Search Results (196)

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

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

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

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

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

In this study, insoluble CaSO₃ was applied to replace soluble sulfite/bisulfite salt in the Fe(II)-activated sulfite/bisulfite [S(IV)] process for the efficient 2,4,6-tribromophenol (TBP) degradation. CaSO₃ serves as a low-cost and slow-release source of S(IV), significantly improving S(IV) utilization compared to conventional soluble Na₂SO₃. The Fe(II)/CaSO₃ system generated SO₄^•− and HO^• through Fe(II)/Fe(III) redox cycling. Mechanistic studies confirmed SO₄^•− as the dominant reactive species, selectively attacking C-Br bonds and hydroxyl groups in TBP. Process optimization revealed effective performance under acidic conditions (pH 3.5–4.0) with minimal inhibition by common anions (Cl⁻, HCO₃⁻). The reactive sites of TBP were identified through Fukui function calculations, and the degradation pathway was elucidated based on LC-MS analysis. Toxicity evaluation indicated reduced ecological risk of degradation intermediates due to debromination and benzene ring cleavage. This work provides a sustainable strategy for efficient TBP removal and detoxification in wastewater treatment with benefiting S(IV) utilization. Full article

To express and purify staphylococcal enterotoxin M (SEM) using immobilized metal affinity chromatography (IMAC), a signal peptide-truncated (ΔNsp) wild-type SEM (SEM_WT) was N-terminally fused in pET-28a(+) to a polyhistidine tag (His_6×-) and thrombin cleavage site (TCS; LVPR↓GS), generating His_6×-TCS-ΔNspSEM_WT. Unexpectedly, 4 °C desalting reduced the fusion protein’s molecular weight by ~2.0 kDa on sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). N-terminal sequencing and mass spectrometry identified cleavage specifically at the arginine (R) and glycine (G) peptide bond (R–G bond) within the TCS motif. AlphaFold 3 revealed an exposed serine protease catalytic triad: histidine 172, serine 178, and aspartic acid 212 (H₁₇₂/S₁₇₈/D₂₁₂) in the β-grasp domain, suggesting intrinsic thrombin-like activity (TLA). Sequential IMAC and size-exclusion high-performance liquid chromatography (SE-HPLC) purification eliminated contaminant concerns, while chromogenic substrate S-2238 (S-2238) assays demonstrated increasing specific activity and purification fold, supporting intrinsic TLA. Critically, the mutation of serine at position 178 to alanine (His_6×-TCS-ΔNspSEM_S178A) abolished TLA but preserved the secondary/tertiary structure, confirming the activity’s origin within the wild-type construct. Molecular dynamics (MD) simulations probed the atomistic mechanism for specific R–G bond cleavage. This work establishes a foundation for understanding ΔNspSEM_WT’s TLA. Full article

Incineration is a widely adopted method for the disposal of waste energetic materials (SP). Nevertheless, this approach is associated with considerable thermal energy loss and significant environmental pollution. To address these limitations, this study proposes a co-pyrolysis process incorporating pine sawdust (SD) with SP. This technique utilizes the exothermic decomposition of energetic substances and the endothermic pyrolysis of biomass. Through this synergistic thermal interaction, the process enables efficient energy recovery and facilitates the resource valorization of SP. The pyrolysis kinetics and thermodynamics of SP, SD, and their blends were investigated. Synchronous thermal analysis examined the co-pyrolysis reaction heat at varying blend ratios, while the temperature’s effects on the gas–liquid–solid product distribution were explored. The results indicate that the apparent activation energy (E_a) required for co-pyrolysis of the SP and SD exhibits an initial increase followed by a decrease in both Stage 1 and Stage 2. Furthermore, the mean apparent activation energy (E_avg) during Stage 1 (FWO: 101.87 kJ/mol; KAS: 94.02 kJ/mol) is lower than that in Stage 2 (FWO: 110.44 kJ/mol; KAS: 100.86 kJ/mol). Co-pyrolysis reaction heat calculations indicated that SD addition significantly mitigates the exothermic intensity, shifts decomposition to higher temperatures (the primary exothermic zone shifted from 180–245 °C to 265–400 °C), and moderates heat release. Elevated temperatures increase the gas yield (CO and H₂ are dominant). High temperatures promote aromatic bond cleavage and organic component release; the char’s calorific value correlates positively with the carbon content. Higher co-pyrolysis temperatures increase the nitrogenous compounds in the oil, while the aldehyde content peaks then declines. This work proposes a resource recovery pathway for SP, providing fundamental data for co-pyrolysis valorization or the development of catalytic conversion precursors. Full article

