Search Results (5,436)

Rouaite (Cu₂(OH)₃NO₃) long hexagonal multilayered nanoplates with high purity and high crystallinity were prepared from acidic reaction solution (pH = 4.4–4.8) with the assistance of ZnO. The ZnO-assisted strategy is remarkably different from the conventional synthetic protocol that was regularly carried out in alkaline solution (pH > 11). The rouaite multilayer nanoplates displayed exceptionally high catalytic activity in the catalytic wet peroxide oxidation (CWPO) of Congo red (CR). The catalytic efficiency for CR decolorization achieved an impressive 96.3% in 50 min under near-neutral (pH = 6.76) and ambient conditions (T = 20 °C, p = 1 atm), without increasing the temperature and/or decreasing the pH value to acidic region (pH = 2–3) as is commonly employed in CWPO process for improved degradation efficiency. Full article

This study evaluates the production of base oils for biolubricants using fatty acid methyl esters (FAMEs) derived from sunflower oil as the raw material. The production process involved the synthesis of oleochemical esters through a single-step alkaline transesterification reaction with a high-molecular-weight polyol, such as trimethylolpropane (TMP). To assess the effectiveness of the developed catalytic system in conducting the transesterification reactions and its impact on the properties of the final product, two types of alkaline catalysts were used. Specifically, the reactions were carried out using either Ca/TEA alkoxide or sodium methoxide as catalysts in various configurations and concentrations to determine the optimal catalyst concentration and reaction conditions. Sodium methoxide served as the commercial benchmark catalyst, while the Ca/TEA alkoxide was prepared in the laboratory. The optimal concentration of Ca/TEA was determined to be 3.0% wt. in the presence of iso-octane and 3.5% wt. under vacuum, while the corresponding concentrations of CH₃ONa for both cases were determined to be 2.0% wt. The synthesized biolubricant esters exhibit remarkable performance characteristics, such as high kinematic viscosities and low pour points—ranging from 33–48 cSt at 40 °C, 7.68–10.03 cSt at 100 °C, to −14 to −7 °C, respectively—which are comparable to or improved over those of mineral oils such as SN-150 or SN-500, with the Ca/TEA alkoxide-catalyzed systems showing superior oxidation stability and reduced byproduct formation. Full article

Divinylisoprene rubber, a copolymer of butadiene and isoprene, is used as raw material for rubber technical products, combining isoprene rubber’s elasticity and butadiene rubber’s wear resistance. These properties depend quantitatively on the copolymer composition, which depends on the kinetics of its synthesis. This work aims to theoretically describe how the monomer mixture composition in the butadiene–isoprene copolymerization affects the activity of the TiCl₄–Al(i-C₄H₉)₃ catalytic system (expressed by active sites concentration) via kinetic modeling. This enables development of a reliable kinetic model for divinylisoprene rubber synthesis, predicting reaction rate, molecular weight, and composition, applicable to reactor design and process intensification. Active sites concentrations were calculated from experimental copolymerization rates and known chain propagation constants for various monomer compositions. Kinetic equations for active sites formation were based on mass-action law and Langmuir monomolecular adsorption theory. An analytical equation relating active sites concentration to monomer composition was derived, analyzed, and optimized with experimental data. The results show that monomer composition’s influence on active sites concentration is well described by a two-step kinetic model (physical adsorption followed by Ti–C bond formation), accounting for competitive adsorption: isoprene adsorbs more readily, while butadiene forms more stable active sites. Full article

