Search Results (744)

The pursuit of sustainable ammonia production has accelerated the development of electrocatalytic pathways capable of operating under ambient conditions with renewable electricity. Recent studies have revealed that the efficiency and selectivity of both electrochemical nitrogen reduction reaction (eNRR) and nitrate reduction reaction (eNO₃RR) are not governed solely by catalyst composition, but by the synergistic interplay among electrolyte identity, interfacial solvation structure, and catalyst architecture. Hydrated cations such as Li⁺ profoundly reshape the electric double layer, polarize interfacial water, and lower activation barriers for key proton–electron transfer steps, thereby redefining the electrolyte as an active promoter. Parallel advances in structural engineering, including alloying, heteroatom doping, controlled defect formation, and nanoscale morphological control, have enabled the optimization of intermediate adsorption energies while simultaneously suppressing competing hydrogen evolution. In addition, the emergence of metal–organic-framework (MOF)-derived single-atom catalysts has demonstrated that atomically dispersed transition-metal centers anchored within dynamically adaptable matrices can deliver exceptional Faradaic efficiencies, high turnover rates, and long-term operational durability. These developments highlight a unified strategy in which electrolyte–catalyst coupling, rational structural modification, and atomic-scale design principles converge to enable predictable and high-performance ammonia electrosynthesis. This review integrates mechanistic insights across these domains and outlines future directions for translating molecular-level understanding into scalable technologies for green ammonia production. Full article

Plant polyphenols, particularly flavonoids, are prominent bioactives in preventive/complementary therapeutic strategies. This article analyzes how some polyphenols can mitigate oxidative stress and inflammation. These processes are involved in cardiovascular disease, cancer, neurodegeneration, and metabolic disorders. Polyphenols are explored through the integration of direct antioxidant chemistry (radical scavenging via hydrogen atom transfer/single-electron transfer/metal chelation), redox signaling (Keap1–Nrf2/ARE and inflammatory pathways), endogenous antioxidant enzyme systems, and mitochondrial quality control. Unlike previous descriptive reviews, a novel aspect of this manuscript is its evidence-based synthesis, fully supported by structured summary tables that explicitly detail limitations, contradictions, and context dependencies in in vitro, in vivo, and human studies, and identify clinically interpretable endpoints for their application. We describe relevant flavonoids and dietary sources, along with functional outcomes in cardiometabolic–cognitive/neuroprotective–immunometabolic contexts. We integrate representative clinical interventions and nutraceutical applications, highlighting where reported benefits are supported and where the evidence is preliminary. Bioavailability, microbiota-driven biotransformation, and dose realism are considered the primary determinants of in vivo relevance, rather than secondary or descriptive considerations. Future research should prioritize standardized exposure and metabolite profile, dose-appropriate interventions, harmonized clinical endpoints, and stratification strategies that account for microbiome-driven interindividual variability to improve reproducibility and inform nutraceutical and therapeutic use. Full article

The flotation efficiency of magnesite in the slurry system is critically influenced by its surface wettability. In this work, molecular dynamics (MD) and density functional theory (DFT) calculations were employed to investigate the interactions between water molecules and the magnesite (104) surface. To elucidate the underlying mechanisms, systematic evaluations were conducted, encompassing frontier orbital energies, water molecule adsorption behavior, and the water wetting process. Results indicate that electrons readily transfer from the highest occupied molecular orbital (HOMO) of water to the lowest unoccupied molecular orbital (LUMO) of magnesite. Specifically, the chemisorption of a single water molecule onto the magnesite surface was observed, with a calculated adsorption energy of −91.6 kJ/mol. This process involves an interaction between the oxygen atom of water and a surface magnesium atom, leading to the formation of an Mg–O_W bond. This bond primarily arises from hybridization between the Mg 2p, Mg 2s, and O_W 2p orbitals. Furthermore, water molecules within the first adsorbed monolayer exhibited an average adsorption energy of −66.3 kJ/mol, which further confirms the occurrence of chemisorption. Notably, minimal changes were observed in the orbital interactions between water molecules and surface Mg atoms, a trend consistent with the single-molecule adsorption case. The average adsorption energies for the second and third water layers were calculated to be −63.2 kJ/mol and −45.6 kJ/mol, respectively. The stabilization of the hydration layer structure is attributed to the hydrogen-bonding network formed among water molecules in the outer layers. As the number of water layers increases, the structural disorder of water molecules on the magnesite surface progressively intensifies. This decrease in adsorption energy with increasing layer number is attributed to the progressively enhanced contribution of hydrogen-bonding interactions between water molecules across different layers. Consequently, the magnesite surface exhibits a low contact angle, indicating high intrinsic hydrophilicity. Collectively, these findings provide molecular-level insights into the wettability of the magnesite surface, thereby contributing to a more fundamental understanding of magnesite flotation mechanisms. Full article

