Simulation results from examining both sets of diads and single diads highlight that progression through the usual water oxidation catalytic sequence is not driven by the relatively low solar irradiation or loss of charge/excitation, but instead is governed by the accumulation of intermediates whose chemical reactions are not stimulated by photoexcitation. The probability distributions of these thermal reactions determine the extent of coordination between the dye and the catalyst. The catalytic effectiveness of these multiphoton catalytic cycles may be improved through the provision of a method for the photostimulation of all intervening compounds, resulting in a catalytic rate that is solely dictated by charge injection under the influence of solar illumination.

Metalloproteins are fundamental to a wide array of biological activities, including reaction catalysis and free radical detoxification, and are critically involved in various diseases like cancer, HIV infection, neurodegeneration, and inflammatory responses. Metalloprotein pathologies are addressed by the discovery of high-affinity ligands. Significant investments have been made in computational methods, including molecular docking and machine learning algorithms, to rapidly pinpoint ligands interacting with diverse proteins, but only a limited number of these approaches have focused specifically on metalloproteins. We have constructed a substantial dataset of 3079 high-quality metalloprotein-ligand complexes, which we used to systematically evaluate the docking and scoring capabilities of three key docking methods: PLANTS, AutoDock Vina, and Glide SP, for metalloproteins. For predicting interactions between metalloproteins and ligands, a deep graph model, specifically MetalProGNet, was built on structural foundations. The model explicitly modeled the coordination interactions between metal ions and protein atoms, and the interactions between metal ions and ligand atoms, employing graph convolution. Predicting the binding features followed the learning of an informative molecular binding vector from a noncovalent atom-atom interaction network. Through evaluation on the internal metalloprotein test set, the independent ChEMBL dataset of 22 metalloproteins, and the virtual screening dataset, MetalProGNet's performance surpassed various baseline models. For the purpose of interpreting MetalProGNet, a method employing noncovalent atom-atom interaction masking was implemented, yielding knowledge that harmonizes with our physical comprehension.

Through a combined photochemical and rhodium catalyst system, the borylation of aryl ketone C-C bonds successfully led to the formation of arylboronates. A cooperative system enables the cleavage of photoexcited ketones through the Norrish type I reaction, yielding aroyl radicals that are decarbonylated and subsequently borylated by a rhodium catalyst. A novel catalytic cycle, fusing the Norrish type I reaction with rhodium catalysis, is presented in this work, demonstrating the emerging synthetic utility of aryl ketones as aryl sources for intermolecular arylation reactions.

The quest to convert CO, a C1 feedstock molecule, into useful commodity chemicals is both desirable and demanding. IR spectroscopy and X-ray crystallography clearly demonstrate that the U(iii) complex [(C5Me5)2U(O-26-tBu2-4-MeC6H2)], exposed to one atmosphere of CO, exhibits solely coordination, thus establishing a novel and structurally characterized f-element carbonyl. The reaction of [(C5Me5)2(MesO)U (THF)], with Mes being 24,6-Me3C6H2, with carbon monoxide, produces the bridging ethynediolate species, [(C5Me5)2(MesO)U2(2-OCCO)]. While ethynediolate complexes are well-established, a detailed understanding of their reactivity to allow for further functionalization remains limited. The reaction of the ethynediolate complex with supplementary CO, under elevated temperatures, generates a ketene carboxylate, [(C5Me5)2(MesO)U2( 2 2 1-C3O3)], which can then be subjected to further reaction with CO2 to result in the formation of a ketene dicarboxylate complex, [(C5Me5)2(MesO)U2( 2 2 2-C4O5)]. Given the ethynediolate's propensity to react with more carbon monoxide, we undertook a more thorough examination of its reactivity. Diphenylketene's [2 + 2] cycloaddition gives rise to both [(C5Me5)2U2(OC(CPh2)C([double bond, length as m-dash]O)CO)] and [(C5Me5)2U(OMes)2]. The reaction of SO2, surprisingly, showcases a rare breakage of the S-O bond, generating the unusual [(O2CC(O)(SO)]2- bridging ligand between two U(iv) centers. Thorough spectroscopic and structural investigations have been undertaken on every complex, and the computational analysis of ethynediolate's reaction with both CO, producing ketene carboxylates, and SO2 has been carried out.

