Search Results (100)

Demand for greener and safer chemistries has driven the innovation of bioinspired and enzyme-mimicking catalysts for selective and efficient oxidation and hydrogenation under mild conditions. Natural catalysts, including peroxidases, oxidases, hydrogenases, oxygenases and dehydrogenases, boast remarkable activity, specificity, stability, selectivity, low energy requirements and atom economy. Disadvantages of enzymes, such as poor thermal stability, a narrow operational range, low recovery yield and the expense of purification, are motivating the discovery and design of enzyme substitutes. Several artificial platforms have appeared recently: nanozymes, artificial metalloenzymes, biomimetic metal Complexes, MOFs, atomic catalysts, bioinorganic hybrid systems, among others. These systems aim to replicate key structural and mechanistic features of enzymes while providing greater operational stability, recyclability, and scalability. Recent work has demonstrated the benefit of enzyme mimics in increasing eco-sustainability in reactions such as alcohol oxidation, selective alkane oxidation, waste degradation, catalytic photooxygen activation and biomass waste conversion. Similarly, biomimetic hydrogenation catalysts have shown outstanding activity in asymmetrically hydrogenating chemicals, reducing CO₂ into chemicals, hydrogenation by hydrogen transfer and creating hydrogen through water. Through control of active sites, second coordination sites, defects and electrons/protons in the system, significant gains have been seen in reaction selectivity and frequency of turning over substrate into product. Nanozymes, biohybrid catalysis and artificial catalysts guided by deep learning are further broadening the applications of biomimetic catalysis in oxidation and hydrogenation. The article review aims to provide a summary of the most current progress with bioinspired and enzyme-mimicking catalysts, focusing on catalytic mechanisms, how to design such catalysts, how green chemistry benefits from their development and where further application is likely in the coming years. Full article

The hydrogen evolution reaction (HER) plays a central role in electrochemical hydrogen production and requires catalysts that combine high activity with reduced noble metal usage. In this work, palladium nanoparticles (PdNPs) were deposited onto silver nanowire-modified graphite electrodes (Pd/AgNW/C) to investigate the influence of Pd loading on HER kinetics and catalytic efficiency. The electrodes were prepared by constant-current electrodeposition and characterized using polarization measurements and electrochemical impedance spectroscopy (EIS). The direct current (DC) results showed a pronounced enhancement of HER activity in the presence of Pd, while the highest mass-specific activity was observed at low Pd loadings. Increasing the Pd content further increased the overall current but reduced the catalytic efficiency when normalized to the Pd mass. EIS measurements revealed two contributions to the impedance response associated with processes occurring on different timescales. With increasing cathodic overpotential, both the charge transfer resistance and the low-frequency resistance decreased markedly, indicating accelerated reaction kinetics. The combined DC and alternating current (AC) analyses suggest that the silver nanowire network facilitates efficient electron transport and promotes a favorable dispersion of Pd nanoparticles at low loadings, enabling efficient HER catalysis with reduced noble metal usage. Full article

