Search Results (1,185)

The rational design of metal-free catalysts capable of efficiently converting CO₂ under atmospheric pressure remains a significant challenge in sustainable chemistry. Herein, we report a series of clamp-shaped dihydrogen-bonded iodide catalysts (CDBI catalysts) featuring a preorganized bifunctional framework that integrates dual hydrogen-bond donors and an intrinsic iodide nucleophile within a single molecular scaffold. Systematic structural variation revealed that catalytic activity is highly sensitive to electronic modulation, steric accessibility, and precise spatial arrangement between the hydrogen-bonding units and the iodide center. The optimal catalyst enabled solvent-free cycloaddition of CO₂ with epoxides at 1 atm CO₂, affording up to 99% conversion and >99% selectivity at 80 °C within 12 h. Substrate scope studies demonstrated efficient transformation of a wide range of terminal epoxides, while sterically demanding substrates exhibited reduced reactivity consistent with a confined activation mode. Mechanistic investigations support a cooperative pathway in which dual hydrogen-bond activation and proximal halide nucleophilicity operate synergistically within a preorganized clamp-shaped pocket. Comparative analysis with representative catalytic systems highlights the ability of this metal-free design to achieve high efficiency under atmospheric CO₂ without cocatalysts or solvents. These findings demonstrate that structural preorganization represents an effective strategy for promoting sustainable CO₂ utilization under operationally simple conditions. Full article

Access to clean and safe drinking water for all remains a global challenge, mainly for rural populations and areas affected by natural disasters or humanitarian crises. The traditional water quality treatment technologies can work well in laboratory or controlled settings, but they are usually applied under conditions unavailable in these types of conditions. Traditional water quality treatment methods are limited by established infrastructure, expensive operating costs, energy requirements, and the ability to perform in-field water treatment. To improve the barriers of traditional water quality treatment technologies, recently developed scientific discoveries of nanozymes, a new class of nanomaterials with enzyme-like catalytic activity, have shown the ability to decentralise water purification. Nanozymes provide a mechanism for water treatment that does not require the infrastructure or the cost of traditional water quality treatment methods. Also, nanozymes possess extremely high catalytic activity, chemical stability, are inexpensive, and are suitable for a variety of contaminants. This review gives a systematic overview of the development of suitable nanozyme-based portable water purification systems. It shows their catalytic mechanisms, the class of nanozymes used, and the design characteristics related to their working use, also highlighting the developments that consider the specific needs of rural contexts, provide rapid responses to disaster areas, and offer drinking water with reliable, simple, and sustainable apparatus. Full article

Castration-resistant prostate cancer (CRPC) remains a significant clinical challenge due to the ability of tumor cells to undergo intratumoral androgen synthesis, a process catalyzed by the CYP17A1 enzyme. The only CYP17A1 inhibitor available in therapy, abiraterone acetate, faces significant limitations due to its steroidal structure, which causes off-target effects and generates agonistic metabolites that paradoxically stimulate the androgen receptor (AR). This study presents the development of the D2AAK1M series, a novel class of non-steroidal potential CYP17A1 inhibitors based on a pyridine–piperidine scaffold. Through biomimetic design and molecular docking, we demonstrated that these compounds have the potential to coordinate the heme iron while achieving high shape complementarity within the catalytic pocket. In silico ADME profiling indicated superior physicochemical properties compared to abiraterone, including optimal lipophilicity, enhanced water solubility, and the potential to penetrate the blood–brain barrier for targeting CNS metastases. In vitro assay results correlated with a suggested mechanism, showing preferential cytotoxicity toward androgen-dependent LNCaP cells (AR+) while sparing AR-negative lines (DU145, PC3) and healthy human fibroblasts (BJ). Our compounds present a promising starting point for further development of non-steroidal CYP17A1 inhibitors. Full article