The significant benefits of aqueous zinc-ion batteries (AZIBs) are substantially mitigated by the dendritic growth occurring on the zinc anode, a phenomenon induced by the uneven electrical field and constrained ion movement at the zinc anode-electrolyte interface, particularly during the plating and stripping cycles. We propose a hybrid electrolyte, composed of dimethyl sulfoxide (DMSO) and water (H₂O), augmented with polyacrylonitrile (PAN) additives (PAN-DMSO-H₂O), to enhance the electrical field and facilitate ion transport at the zinc anode, thereby effectively mitigating dendrite formation. Solubilization of PAN in DMSO results in preferential adsorption onto the Zn anode surface, as confirmed by both experimental characterization and theoretical calculations. This process creates abundant zincophilic sites, leading to a balanced electric field and the initiation of lateral zinc plating. Through its regulation of Zn2+ ion solvation structures and strong bonding with H2O, DMSO simultaneously reduces side reactions and augments ion transport. The Zn anode's dendrite-free surface formation during plating/stripping is facilitated by the synergistic interaction of PAN and DMSO. Additionally, the Zn-Zn symmetric and Zn-NaV3O815H2O full cells, using the PAN-DMSO-H2O electrolyte, achieve improved coulombic efficiency and cycling stability compared to those employing a pristine aqueous electrolyte. Other electrolyte designs for high-performance AZIBs are likely to be inspired by the results detailed in this report.

In a broad range of chemical processes, single electron transfer (SET) has had a considerable impact, with radical cation and carbocation intermediates proving invaluable for understanding the underlying reaction mechanisms. In accelerated degradation studies, single-electron transfer (SET), initiated by hydroxyl radicals (OH), was demonstrated via online examination of radical cations and carbocations, using electrospray ionization mass spectrometry (ESSI-MS). check details Efficient degradation of hydroxychloroquine occurred within the green and effective non-thermal plasma catalysis system (MnO2-plasma), resulting from a single electron transfer (SET) process generating carbocations. MnO2 surfaces, situated within the plasma field abundant in active oxygen species, produced OH radicals that initiated the degradation via SET mechanisms. Theoretical modeling underscored a preference by the hydroxyl group for electron withdrawal from the nitrogen atom conjugated to the benzene ring. SET-driven radical cation formation was succeeded by the sequential construction of two carbocations, which in turn accelerated degradation processes. Computational methods were used to calculate energy barriers and transition states, allowing for a study of the formation process of radical cations and subsequent carbocation intermediates. The current work demonstrates a carbocation-mediated, accelerated degradation pathway initiated by OH-radical single electron transfer (SET). This enhances our knowledge and suggests possibilities for broader application of the SET mechanism in eco-friendly degradations.

To advance the design of catalysts for plastic waste chemical recycling, it's essential to possess a detailed understanding of the intricate interplay between polymer and catalyst at their interface, which dictates the distribution of reactants and products. We analyze the interplay between backbone chain length, side chain length, and concentration on the density and conformation of polyethylene surrogates at the Pt(111) surface, establishing a link between these observations and the resulting experimental product distribution from carbon-carbon bond fracture. Employing replica-exchange molecular dynamics simulations, we analyze the interface conformations of polymers, taking into account the distributions of trains, loops, and tails and their respective first moments. check details The prevalence of short chains, comprising around 20 carbon atoms, is confined to the Pt surface, whereas longer chains exhibit a more diffuse distribution of conformational characteristics. The average length of trains, remarkably, is unaffected by the chain length, yet can be adjusted through polymer-surface interaction. check details Branching substantially influences the conformations of long chains at the interface, causing the distributions of trains to become less dispersed and more structured around short trains. This change leads to a wider distribution of carbon products upon the cleavage of C-C bonds. Localization intensity escalates in conjunction with the proliferation and expansion of side chains. Long polymer chains' adsorption onto the Pt surface from the melt is possible, even in the presence of a high concentration of shorter polymer chains within the melt mixture. Experimental confirmation of key computational predictions indicates that mixtures may offer a solution to reduce the selectivity of undesirable light gases.

Volatile organic compounds (VOCs) adsorption is greatly facilitated by high-silica Beta zeolites, typically synthesized through hydrothermal methods using fluorine or seed crystals. The pursuit of fluoride-free and seed-free approaches to producing high-silica Beta zeolites is actively researched. By utilizing a microwave-assisted hydrothermal technique, Beta zeolites with high dispersion, sizes between 25 and 180 nanometers, and Si/Al ratios of 9 or above, were synthesized with success.