Background/Objectives: First row transition metal ions have recently regained attention in coordination chemistry as alternatives to gadolinium-based paramagnetic contrast agents, motivated by emerging safety concerns associated with certain Gd³⁺-based contrast agents. In this study, we report the development of a novel homoleptic diketonate Fe³⁺ complex functionalized with biocompatible indole moieties. We investigate its potential as a paramagnetic relaxation agent by evaluating its ability to modulate the T₁ and T₂ relaxation times of water proton. Methods: Iron(III) tris-1,3-(1-methylindol-3-yl)propanedionate [Fe(BIP)₃] was synthesized via a thermal method from bis(1-methylindol-3-yl)-1,3-propanedione (HBIP) using Fe(ClO₄)₃∙6 H₂O as the metal source. The complex was characterized by UV-Vis, IR and NMR spectroscopy, differential scanning calorimetry–thermogravimetric analysis, and single-crystal X-ray diffraction. Fe(BIP)₃ aggregation behavior in aqueous environment, including size and morphology of aggregates, was investigated using dynamic light scattering and scanning electron microscopy. Incorporation of the aggregates into phospholipid vesicles was evaluated by fluorescence resonance energy transfer and fluorescence correlation spectroscopy. The paramagnetic properties of monomeric Fe(BIP)₃ were probed in solution by nuclear magnetic resonance recurring to the Evans bulk magnetization method. Results: The designed synthetic procedure successfully afforded Fe(BIP)₃, which was fully characterized by UV-Vis and IR spectroscopy, as well as single-crystal X-ray diffraction. Aqueous solutions of Fe(BIP)₃ spontaneously formed rice-grain-shaped nanoscale aggregates of hydrodynamic radius ≈ 30 nm. Incorporation of these aggregates into phospholipid vesicles enhanced their stability. The longitudinal r₁ and transverse r₂ relaxivities of Fe(BIP)₃ aggregates were assessed to be 1.92 and 52.3 mM⁻¹s⁻¹, respectively, revealing their potential as paramagnetic relaxation agents. Conclusions: Fe(BIP)₃ aggregates, stabilized through incorporation into phospholipid vesicles, demonstrate promising potential as novel paramagnetic relaxation agents in aqueous environments. Full article

The synthesis of monocyclic and bicyclic compounds plays a fundamental role in organic chemistry, and the need for novel synthetic methodologies is still under investigation. In particular, α,β-unsaturated (bis)enones have emerged as valuable precursors for the formation of cyclic (both mono and bicyclic) structures through single-electron transfer (SET) processes. Single-electron transfer (SET) is a redox process where one electron moves from a donor species to an acceptor, generating radical ions or neutral radicals that drive unique reaction pathways. Thanks to the advent of radical chemistry, it was possible to discover an entirely new reactivity of α,β-unsaturated (bis)enones, which, after a SET event, undergo the formation of cyclic molecules, both in intra and inter-molecular reactions, under several possible pathways, including formal [2+2] cycloaddition reaction (22CA) and 5-exo-trig cyclization, for ring closure. Today, the generation of radical species can be broadly classified into three main approaches: photochemical and photocatalytic, metal-driven and electrochemical processes. In this review, we summarize the progress achieved to date in the synthesis of cyclic molecules from α,β-unsaturated (bis)enones via single-electron transfer events under these three main classes of processes. Whenever possible, the reaction pathway and fate of the radical species generated through SET is discussed. Full article