The potency of urate, an abundant human plasma antioxidant, in preventing oxidative damage caused by the carbonate radical anion CO₃^•−, was studied using quantum chemical calculations. The influence of microhydration of CO₃^•−/CO₃²⁻ and urate⁻/urate^• couples on the thermodynamic and kinetics of the one-electron oxidation process was investigated. Depending on the degree of microhydration, the estimated rate constant for one-electron transfer is in the range of 2.0–7.3 × 10⁹ M⁻¹ s⁻¹, in good agreement with the experimental value of 1.3 × 10⁹ M⁻¹ s⁻¹. Modeling using vertical detachment energy and electron affinity, the driving forces of single electron transfer revealed urate(H₂O)₆⁻ and CO₃(H₂O)₉^•− clusters as the most likely existing species in water. Molecular docking revealed a favorable interaction of urate with the catalytic pocket of SOD1. Urate binds more strongly to the anionic active center of SOD1 than the reference inhibitor LSC-1, indicating its potency to prevent HCO₃⁻-supported CO₃^•− formation. In contrast, the known OGG1 inhibitor TH13264 shows substantially stronger binding than urate, indicating urate’s weaker affinity toward the DNA repair enzyme catalytic pocket. The molecular dynamics data indicate that urate binding does not destabilize either SOD1 or OGG1. In light of increasing evidence that the major source of oxidative stress could be CO₃^•−, rather than the commonly assumed hydroxyl radical HO^•, the obtained results indicate the inherent ability of plasma to combat oxidative stress induced by this selective, milder oxidant. Such an ability with respect to the non-selective, highly reactive HO^• does not exist in vivo. Full article

A novel K-resistant CeSbTi mixed oxide catalyst was prepared by co-precipitation method for ammonia selective catalytic reduction (NH₃-SCR) of NO_x. The experimental results show that the introduction of Sb₂O₅ can significantly improve the catalytic activity of the CeTi catalyst. The modulated CeSbTi catalyst has good resistance to K, and the NO_x conversion rate was as high as 95% after K poisoning. Its superior catalytic activity could be ascribed to the large specific surface area with increased acid sites and more oxygen defects and Ce³⁺ species after the introduction of Sb₂O₅, which prompt NH₃ adsorption and activation. In addition, NH₃-SCR reaction over CeSbTi and K/CeSbTi catalysts follows the E-R mechanism. The introduced Sb-O bond as the base capture site preferentially binds to potassium and releases part of the active Ce sites, thus retaining more acid sites and oxygen defects to a certain extent. Full article

Metalloporphyrins play an important role in biomedicine, catalysis, and energy, among other fields, due to their structural complexity and functional diversity. In this study, GO was used as the precursor support and chitosan was employed to reduce and functionalize GO into chitosan-functionalized rGO. Furthermore, metalloporphyrins were covalently linked to the amino side chains of chitosan via an amide crosslinking method, and a series of metalloporphyrin–chitosan-functionalized rGO nanocomposites were designed and synthesized. A set of poly(metalloporphyrin–chitosan)-functionalized rGO working electrodes was constructed by drop-coating onto glassy carbon electrodes, and their electrocatalytic performance toward dopamine was investigated in PBS solution. Finally, zinc(II) porphyrin, with the best performance, was selected as the core catalytic unit to fabricate an enzyme-free dopamine sensor. Under optimal working conditions, the sensor exhibited a sensitivity of 0.30 mA mM⁻¹cm⁻², a linear detection range of 0.001~1.0 mM, and a low detection limit of 0.05 μM (S/N = 3). The sensor showed anti-interference ability against various interfering ions and electroactive substances, as well as good stability and repeatability. Full article