The field of developing effective catalysts for heterogeneous catalysis has recently focused on controlling the structures of catalysts themselves to optimise the density and energy of crystal lattice defects. This can significantly influence catalytic activity in terms of both reaction rates and reaction mechanisms, and thus the selective production of desired substances as well. In many cases, these crystal lattice defects manifest themselves as so-called electron traps (ETs) and thus significantly influence charge transfer between the catalyst and reactants. ETs provide the missing electronic link between atomic-scale defects and macroscopic performance in heterogeneous catalysis. Therefore, the importance of ETs for catalysis is particularly evident in areas where charge transfer plays a fundamental role in the reaction mechanism, such as photocatalysis and electrocatalysis. In the field of thermally initiated reactions, the importance of ETs in heterogeneous catalysis has not yet been fully appreciated. However, several studies have already addressed the importance of ETs for this type of reaction. This review consolidates and extends the concept of ETs to purely thermal-initiated reactions, with a focus on CO₂ hydrogenation using typical transition metal catalysts. Firstly, in this review, ETs are defined as band gap states associated with internal and external defects, and their depth, density, spatial location, and dynamics are then coupled with key steps in thermocatalytic cycles, including charge storage/release, reactant activation, intermediate stabilisation, and redox turnover. Secondly, electron trap detection is reviewed based on advanced spectroscopic techniques, including reversed double-beam photoacoustic spectroscopy (RDB-PAS), thermally stimulated current (TSC), deep-level transient spectroscopy (DLTS), thermoluminescence (TL), electron paramagnetic resonance (EPR), and photoluminescence (PL), highlighting how each method describes trap energetics and populations under realistic operating conditions. Finally, case studies on the application of metal oxides and supported metals are discussed, as these are typical catalysts for the reaction mentioned above. This review highlights how oxygen vacancies (OVs), polarons, and metal–support interfacial sites act as robust electron reservoirs, lowering the barriers for CO₂ activation and hydrogenation. By reframing thermocatalysts through the lens of ET chemistry, this review identifies ETs as actionable targets for the rational design of next-generation materials for CO₂ hydrogenation and related high-temperature transformations. Full article

For those who did not follow the invention and development of enantioselective catalysis, this review introduces pertinent historical aspects of the field and presents the scientific concepts of asymmetric bio- and organocatalysis. They are powerful technologies applied in organic laboratories and industry. They realize chiral amplification by converting inexpensive achiral substrates and reagents into enantiomerically enriched products using readily recoverable solvents, if any are used. Racemic substrates can also be deracemized catalytically. More sustainable fabrications are now available that require neither toxic metallic species nor costly reaction conditions in terms of energy, atmosphere control, product purification, and safety. Nature has been the source of the first asymmetric catalysts (microorganisms, enzymes, alkaloids, amino acids, peptides, terpenoids, sugars, and their derivatives). They act as temporary chiral auxiliaries and lower the activation free energy of the reaction by altering the reaction mechanism. Reductions, oxidations, carbon-carbon and carbon-heteroatom bond-forming reactions are part of the process panoply. Asymmetric catalyzed multicomponent and domino reactions are becoming common. Typical modes of activation are proton transfers, hydrogen bonded complex formation, charged or uncharged acid/base pairing (e.g., σ-hole catalysts), formation of equilibria between achiral aldehydes and ketones with their chiral iminium salt or/and enamine intermediates, umpolung of aldehydes and ketones by reaction with N-heterocyclic carbenes (NHCs), phase transfer catalysis (PTC), etc. Often, the best enantioselectivities are observed with polyfunctional catalysts derived from natural compounds, but not always. They may combine to form chiral structures containing nitrogen, phosphorus, sulfur, selenium, and iodine functional moieties. Today, man-made enantiomerically enriched catalysts, if not enantiomerically pure, are available in both enantiomeric forms. Being robust, they are recovered and reused readily. Full article

Alkyl-substituted pyridines are ubiquitous structural motifs found in natural products, pharmaceuticals, agrochemicals, and functional organic materials. However, their direct synthesis remains challenging because of the electron-deficient nature of the pyridine ring and the harsh conditions typically required for conventional carbonyl-to-alkane reduction. Herein, we report a mild and environmentally benign Pd/C–H₂ catalytic system that enables one-pot oxidative aromatization–deoxygenation of dihydropyridinedione derivatives to afford alkyl-substituted pyridines. The transformation proceeds efficiently at room temperature under atmospheric hydrogen pressure using ethanol as a green solvent, delivering the desired products in up to 91% isolated yield. The protocol exhibits broad substrate scope, high chemoselectivity, operational simplicity, and excellent catalyst recyclability. Mechanistic studies, including hydrogen-free control experiments and intermediate isolation, support a sequential Pd-mediated pathway involving oxidative aromatization, stepwise hydrogen-transfer reduction, and final deoxygenation, with water as the sole stoichiometric by-product. This method provides a sustainable and scalable alternative to classical harsh or reagent-intensive deoxygenation strategies for the synthesis of alkyl-substituted pyridines. Full article

