Chemistry - A European Journal最新文献

The identification of drug targets remains one of the most critical challenges in pharmaceutical research. The rapid progress of artificial intelligence (AI) is significantly advancing this landscape by enabling more efficient and accurate drug-target interaction prediction. AI-driven approaches can integrate and analyze massive biomedical datasets, elucidating complex signaling networks and providing systematic insights into drug mechanisms of action. These developments have greatly accelerated virtual screening, binding affinity estimation, and target identification. However, despite these advancements, key challenges persist, such as ensuring the precision of predictions and overcoming the barriers to integrating AI tools with drug target discovery. This review provides a comprehensive overview of recent public databases, advanced computational methods, and user-friendly AI tools, highlighting both their potential and challenges. It also offers practical guidance for researchers without computational expertise, illustrating how these technologies can be effectively incorporated into current research workflows to advance drug target discovery and ultimately accelerate the development of novel therapeutic drugs.

Two hydrogen-bonding monomers containing tetraethylene glycol (TEG) chains have been synthesized and characterized. The monomers are based on a bicyclic scaffold appended with either 4H-bonding benzyl-substituted ureidopyrimidinone motifs or 2H-bonding unsubstituted pyrrole-fused ureidopyrimidinone motifs, with the TEG chains introduced with the aim of developing amphiphilic monomers soluble in nonpolar and polar organic solvents in order to extend the utility of H-bonding in supramolecular chemistry. In CDCl₃, both monomers formed cyclic tetramers. The monomer containing 2H-bonding motifs was found to form significantly less-stable aggregates than its previously reported alkylated analogue, most likely due to interference from the TEG chains. Despite the weaker aggregation, the 2H-bonded tetramers were able to stack into tubular polymers through orthogonal H-bonding in less polar solvent (toluene) or when a suitable guest (C₇₀) was introduced. Comparison of the TEGylated monomers with previously reported alkylated analogues showed that the introduction of TEG chains resulted in increased solubility in a wide range of solvents. By using one of the TEGylated monomers, nonpolar C₆₀ could be solubilized in polar solvent acetonitrile by forming an inclusion complex. This complex was used as a homogeneous catalyst for photochemical oxidation of sulfides to sulfoxides in acetonitrile.

In the domain of bottom-up approach, regioselective fusion of aromatic moiety onto an arene templet remains scarcely explored, yet represents a crucial tool for the rapid generation of polycyclic aromatic hydrocarbons (PAHs). An unprecedented bottom-up strategy for the rapid construction of PAHs is developed by employing arene-derived ketones and carbon-rich 1,3-diynes. Many of these synthesized PAHs have tilted π-electronic structure, unique edges and topologies. A range of arene-derived ketones participated in this annulative-π-extension-cyclization cascade under first-row Co(III)-catalysis. Electronic nature of the 1,3-diynes guided the final mode of cyclization leading to the formal fusing of one fluorene moiety via 5-exo-dig cyclization or phenanthrene nucleus through 6-endo-dig cyclization. Intermediate ethynyl-PAHs were also isolated in case of relatively electron-deficient diynes. The contorted π-planes of the synthesized PAHs were elucidated by single-crystal X-ray analysis. Detailed DFT studies reinforce the proposed mechanistic pathway, validating the formation of the major regioisomer of PAHs. Furthermore, less aromatic character of fluorene moiety over phenanthrene nucleus is supported by the NICS(1)_zz and ACID calculations.

2D materials have attracted a lot of interest since the invention of graphene because of their remarkable qualities and adaptability. The distinct architectures and complementary qualities of MOFs (metal-organic frameworks) and MXenes offer intriguing prospects in various sectors. Derived from MAX phases, MXenes have hydrophilic surfaces, and excellent electrical conductivity. MOFs, on the other hand, provide large surface area, adjustable porosity, and diverse chemical functions. Nevertheless, there are drawbacks associated with both materials. MXenes are prone to oxidation and self-stacking, whereas MOFs have limited structural stability and poor electrical conductivity. The development of MXene@MOF composites provides a synergistic solution, combining the advantages of both materials while reducing their individual drawbacks. In this review, we highlight the most recent advances in MXene@MOF composites and provide a focused discussion on their unique structural features, emerging synthesis trends, and rapidly expanding applications. These elements distinguish this work from earlier reviews. This review systematically explores the structures and synthesis methods of these materials, including solvothermal, hydrothermal, and in-situ growth techniques, and examines their wide range of applications. Superior electron transport, high surface area, and improved structural stability lead to enhanced performance of MXene@MOF composites in supercapacitors, water splitting, photocatalysis, and sensing.

