Latest ArticlesDespite the 1,2-difunctionalization reactions of styrenes have been well developed, the 1,1-regioselective addition reaction remains challenging. We disclose herein a palladium-catalyzed, highly 1,1-regioselective alkenylboration of styrenes by using alkenyl triflates and a diboron reagent as the coupling partners. A wide scope of styrenes derivatives and alkenyl triflates participate this reaction to provide the corresponding allyl boronates with high regioisomeric ratios. The success of this reaction is ascribed to the application of 1,10-phenanthroline-derivated ligand and the addition of ammonium chloride salt. Moreover, acrylate esters can also selectively afford the 1,1-alkenylboration products under the same reaction conditions.
Electrochemical reduction of CO2 (CO2RR) to value-added chemicals is an attractive strategy for greenhouse gas mitigation and carbon recycle. Carbon material is one of most promising electrocatalysts but its product selectivity is limited by few modulating approaches for active sites. Herein, the predominant pyridinic N-B sites (accounting for 80% to all N species) are fabricated in hierarchically porous structure of graphene nanoribbons/amorphous carbon. The graphene nanoribbons and porous structure can accelerate electron and ion/gas transport during CO2RR, respectively. This carbon electrocatalyst exhibits excellent selectivity toward CO2 reduction to CH4 with the faradaic efficiency of 68% at -0.50 V vs. RHE. As demonstrated by density functional theory, a proper adsorbed energy of *CO and *CH2O are generated on the pyridinic N-B site resulting into high CH4 selectivity. Therefore, this study provides a novel method to modulate active sites of carbon-based electrocatalyst to obtain high CH4 selectivity.
Derivatives of piperazine, which is one of the most important heterocycles, are often used as linkers to connect active substructures that show promising bioactivities, especially in the field of agrochemicals. From 2000 to 2022, many piperazine-containing compounds were found to exhibit excellent activities against fungi, bacteria, insects, plant viruses, and weeds and have also been used as plant growth regulators. Currently, the development of novel pesticides to prevent the invasion of crop pathogens and ensure the quality and yields of crops is still needed. We herein investigated and summarized the role that piperazine plays in the discovery of pesticides to provide a comprehensive summary of the broad activities of piperazine derivatives in agricultural applications and offer a potential reference for novel pesticide design using piperazine-containing compounds. Moreover, structure–activity relationships (SARs) analyses of bioactive piperazine-containing compounds are also discussed for a deeper understanding.
Exosomes offer ideal biomarkers for liquid biopsies. However, high-efficient capture of exosomes has been proven to be extreme challenging. Here, we report a soluble pH-responsive host-guest-based nanosystem (pH-HGN) for homogeneous isolation of exosomes around physiological pH. The pH-HGN consists of two specifically functionalized modules. First, a pH-responsive module, poly-dimethylaminoethyl methacrylate, provides homogeneous capture circumstances and sharp pH-triggered self-assembly separation in aqueous solution to improve capture efficiency and reduce nonspecific adsorption. Second, a host-guest module, poly-acrylamide azobenzene and β-cyclodextrin linked with exosomes-specific antibody, could act as the "cleavable bridge" to specific capture and subsequent rapid release of captured exosomes through host-guest interaction between β-cyclodextrin and AAAB moieties. The pH-HGN offered high capture efficiencies for exosomes from two different cell lines, which were 90.2% ± 0.28% and 87.0% ± 4.6% for H1299 and MCF-7 cell-derived exosomes, respectively. The purity of isolated exosomes was (1.49 ± 0.71) × 1011 particles/μg, which was 4.1 times higher compared with the gold standard ultracentrifugation (UC) method. Furthermore, the isolated exosomes via the pH-HGN can preserve well integrity and biological activity. The developed pH-HGN was further successfully applied to differentiate lung cancer patients from healthy persons. These findings indicated that pH-HGN is a promising strategy in exosomes-based research and downstream applications.
The design and synthesis of photoactive macrocyclic molecules continue to attract attention because such species play important roles in supramolecular chemistry as well as photoelectronic applications. Donor-acceptor (D-A) conjugated macrocycles are an emerging class of photoactive molecules due to their D-A conjugated structural characteristics and tunable optical properties. In addition, the well-defined cavities in such D-A macrocycles endow them with versatile host-guest properties. In this review, we provide a comprehensive summary of D-A conjugated macrocycle chemistry, detailing recent progress in the area of synthetic methods, optical properties, host-guest chemistry and applications of the underlying chemistry to chemical sensors, bioimaging and photoelectronic devices. Our objective is to provide not only a review of the fundamental findings, but also to outline future research directions where D-A conjugated macrocycles and their constructs may have a role to play.