Biocatalysis is one of the oldest fields that has been used in industrial applications, with one of the earliest purposeful examples being the mass production of acetic acid from an immobilized Acinetobacter strain in the year 1815. Efficiency, specificity, reduced reaction times, lower overall costs, and environmental friendliness are some advantages biocatalysis has over conventional chemical synthesis, which has made biocatalysis increasingly used in industry. We highlight three necessary fields that are fundamental to advancing industrial biocatalysis, including biocatalyst engineering, solvent engineering, and mechanistic engineering. However, the fundamental mechanism of enzyme function is often overlooked or given less attention, which can limit the engineering process. In this review, we describe how mechanistic enzymology benefits industrial biocatalysis by elucidating key fundamental principles, including the k_cat and k_cat/K_m parameters. Mechanistic enzymology presents a unique field that provides in-depth insights into the molecular mechanisms of enzyme activity and includes areas such as reaction kinetics, catalytic mechanisms, structural analysis, substrate specificity, and protein dynamics. In line with the objective of protein engineering to optimize enzyme activity, we summarize a range of strategies reported in the literature aimed at improving the product release rate, the chemical step of catalysis, and the overall catalytic efficiency of enzymes. Further into this review, we delineate kinetic solvent viscosity effects (KSVEs) as a very efficient, cost-effective, and easy-to-perform method to probe different aspects of enzyme reaction mechanisms, including diffusion-dependent kinetic steps and rate-limiting steps. KSVEs are cost-effective because simple kinetic enzyme assays, such as the Michaelis–Menten kinetic approach, can be combined with them without the need for specialized and costly equipment. Other techniques in protein engineering and genetic engineering are also covered in this review. Additionally, we provide information on solvent systems in enzymatic reactions, details on immobilized biocatalysts, and common misconceptions that misguide enzyme design and optimization processes. Full article

Sorption and advanced oxidative processes (AOPs) are potential strategies for the removal of organic compounds, such as caffeine, from aqueous media. Such strategies tend to be more promising when combined with biopolymeric membranes as sorbents and photocatalyst supports. Therefore, the aim of the present study was to investigate sorption and AOP parameters in the performance of chitosan membranes and chitosan/TiO₂ composite membranes in individual and hybrid systems involving the photolysis, photocatalysis, and sorption of caffeine. Caffeine degradation by photolysis was 19.51 ± 1.14, 28.61 ± 0.05, and 30.64 ± 6.32%, whereas caffeine degradation by photocatalysis with catalytic membrane was 18.33 ± 2.20, 20.83 ± 1.49, and 31.41 ± 3.08% at pH 6, 7, and 8, respectively. In contrast, photocatalysis with the dispersed catalyst achieved degradation of 93.56 ± 2.12, 36.42 ± 2.59, and 31.41 ± 1.07% at pH 6, 7, and 8, respectively. These results indicate that ions present in the buffer solutions affect the net electrical charge on the surface of the composite biomaterial with the change in pH variation, occupying active sorption sites in the structure of the biomaterial, which was characterized by Fourier transform infrared spectrometry, thermogravimetric analysis, differential scanning thermogravimetry, and X-ray diffraction. Thus, it is verified that in a combined process of caffeine removal under UV irradiation and use of chitosan/TiO₂ composite membranes in phosphate-buffered medium, the photolysis mechanism is predominant, with little or no contribution from sorption, and that the TiO₂ catalyst promotes a significant reduction in the percentage of pollutant in the medium only when used dispersed and at low pH. Full article

The rabies virus (RABV) phosphoprotein (P protein) has multiple functions, including acting as the essential non-catalytic cofactor of the viral polymerase (L protein) for genome replication and transcription; the principal viral antagonist of the interferon (IFN)-mediated innate immune response; and the chaperone for the viral nucleoprotein (N protein). Although P protein is known to undergo phosphorylation by cellular kinases, the location and functions of the phosphorylation sites remains poorly defined. Here, we report the identification by mass-spectrometry (MS) of residues of P protein that are modified by phosphorylation in mammalian cells, including several novel sites. Analysis of P protein with phospho-mimetic and phospho-inhibitory mutations of three novel residues/clusters that were commonly identified by MS (Ser48, Ser183/187, Ser217/219/220) indicate that phosphorylation at each of these sites does not have a major influence on nuclear trafficking or antagonistic functions toward IFN signalling pathways. However, phosphorylation of Ser48 in the N-terminus of P protein impaired function in transcription/replication and in the formation of replication structures that contain complexes of P and N proteins, suggestive of altered interactions of these proteins. The crystal structure of P protein containing the S48E phospho-mimetic mutation indicates that Ser48 phosphorylation facilitates the binding of residues 41–52 of P protein into the RNA-binding groove of non-RNA-bound N protein (N⁰), primarily through the formation of a salt bridge with Arg434 of N protein. These data indicate that Ser48 modification regulates the cycling of P-N⁰ chaperone complexes that deliver N protein to RNA to enable transcription/replication, such that enhanced interaction due to S48E phospho-mimetic mutation reduces N protein delivery to the RNA, inhibiting subsequent transcription/replication processes. These data are, to our knowledge, the first to implicate phosphorylation of RABV P protein in conserved replication functions of the P gene. 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