Hydrogen peroxide (H₂O₂) is a key oxidant for green chemical processes, yet its catalytic utilization and activation efficiency remain limited by material instability and uncontrolled radical release. Here, we report a dual-functional, hollow conductive polymer nanostructure that enables selective modulation of H₂O₂ reactivity through interfacial physicochemical design. Hollow polypyrrole nanospheres functionalized with carboxyl groups (PPy@PyCOOH) were synthesized via a one-step Fe²⁺/H₂O₂ oxidative copolymerization route, in which H₂O₂ simultaneously served as oxidant, template, and reactant. The resulting structure exhibits enhanced hydrophilicity, rapid redox degradability (>80% optical loss in 60 min (82.5 ± 4.1%, 95% CI: 82.5 ± 10.2%), 10 mM H₂O₂, pH 6.5), and strong electronic coupling to reactive oxygen intermediates. Subsequent tannic acid–copper (TA–Cu) coordination produced a conformal metal–polyphenol network that introduces a controllable Fenton-like catalytic interface, achieving a 50% increase in ROS yield (1.52 ± 0.08-fold vs. control, 95% CI: 1.52 ± 0.20-fold) while maintaining stable photothermal conversion under repeated NIR cycles. Mechanistic analysis reveals that interfacial TA–Cu complexes regulate charge delocalization and proton–electron transfer at the polymer–solution boundary, balancing redox catalysis with energy dissipation. This work establishes a sustainable platform for H₂O₂-driven redox and photo-thermal coupling, integrating conductive polymer chemistry with eco-friendly catalytic pathways. Full article

This work presents a catalysis-based electrochemical biosensor to evaluate the peroxidase-like activity of methemoglobin (Hb-PLA) after exposure to cigarette smoke (CS) at different time intervals. The system consists of a microelectrode array coupled with a PDMS chamber containing a methemoglobin solution (biorecognition element). Hydrogen peroxide (H₂O₂) acts as the substrate, while 3,3′,5,5′-tetramethylbenzidine (TMB) functions as the chromogenic substrate for the Hb-PLA through its oxidation reaction. A spectrophotometric technique is used as a reference method to assess the catalytic activity of methemoglobin. Positive control samples exhibited higher absorbance, indicating strong catalytic activity, whereas CS-exposed samples showed a marked reduction, which was confirmed by the negative control. Cyclic voltammetry revealed significant alterations in the oxidation and reduction peaks of the CS-exposed samples. Therefore, chronoamperometry was employed to quantify the charge transfer as the electrochemical response associated with Hb-PLA, yielding a sensitivity of 0.86 ± 0.06 (%Hb-PLA/mC) and a limit of detection (LOD) of 0.23 (mC). The results demonstrate that cigarette smoke impairs the Hb-PLA in a time-dependent manner, with longer exposure reducing the activity by up to 25%. The proposed biosensor provides a rapid, sensitive, and straightforward strategy for detecting functional alterations in solutions of methemoglobin induced by environmental pollutants such as cigarette smoke. Full article

This work reports the synthesis and characterization of a novel rhenium(I) complex incorporating a phosphorus–nitrogen (P,N) ligand. The compound crystallizes in a distorted octahedral geometry, as confirmed by single-crystal X-ray diffraction analysis. The complexes were evaluated as catalysts in the transfer hydrogenation of acetophenone using 2-propanol as the hydrogen source. Comparative studies with other rhenium(I) complexes bearing polypyridine ligands revealed high catalytic performance, achieving conversions between 68% and 99%. These results highlight the promising potential of P,N-ligand rhenium complexes in homogeneous transfer hydrogenation catalysis. The optimal reaction time was found to be 4 h for the complexes studied, with only the fac-[Re(CO)₃(PN)Cl] complex showing improved conversion upon extending the reaction time to 7 h, likely due to the donor effects provided by the P,N-ligand. Full article

