Search Results (325)

A method for the mechanochemical CuAAC click reaction (Cu⁺-promoted azido–alkyne cycloaddition) in the presence of bronze powder/copper beads without the use of a pre-introduced catalyst and ligands with greener prospect is presented. A new type of tri-, tetra-, and penta-ethylene glycols (PEGs) α,ω-disubstituted with 4-(PAH)-1H-1,2,3-triazole moieties has been synthesized by means of solvent-free click reaction in the planetary ball-milling in absence of a pre-introduced Cu(I) catalyst. The reaction afforded the above-mentioned compounds at room temperature in as short as 3 h in up to 96% yields and with E-factor values as low as 0.38. For the comparison, some of the key compounds were obtained by the conventional click synthesis in DMF solution. The compounds obtained were synthesized for the first time and can be considered as representative examples of bola-type chemosensors for the detection of electron-deficient species. This work presents a method for catalyzing a click reaction using bronze microparticles that are formed in situ during powder milling. This heterophase catalyst has been shown to be efficient and inexpensive and is suitable for green chemistry methods under solvent-free ball-milling conditions. Full article

ZnO semiconductor-based photocatalysts are mainly studied for the elimination of toxic textile dyes. Metal-doped ZnO displays better performance for this purpose. Herein, Al-doped ZnO (Al–ZnO) was prepared using the mechanochemical calcination method with varying aluminum concentrations for the degradation of the persistent methylene blue (MB) dye. Various characterization techniques, including XRD, FTIR, FESEM, TEM, UV-DRS, and XPS, revealed the improved properties of 3% Al–ZnO in degrading the MB dye. It exhibits 96.56% degradation of 25 mg/L MB dye under 60 min of natural sunlight irradiation with a catalyst dose of 0.5 g/L at a natural pH of 6.4. A smaller particle size, a lower band gap energy of 3.264 eV, and the presence of oxygen vacancies and defect states all facilitate photocatalytic degradation. Radical scavenger experiments using ascorbic acid (for •O₂⁻), 2-propanol (for •OH), and diammonium oxalate (for h⁺) confirmed the crucial role of superoxide (•O₂⁻) and hydroxyl (•OH) radicals in the degradation mechanism. The achievement of 82.80% MB degradation efficiency at the 4th cycle validates the notable stability and excellent reusability of Al–ZnO. Full article

Magnesium aluminate spinel nanoparticles (MgAl₂O₄-S-NPs) represent a promising class of nanoceramics with potential biomedical applications due to their physicochemical stability and antimicrobial properties. This study aimed to determine the structural characteristics, composition, and biological performance of MgAl₂O₄ spinel nanoparticles that were synthesized via a mechanochemical method. Structural and compositional characterization was performed using X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM). Antibacterial activity was evaluated against Helicobacter pylori and Enterococcus faecalis using bacterial viability assays. Structural and morphological analyses confirmed the successful formation of single-phase cubic MgAl₂O₄ with a polyhedral morphology and nanoscale size distribution. Bacterial viability was quantified through optical density measurements following exposure to MgAl₂O₄-S-NPs at different concentrations. The nanoparticles exhibited both bacteriostatic and bactericidal effects, with activity being demonstrated against the tested bacterial strains. Mechanochemically synthesized MgAl₂O₄-S-NPs are promising candidates for biomedical applications, including dental materials, antimicrobial coatings, and infection-control strategies. Overall, the findings highlight the potential of MgAl₂O₄-S-NPs as effective antimicrobial agents that can be produced through an environmentally friendly synthesis route. Full article

