.g., $m/z=307.59$ and 247.88), confirming stronger cracking and a larger number of distinct products. End groups inferred from $\Delta m$ include alkenes (C₃–C₇), alkanes (C₄, C₇), cyclic C₆–C₇ fragments, and alcohols, which are consistent with protolytic C–C bond cleavage (Haag–Dessau), oxidative dehydrogenation, and subsequent hydrogenation/hydration on metal/carbide sites. Overall, the results show that water-activated carbide–alloy catalysts can drive PS deconstruction at low temperature, shifting products toward shorter chains with useful functional groups, while a simple MS-based rule set provides a transparent and reproducible approach to product assignment. Full article

Rapid and specific detection of toxic Novichok agents (A230, A232, A234) is crucial for forensic investigations and the prevention of chemical weapon misuse. While A232 and A234 are relatively stable, A230 is less stable and primarily undergoes hydrolysis via P–F bond cleavage. This product indicates the presence of the Novichok core but does not indicate the agent’s prior existence. In this study, a method with high sensitivity for determining the presence of the minor A230 hydrolysis product—namely methylphosphonofluoridic acid (MPFA), which is generated via P-N bond cleavage—in environmental matrices was established. 2-[(Dimethylamino)methyl]phenol (2-DMAMP) was found to be effective for the derivatization of MPFA in water. The derivatization protocol after optimization involved adding 2-DMAMP followed by agitating for 72 h at 50 °C before LC–MS/MS analysis. The derivatized MPFA, analyzed by ESI–MS/MS, showed two main fragment ions with m/z values of 185.0 and m/z 107.0. The approach was applied to tap water, aqueous soil extract, and saline samples. While intact MPFA exhibited reduced detectability due to strong matrix effects, derivatization enhanced its stability and minimized interferences, resulting in its significantly higher detection sensitivity. The detection of MPFA provides a clear indication that the toxic Novichok compound was present prior to hydrolysis. Full article

Hexafluoroethane and 1,1,1,3,3,3-hexafluoropropane (abbreviated as HFC-236fa and R-116, respectively, referred to as C₂F₆ and C₃H₂F₆ based on their molecular formulas) were selected as the object to study the corrosion effects of gas fire-extinguishing agents on different metal materials in the storage state. Typical metal materials used in storage containers including 304 stainless steel, Q235 carbon steel, 6061 aluminum alloy, H59 brass, and T2 copper were subjected to full-immersion corrosion experiments under simulated storage conditions with high-pressure and alternating high–low temperature cycles. High-definition cameras, a scanning electron microscope (SEM), high-precision electronic balances, an energy-dispersive spectrometer (EDS), and X-ray photoelectron spectroscopy (XPS) were used to explore the corrosion characteristics. The chemical reactions and mechanisms were analyzed. The results indicate the following: (1) A thin corrosion layer appears on the surface of the metal with varying degrees of severity but low prevalence. (2) The corrosion rates of C₂F₆ and C₃H₂F₆ were comparable and varied in the following order: 6061 aluminum alloy > Q235 carbon steel > H59 brass > 304 stainless steel > T2 copper. (3) C₃H₂F₆ is slightly higher than C₂F₆ in all corrosion rate values. (4) The corrosion of metal materials is mainly attributed to the reaction between metal elements and the F-containing groups produced by the cleavage of C₂F₆ and C₃H₂F₆. The generated metal halides in turn catalyze the cleavage of C₂F₆ and C₃H₂F₆. This catalytic effect may be positively correlated with the reactivity of the metal element. (5) The higher corrosive activity of C₃H₂F₆ compared to C₂F₆ is attributed to the ease of C–C bond cleavage, catalyzed by metal halogens. This study provides theoretical insights into the corrosion ability of halogenated alternatives as a replacement for halon-based fire extinguishers. Full article

Polyethylene terephthalate (PET) is widely used, yet the accumulation of its waste poses serious environmental challenges, making efficient recycling essential. PET glycolysis using EG as a solvent has emerged as a green recycling strategy. In this study, a cyclic alkylamino carbene copper (CAAC-Cu) complex was prepared as a catalyst for PET glycolysis. Under optimized conditions (160 °C, 90 min, catalyst amount 3 wt%, and PET/EG = 1:4.), PET conversion reached 98.2%, the selectivity toward BHET was 88.1%, and the yield was 86.5%. Kinetic analysis indicated that the glycolysis follows first-order kinetics with an activation energy of 98.7 kJ mol⁻¹. In addition, the catalyst can be recovered together with excess EG, and after multiple recycles, PET degradation remained above 95% and BHET yield remained above 80%. A possible mechanism has also been proposed: Cu acts as a Lewis acid coordinating to the carbonyl oxygen of PET, facilitating ester bond activation, while the amino-carbene forms hydrogen bonds with EG, assisting bond cleavage in a Brønsted-base manner. This catalytic system provides a novel and efficient approach for the green, high-performance glycolysis of PET. Full article