Chiral coordination compounds are of growing interest due to their structural diversity and wide applicability. Besides chirality, alcohol and especially oxime-functionalized limonene derivatives confer water solubility, stability, and the appropriate reactivity to enable their use in asymmetric catalysis—such as allylic substitution, alkynylation, transfer hydrogenation, and selective C–C bond formation. Biologically, they have shown promising anticancer, antibacterial, and antibiofilm activity. This review presents an integrated overview of the synthesis, properties, and applications of chiral transition metal complexes featuring ligands derived from inexpensive, naturally occurring R- and S-limonene substrates, and explore their roles in catalysis and biological activity. Full article

Constructing heterojunction photocatalysts with efficient interfacial charge transfer is critical for solar-driven hydrogen evolution. In this study, a highly dispersed MoS₂/g-C₃N₄ composite was successfully synthesized via a stirring-assisted hydrothermal in situ growth strategy. The introduction of stirring during synthesis significantly enhanced the uniform dispersion of MoS₂ nanosheets and exposed abundant edge sites, leading to well-integrated heterojunctions with enhanced interfacial contact. Comprehensive structural and photoelectronic characterizations (XRD, SEM, TEM, EDS mapping, UV–Vis, TRPL, EIS, EPR) confirmed that the composite exhibited improved visible-light absorption, accelerated charge separation, and suppressed recombination. Under simulated solar irradiation with triethanolamine (TEOA) as a sacrificial agent, the optimized 24% MoS₂/g-C₃N₄-S catalyst achieved a high hydrogen evolution rate of 14.33 mmol·g⁻¹·h⁻¹ at a catalyst loading of 3.2 mg, significantly outperforming the unstirred and pristine components, and demonstrating excellent cycling stability. Mechanistic studies revealed that the performance enhancement is attributed to the synergistic effects of Type-II heterojunction formation and edge-site-rich MoS₂ co-catalysis. This work provides a scalable approach for non-noble metal interface engineering and offers insight into the design of efficient and durable photocatalysts for solar hydrogen production. 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 dynamic phosphorylation of the human RNA Pol II CTD establishes a code applicable to all eukaryotic transcription processes. However, the ability of these specific post-translational modifications to convey molecular signals through structural changes remains unclear. We previously explained that each gene can be modeled as a combination of n circuits connected in parallel. RNA Pol II accesses these circuits and, through a series of pulses, matches the resonance frequency of the DNA qubits, enabling it to extract genetic information and quantum teleport it. Negatively charged phosphates react under RNA Pol II catalysis, which increases the electron density on the deoxyribose acceptor carbon (2’C in the DNA sugar backbone). The phosphorylation effect on the stability of a carbon radical connects tyrosine to the nitrogenous base, while the subsequent pulses link the protein to molecular water through hydrogen bonds. The selective activation of inert C(sp³)–H bonds begins by reading the quantum information stored in the nitrogenous bases. The coupling of hydrogen proton transfer with electron transfer in water generates a supercurrent, which is explained by the correlation of pairs of the same type of fermions exchanging a boson. All these changes lead to the formation of a molecular protein–DNA–water transcriptional condensate. Full article

