Chemistry - An Asian Journal最新文献

Given the high similarity in physical and chemical properties, especially in terms of molecular size and boiling point, of acetylene (C2H2), carbon dioxide (CO2), and ethylene (C2H4) molecules, traditional separation techniques encounter great challenges. Fortunately, metal organic framework (MOF) materials have demonstrated significant potential for efficient separation of these gases at the molecular level due to their finely tunable pore structure and surface functional properties. In this paper, we have successfully synthesized a cadmium-based MOF (FJI-W-708), which exhibits negative electrostatic potential pores and exceptional thermal stability. It is worth noting that FJI-W-708 exhibits high C2H2 capacity (61 cm3/g), as well as appropriate selectivity towards C2H2/CO2 (3.39) and C2H2/C2H4 (3.47). The dynamic breakthrough experiments of C2H2/CO2 (50/50) mixture and C2H2/C2H4 (1/99) mixture clearly demonstrated the actual separation performance. The breakthrough time for C2H2/CO2 (50/50) was observed to be 23 min/g, while for a C2H2/C2H4 (1/99) mixture it could reach up 46 min/g, demonstrating excellent recyclability and achieving a benchmark productivity of C2H4 at 4.12 mmol/g.

The molecular design of a series of perfluoroarylbisselanes (30-68 %) o-, m- and p-(Ar^FSe)₂C₆F₄ and (Ar^FSe)₂C₁₂F₈ (Ar^F=C₆F₅ and p-C₆F₄CF₃) were achieved through the reaction of Ar^FSeCu with diiodoperfluoroarenes bearing phenyl and biphenyl rings. Analysis of the X-ray diffraction (XRD) data for the resulting perfluoroaromatic bisselanes 5-12 demonstrated their significant potential for constructing supramolecular architectures through tandem noncovalent interactions, including chalcogen bonding (ChB) and π_hole-π interactions. 1,2-Bis(pentafluorophenylseleno)tetrafluorobenzene 5 was cocrystallized with dibenzyl ether, yielding the adduct 5₂⋅Bn₂O, which exhibited a triad structural motif. Its XRD data provided structural insights into the ChB-based catalysis mechanism of Friedel-Crafts type reaction involving benzyl ether derivatives. Comprehensive density functional theory studies: energy decomposition analysis (EDA), molecular electrostatic potential (MEP) assessments, van der Waals potential evaluations, electrostatic potential and energy density (ED/ESP) plots, as well as natural bond orbital (NBO) analysis - revealed that Se⋅⋅⋅O chalcogen bonding (10.1 kcal/mol) and π_hole-π interactions (12.6 kcal/mol) contribute comparably to the overall energetics, thus playing a significant role in guiding molecular assembly.

A catalytic strategy for indirect reductive quenching based on a photoredox and sulfide dual catalysis system has been developed, enabling the synthesis of diverse furan frameworks, including spirofurans and phthalans. Mechanistic studies and DFT calculations revealed the formation of sulfonium species from sulfide radical cations, followed by intramolecular cyclization to construct furan rings. More details can be found in article number e202401442 by Nozomi Saito and co-workers.

Vesicling along Wat Arun (Temple of Dawn): Situated on the Chao Phraya River in Bangkok, the river has supported civilizations for centuries. Similarly, water proves essential as a green reaction medium. N,N-Didodecylammonium N,N-didodecyldithiocarbamate (AmDTC-C₁₂C₁₂), a CatAnionic vesicular nanoreactor, enables cascade synthesis in water. Reactions between 2-hydroxy-trans-β-nitrostyrenes and 1,3-dicarbonyls yield 4H-chromenes and γ-nitro ketones efficiently, demonstrating the potential of vesicular nanoreactor for sustainable synthesis. More details can be found in article number e202400853 by Panuwat Padungros and co-workers.

This review discloses nickel- and cobalt-catalyzed coupling reactions that allow C-P bond formation. Activation of C-halide bonds to form phosphonium, pentavalent phosphorus, or trivalent phosphorous compounds has been reported with both metals. However, the conversion of C-O bonds ((activated) ethers, carbonates, acetates) into C-P ones has been only described with Ni. Similarly, there are more examples of C-Y (Y=C, S, N, B) bond activations catalyzed by Ni than by Co. Nevertheless, the cross-dehydrogenative coupling reaction between a P-H reagent and a C-H bond has been reported more often with cobalt than with nickel. In addition, for both metals, electrolytic and photocatalytic processes have been shown to produce a variety of C-P containing molecules. This review aims to provide an overview of the potential of both metals for C-P bond formation and to highlight the remaining challenges.