Snake venoms are rich sources of molecules with pharmacological potential, with approximately 90% of their composition consisting of proteins and peptides responsible for their biological activities. These proteins are classified as enzymatic or non-enzymatic. Enzymatic proteins function as catalysts in regulatory chemical reactions, whereas non-enzymatic proteins, despite lacking catalytic activity, play essential roles in physiological processes. Lectins are non-enzymatic proteins of non-immune origin characterized by carbohydrate- and glycoprotein-binding domains, enabling their ability to agglutinate erythrocytes. C-type lectins and C-type lectin-like proteins are commonly found in snake venoms and are associated with hemostatic disturbances, particularly bleeding and coagulation disorders. This review provides a comprehensive analysis of studies published over the past decade on lectins isolated from snake venom, addressing their definitions, classifications, structural characteristics, and mechanisms of action, as well as their relevance in biotechnological applications. Although progress has been made in elucidating their pharmacological properties, most studies have focused on plant lectins. In contrast, research on snake venom lectins remains limited, particularly regarding their heterologous activities. This gap, especially compared to other venom-derived molecules, highlights the need to further expand research on this class of proteins. Full article

Gram-positive bacteria covalently anchor specific proteins to the peptidoglycan cell wall via sortase, a cysteine transpeptidase that targets proteins with a cell wall sorting signal. Sortase enzymes are critical for bacterial pathogenesis, and their inhibitors have become promising therapeutic targets for infection management. Filifactor alocis, a Gram-positive anaerobic bacterium, is now proposed as a diagnostic indicator of periodontal disease. Unlike other bacteria, F. alocis encodes a single putative sortase, FA1364. In this study, we functionally characterized the putative sortase FA1364 and found that it belongs to the class A family (SrtA). The SrtA-anchored surface proteins (FA1006, FA1336, FA1424, and FA1750) were identified, and MS/MS analysis confirmed that SrtA is required for their cell-surface localization. The recombinant SrtA protein could recognize and cleave the LPKTG sorting motif with cysteine 191 and arginine 200 as essential catalytic residues. F. alocis FLL101 (ΔFA1364::ermF) showed reduced ability to coaggregate and form biofilm, along with decreased collagen binding and survival in epithelial cells. Additionally, the FA1364-defective mutant exhibited increased sensitivity to air exposure. Collectively, these results suggest that the F. alocis SrtA protein is an important virulence factor and may represent a novel therapeutic target for the control of periodontal diseases. Full article

Water pollution caused by the continuous emergence of organic contaminants poses increasing challenges to conventional treatment technologies. Although advanced oxidation processes (AOPs) based on nanoconfined materials show great promise, their practical application remains constrained by short radical lifetimes, mass transfer limitations, and catalyst deactivation. This review systematically summarizes the critical role of nanoconfinement effects in AOPs. Through size exclusion and electrostatic regulation, confined spaces promote reactant enrichment and interference exclusion, while confined mass transfer and capillary-driven effects accelerate reaction kinetics. Particular emphasis is placed on multidimensional nanoconfined systems, ranging from zero-dimensional to three-dimensional structures and catalytic membranes, and on how structural design improves reaction microenvironments and active-site accessibility. The synergistic integration of confined structures with external fields, such as electric fields, is further discussed, highlighting their ability to regulate the electronic structure of active sites and shift reaction pathways from non-selective radical oxidation to efficient and highly selective non-radical routes. By optimizing parameters such as pH and catalyst-to-oxidant ratio, nanoconfined systems can achieve efficient pollutant degradation under near-neutral conditions while maintaining strong anti-interference capability and stability in real water matrices containing natural organic matter and inorganic ions. Full article