Metal-based catalysts with different site sizes (e.g., metal nanoparticles (NPs) and single atom catalysts (SACs)) demonstrated outstanding catalytic activities in versatile Fenton-like reactions. However, the surface/structural instability is a critical issue, which will result in rapid passivation in Fenton-like reaction and fail in long-term operation. The catalytic stability of the catalysts with different metal sizes considering versatile peroxides (H2O2, peroxymonosulfate (PMS), and peroxodisulfate (PDS)) should be analyzed. In addition, strategies for catalyst regeneration and recyclability improvement are also important to realize the metal-based catalysts for practical applications. In this review, catalytic stability of catalysts with different metal sizes in the backgrounds of versatile peroxides and water matrixes in Fenton-like reactions were first evaluated. Regeneration of metal catalytic sites with different methods were also reviewed. Finally, major challenges and development of methods concerning the stability and regeneration of metal catalytic sites with different sizes were discussed to understand the future researches of metal catalytic sites in Fenton-like reactions.
To tackle undesirable shuttle reaction and sluggish reaction kinetics in lithium–sulfur (Li–S) batteries, we develop a porous and high-density oxygen-doped tantalum nitride nanostructure (nano-TaNO) as an efficient catalyst through delicate tailoring. Benefiting from well-defined interior and surface nanopore channels, the nano-TaNO favors abundant sulfur storage, easy electrolyte infiltration and good electrons/Li+ transport. More importantly, high-density O dopant in nano-TaNO not only provides high conductivity, but also promotes polysulfide adsorption/conversion via Li–O chemical interactions and the generation of S3*− radicals to activate additional evolution path from S8 to Li2S. Consequently, the nano-TaNO-based cathode exhibits excellent specific capacity and cyclability even under high sulfur loading condition. These interesting findings suggest the great potential of tantalum nitride and a high amount of anion doping engineering in manipulating intermediates and building high-performance Li−S rechargeable batteries.
The key building blocks, tetrachlorinated terrylene diimides and the targeted sila-annulated terrylene diimides (Si-TDIs and 2Si-TDIs) were synthesized for the first time. Single-crystal analysis verified the almost planar molecular configurations of both Si-TDIs and 2Si-TDIs. They exhibited intriguing optical properties including red-shifted absorption and near-infrared emission properties with excellent fluorescence quantum yields, as well as precisely controlled HOMO/LUMO energy levels by Si-heteroannulation. The single-crystal organic field-effect transistors based on 2Si-TDI 5a featuring long and branched alkyl chains demonstrated well-balanced ambipolar transporting properties with electron/hole mobilities of 0.10/0.18 cm2 V−1 s−1.
Aqueous zinc ion batteries (AZIBs) have attracted much attention in recent years due to their high safety, low cost, and decent electrochemical performance. However, the traditional electrodes development process requires tedious synthesis and testing procedures, which reduces the efficiency of developing high-performance battery devices. Here, we proposed a high-throughput screening strategy based on first-principles calculations to aid the experimental development of high-performance spinel cathode materials for AZIBs. We obtained 14 spinel materials from 12,047 Mn/Zn-O based materials by examining their structures and whether they satisfy the basic properties of electrodes. Then their band structures and density of states, open circuit voltage and volume expansion rate, ionic diffusion coefficient and energy barrier were further evaluated by first-principles calculations, resulting in five potential candidates. One of the promising candidates identified, Mg2MnO4, was experimentally synthesized, characterized and integrated into an AZIB based cell to verify its performance as a cathode. The Mg2MnO4 cathode exhibits excellent cycling stability, which is consistent with the theoretically predicted low volume expansion. Moreover, at high current density, the Mg2MnO4 cathode still exhibits high reversible capacity and excellent rate performance, indicating that it is an excellent cathode material for AZIBs. Our work provides a new approach to accelerate the development of high-performance cathodes for AZIBs and other ion batteries.
Single-atom nanozymes (SANs) have attracted extensive attention due to their characteristics of both single-atom catalysts (SACs) and enzymes. Using spin-polarized density functional theory (DFT) calculations combined with the hybrid solvation model, this work designed a series of carbon-supported Group Ⅷ transition metals TMS4-C SANs, similar to the TMS4 active center of formate dehydrogenase (FADH), aiming to develop highly efficient SANs for CO2 electroreduction. DFT calculations show that compared with TMN4-C, TMS4-C have FADH-like feature, which can selectively reduce CO2 to formic acid. Particularly, CoS4-C is the most promising SAN for CO2 reduction, with a low limiting potential of -0.07 V, which exceeds most reported catalysts. Two descriptors of TMX4-C (X = N, S) based on intrinsic and electronic structure properties were proposed to shed light on the origin activity of candidates. The findings presented here will provide new insights into the design of novel enzyme-like catalysts for electrochemical CO2 reduction.
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