Cu₂ZnSnSe₄ is a promising light-absorbing material for cost-effective and eco-friendly thin-film solar cells; however, its synthesis often leads to secondary phases that limit device efficiency. To overcome these challenges, we devised a straightforward and efficient method to obtain single-phase Cu₂ZnSnSe₄ nanocrystalline powders directly from the elements Cu, Zn, Sn, and Se via mechanochemical synthesis followed by vacuum annealing at 450 °C. Phase evolution monitored by X-ray diffraction (XRD) and Raman spectroscopy at two-hour milling intervals confirmed the formation of phase-pure kesterite Cu₂ZnSnSe₄ and enabled tracking of transient secondary phases. Raman spectra revealed the characteristic A₁ vibrational modes of the kesterite structure, while XRD peaks and Rietveld refinement (χ² ~ 1) validated single-phase formation with crystallite sizes of 10–15 nm and dislocation densities of 3.00–3.20 10¹⁵ lines/m². Optical analysis showed a direct bandgap of ~1.1 eV, and estimated linear and nonlinear optical constants validate its potential for photovoltaic applications. Scanning electron microscopy (SEM) analysis showed uniformly distributed particles 50–60 nm, and energy dispersive X-ray (EDS) analysis confirmed a near-stoichiometric Cu:Zn:Sn:Se ratio of 2:1:1:4. X-ray photoelectron spectroscopy (XPS) identified the expected oxidation states (Cu⁺, Zn²⁺, Sn⁴⁺, and Se²⁻). Electrical characterization revealed p-type conductivity with a mobility (μ) of 2.09 cm²/Vs, sheet resistance (ρ) of 4.87 Ω cm, and carrier concentrations of 1.23 × 10¹⁹ cm⁻³. Galvanostatic charge–discharge testing (GCD) demonstrated an energy density of 2.872 Wh/kg⁻¹ and a power density of 1083 W kg⁻¹, highlighting the material’s additional potential for energy storage applications. Full article

With the rapid increase in plastic consumption, waste polypropylene (WPP) has become one of the major components of municipal solid waste, posing significant environmental and resource challenges. According to statistics, polypropylene accounts for approximately 19.1% of the total global plastic waste, posing significant environmental challenges. In recent years, the recycling and reuse of WPP in asphalt pavement materials have received increasing attention due to its excellent mechanical properties, thermal stability, and low cost. This review systematically summarizes the physicochemical properties and recycling technologies of WPP, including mechanical, chemical, and energy recovery routes. Furthermore, the modification mechanisms, preparation methods, and performance characteristics of WPP-modified asphalt binders and mixtures are comprehensively discussed, focusing on their high-temperature stability, compatibility, low-temperature cracking resistance, and anti-moisture damage. Research indicates that WPP modification significantly enhances high-temperature rutting resistance, and thermo-chemical modifiers have successfully enabled the application of WPP in warm-mix asphalt. This review uniquely integrates recent advances in thermo-mechanochemical upcycling with mixture-level performance, bridging molecular design and field application. However, critical challenges, including poor compatibility, insufficient storage stability, and the lack of a unified assessment for the high variability of WPP raw materials, still need to be addressed. Finally, this review primarily focuses on the recycling technologies of WPP, its modification mechanisms in asphalt binders, and the resulting impact on the pavement performance of WPP-modified mixtures. Full article

This study evaluates the feasibility of achieving chemoselective aldol reactions over competing Henry reactions and employs competition experiments to establish proof of concept. A typical reaction involved using in-water reaction conditions where a concentrated organic layer containing an aldol nucleophile (1.5 equiv), a Henry nucleophile (1.5 equiv), an aldehyde electrophile (1.0 equiv), and a proline-based amino acid catalyst (2.5 mol%) constituted one phase, while the second phase was water (15 equiv). Highly enantioenriched aldol products were formed in practical yields, and a variety of Henry nucleophiles (nitroalkanes, allylic nitro compounds, and ethyl nitroacetate) were tolerated. This systematic examination of nitro compounds (pK_a 5.5–10.0) established a pK_a of ≈7.0 as the critical threshold at which nitronate formation results in Henry product formation under catalysis with 1. Reactions alternatively performed in MeOH/H₂O (3:2 equiv) solvent combinations, at times, provided improved chemoselectivity or product dr over the use of water (15 equiv) alone but required longer reaction times to produce similar yields. Reactions constrained by solubility were investigated using mechanochemical methods, but these conditions failed to deliver practical yields of either competition product. In summary, defining this category of aldol chemoselectivity may provide new tactical opportunities for the synthesis of complex molecular targets. Full article