Dispersion stabilization of nanoparticles for catalytic reactions is an important issue. However, dispersing agents should be carefully selected not to hinder catalytic performance. In the present study, physisorption of cyclic poly(ethylene glycol) (c-PEG) onto platinum nanoparticles (PtNPs) was investigated in comparison with unmodified PtNPs (PtNPs/No PEG), PtNPs mixed with linear PEG (PtNPs/HO-PEG-OH), and PtNPs chemisorbed with HS-PEG-OMe (PtNPs/HS-PEG-OMe). DLS showed a significant increase in the particle size for PtNPs/c-PEG and PtNPs/HS-PEG-OMe compared to PtNPs/No PEG and PtNPs/HO-PEG-OH. ζ-potential measurements revealed values around −30 mV for PtNPs/No PEG and PtNPs/HO-PEG-OH, whereas PtNPs/c-PEG and PtNPs/HS-PEG-OMe approached 0 mV, which indicated that c-PEG and HS-PEG-OMe adsorb onto PtNPs to form a shielding layer. Moreover, PtNPs/c-PEG and PtNPs/HS-PEG-OMe were stable in a phosphate-buffered saline (PBS) solution, but PtNPs/No PEG and PtNPs/HO-PEG-OH immediately aggregated. This suggests that high dispersion stability by c-PEG is comparable to ordinary surface modification using HS-PEG-OMe. Furthermore, the catalytic ability of PtNPs/c-PEG and PtNPs/HS-PEG-OMe was compared in various reactions. As a result, physisorbed PtNPs/c-PEG showed suitable catalytic activities, whereas chemisorbed PtNPs/HS-PEG-OMe was significantly hampered by the blocking of the catalytic sites with thiol in some reactions. Thus, physisorption of c-PEG endows PtNPs with dispersion stability and maintains the catalytic ability, leading to an alternative way of modifying metal nanoparticles. Full article

The combination of photochemistry with stereoselective catalysis has emerged as an effective strategy to achieve stereocontrol in light-driven transformations. Chiral phosphoric acids (CPAs) have recently attracted attention in this context due to their ability to activate substrates while providing a defined chiral environment. This minireview highlights recent developments in CPA-enabled asymmetric photochemical transformations, focusing on systems in which CPAs incorporate a chromophore on the chiral backbone or form light-absorbing CPA-substrate complexes that enable photoactivation without the presence of an external photocatalyst. The main catalytic strategies, mechanistic features, and current limitations are discussed. Full article

The Fenton reaction remains one of the most widely investigated advanced oxidation processes for wastewater treatment due to its ability to generate highly reactive oxygen species capable of degrading persistent organic pollutants. However, classical homogeneous Fenton systems suffer from significant limitations, including narrow pH applicability, iron sludge generation, and poor catalyst reusability. In response, extensive research has focused on the development of heterogeneous and advanced Fenton-like catalysts aimed at overcoming these challenges while enhancing catalytic efficiency and operational stability. This review provides a comprehensive and critical analysis of the evolution of Fenton catalysis, from classical homogeneous systems to advanced materials, including nanostructured catalysts, carbon-based Fe–N–C systems, metal–organic frameworks, and single-atom catalysts. A unified evaluation framework is proposed, integrating key performance parameters such as catalytic activity, manufacturability, stability, and catalyst lifespan. Comparative analysis reveals that improvements in activity are often accompanied by trade-offs in cost and scalability, indicating that the most advanced materials do not necessarily provide the best practical performance. A life cycle-oriented perspective is incorporated, emphasizing catalyst reuse, lifespan, and iron leaching, and providing quantitative insight into cumulative catalytic performance. The results demonstrate that long-term efficiency is governed not only by intrinsic activity but also by durability and operational stability under realistic conditions. Finally, current challenges and future directions are discussed, including scalable synthesis, improved mechanistic understanding, and integration into hybrid treatment systems. This review bridges the gap between fundamental research and practical application by highlighting the importance of balancing performance, stability, and sustainability in the design of next-generation Fenton catalysts. Full article