The widespread occurrence of pharmaceutical contaminants in aquatic environments poses significant risks to ecosystems and public health, necessitating the development of efficient and sustainable treatment technologies. Herein, a visible-light (VL)–active zinc single-atom catalyst supported on biochar (SAZn@BC) was synthesized via pyrolysis and applied for the degradation of ibuprofen (IBP), sulfamethoxazole (SMX), trimethoprim (TMP), and carbamazepine (CBZ) in water. Structural characterization confirmed the presence of g-C₃N₄ domains, abundant oxygen-containing functional groups, and atomically dispersed Zn sites with a Zn–N₄ coordination environment. Under VL irradiation, SAZn@BC achieved degradation efficiencies of 43.9%, 64.4%, and 61.9% for IBP, SMX, and TMP, respectively, within 30 min, while CBZ exhibited limited removal. Mechanistic investigations combining quenching experiments, electrochemical analyses, and X-ray photoelectron spectroscopy revealed that superoxide and hydroperoxyl radicals were the dominant reactive oxygen species, with hydroxyl radicals and singlet oxygen contributing to a lesser extent. In addition, a nonradical pathway involving direct interfacial electron transfer between oxygen functional groups on the biochar support and pharmaceutical molecules played a critical role, mediated by single-atom Zn sites and enhanced under VL irradiation. These findings demonstrate that SAZn@BC enables synergistic radical and nonradical pathways for pharmaceutical degradation and represents a promising strategy for water treatment applications. Full article

Hardware-in-the-loop (HIL) simulation is an essential tool for rapid and cost-effective development and validation of power-electronic systems. The primary objective of this work is to validate and fine-tune a PLECS-based HIL model of a single dual active bridge (DAB) DC-DC converter, thereby laying the foundation for building more complex models (e.g., multiple converters connected in series or parallel). To this end, the converter is experimentally characterized, and the HIL model is validated across a wide range of operating conditions by varying the PWM phase-shift angle, voltage gain, switching frequency, and leakage inductance. Power transfer and efficiency are analyzed to quantify the influence of these parameters on converter performance. These experimental trends provide insight into the optimal modulation range and the dominant loss mechanisms of the DAB under single phase shift (SPS) control. A detailed comparison between HIL simulations and hardware measurements, based on transferred power and efficiency, shows close agreement across all the tested operating points. These results confirm the accuracy and robustness of the proposed HIL model, demonstrate the suitability of the PLECS platform for DAB development and control validation, and support its use as a scalable basis for more complex multi-converter studies, reducing design time and prototyping risk. Full article

Proteins are generally characterized by three-dimensional structures that are well suited for their specific function. It is much less accepted that a particular flexibility or plasticity of a protein is essential for performing its function. The latter plasticity encompasses the stochastic motions of small protein sidechains on the picosecond timescale that serve as “lubricating grease”, allowing slower functionally relevant conformational changes. Some remarkable examples of potential correlations between protein dynamics and function were observed for pigment–protein complexes in photosynthesis. For example, electron transfer and protein plasticity are concurrently suppressed in Photosystem II upon decreases in temperature or hydration, thus suggesting a prominent functional role of protein dynamics. An unusual dynamics–function correlation was observed for the major light-harvesting complex II, where the dynamics of charged protein residues affect the pigment absorption frequencies in photosynthetic light-harvesting. Generally, proteins exhibit a wide variety of motions on multiple time and length scales. However, there is an approach to characterize the plasticity of a protein as a single effective force constant that permits a straightforward comparison between different protein systems. Within this review, we determine the latter effective force constant for three photosynthetic proteins in different functional and organizational states. The force constant values determined appear to be rather different for each protein and are consistent with the requirements imposed by the various functions. These findings highlight the individual character of a protein’s flexibility and the role(s) it is playing for the specific function. Full article

