Chemistry - An Asian Journal最新文献

The swift pace of socioeconomic development and climatic change have put significant strain on the quality of water resources. While, the bulk availability of agro-based materials arising from nature and agricultural practices has paved the way for researchers to utilize them in eradicating toxic industrial pollutants such as dyes, heavy metals, phenolic compounds, pesticides, etc. by using them as adsorbents. In the area of pollution remediation, inventive technologies have been developing. The adsorption technique stands out among the other wastewater treatment methods as it is simple, easy, efficient, and cost-effective. The agro-based adsorbents not only have great potential for the treatment of polluted water but also their use in this area contributes to minimizing natural waste. The agro-based adsorbent can be employed in its original raw form or after undergoing simple processes such as drying, grinding, and carbonization. Moreover, these adsorbents are typically modified physically or chemically to change their surface properties and improve their adsorption efficiency. The low-cost agro adsorbents have shown efficient adsorption capacities towards removing various organic and hazardous water pollutants. With a few exceptions, the majority of adsorbents have demonstrated heavy metals, dyes and phenol removal efficiencies exceeding 90 %. This review summarises the available information and strategies for using agro-based adsorbents to eliminate hazardous water pollutants. It is a prospective area for research in the field of environmental pollution.

This report describes a systematic approach for precise engineering of a catalyst-metal oxide interface through combining complementary approaches of chemical vapor deposition and atomic layer deposition. Specifically, Chemical Vapor Deposition (CVD) fabricated nanostructured hard-carbon framework (NCF) is employed as synergistic support for precise deposition of NiO_x particles through Atomic Layer Deposition (ALD). The three variants of NCF-NiO_x system (dimensions ranging from 3-12 nm, surface coverage ranging from 0.14 %-2 %) achieved exhibit unique electrocatalytic water oxidation activities, that are further strongly influenced by an external magnetic field (H_ext). This confluence of size engineering and associated magnetic field effects interplay to produce the largest lowering in R_ct at H_ext=200 mT. A comprehensive analysis of electrocatalytic parameters including the Tafel slope and double layer capacitance establishes further insights on co-relation of size effect and magnetic properties to understand the role of nanocarbon supported transition metal oxides in water electrolysis.

Asymmetric synthesis of chiral chemicals in high enantiomeric excess (ee) is pivotal to the pharmaceutical industry, but classic chemistry usually requires multi-step reactions, harsh conditions, and expensive chiral ligands, and sometimes suffers from unsatisfactory enantioselectivity. Enzymatic catalysis is a much greener and more enantioselective alternative, and cascade biotransformations with multi-step reactions can be performed in one pot to avoid costly intermediate isolation and minimise waste generation. One of the most attractive applications of enzymatic cascade transformations is to convert easily available simple racemic substrates into valuable functionalised chiral chemicals in high yields and ee. Here, we review the three general strategies to build up such cascade biotransformations, including enantioconvergent reaction, dynamic kinetic resolution, and destruction-and-reinstallation of chirality. Examples of cascade transformations using racemic substrates such as racemic epoxides, alcohols, hydroxy acids, etc. to produce the chiral amino alcohols, hydroxy acids, amines, and amino acids are given. The product concentration, ee, and yield, scalability, and substrate scope of these enzymatic cascades are critically reviewed. To further improve the efficiency and practical applicability of the cascades, enzyme engineering to enhance catalytic activities of the key enzymes using the latest microfluidics-based ultrahigh-throughput screening and artificial intelligence-guided directed evolution could be a useful approach.

The application of photo responsive crystals to useful actuation demands a rational design to elicit controllable movement. The [2+2] photocycloaddition reaction triggers mechanical motion using associated photosalient (PS) effects. We herein report a coordination site selective occupation strategy to modulate the arrangement of C=C bonds and thereby tune the PS effect. Replacing or repositioning the donor atom at one end of the linear ligand allowed for a greater level of molecular structural flexibility, facilitating [2+2] photocycloaddition. The distance between photoreactive centres and coordination sites was adjusted by ligand design to regulate PS behaviour. This work suggests new avenues for modulating PS movement to achieve useful motion.

Highly selective and divergent syntheses, which are crucial in both organic synthesis and medicinal chemistry, involve significant advancements in compound accessibility. By modifying α-cyano esters into α-cyano ketones, the synthesis pathway broadens to include a diverse range of 4-CN, 5-amino, and 5-arylamino derivatives of 1,2,3-triazoles, which are achieved notably through the Dimroth rearrangement. This versatility extends further with the potential for a triple cascade reaction, leading to the production of carboximidamide compounds, which are facilitated by the Cornforth rearrangement. Advancements in compound accessibility not only expand the repertoire of synthesized molecules but also open new avenues for potential pharmacological agents. Building on these findings, we have developed an innovative and efficient method for the divergent synthesis of functionalized 1,2,3-triazoles. This method strategically utilizes α-cyanocarbonyls and arylazides by harnessing their reactivity and compatibility to orchestrate a variety of molecular transformations. By optimizing these substrates, our goal is to simplify synthetic routes, improve product yields, and accelerate the discovery and development of new chemical entities with promising biological activities.