N₂O (Nitrous oxide) is a potent greenhouse gas with a global warming potential nearly 300 times that of CO₂ and poses a critical environmental challenge, particularly in semiconductor and display manufacturing, where it is emitted during plasma processes. However, catalytic N₂O abatement in O₂-rich environments remains inefficient because O₂ competitively occupies active sites and hinders the turnover of surface oxygen species. To clarify how support properties govern this inhibition, Co-based catalysts supported on beta zeolite, CeO₂, and TiO₂, together with unsupported Co₃O₄, were comparatively evaluated for direct N₂O decomposition. Among them, Co/Beta exhibited the highest performance, achieving >95% N₂O conversion at 450 °C in the presence of 5% O₂ with excellent long-term stability. Co/Beta possessed a high specific surface area (649 m² g⁻¹) and a mesoporous framework that favored uniform Co dispersion and reactant accessibility, while its high Co²⁺/(Co²⁺ + Co³⁺) ratio (75.5%) and large fraction of chemisorbed oxygen species (79.9%) promoted oxygen-vacancy formation and facile oxygen exchange. These results indicate that the ability of Co/Beta to maintain high activity in the presence of oxygen stems from support-modulated cobalt surface states and enhanced oxygen turnover behavior. These findings provide a support-design principle for stable N₂O decomposition under oxygen-containing exhaust conditions. Full article

A ligand-free Ni(acac)₂/EASC Ziegler–Natta catalytic system was developed for the efficient synthesis of low molecular weight liquid polybutadiene (LPB) featuring high 1,4 content. The influences of key polymerization parameters, including Al/Ni ratio, polymerization temperature, monomer-to-catalyst ratio ([Bd]/[Ni]), and external donors, were systematically investigated to elucidate structure–reactivity relationships. Increasing the Al/Ni ratio significantly enhances catalytic activity while promoting chain transfer reactions, leading to reduced molecular weights and broader molecular weight distributions, with minimal impact on overall 1,4 selectivity. Polymerization temperature strongly affects both activity and stereoselectivity; elevated temperatures accelerate chain transfer processes and broaden dispersity, while inducing a shift from kinetically favored cis-1,4 insertion toward increased trans-1,4 incorporation. Variation of the [Bd]/[Ni] ratio provides an effective handle for molecular weight regulation, where higher ratios favor chain propagation over chain transfer, affording higher molecular weights but lower monomer conversion. Notably, the system maintains consistently high 1,4 content (>98%) across a wide range of conditions. In contrast, the introduction of external donors markedly affects catalytic behavior depending on their coordination ability. Strongly coordinating O- and S-containing donors partially deactivate the catalyst and significantly shift regioselectivity toward 1,2-vinyl incorporation (up to ~20%), while N- and P-containing donors are well tolerated and can increase molecular weight by suppressing chain transfer pathways, which also results in products with higher 1,2 content. Full article

Aflatoxin B₁ (AFB₁) is a highly stable mycotoxin that can persist during conventional food processing and therefore poses a serious risk to food and feed safety. In this study, two enzymes (CotA and Prx) were heterologously expressed in Bacillus subtilis, purified by Ni–NTA affinity chromatography, and evaluated for their ability to degrade AFB₁. Both enzymes exhibited remarkable thermostability and distinct catalytic optima. CotA exhibited its highest activity at 80 °C with an AFB₁ removal of 38.4%, whereas Prx showed its highest activity at 90 °C with a removal of 82.6%. The optimal pH values were near neutral, with CotA performing best at pH 7.0 and Prx at pH 7.5, and both reactions approached maximal conversion within approximately 10 h. When the two enzymes were combined, a clear cooperative effect was observed. The mixed system achieved 91.0% AFB₁ removal at 80 °C after 10 h, with the best degradation activity occurring at a CotA to Prx ratio of 1:3. At 50 °C, neither enzyme alone caused appreciable AFB₁ degradation, but the addition of hydrogen peroxide markedly enhanced catalytic activity. Both enzymes also retained substantial activity after boiling and autoclaving. In a maize flour model, the mixed-enzyme system showed strong AFB₁ degradation capacity, and peroxide-assisted treatment further improved activity. These results establish a thermostable and peroxide-responsive enzymatic platform for AFB₁ degradation and support future development of enzyme-based detoxification strategies for food and feed applications. Product identification and toxicological validation will be needed to confirm the safety of the treated products. Full article