Chemistry - An Asian Journal最新文献

Development of elegant, selective, and efficient strategies for the production of value-added platform chemicals from renewable feedstocks are in high demand to achieve the future needs and sustainable goals. In this context, an efficient acid-promoted synthesis of highly valuable hydroxymethylfurfural (HMF) has been demonstrated from glucose, a major constituent of lignocellulosic biomass. The major challenge in the conversion of glucose to HMF is the selective isomerization of glucose to ketose, which in the present work has been successfully addressed through the amine-mediated rearrangement of glucose to aminofructose under Amadori rearrangement. Importantly, subsequent dehydration step affords HMF and regenerates the amine employed in the first step, which could be readily recovered. In addition, scale-up and successful integration in to one-pot synthesis of HMF proves the efficiency and applicability of the present transformation in large scale application. In addition, the method was also successfully extended to other monosaccharides and disaccharides to produce HMF.

The cover image shows a self-assembled structure of two open-[60]fullerene dimers. The synthesis of the dimer requires the use of phosphine which in situ produces ylide and α-methylene carbonyl variants of an open-[60]fullerene monomer. Nevertheless, control experiments excluded reaction mechanisms via Wittig reaction and aldol condensation. Alternatively, the computational study suggested a betaine variant of the monomer as a nucleophile to realize intermolecular C–C bond formation. In this transformation, homo- and heterochiral dimers would be potentially yielded while a rate-determining step was suggested to be different from each other. More details can be found in article number e202400142 by Shu Okamoto, Yoshifumi Hashikawa, and Yasujiro Murata.

Creating an innovative and environmentally friendly energy storage system is of vital importance due to the growing number of environmental problems and the fast exhaustion of fossil fuels. Energy storage using porous carbon composites generated from biomass has attracted a lot of attention in the research community. This is primarily due to the environmentally friendly nature, abundant availability in nature, accessibility, affordability, and long-term viability of macro/meso/microporous carbon sourced from a variety of biological materials. The energy density of symmetric supercapacitors is also considered, with values between 5.1 and 138.4 Wh/kg. In this review, we look at the basic structures of biomass and how they affect porous carbon synthesis. It also discusses the effects of different structured porous carbon materials on electrochemical performance and analyzes them. In recent developments, significant steps have been made across various fields including fuel cells, carbon capture, and the utilization of biomass-derived carbonaceous nanoparticles. Notably, our study delves into the innovative energy conversion and storage potentials inherent in these materials. This comprehensive investigation seeks to lay the foundation for forthcoming energy storage research endeavors by delineating the current advancements and anticipating potential challenges in fabricating porous carbon composites sourced from biomass.

Dry reforming of methane (DRM), the catalytic conversion of CH4 and CO2 into syngas (H2 + CO), is an important process closely correlated to the environment and chemical industry. NiAl-based catalysts have been reported to exhibit excellent activity, low cost, and environmental friendliness. At the same time, the rapid deactivation caused by carbon deposition, Ni sintering, and phase transformation exerts great challenges for its large-scale applications. This review summarizes the recent advances in NiAl-based catalysts for DRM, particularly focusing on the strategies to construct efficient and stable NiAl-based catalysts. Firstly, the thermodynamics and elementary steps of DRM, including the activation of reactants and coke formation and elimination, are summarized. The roles of Al2O3 and its mixed oxides as the support, and the influences of the promoters employed in NiAl-based catalysts over the DRM performance, are then illustrated. Finally, the design of anti-coking and anti-sintering NiAl-based catalysts for DRM is suggested as feasible and promising by tailoring the structure and states of Ni and the modification of Al-based supports including small Ni size, high Ni dispersion, proper basicity, strong metal-support interaction (SMSI), active oxygen species as well as high phase stability.