Metallaphotoredox catalysis merges the powerful bond-forming abilities of transition metal catalysis with unique electron or energy transfer pathways accessible in photoexcited states, injecting new vitality into organic synthesis. However, most transition metal catalysts cannot be excited by visible light. Thus, prevalent metallaphotoredox catalytic systems require dual catalysts: a transition metal catalyst and a separate photosensitizer. This leads to inefficient electron transfer between these two low-concentration catalytic species, which often limits overall photocatalytic performance. Single-atom site catalysts (SASCs) offer a promising solution, wherein isolated and quasi-homogeneous transition metal sites are anchored on heterogeneous supports. When semiconductors are employed as the support, the photosensitive unit and transition metal catalytic site can be integrated into one system. This integration switches the electron transfer mode from intermolecular to intramolecular, thereby significantly enhancing photocatalytic efficiency. Furthermore, such heterogeneous catalysts are easier to separate and reuse. This review summarizes recent advances in the application of SASCs for photocatalytic organic synthesis, with a particular focus on elucidating structure–activity relationships of the single-atom sites. Full article

Corrosion in harsh environments causes global economic losses exceeding 3 trillion US dollars annually. Traditional silicone epoxy (SE) coatings are prone to failure due to insufficient physical barrier properties and lack of active protection. In this study, cerium dioxide (CeO₂) was in situ grown on the surface of hexagonal boron nitride (h-BN) mediated by polydopamine (PDA) to prepare BN-PDA-CeO₂ ternary nanocomposites, which were then incorporated into SE coatings to construct a multi-scale synergistic corrosion protection system. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and transmission electron microscopy (TEM) confirmed the successful preparation of the composites, where PDA inhibited the agglomeration of h-BN and CeO₂ was uniformly loaded. Electrochemical tests showed that the corrosion inhibition efficiency of the extract of this composite for 2024 aluminum alloy reached 99.96%. After immersing the composite coating in 3.5 wt% NaCl solution for 120 days, the coating resistance (Rc) and charge transfer resistance (Rct) reached 8.5 × 10⁹ Ω·cm² and 1.2 × 10¹⁰ Ω·cm², respectively, which were much higher than those of pure SE coatings and coatings filled with single/binary fillers. Density functional theory (DFT) calculations revealed the synergistic mechanisms: PDA enhanced interfacial dispersion (adsorption energy of −0.58 eV), CeO₂ captured Cl⁻ (adsorption energy of −4.22 eV), and Ce³⁺ formed a passive film. This study provides key technical and theoretical support for the design of long-term corrosion protection coatings in harsh environments such as marine and petrochemical industries. Full article

Biofuel cells (BFCs) generate electricity by converting chemical energy into electrical energy using biological systems. Saccharomyces cerevisiae (yeast) is an attractive biocatalyst for BFCs due to its robustness, low cost, and metabolic versatility; however, electron transfer from the intracellular reactions to the electrode is limited by the cell membrane. Nystatin is an antifungal antibiotic that increases the permeability of fungal membranes. We hypothesized that sub-lethal nystatin treatment could enhance mediator-assisted electron transfer without compromising cell viability. In this work, yeast was treated with nystatin during cultivation at concentrations of up to 6 µg/mL and combined with a dual-mediator system consisting of a lipophilic mediator (9,10-phenanthrenequinone, PQ) and a hydrophilic mediator (potassium ferricyanide). Scanning electrochemical microscopy revealed that the dual-mediator system increased local current responses by approximately fivefold compared to a single mediator (from ~11 pA to ~59 pA), and that nystatin-treated yeast exhibited higher local electrochemical activity than untreated yeast (maximum currents of ~0.476 nA versus ~0.303 nA). Microbial fuel cell measurements showed that nystatin treatment increased the maximum power density from approximately 0.58 mW/m² to approximately 0.62 mW/m² under identical conditions. Nystatin concentrations between 4 and 5 µg/mL maintain yeast viability at near-control levels, while higher concentrations cause a decrease in viability. These results demonstrate that controlled, sub-lethal membrane permeabilization combined with a dual-mediator strategy can enhance electron transfer in yeast-based biofuel cells. Full article