Accelerated industrialization and surging energy demands have led to continuously rising atmospheric CO₂ concentrations. Developing sustainable methods to reduce atmospheric CO₂ levels is crucial for achieving carbon neutrality. Concurrently, the rapid development of new energy vehicles has driven a significant increase in demand for lithium-ion batteries (LIBs), which are now approaching an end-of-life peak. Efficient recycling of valuable metals from spent LIBs represents a critical challenge. This study employs conventional hydrometallurgical processing to recover valuable metals from spent LIBs. Subsequently, Ni-doped Co₃O₄ (Ni:Co₃O₄) supported on the natural mineral attapulgite (ATP) was synthesized via a sol–gel method. The incorporation of a small amount of Ni into the Co₃O₄ lattice generates oxygen vacancies, inducing a localized surface plasmon resonance (LSPR) effect, which significantly enhances charge carrier transport and separation efficiency. During the photocatalytic reduction of CO₂, the primary product CO generated by the Ni:Co₃O₄/ATP composite achieved a high production rate of 30.1 μmol·g⁻¹·h⁻¹. Furthermore, the composite maintains robust catalytic activity even after five consecutive reaction cycles. Full article

Carbon monoxide (CO) is a major toxic gas emitted from vehicle exhaust, industrial processes, and incomplete fuel combustion, posing serious environmental and health risks. Catalytic oxidation of CO into less harmful CO₂ is an effective strategy to reduce these emissions. In this study, we investigated the catalytic performance of platinum (Pt) single atoms doped on C₃N monolayers with various vacancy defects, including single carbon (C_V) and nitrogen (N_V) vacancies, using density functional theory (DFT) calculations. Our results demonstrate that Pt@N_V-C₃N exhibited the most favorable catalytic properties, with the highest O₂ adsorption energy (−3.07 eV). This performance significantly outperforms Pt atoms doped at other vacancies. It can be attributed to the strong binding between Pt and nitrogen vacancies, which contributes to its excellent resistance to Pt aggregation. CO oxidation on Pt@N_V-C₃N proceeds via the Eley–Rideal (ER2) mechanism with a low activation barrier of 0.41 eV for the rate-determining step, indicating high catalytic efficiency at low temperatures. These findings suggest that Pt@N_V-C₃N is a promising candidate for CO oxidation, contributing to developing cost-effective and environmentally sustainable catalysts. The strong binding of Pt atoms to the nitrogen vacancies prevents aggregation, ensuring the stability and durability of the catalyst. The kinetic modeling further revealed that the ER2 mechanism offers the highest reaction rate constants over a wide temperature range (273–700 K). The low activation energy barrier also facilitates CO oxidation at lower temperatures, addressing critical challenges in automotive and industrial pollution control. This study provides valuable theoretical insights for designing advanced single-atom catalysts for environmental remediation applications. Full article

Background: Clinical diagnostics, food industries, and biotechnological processes typically use an enzyme called alpha-amylase to metabolize carbohydrates. Objective: The aim of this study is to investigate how low-level laser irradiation (LLLI) affects alpha-amylase activity towards determining the usability of LLLI in non-invasive enzymatic modulation. Methods: Enzyme solutions were irradiated at 10, 20, 30, and 40 J/cm² utilizing 589 nm and 532 nm diode-pumped solid-state lasers. The iodine–starch colorimetric method was used to quantify post-irradiation enzymatic activity, with inverse correlations found between absorbance and activity levels. Modulation was determined by the wavelength and dosage. Results: Enzymatic activity significantly improved when utilizing 589 nm irradiation at lower doses, maximizing at 120% at 20 J/cm² (p < 0.01). Neutral or inhibitory effects were revealed when higher doses were applied. Enzymatic activity showed progressive inhibition when 532 nm irradiation was applied, declining to 75% at 40 J/cm² (p < 0.01). Conclusions: These outcomes indicate that conformational flexibility and catalytic efficiency occur when applying lower-energy photons at 589 nm, whilst oxidative stress and impaired enzymatic function are induced by higher-energy photons at 532 nm. This is consistent with the biphasic dose–response characteristic of photobiomodulation. Full article