Hydrogen (H₂) is being acknowledged as the future energy carrier due to its high energy density and potential to mitigate the intermittency of other renewable energy sources. H₂ also ensures a clean, carbon-neutral, and sustainable environment for current and forthcoming generations by contributing to the global missions of decarbonization in the transportation, industrial, and building sectors. Several H₂ storage technologies are available and have been employed for its secure and economical transport. The existing H₂ storage and transportation technologies like liquid-state, cryogenic, or compressed hydrogen are in use but still suffer from significant challenges regarding successful realization at the commercial level. These factors affect the overall operational cost of technology. Therefore, H₂ storage demands novel technologies that are safe for mobility, transportation, long-term storage, and yet it is cost-effective. This review article presents potential opportunities for H₂ storage technologies, such as physical and chemical storage. The prime characteristics and requirements of H₂ storage are briefly explained. A detailed discussion of chemical-based hydrogen storage systems such as metal hydrides, chemical hydrides (CH₃OH, NH₃, and HCOOH), and liquid organic hydrogen carriers (LOHCs) is presented. Furthermore, the recent developments and challenges regarding hydrogen storage, their real-world applications, and prospects have also been debated.

Direct installation of key functionalities in a molecule through C-H bond activation is one of the thrust areas as well as challenging task in organic synthesis. Particularly, introduction of chlorine in a molecule imparts additional benefits for further functionalizations as well as improves the electronic behaviour such as lipophilicity and polarity towards drug development process. The chlorinated molecules have also been established as efficient biologically relevant scaffolds. Current manuscript has been focused on the direct installation of the chlorine atom at various aromatic and aliphatic positions to produce functional molecules. The key highlight of the manuscript belongs to the site selectivity (regioselectivity) for the installation of chlorine functionality. Manuscript describes the advanced methods developed for the direct C-H chlorination reactions and further simplified for the chlorination reactions at various positions including aromatic (o-, m-, and p-), benzylic, heteroaromatic, and aliphatic positions. Directing groups (DGs) and the coordination with the catalyst is the key for the enhancement of regioselectivities during direct C-H chlorination reactions.

Reaction of a P/N/S hybrid ligand dpppyatc (N,N-bis((diphenylphosphaneyl)methyl)-N-(pyridin-2-yl)-amino-thiocarbamide) with Au(tht)Cl (tht = tetrahydrothiophene) and [Cu(MeCN)4]BF4 afforded cluster complex [Au2Cu(dpppyatc)2](BF4)2Cl (1). Upon excitation at 480 nm, 1 emitted orange phosphorescence at 646 nm, which was red-shifted to ~698 nm selectively in the presence of ammonia or amine vapor. This chromic photoluminescent response toward ammonia was sensitive and reversible. Complex1 could detect ammonia in aqueous solution down to concentrations of 2 ppm (w/w).

A novel inorganic-organic-inorganic ternary bioactive material formulated on antimicrobial peptide-based polymer has been reported. Supramolecular approach has been employed to incorporate molecularly crowded tyrosine-based polymer stabilized silver nanoparticles into membrane bound vesicles exploiting polyoxometalate-triggered surface templating strategy. Utilizing the covalent reversible addition fragmentation chain transfer (RAFT) polymerization and exploiting templated supramolecular architectonics at biopolymer interface, the bioactive ternary polymeric nanohybrids have been designed against Shigellosis leveraging the antibacterial activities of silver nanoparticle, cationic amphiphilic tyrosine polymer and inorganic polyoxometalate. The detail investigation against Shigella flexneri 2a cell line demonstrates that the collaborative mechanism of the ternary hybrid composite enhances the bactericidal activity in comparison to only polyoxometalate and polymer stabilized silver nanoparticle with an altered mechanism of action which is established via detailed biological analysis.

Tricolor electrochromism was realized through the interconversion among the neutral (yellow), dicationic (green), and tetracationic (blue) states, even though only one kind of chromophore is generated upon oxidation. Both dicationic and tetracationic states were isolated as stable salts, and their different colors come from the effective interchromophore interaction only in the tetracationic state but not in the dicationic state. Despite the negligible Coulombic repulsion in the tetracationic state with four cyanine-type chromophores, pentacenebisquinodimethane undergoes stepwise two-stage two-electron oxidation when radical-stabilizing 5-(4-octyloxyphenyl)-2-thienyl groups are attached on the exomethylene bonds. A contribution from the biradical form only in the neutral state but not in the dicationic state is the reason for the observed negative cooperativity during the electrochemical oxidation.