This study is motivated by the severe tribological regime of PA6 composites in VR platforms operating under dry or boundary lubrication, where alternating shear during foot rotation, localised contact pressures, and third-body abrasion concurrently challenge wear resistance and retention of strength. This paper presents the results of research into the properties of composites based on polyamide PA6 and molybdenum disulphide, obtained by combining the components through high-intensity mechanochemical activation in a planetary mill and classical mixing in a turbulence mixer. We demonstrate that varying the energy of the premixing stage (mechanochemical activation versus low-energy premixing) serves as an effective means of interfacial engineering in PA6/MoS₂ composites, enabling simultaneous enhancement of mechanical and tribological properties at low filler contents. Analysis of experimental composite samples using Fourier-transform infrared spectroscopy (FTIR) indicates the interaction between MoS₂ and oxygen-containing groups of polyamide while maintaining its overall chemical composition. According to the TG-DSC curves, modification of polyamide leads to an increase in the melting temperature by 2 °C, while mechanical activation ensures stronger interaction between the matrix and the filler. Compared to pure PA6, the tensile strength of composites increases by 10–20% for mechanoactivated materials and by 5–10% for materials obtained by conventional methods. The mechanical activation effect is observed even at minimal amounts (0.25 and 0.5%) of MoS₂ in composites. The toughness of all composites, regardless of the mixing method, increases by 5–7% compared to pure polyamide. All composites show a 10–20% reduction in the coefficient of friction on steel. Simultaneously, the water absorption of composites becomes 5–20% higher than that of the original material, which indicates a change in structure and an increase in porosity. The obtained composite materials are planned to be used for manufacturing platforms for the movement of virtual reality (VR) operators. Full article

Dry reforming of methane (DRM) is a promising method for turning two major greenhouse gases, CO₂ and CH₄, into syngas (H₂ + CO). This syngas has the right H₂/CO ratio for making valuable chemicals and liquid fuels. However, there are significant challenges that make it tough to implement commercially. One big issue is that the process requires a lot of energy because it is highly endothermic, needing temperatures over 700 °C. This high heat can quickly deactivate the catalyst due to carbon build-up (coking) and the thermal sintering of metal nanoparticles. Researchers increasingly recognize mechanochemistry—a non-thermal, solid-state technique employing mechanical force to drive chemical transformations—as a sustainable, solvent-free strategy to address these DRM challenges. This mini-review critically assesses the dual role of mechanochemistry in advancing DRM. First, we examine its established role in creating advanced catalysts at lower temperatures. Here, mechanochemical methods help produce well-dispersed nanoparticles, enhance strong interactions between metal and support, and develop bimetallic alloys that resist coke formation and show great stability. Second, we delve into the exciting possibility of using mechanochemistry to directly engage in the DRM reaction at near-ambient temperatures, which marks a major shift from traditional thermocatalysis. Lastly, we discuss the key challenges ahead, like scalability and understanding the mechanisms involved, while also outlining future directions for research to fully harness mechanochemistry for converting greenhouse gases sustainably. Full article

In this work, we report on the mechanochemical preparation and characterization of binary (CdS, CdSe, and CdTe) and ternary (CdS_0.5Se_0.5, CdS_0.5Te_0.5, and CdSe_0.5Te_0.5) cadmium chalcogenides. The compounds were synthesized in a planetary micro mill using a zirconia grinding bowl and zirconia grinding balls. The products were examined by powder X-ray diffraction (pXRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS), UV–Vis spectroscopy, and differential scanning calorimetry (DSC). Interestingly, CdO formed as a by-product only during milling of Cd+S and Cd+Se in air, while it was absent in the Cd+Te and all ternary systems. The materials were obtained in the form of irregularly shaped aggregates measuring up to several hundred nanometers, composed of nearly spherical primary nanoparticles with diameters in the 10–20 nm range. The band gap energies calculated using Tauc plots for CdS_0.5Se_0.5, CdS_0.5Te_0.5, and CdSe_0.5Te_0.5 were 2.01 eV, 1.72 eV, and 1.53 eV, respectively. These results demonstrate the expected tunability of band gaps in ternary cadmium chalcogenides and attest to the potential of such materials for semiconducting applications, particularly in solar cells. The mechanochemical approach is once again shown to be a simple and effective method for the preparation of both binary and ternary chalcogenides, avoiding the use of solvents, toxic precursors, and energy-consuming reaction conditions. Full article