: This study reports the development of a sustainable biocatalyst system for free fatty acid (FFA) production from cocoa bean shell (CBS) oil using Burkholderia cepacia lipase (BCL). CBS was explored as both a support material and a reaction substrate. Six immobilized systems were prepared using organic (CBS), inorganic (silica), and hybrid (CBS–silica) supports via physical adsorption or covalent binding. Among them, the covalently immobilized enzyme on CBS (ORG-CB) showed the most balanced performance, achieving a catalytic efficiency (Ke) of 0.063 mM⁻¹·min⁻¹ (18.6% of the free enzyme), broad pH–temperature tolerance, and over 50% activity retention after eight reuse cycles. Thermodynamic analysis confirmed enhanced thermal resistance for ORG-CB (Ed = 32.3 kJ mol⁻¹; ΔH‡ = 29.7 kJ mol⁻¹), while kinetic evaluation revealed that its thermal deactivation occurred faster than for the free enzyme under prolonged heating. In application trials, ORG-CB reached 60.1% FFA conversion from CBS oil, outperforming the free enzyme (49.9%). These findings validate CBS as a dual-function material for enzyme immobilization and valorization of agro-industrial waste. The results also reinforce the impact of immobilization chemistry and support composition on the operational and thermal performance of biocatalysts, contributing to the advancement of green chemistry strategies in enzyme-based processing. Full article

In recent years, Ga-based liquid metals have emerged as a prominent research focus in catalysis, owing to their unique properties, including fluidity, low melting point, high thermal and electrical conductivity, and tunable surface characteristics. This review summarizes the synthesis strategies for Ga-based liquid metal catalysts, with a focus on recent advances in their applications across electrocatalysis, thermal catalysis, photocatalysis, and related fields. In electrocatalysis, these catalysts exhibit potential for reactions such as electrocatalytic CO₂ reduction, electrocatalytic ammonia synthesis, electrocatalytic hydrogen production, and the electrocatalytic oxidation of alcohols. As to thermal catalysis, these catalysts are employed in processes such as alkane dehydrogenation, selective hydrogenation, thermocatalytic CO₂ reduction, thermocatalytic ammonia synthesis, and thermocatalytic plastic degradation. In photocatalysis, they can be used in other photocatalytic reactions such as organic matter degradation and overall water splitting. Furthermore, Ga-based liquid metal catalysts also exhibit distinct advantages in catalytic reactions within battery systems and mechano-driven catalysis, offering innovative concepts and technical pathways for developing novel catalytic systems. Finally, this review discusses the current challenges and future prospects in Ga-based liquid metal catalysis. Full article

This review surveys recent advances and emerging prospects in phase-transfer catalysis (PTC) for fuel desulfurization. In response to increasingly stringent environmental regulations, the removal of sulfur from transportation fuels has become imperative for curbing SO_x emissions. Conventional hydrodesulfurization (HDS) operates under severe temperature–pressure conditions and displays limited efficacy toward sterically hindered thiophenic compounds, motivating the exploration of non-hydrogen routes such as oxidative desulfurization (ODS). Within ODS, PTC offers distinctive benefits by shuttling reactants across immiscible phases, thereby enhancing reaction rates and selectivity. In particular, PTC enables efficient migration of organosulfur substrates from the hydrocarbon matrix into an aqueous phase where they are oxidized and subsequently extracted. The review first summarizes the deployment of classic PTC systems—quaternary ammonium salts, crown ethers, and related agents—in ODS operations and then delineates the underlying phase-transfer mechanisms, encompassing reaction-controlled, thermally triggered, photo-responsive, and pH-sensitive cycles. Attention is next directed to a new generation of catalysts, including quaternary-ammonium polyoxometalates, imidazolium-substituted polyoxometalates, and ionic-liquid-based hybrids. Their tailored architectures, catalytic performance, and mechanistic attributes are analyzed comprehensively. By incorporating multifunctional supports or rational structural modifications, these systems deliver superior desulfurization efficiency, product selectivity, and recyclability. Despite such progress, commercial deployment is hindered by the following outstanding issues: long-term catalyst durability, continuous-flow reactor design, and full life-cycle cost optimization. Future research should, therefore, focus on elucidating structure–performance relationships, translating batch protocols into robust continuous processes, and performing rigorous environmental and techno-economic assessments to accelerate the industrial adoption of PTC-enabled desulfurization. Full article