To develop fast-charging lithium-ion batteries (LIBs), optimizing insertion-type anode structure is crucial for achieving fast lithium-ion diffusion and high electronic conductivity. Here, we combine insertion-type TiO₂ with high-capacity FeCoS to construct a TiO₂/FeCoS heterojunction, which enhances electron/ion transport, lowers the ion diffusion energy barrier, and thereby improves quick-charging performance. The resulting anode exhibits a high reversible capacity of 627.7 mAh g^-1 at 0.1 A g^-1, 2.3 times that of TiO₂. Notably, it gives a remarkable capacity of 241.7 mAh g^-1 at 10 A g^-1 and maintains excellent stability over 10,000 cycles with an ultralow capacity decay of just 0.002% per cycle. Experiments and theoretical calculations confirm the superior performance originates from enhanced Li⁺ ions adsorption and reduced diffusion barrier at the heterointerface, which accelerates Li⁺ insertion/extraction kinetics. This work provides an effective pathway to accelerate electrochemical kinetics and enable fast-charging LIBs.

The functionalization of solid surfaces with responsive macrocyclic compounds is a key strategy for developing advanced functional materials, with applications in molecular sensing, catalysis, and nanoscale electronics. Here, we report the self-assembly and lateral cobalt coordination, on an Au(111) surface and under ultra-high vacuum conditions, of a fivefold symmetric cyanostar macrocycle, a class of anion recognition molecules. This represents the first example of a close-packed regular assembly of a pentagonal macrocycle at the solid-vacuum interface.

Extremely high base concentrations (c_B) in ultra-alkaline liquids, also known as hydroflux, alter the thermodynamic and structural properties of water. Mixtures of water and alkali (AOH, A = Na, K) with molar base ratios of q(A) = n(H₂O):n(AOH) ≤ 2:1 (c_B ≥ 25 mol L^-1) show an overproportionally reduced vapor pressure compared to more diluted systems. The vapor pressure of a melt with q(A) = 0.8 (c_B = 70 mol L^-1) at 200°C is negligible. Ab initio molecular dynamics simulations revealed substantial structural reorganization of the hydrogen bonding network in the equimolar mixture of KOH and water. Distinctive molecular features included altered coordination geometries, shortened hydrogen bonds, and frequent proton transfer events, including Grotthuss diffusion, indicative of an altered hydrogen-bond network and increased proton mobility. Cluster population analysis shows that a significant number of H₃O₂ ^- anions are present, which exhibit a near symmetrical hydrogen bond with O···H distances <1.28 Å. The hydroflux can be seen as an intermediate between an alkaline solution and a molten salt {K⁺·H⁺·2OH-}, in which the water has a vanishing chemical activity.

A novel J-aggregates configuration, termed π-π-coupled J-aggregates, was successfully constructed based on low-molecular-weight hemicyanine dyes (HCY-3). Unlike classical J-aggregates, the π-π-coupled J-aggregates are formed through synergistic π-π stacking and hydrogen bonding interactions between monomeric molecules, The rigidified- molecular planar architecture not only avoids fluorescence quenching of the photosensitizer but also significantly broadens the bathochromic absorption band owing to enhanced conjugation effects while preserving photodynamic activity. As a result, a broad bathochromic absorption from 600 nm to an absorption tail over 1100 nm was achieved, allowing the photosensitizer to be compatible with a variety of laser sources. The enhanced-receptor conjugation significantly boosts singlet oxygen generation efficiency while reinforcing π-π interactions, endowing the J-aggregates with exceptional thermal stability, chemical stability, and photothermal generation capability. Under 980 nm laser excitation, the π-π-coupled J-aggregations based on HCY-3 J-NPs exhibited excellent ROS generation capacity and NIR-II fluorescence emission, successfully achieving multimodal photothermal/photodynamic antitumor therapy guided by NIR-II FL imaging. Such π-π-coupled J-aggregates may represent a new route for the design of NIR-II photosensitizers.

Since the 1980s, the patch-clamp technique has revealed subconductance states (substates) in natural ion channels in addition to the traditional closed and fully open states. While subconductance states offer critical insights into the structure and function of ion channels, the structural basis underlying this behavior remains unclear. Artificial ion channels can serve as simplified molecular models to establish structure-function relationships; however, replicating subconductance behavior is extremely challenging. Here, we present a concept for a conformationally self-tuning macrocyclic skeleton designed to observe and modulate subconductance states in artificial channels. This concept was experimentally validated using oxacalix[2]arene[2]triazine-based molecular funnels.

A series of rigid-flexible unsymmetrical bulky α-diimine palladium catalysts was employed for the gas-phase polymerization of ethylene, enabling the synthesis of hyperbranched ultrahigh molecular weight polyethylene (UHMWPE). Compared to conventional solution-phase polymerization, the gas-phase method significantly suppresses chain transfer while promoting chain walking, leading to a simultaneous increase in both molecular weight and branching density. Under optimized conditions, the resulting polyethylene exhibited high molecular weight (up to 2053 kg/mol) and branching densities as high as 107 branches per 1000 carbon atoms. Structural characterization confirmed the presence of long-chain branches and branch-on-branch architectures, indicative of a hyperbranched topology. The unsymmetrical palladium catalysts produced polyethylene with higher molecular weight and branching density than the benchmark catalysts, by combining suppressed chain transfer with high chain-walking ability. This work demonstrates the potential of gas-phase polymerization as a solvent-free, environmentally benign route to advanced polyolefin materials with tailored architectures.