This cover feature represents the research for the utilization of a Zn-based 2D MOF in selective detection of nitrofuran-based antibiotics, such as nitrofurantoin and nitrofurazone, in aqueous medium in ppb level. These analytes interact with the 2D MOF through hydrogen bonding and p-p interactions. The 2D MOF can also efficiently detect the presence of Martifur-100 tablet, which has nitrofurantoin as one of the active ingredients, in aqueous medium. More details can be found in article number e202401206 by Alokananda Chanda and Sanjay K. Mandal.

Simple operation, easily accessible starting materials, and short syntheses of the privileged scaffold thiochromane 1,1-dioxide that widely exist in bioactive molecules was achieved by photocatalytic divergent cyclization of α-allyl-β-ketosulfones with arylsulfonyl chlorides. Optimization and scope and limitations of this short and general pathway are described. The methodology provides an efficient strategy for the construction of a wide variety of thiochromane 1,1-dioxide derivatives.

Water desalination via reverse osmosis (RO) to produce fresh water represents an ideal solution to address water shortage. Membranes of large water permeability and high salt rejection are desired, and these properties are subject to the design of the membrane structure. The structural tunability of metal-organic frameworks (MOFs) therefore provides tremendous opportunities, but their potential has not yet been systematically explored. In this study, molecular dynamics simulations are conducted to investigate MOFs with a focus on a subclass of water stable Zirconium-based MOFs as RO membranes in water desalination. The results show that MOF membranes can indeed achieve a perfect salt rejection while allowing notably high permeability as compared to commercial polymeric membranes. Moreover, the structure-performance relationship is explored, and the critical role of channel homogeneity is identified. Overall, the outcomes of this study demonstrate the great promise of MOFs and provide guidelines on the selection and design of MOFs for effective and efficient water desalination.

Traditional liquid electrolyte-based lithium-ion batteries (LIBs) are constrained by safety risks such as flammability and explosion, as well as a relatively low theoretical specific capacity (~300 mAh g^-1). Lithium-metal batteries (LMB), which offer higher energy density and enhanced safety, have emerged as competitive candidates for next-generation lithium-based batteries. As a key component of LMBs, polymer electrolytes are expected to exhibit excellent ionic conductivity, robust mechanical properties, and stable interfacial compatibility with electrode materials. Among the diverse range of polymer electrolytes, polyvinylidene fluoride (PVDF)-based polymer electrolytes stand out due to their unique properties. PVDF, with its high dielectric constant, effectively facilitates lithium salt dissociation and ion migration, while maintaining excellent mechanical flexibility. These characteristics position PVDF-based polymer electrolytes as a promising material for LMBs. This review begins by introducing the classification of polymer electrolytes and the mechanisms of lithium-ion migration within them. It then focuses on PVDF-based polymer electrolytes, systematically discussing the synthetic and modification strategies categorized into four main approaches: composite fabrication, inorganic filler doping, liquid additive modification, and multi-strategy modification. Finally, the challenges and future prospects of PVDF-based polymer electrolytes are reviewed to provide insights for developing high-performance polymer electrolytes in the future.

Metal-organic frameworks (MOFs) and their derivatives have recently attracted significant interest as promising candidates in water splitting due to their well-defined structural and electronic features, three-dimensional architecture, high surface area, abundance of active sites, remarkable stability, and improved capabilities for mass transport and diffusion. Mn-based MOFs and their derivatives have been extensively studied and demonstrated significant potential in water splitting, inspired largely by the natural photosystem-II. Despite the development of numerous Mn-based electrocatalysts, Mn-MOFs stand out due to their strong synergistic interactions, tunable electronic properties, efficient charge and mass transfer, and straightforward synthesis. However, recent reviews on MOFs have largely overlooked the specific advancements in Mn-MOFs and their derivatives for water-splitting applications. By providing an overview of the uses of Mn-MOFs and their materials, this article seeks to close that gap. It looks at their stability, porosity, and structure as well as how they are used in water splitting. This study offers a deeper knowledge of the properties and uses of Mn-MOFs and their related materials by drawing on groundbreaking research. The link between structure, property, and performance is examined, current advancements in the subject are discussed, difficulties faced are addressed, and potential future developments are taken into account.