Defect engineering has recently emerged as a cutting-edge discipline for precise modulation of electronic structures in nanomaterials, shifting the paradigm in nanoscience from passive ‘inherent defect tolerance’ to proactive ‘defect-controlled design’. The deliberate introduction of defect—including vacancies, dopants, and interfaces—breaks the rigid symmetry of crystalline lattices, enabling new pathways for optimizing catalysis performance. This review systematically summarizes the mechanisms underlying defect-mediated electronic structure at active sites regulation, including (1) reconstruction of the electronic density of states, (2) tuning of coordination microenvironments, (3) charge transfer and localization effects, (4) spin-state and magnetic coupling modulation, and (5) dynamic defect and interface engineering. These mechanisms elucidate how defect-induced electronic restructuring governs catalytic activity and selectivity. We further assess advanced characterization techniques and computational methodologies for probing defects-induced electronic states, offering deeper mechanistic insights at atomic scales. Finally, we highlight recent breakthroughs in defect-engineered nanomaterials for catalytic applications, including hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and beyond, while discussing existing challenges in scalability, defect stability, and structure–property causality. This review aims to provide actionable principles for the rational design of defects to tailor electronic structures toward next-generation energy technologies. Full article

Ru/TiO₂ catalysts are well known for their high activity in the hydrogenation of CO₂ to CH₄ (the Sabatier reaction). This activity is commonly attributed to strong metal–support interactions (SMSIs), associated with reducible oxide layers partly covering the Ru-metal particles. Moreover, isothermal rates of formation of CH₄ can be significantly enhanced by the exposure of Ru/TiO₂ to light of UV/visible wavelengths, even at relatively low intensities. In this study, we confirm the significant enhancement in the rate of formation of methane in the conversion of CO₂, e.g., at 200 °C from ~1.2 mol g_Ru⁻¹·h⁻¹ to ~1.8 mol g_Ru⁻¹·h⁻¹ by UV/Vis illumination of a hydrogen-treated Ru/TiO_x catalyst. The activation energy does not change upon illumination—the rate enhancement coincides with a temperature increase of approximately 10 °C in steady state (flow) conditions. In-situ DRIFT experiments, performed in batch mode, demonstrate that the Ru–CO absorption frequency is shifted and the intensity reduced by combined UV/Vis illumination in the temperature range of 200–350 °C, which is more significant than can be explained by temperature enhancement alone. Moreover, exposing the catalyst to either UV (predominantly exciting TiO₂) or visible illumination (exclusively exciting Ru) at small intensities leads to very similar effects on Ru–CO IR intensities, formed in situ by exposure to CO₂. This further confirms that the temperature increase is likely not the only explanation for the enhancement in the reaction rates. Rather, as corroborated by photophysical studies reported in the literature, we propose that illumination induces changes in the electron density of Ru partly covered by a thin layer of TiO_x, lowering the CO coverage, and thus enhancing the methane formation rate upon illumination. Full article

Superoxide dismutase 1 (SOD1) is a crucial enzyme that protects cells from oxidative damage by converting superoxide radicals into H₂O₂ and O₂. This detoxification process, essential for cellular homeostasis, relies on a precisely orchestrated catalytic mechanism involving the copper cation, while the zinc cation contributes to the structural integrity of the enzyme. This study presents the 2.3 Å crystal structure of human SOD1 (PDB ID: 9IYK), revealing an assembly of six homodimers and twelve distinct active sites. The water molecules form a complex hydrogen-bonding network that drives proton transfer and sustains active site dynamics. Our structure also uncovers subtle conformational changes that highlight the intrinsic flexibility of SOD1, which is essential for its function. Additionally, we observe how these dynamic structural features may be linked to pathological mutations associated with amyotrophic lateral sclerosis (ALS). By advancing our understanding of hSOD1’s mechanistic intricacies and the influence of water coordination, this study offers valuable insights for developing therapeutic strategies targeting ALS. Our structure’s unique conformations and active site interactions illuminate new facets of hSOD1 function, underscoring the critical role of structural dynamics in enzyme catalysis. Moreover, we conducted a molecular docking analysis using SOD1 for potential radical scavengers and Abelson non-receptor tyrosine kinase (c-Abl, Abl1) inhibitors targeting misfolded SOD1 aggregation along with oxidative stress and apoptosis, respectively. The results showed that CHEMBL1075867, a free radical scavenger derivative, showed the most promising docking results and interactions at the binding site of hSOD1, highlighting its promising role for further studies against SOD1-mediated ALS. Full article