The article examines the synthesis and electrophysical properties of spinel ferrite ZnFe₂O₄, produced using the sol–gel method with a solid-state finishing process; as well as through classical ceramic technology with mechanochemical activation. The study includes a detailed analysis of the phase composition and crystalline structure using X-ray diffraction; infrared spectroscopy; mass spectrometry; and thermogravimetric and differential thermal analyses. These methods help identify thermal effects and the stages of synthesis. Impedance spectroscopy is used to investigate the electrophysical properties, revealing a significant influence of firing temperature on electrical ionic conductivity. The results show that the electrophysical properties differ based on the synthesis conditions and methods. This suggests potential applications for ZnFe₂O₄ as a cathode material in metal-ion batteries. The work highlights the importance of optimizing synthesis conditions to achieve high-performance characteristics in electrode materials. Full article

This study presents a novel, circular-economy-driven strategy for valorizing post-consumer denim waste into high-performance hydrogels through a fully integrated and eco-friendly process. Unlike conventional approaches that rely on virgin cellulose or harsh chemical treatments, our method uniquely combines high-energy mechanochemical pretreatment, in situ carboxymethylation to produce carboxymethylcellulose (CMC), and citric acid/urea-based crosslinking, all using recycled denim as the sole cellulose source. High-energy milling effectively reduced particle size and lowered the crystallinity index (CI) from 75.7% to 66.1%, transforming the fibrous structure into a more reactive substrate for etherification. Successful CMC synthesis was confirmed by FTIR (COO⁻ stretch at 1587 cm⁻¹), while citric acid crosslinking generated ester bonds (C=O at ~1724 cm⁻¹), forming a 3D network further tailored by urea, acting as a green porogen. The resulting hydrogels exhibited enhanced thermal stability (TGA) and a tunable porous morphology (SEM), with pore sizes reaching up to 147 µm as the urea content increased. Notably, the hydrogel Hy/CMC/U2/CA achieved an exceptional swelling capacity of 1900%, which is among the highest reported for denim-derived or citric acid-crosslinked systems. The objective of this work is to demonstrate, for the first time, the feasibility of converting waste denim directly into functional hydrogels without intermediate purification steps, offering a scalable and sustainable route for agricultural applications, such as soil water retention, controlled nutrient release, or environmental remediation, within a true circular economy framework. Full article

Metal–organic frameworks (MOFs) have been increasingly recognized as promising platforms for enzyme modulation, owing to their tunable porosity, high surface area, and versatile chemical functionality. In this review, the potential of MOFs for the inhibition and modulation of protein kinases and phosphatases—key regulators of cellular signaling and disease progression—is examined. The structural fundamentals of MOFs are outlined, followed by a discussion of common synthesis strategies, including solvothermal, microwave-assisted, sonochemical, and mechanochemical methods. Emphasis is placed on how synthesis conditions influence critical features such as particle size, crystallinity, surface chemistry, and functional group accessibility, all of which impact biological performance. Four primary mechanisms of MOF–enzyme interaction are discussed: surface adsorption, active site coordination, catalytic mimicry, and allosteric modulation. Each mechanism is linked to distinct physicochemical parameters, including pore size, surface charge, and metal node identity. Special focus is given to biologically relevant metal centers such as Zr⁴⁺, Ce⁴⁺, Cu²⁺, Fe³⁺, and Ti⁴⁺, which have been shown to contribute to both MOF stability and enzymatic inhibition through Lewis acid or redox-mediated mechanisms. Recent in vitro studies are reviewed, in which MOFs demonstrated selective inhibition of disease-relevant enzymes with minimal cytotoxicity. Despite these advancements, several limitations have been identified, including scalability challenges, limited physiological stability, and potential off-target effects. Strategies such as post-synthetic modification, green synthesis, and biomimetic surface functionalization are being explored to overcome these barriers. Through an integration of materials science, coordination chemistry, and molecular biology, this review aims to provide a comprehensive perspective on the rational design of MOFs for targeted enzyme inhibition in therapeutic contexts. Full article