In this study, a novel Bi₂O₃/BiOBr_0.9I_0.1 (BO0.9−BBI0.1) composite photocatalyst was successfully synthesized via a single-pot solvothermal method for the efficient degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) under visible light. The structure, morphology, and optical properties of the photocatalyst were characterized through X-ray diffraction (XRD), Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectra (DRS), Steady-state photoluminescence (PL), and Electrochemical Impedance Spectroscopy (EIS). The composite exhibits a 3D hierarchical morphology with increased specific surface area and optimized pore structure, enhancing pollutant adsorption and providing more active sites. Under visible light irradiation, BO0.9−BBI0.1 achieved a 92.4% removal rate of 2,4-D within 2 h, with a reaction rate constant 5.3 and 4.6 times higher than that of pure BiOBr and BiOI, respectively. Mechanism studies confirm that photogenerated holes (h⁺) and superoxide radicals (·O₂⁻) are the primary active species, and the Z-scheme charge transfer pathway significantly promotes the separation of electron-hole pairs while maintaining strong redox capacity. The catalyst also demonstrated good stability over multiple cycles. This work provides a feasible dual-modification strategy for designing efficient bismuth-based photocatalysts for pesticide wastewater treatment. Full article

High-precision prediction of the crystal diameter during the growth of electronic-grade silicon single crystals is a critical step for the fabrication of high-quality single crystals. However, the process features high-temperature operation, strong nonlinearities, significant time-delay dynamics, and external disturbances, which limit the accuracy of conventional mechanism-based models. In this study, mechanism-based models denote physics-informed heat-transfer and geometric models that relate heater power and pulling rate to diameter evolution. To address this challenge, this paper proposes a hybrid deep learning model combining a convolutional neural network (CNN), a bidirectional long short-term memory network (BiLSTM), and self-attention to improve diameter prediction during the shoulder-formation and constant-diameter stages. The proposed model leverages the CNN to extract localized spatial features from multi-source sensor data, employs the BiLSTM to capture temporal dependencies inherent to the crystal growth process, and utilizes the self-attention mechanism to dynamically highlight critical feature information, thereby substantially enhancing the model’s capacity to represent complex industrial operating conditions. Experiments on operational production data collected from an industrial Czochralski (Cz) furnace, model TDR-180, demonstrate improved prediction accuracy and robustness over mechanism-based and single data-driven baselines, supporting practical process control and production optimization. Full article

The objective of this study was to use Density Functional Theory (DFT) calculations to examine how boron doping modulates the electronic properties of graphene quantum dots (GQDs) and their interaction with the Hg²⁺ ion. Boron doping decreases the HOMO-LUMO gap and increases the GQD’s electrophilic character, facilitating charge transfer to the metal ion. The adsorption energy results were negative, indicating electronic stabilization of the combined systems, without implying thermodynamic favorability, with the GQD@3B_Hg²⁺ system being the strongest at −349.52 kcal/mol. The analysis of global parameters (chemical descriptors) and the study of non-covalent interactions (NCIs) supported the affinity of Hg²⁺ for doped surfaces, showing that the presence of a single boron atom contributes to clear attractive interactions. In general, configurations doped with 1 or 2 boron atoms exhibit satisfactory performance, demonstrating that boron doping effectively modulates the reactivity and adsorption properties of GQD for efficient Hg²⁺ capture. Full article

In this study, first-principles density functional theory (DFT) calculations were employed to investigate the effects of single and binary gas adsorption of NO, CO, CO₂, NO₂, H₂S, and O₃ on the ZnGa₂O₄(111) surface. For single-gas adsorption, O₃ adsorbed on surface Ga sites induces a pronounced work-function increase of 0.97 eV, whereas H₂S adsorption at surface O sites yields the strongest adsorption energy (−1.21 eV), highlighting their distinct electronic interactions with the surface. For binary co-adsorption, the NO₂-O₃ pair adsorbed at Ga-coordinated sites produces the largest work-function shift (1.88 eV), while adsorption at Zn sites results in the most stable configuration, with an adsorption energy reaching −3.98 eV. These results indicate that co-adsorption of highly electronegative gases can significantly enhance charge transfer and sensing response. In contrast, mixed oxidizing–reducing gas pairs, such as NO₂-H₂S, lead to a markedly suppressed work-function variation (−0.02 eV), suggesting reduced sensor sensitivity due to compensating charge-transfer effects. Overall, this work demonstrates that gas-sensing behavior on ZnGa₂O₄(111) is governed not only by individual gas–surface interactions but also by cooperative and competitive effects arising from binary co-adsorption, providing insights into realistic multi-gas sensing environments. Full article