Spinning fibers from carbon nanotube (CNT)/superacid dispersions has emerged as a promising strategy for industrial-scale production of high-performance CNT fibers (CNTFs). The oxygen content and types of functional groups on CNT surfaces significantly influence dispersion, assembly processes, and fiber properties. In this study, Tuball-SWCNTs were purified and oxidized at varying levels. The dispersion behavior of CNTs with different oxidation levels in chlorosulfonic acid was systematically observed, and the mechanical properties of fibers spun from these dispersions were compared. By adjusting the dispersion concentration, highly oriented CNTFs were produced with a specific strength of 1.03 N/tex, a tensile strength of 1.59 GPa, and an electrical conductivity of 3.58 MS/m. Further investigations indicated that oxygen-containing functional groups decrease the coagulation rate, increasing the maximum draw ratio during spinning and improving CNT alignment in the fibers. Molecular dynamics simulations demonstrated that these functional groups (-OH, -COOH) enhance load transfer between CNTs through hydrogen bonding. This specific strength is the highest achieved using Tuball-SWCNTs for superacid-spun fibers, surpassing previous works due to the oxidation-controlled coagulation rate, enhanced fiber orientation, and improved load transfer via hydrogen bonding. This study provides insights for designing and optimizing high-performance CNTFs.

This study investigates the anion-directed assembly of discrete copper (II) complexes. The ligands of choice are two unusual N7-alkyl-purine-based neutral ligands. These ligands facilitate the exclusive coordination through the N3 and N9 positions, preventing polymeric chain formation. Perchlorate ions promoted the formation of discrete paddlewheel-like complexes with the general formula [Cu2(μ-Pur)4(CH3CN)2]4+, while chloride ions yielded chloride-bridged dimers of the form [Cu2(Pur)2(μ-Cl)2Cl2]. Copper-copper bond distances within these complexes ranged from 2.92 to 2.98 Å. Magnetic susceptibility measurement of chloride-bridged complexes exhibited antiferromagnetic coupling, whereas paddlewheel complexes displayed more complex alternating ferromagnetic and antiferromagnetic interactions. Chloride-bridged compounds exhibited strong near-infrared absorption.

Lignin-based carbon nanomaterials offer several advantages, including biodegradability, biocompatibility, high specific surface area, ease of functionalization, low toxicity, and cost-effectiveness. These materials show promise in biochemical sensing applications, particularly in the detection of metal ions, organic compounds, and human biosignals. Various methods can be employed to synthesize carbon nanomaterials with different dimensions ranging from 0D-3D, resulting in diverse structures and physicochemical properties. This study provides an overview of the preparation techniques and characteristics of multidimensional (0-3D) lignin-based carbon nanomaterials, such as carbon dots (CDs), carbon nanotubes (CNTs), graphene, and carbon aerogels (CAs). Additionally, the sensing capabilities of these materials are compared and summarized, followed by a discussion on the potential challenges and future prospects in sensor development.

In this study, a difluorocarbene-promoted O-O bond activation of peroxy acids is developed through the insertion of difluorocarbene into O-H bond. This activation strategy in synergy with O-B coordination with boronic acids/ester greatly polarizes the O-O bond for in-situ generation of carboxylium species that reacts with the nucleophilic part of boronic acids in a concerted way to produce carboxylic esters. Good efficiency and functional group tolerance are demonstrated. Application of this method to the functionalization of a boronic acid drug used as HSL enzyme inhibitor produces smoothly the ester derivative. This difluorocarbene-mediated O-O bond activation strategy is conceptually different from traditional radical type methods, and is also complementary to conventional esterification methods with a distinct retro-synthetic disconnection.

An assembly of metal nanoclusters driven by appropriate surface ligands and solvent environment may engender entirely new photoluminescence (PL). Herein, we first synthesize histidine (His) stabilized copper nanoparticles (CuNPs) and, subsequently, copper nanoclusters (CuNCs) from it using 3-mercaptopropionic acid (MPA) as an etchant. The CuNCs originally emit bluish-green (λ_em=470 nm) PL with a low quantum yield (QY∼1.8 %). However, it transformed into a dual-emissive nanocluster assembly (Zn-CuNCs) in the presence of Zn(II) salt, having a distinct blue emission band (λ_em=420 nm) and a red emission band (λ_em=615 nm) with eight times QY (∼9.1 %) enhancement. The temperature-dependent emission spectra of Zn-CuNCs depicted that the blue emission band persists for all the temperature ranges (0-80 °C) while the red emission band vanishes at high temperatures (70-80 °C). Thus, the blue emission may originate from the locally excited state (LES) emission of the nanoclusters, while the red emission originates from through-space interaction (TSI) and Cu(I)…Cu(I) interaction within the assembly. Adding dimethyl sulfoxide (DMSO) further modifies the emission intensities; the red band was amplified four times, while the blue band was diminished by 2.5 times. The transmission electron microscopy (TEM) images unveiled that the Zn-CuNCs are a large assembly of tiny nanoclusters, which become more compact in DMSO. The blue emission possesses steady-state fluorescence anisotropy, while the red emission shows no anisotropy. Further, near-perfect white light emission(WLE) was rendered with CIE coordinates of (0.33, 0.32) by combining the dual emission of the Zn-CuNCs with the original green emission of the CuNCs.