A solvent-free, solid-state mechanochemical method was developed to synthesize the chalcohalide compound SbSI at room temperature. Dry high-energy planetary ball milling of elemental antimony, sulfur, and iodine produced a pure, stoichiometric polycrystalline SbSI powder with an orthorhombic structure. This powder was then sintered under mild thermal conditions to create dense targets. Amorphous SbSI thin films were subsequently deposited from these targets at room temperature using Pulsed Electron Deposition. The films maintained the correct stoichiometry and exhibited an optical bandgap of 1.89 eV. Post-deposition annealing at 90 °C in air successfully induced crystallization, demonstrating a viable, low-temperature, and eco-friendly route to produce polycrystalline SbSI thin films. This scalable approach has promising potential for optoelectronic and energy-harvesting applications. Full article

Growing interest in sustainable hydrogen production has brought renewed attention to photoelectrochemical (PEC) water splitting as a promising route for direct solar-to-chemical energy conversion. This study explores how integrating hematite (α-Fe₂O₃) and cupric oxide (CuO) photoelectrodes with a series of nickel-based co-catalysts can improve photoelectrochemical activity. Photoanodic (NiO_x, NiFeO_x, NiWO₄) and photocathodic (Ni, NiCu, NiMo) co-catalysts were synthesized via co-precipitation and mechanochemical methods and characterized through X-ray Diffraction (XRD), X-ray Fluorescence (XRF), Transmission Electron Microscopy–Energy Dispersive X-ray Spectroscopy (TEM-EDX), Scanning Electron Microscopy–Energy Dispersive X-ray Spectroscopy (SEM-EDX), X-ray photoelectron spectroscopy (XPS) and Brunauer–Emmett–Teller (BET) gas-adsorption analyses to clarify their crystallographic, morphological, and compositional properties, as well as their surface chemistry and textural properties (surface area and porosity). Electrochemical tests under 1 SUN illumination showed that NiO_x significantly improves the photocurrent of hematite photoanodes. Among the cathodic co-catalysts, NiMo demonstrated the best performance when combined with CuO photocathodes. For both photoelectrodes, an optimal co-catalyst loading was identified, beyond which performance declined due to potential charge transfer limitations and light attenuation. These findings highlight the critical role of co-catalyst composition and loading in optimizing the efficiency of PEC systems based on earth-abundant materials, offering a pathway toward scalable and cost-effective hydrogen production. Full article

This study investigates the structural and magnetic properties of CoFe₂O₄ nanoparticles prepared by five different synthesis methods: coprecipitation, ultrasound-assisted coprecipitation, coprecipitation coupled with mechanochemical treatment, microemulsion and microwave-assisted hydrothermal synthesis. The produced powders were additionally functionalized with starch to improve biocompatibility and colloidal stability. The starch-coating procedure itself by sonication in starch solution, as well as its result, affects the structural and magnetic properties of functionalized nanoparticles. The resulting changes of properties in the process of ligand addition depend significantly on the starting nanoparticles, or rather, on the method of their synthesis. The structural, magnetic and spectroscopic properties of the resulting materials were systematically investigated using X-ray diffraction (XRD), Raman spectroscopy, Mössbauer spectroscopy and magnetic measurements. Taken together, XRD, Raman and Mössbauer spectroscopy show that starch deposition reduces structural disorder and internal stress, resulting in nanoparticles with a more uniform size distribution. These changes, in turn, affect all magnetic properties—magnetization, coercivity and magnetic anisotropy. Magnetic responses are preserved what is desirable for future biomedical applications. This work emphasizes the importance of surface modification for tailoring the properties of magnetic nanoparticles while maintaining their desired functionality. Full article