As a model compound for lignin derivatives, anisole and its conversion are crucial for the upgrading of biomass resources. Anisole molecule contains a characteristic aryl ether bond (C_aryl-O-CH₃); therefore, the selective cleavage of the C-O bond to efficiently produce high-value chemicals poses a significant challenge. Constructing bimetallic synergistic active sites through tuning the metal-support interface is considered an effective strategy. In this work, the WO₃-promoted Pt/SiO₂ catalysts were investigated to enhance the performance of anisole hydrodeoxygenation (HDO) to hydrocarbons. Experimental results demonstrate that WO₃ significantly promotes HDO selectivity, increasing from 37.8% to 86.8% at 250 °C. Moreover, moderate doping improves low-temperature (<250 °C) HDO activity, confirming the presence of synergistic effects. In contrast, excessive WO₃ suppresses anisole conversion. Characterization results reveal that WO₃ stabilizes metallic Pt and facilitates H₂ dissociation. Concurrently, strong hydrogen spillover between Pt and WO₃ promotes oxygen vacancy formation on WO₃. This transforms disordered adsorption of anisole on SiO₂ into directed adsorption of the anisole’s oxygen species onto WO₃. This work achieves high anisole HDO selectivity through the Pt-WO₃ interface tuning, offering novel insights for efficient lignin conversion. Full article

Phthalic acid esters (PAEs), ubiquitously employed as a plasticizer, have been classified as priority environmental pollutants because of their persistence, bioaccumulation, and endocrine-disrupting properties. As a characterized PAE-degrading strain of marine origin, Mycolicibacterium phocaicum RL-HY01 utilizes di-(2-ethylhexyl) phthalate (DEHP) as its sole carbon and energy source. Genome sequencing and RT-qPCR analysis revealed a previously uncharacterized hydrolase gene (dehpH) in strain RL-HY01, which catalyzes ester bond cleavage in PAEs. Subsequently, recombinant expression of the cloned dehpH gene from strain RL-HY01 was established in Escherichia coli BL21(DE3). The purified recombinant DehpH exhibited optimal activity at 30 °C and pH 8.0. Its activity was enhanced by Co²⁺ and tolerant to most metal ions but strongly inhibited by EDTA, SDS, and PMSF. Organic solvents (Tween-80, Triton X-100, methanol, ethanol, isopropanol, acetone, acetonitrile, ethyl acetate, and n-hexane) showed minimal impact. Substrate specificity assay indicated that DehpH could efficiently degrade the short and long side-chain PAEs but failed to hydrolyze the cyclic side-chain PAE (DCHP). The kinetics parameters for the hydrolysis of DEHP were determined under the optimized conditions, and DehpH had a V_max of 0.047 ± 0.002 μmol/L/min, K_m of 462 ± 50 μmol/L, and k_cat of 3.07 s⁻¹. Computational prediction through structural modeling and docking identified the active site, with mutagenesis studies confirming Ser228, Asp324, and His354 as functionally indispensable residues forming the catalytic triad. The identification and characterization of DehpH provided novel insights into the mechanism of DEHP biodegradation and might promote the application of the target enzyme. Full article

Fungal lytic polysaccharide monooxygenases (LPMOs) have revolutionized the field of biomass degradation by introducing an oxidative mechanism that complements traditional hydrolytic enzymes. These copper-dependent enzymes catalyze the cleavage of glycosidic bonds in recalcitrant polysaccharides such as cellulose, hemicellulose, and chitin, through the activation of molecular oxygen (O₂) or hydrogen peroxide (H₂O₂). Their catalytic versatility is intricately modulated by structural features, including the histidine brace active site, surface-binding loops, and, in some cases, appended carbohydrate-binding modules (CBMs). The oxidation pattern, whether at the C1, C4, or both positions, is dictated by subtle variations in loop architecture, amino acid microenvironments, and substrate interactions. LPMOs are embedded in a highly synergistic fungal enzymatic system, working alongside cellulases, hemicellulases, lignin-modifying enzymes, and oxidoreductases to enable efficient lignocellulose decomposition. Industrial applications of fungal LPMOs are rapidly expanding, with key roles in second-generation biofuels, biorefineries, textile processing, food and feed industries, and the development of sustainable biomaterials. Recent advances in genome mining, protein engineering, and heterologous expression are accelerating the discovery of novel LPMOs with improved functionalities. Understanding the balance between O₂- and H₂O₂-driven mechanisms remains critical for optimizing their catalytic efficiency while mitigating oxidative inactivation. As the demand for sustainable biotechnological solutions grows, this narrative review highlights how fungal LPMOs function as indispensable biocatalysts for the future of the Circular Bioeconomy and green industrial processes. Full article

The Mo:BiVO₄/FeOOH photoelectrode was synthesized through the deposition of FeOOH onto the surface of the Mo:BiVO₄ photoelectrode. The composite photoelectrode demonstrated a photocurrent of 1.8 mA·cm⁻², which is three times greater than that observed for pure BiVO₄. Furthermore, the glycerol conversion rate was recorded at 79 μmol·cm⁻²·h⁻¹, approximately double that of pure BiVO₄, while the selectivity for glyceraldehyde reached 49%, also about twice that of pure BiVO₄. The incorporation of Mo has been shown to enhance the stability of the BiVO₄. Additionally, Mo doping improves the efficiency of electron-hole transport and increases the carrier concentration within the BiVO₄. This enhancement leads to a greater number of holes participating in the formation of iron oxyhydroxide (FeOOH), thereby stabilizing the FeOOH co-catalyst within the glycerol conversion system. The FeOOH co-catalyst facilitates the adsorption and oxidation of the primary hydroxyl group of glycerol, resulting in the cleavage of the C−H bond to generate a carbon radical (C). The interaction between the carbon radical and the hydroxyl group produces an intermediate, which subsequently dehydrates to form glyceraldehyde (GLAD). Full article