The chemical recycling process of polyethylene terephthalate (PET) was executed through aminolysis employing N, N-Diisopropylethylamine (DIPEA) as the catalytic agent, commencing with the systematic collection and comprehensive purification of discarded PET bottles to remove contaminants and additives. The depolymerization reaction utilized hydrazine as the primary amine source, facilitating the cleavage of ester bonds within the polymer matrix under controlled temperature and pressure conditions. The synthesis of the diamine compound, terephthalohydrazide, was successfully achieved through this catalytic aminolysis pathway, demonstrating high conversion efficiency and product selectivity. The resulting terephthalohydrazide served as a crucial intermediate and was subsequently utilized for the further synthesis of bis-1,3,4-Oxadiazole derivatives through a comprehensive methodology rigorously aligned with the fundamental principles of green chemistry, including atom economy, reduced waste generation, and environmentally benign reaction conditions. A diverse series of six distinct products derived from various carboxylic acids employed in the cyclization synthesis of bis-1,3,4-Oxadiazoles were systematically produced under optimized reaction parameters. These products were meticulously characterized using advanced nuclear magnetic resonance (NMR) spectroscopy techniques, including both ¹H and ¹³C NMR analyses, confirming their structural integrity and chemical composition. This sequential approach represents a significant advancement in heterocyclic synthesis methodology, using sustainable pathways to find structural diversity. Full article

The dehydrogenation of cyclohexane is of vital importance for the production of Nylon-6 and Nylon-66, as it enhances atom utilization efficiency. Ca-doped platinum catalysts have been employed in alkane dehydrogenation due to their ability to selectively activate C–H bonds while minimizing C–C bond cleavage. However, owing to their limited selectivity toward cyclohexene, Pt-Ca/Al₂O₃ catalysts have not been widely adopted in the field of partial dehydrogenation to alkenes. In this work, Al₂O₃ supports are fabricated using the direct ink writing (DIW) 3D printing technique, incorporating designed channels. After impregnation and calcination at 550 °C, the distribution of active species, surface acidity, and basicity are optimized, resulting in a cyclohexene yield of 8.9%. The cyclohexene yield and stability of the 3D-printed catalysts are significantly higher than those of the granular catalyst, attributed to enhanced heat and mass transfer performance facilitated by the internal channels. Full article

Environmental problems arising from conventional production models have posed a significant challenge in the search for renewable sources as raw materials for the production of everyday chemical compounds through more sustainable alternatives. The objective of the present work was the electrochemical synthesis of organic acids from the liquid of the natural and technical cashew nut shell (CNSLn and CNSLt), employing chronopotentiometry using a potentiostat and a graphite working electrode. Two concentrations (0.01–0.1% v/v) of CNSLn and CNSLt, two concentrations of NaOH as supporting electrolyte (0.125–2 M), and two current densities (40–60 mA/cm²) were tested in the experiments. Organic acids were detected and quantified by HPLC. To characterize the redox processes occurring in the constituents of CNSL, spectroelectrochemical analysis (FTIR–cyclic voltammetry), FTIR, and chronoamperometry were performed. The maximum concentrations obtained in the treatments were: acetic acid (828.86 mg/L), lactic acid (531.78 mg/L), and formic acid (305.4 mg/L), while other acids present in lower concentrations included oxalic, propionic, citric, and malonic acids. Voltammetry characterizations showed three irreversible oxidation processes in the anodic wave during the first cycle, indicating that the first process involved the formation of the phenoxy radical, the second process the formation of hydroquinones and benzoquinones, and the third process the cleavage of the aromatic ring and the aliphatic chain to form the organic acids. Furthermore, another oxidation pathway was observed, consisting of a fourth process in the second voltammetry cycle, corresponding to the nucleation of the phenoxy radical, evidenced as the formation of the C–O–C bond visible at 1050 cm⁻¹ in the infrared spectrum. From this route, a polymer was formed on the electrode surface, which limited the yield of organic acid synthesis. Finally, this research provides new insights in the field of electrochemistry, specifically in the synthesis of organic acids from CNSL as a renewable feedstock, with the novelty being the production of oxalic, propionic, citric, and malonic acids. Full article

Plastic pollution, driven by the durability and widespread use of polyolefins such as polypropylene (PP) and high-density polyethylene (HDPE), poses a formidable environmental challenge. To address this issue, we have developed an integrated multiscale framework that combines thermocatalytic experimentation, process-scale simulation, and molecular-level modeling to optimize the catalytic pyrolysis of PP and HDPE waste. Under the identified optimal conditions (300 °C, 10 wt % HMOR zeolite), liquid-oil yields of 60.8% for PP and 87.3% for HDPE were achieved, accompanied by high energy densities (44.2 MJ/kg, RON 97.5 for PP; 43.7 MJ/kg, RON 115.2 for HDPE). These values significantly surpass those typically reported for uncatalyzed pyrolysis, demonstrating the efficacy of HMOR in directing product selectivity toward valuable liquids. Above 400 °C, the process undergoes a pronounced shift toward gas generation, with gas fractions exceeding 50 wt % by 441 °C, underscoring the critical influence of temperature on product distribution. Gas-phase analysis revealed that PP-derived syngas contains primarily methane (20%) and ethylene (19.5%), whereas HDPE-derived gas features propylene (1.9%) and hydrogen (1.5%), highlighting intrinsic differences in bond-scission pathways governed by polymer architectures. Aspen Plus process simulations, calibrated against experimental data, reliably predict product distributions with deviations below 20%, offering a rapid, cost-effective tool for reactor design and scale-up. Complementary density functional theory (DFT) calculations elucidate the temperature-dependent energetics of C–C bond cleavage and radical formation, revealing that system entropy increases sharply at 500–550 °C, favoring the generation of both liquid and gaseous intermediates. By directly correlating catalyst acidity, molecular reaction mechanisms, and process-scale performance, this study fills a critical gap in plastic-waste valorization research. The resulting predictive platform enables rational design of catalysts and operating conditions for circular economy applications, paving the way for scalable, efficient recovery of fuels and chemicals from mixed polyolefin waste. Full article