The catalytic decomposition of CH₄ is a promising method for producing high-purity CO_x-free hydrogen. A Ni-Al-LDH catalyst synthesized via coprecipitation was modified with alkali metals (Mg, La, Ca, or Li) through reconstruction to enhance catalytic activity and resistance to deactivation during catalytic methane decomposition (CMD). The catalysts were evaluated by two activation methods: H₂ reduction and direct heating with CH₄. The MgNA-R catalyst achieved the highest CH₄ conversion (65%) at 600 °C when reduced with H₂, attributed to a stronger Ni-Al interaction. Under CH₄ activation, LaNA-C achieved a 55% conversion at the same temperature, associated with a smaller crystallite size and higher reducibility due to La incorporation. Although all catalysts deactivated due to carbon deposition and/or sintering, LaNA-C was the only sample that could resist deactivation for a longer period, as La appears to have a protective effect on the active phase. Post-reaction characterizations revealed the formation of graphitic and filamentous carbon. Raman spectroscopy exhibited a higher degree of graphitization and structural order in LaNA-C, whereas SEM showed a more uniform distribution of carbon filaments. TEM confirmed the presence of multi-walled carbon nanotubes with encapsulated Ni particles in La-promoted samples. These results demonstrate that La addition improves the catalytic performance under CH₄ activation and carbon structure. This finding offers a practical advantage for CMD processes, as it reduces or eliminates the need to use hydrogen during catalyst activation. Full article

The physicochemical processes that occur during selective transfer in the contact area of a bronze/steel friction pair lubricated with glycerin are experimentally studied by the polarization method to observe how they influence the tribological properties (friction and wear) of the pair. The proposed method allows for the study of tribochemical transformations of glycerin and the friction pair materials during the work process with selective transfer. The analysis of the experimental results allows for the establishment of the conditions for a stable and stationary selective transfer during the operation of the bronze/steel pair, by friction, at which the friction coefficient (COF) values and wear are low. This was achieved by implementing continuous lubrication with fresh glycerin in the contact area, choosing the optimal flow rate, and maintaining an optimal ratio between glycerin and the chemical transformation products, within well-established limits, to avoid undesirable consequences. Acrolein, as a product of chemical transformation (resulting from the catalytic dehydration of glycerin), is the most important for the initiation and stability of the selective transfer, and as the main reaction product, also represents a pathway of regeneration. Thus, it was found that the friction relative moments and the acrolein concentration presented conclusive/specific results at loads of 4–15 MPa and a sliding speed of 0.3 m/s. The optimum lubricant entry speed is 15–30 mg/min, for a minimum COF and reduced wear (about 0.028–0.03 at relatively high operating temperatures (45 and 60 °C)), and at low temperatures (30 °C) the minimum COF is about 0.038, but the lubricant inlet entry speed increases considerably, by around 1000 mg/min. Therefore, this paper aims to demonstrate the possibility of moving to another stage of practical use of a friction pair (with greatly improved tribological properties) that operates with selective transfer, much different from the ones still present, using a lubricant with special properties (glycerin). The research method used (polarization) highlights the physicochemical properties, tribochemical transformations of the lubricant, and the friction pair materials present in the contact area, for the understanding, maintenance, and stability of selective transfer, based on experiments, as a novelty compared to other studies. Full article