Latest ArticlesThe deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties. However, despite its pharmaceutical value, the general and rapid syntheses of aromatic scaffolds that contains deuterium remain an important yet elusive task. State-of-the-art approaches mainly relied on the transition metal-catalyzed C–H deuteration via the assistance of directing groups (DGs), which often suffered from over-deuteration and lengthy step counts required for installation and/or removal of DG. Herein, we report a generalizable synthetic linchpin strategy for the facile preparation of the ortho-deuterated aromatic core. Through capture of aryne-derived 1,3-zwitterion with heavy water, we synthesized an array of ortho-deuterated aryl sulfonium salts. These novel linchpins not only participated the transition metal catalyzed cross-coupling reaction as nucleophiles, but also served as aryl radical reservoirs under photochemical or electrochemical conditions, enabling facile and precise access to structurally diverse deuterated aromatics. Moreover, we have disclosed a novel EDA complex enabled direct arylation of phosphines under visible-light irradiation, further expanding the utility of our platform approach.
The recovery of gold from waste electronic and electric equipment (WEEE) has gained great attention with the increased number of WEEE, because it can largely alleviate the pressure on the environment and resources. Covalent organic frameworks (COFs) are ideal adsorbents for gold recovery owing to their large surface area, good stability, easily functionalized ability, periodic structures, and definitive nanopores. Herein, a cyano-functionalized COF (COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold. The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance, which possesses fast adsorption kinetics, high cycling stability, and adsorption capacity up to 663.67 mg/g. Excitingly, COF-CN showed extremely high selectivity for gold ions, even in the presence of various competing cations and anions. The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE. The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.
Triclosan (TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects. Therefore, developing an efficient and sustainable technology to degrade TCS is urgently needed. Herein, cobalt oxyhydroxide @covalent organic frameworks (CoOOH@COFs) S−scheme heterojunction was synthesized, which combined the visible-light-driven photocatalysis and peroxymonosulfate (PMS) activation to synergistically generate abundant reactive oxygen species (ROSs) for TCS degradation. The degradation efficiency of TCS reached 100% within 8 min in the Vis-CoOOH@COFs/PMS system, and the reaction rate constant was 0.456 min−1, which was nearly 1.90 and 2.85 times that of single CoOOH and COFs, and 2.36 times that under dark condition, respectively. The density functional theory (DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to CoOOH. Both experimental and theoretical analyses indicated that CoOOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation, enhanced interfacial electron transfer, accelerated PMS activation, and generated multiple ROSs. In particular, photogenerated electrons (e−) accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle, while the PMS captured the e−, which significantly decreased the charge combination of CoOOH@COFs. Radicals (O2•−, •OH, and SO4•−) and non-radicals (such as 1O2, h+, and e−) were both presented in the Vis-CoOOH@COFs/PMS system, with O2− playing a dominant role in TCS degradation. Furthermore, the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification. Importantly, the environmentally friendly CoOOH@COFs S−scheme heterojunction exhibited excellent stability and reusability. In conclusion, this study innovatively designed an S−scheme heterojunction in the photocatalytic-PMS activation system, providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
Developing a chiral material as versatile and universal chiral stationary phase (CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance. In this study, we demonstrated for the first time that a chiral metal-organic cage (MOC), [Zn6M4], as a universal chiral recognition material for both multi-mode high-performance liquid chromatography (HPLC) and capillary gas chromatography (GC) enantioseparation. Two novel HPLC CSPs with different bonding arms (CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn6M4] onto thiolated silica via thiol-ene click chemistry. Meanwhile, a capillary GC column statically coated with the chiral MOC [Zn6M4] was also fabricated. The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC (NP-HPLC) and reversed phase (RP-HPLC) but also in GC, and various racemates were well separated, including alcohols, diols, esters, ketones, ethers, amines, and epoxides. Importantly, CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation, which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns, suggesting the great potential of the two prepared CSPs in enantioseparation. This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC, and also paves the way to expand the potential applications of MOCs.
Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials. Herein, we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission, which is constructed by cucurbit[7]uril (CB[7]), cyanostilbene derivative (DAC) and Laponite XLG (LP) via supramolecular cascade assembly. Compared with the free guest molecule DAC, the confinement of macrocycle CB[7] achieve effective near-infrared fluorescence in the aqueous phase from scratch, and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC, which not only result in a substantial enhancement of the fluorescence intensity, but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states. Further, 8–hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (HPTS) is introduced in the cascade assembly to fabricated photo-controllable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer, which is successfully employed in reversible multiple information encryption.
The brain's functions are governed by molecular metabolic networks. However, due to the sophisticated spatial organization and diverse activities of the brain, characterizing both the minute and large-scale metabolic activity across the entire brain and its numerous micro-regions remains incredibly challenging. Here, we offer a high-definition spatially resolved metabolomics technique to better understand the metabolic specialization and interconnection throughout the mouse brain using improved ambient mass spectrometry imaging. This method allows for the simultaneous mapping of thousands of metabolites at a 30 µm spatial resolution across the mouse brain, ranging from structural lipids to functional neurotransmitters. This approach effectively reveals the distribution patterns of delicate microregions and their distinctive metabolic characteristics. Using an integrated database, we annotated 259 metabolites, demonstrating that the metabolome and metabolic pathways are unique to each brain microregion. The distribution of metabolites, closely linked to functionally connected brain regions and their interactions, offers profound insights into the complexity of chemical processes and their roles in brain function. An initial dataset for future metabolomics research might be obtained from the high-definition mouse brain's spatial metabolome atlas.
RNA binding proteins (RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process. Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progression of numerous diseases, making RBPs potential therapeutic targets. However, the limited tissue penetration of 254 nm UV irradiation makes it difficult to efficiently crosslink weak and dynamic RNA–protein interactions in mammal tissues. Additionally, RNA degradation in metal catalyzed click reaction further hinders the enrichment of RNA-protein complexes (RPCs). Due to these inherent limitations, globally profiling the RNA binding proteome in mammal organs has long been a challenge. Herein, we proposed a novel method, which utilized a dual crosslinking with formaldehyde and 254 nm UV irradiation, metabolic labeling and metal-free thiol-yne click reaction to enable large-scale enrichment and identification of RBPs in mouse liver, called FTYc_UV. In this method, formaldehyde is first used to crosslink the crude RNA-protein complexes (cRPCs) in situ to address the problem of poor tissue penetration of 254 nm UV irradiation. Furthermore, this method integrates metabolic labeling with a metal-free thiol-yne click reaction to achieve non-destructive RNA tagging. After specifically RNA-RBPs crosslinking by 254 nm UV irradiation in tissue lysates, formaldehyde decrosslinking is employed to remove non-specific proteins, leading to effective enrichment of RPCs from mouse liver and thereby overcoming the poor specificity of formaldehyde crosslinking. Application of FTYc_UV in mouse liver successfully identified over 1600 RBPs covering approximately 75% of previously reported RBPs. Furthermore, 420 candidate RBPs, including 151 metabolic enzymes, were also obtained, demonstrating the sensitivity of FTYc_UV and the potential of this method for in-depth exploration of RNA–protein interactions in biological and clinical research.
Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives. However, it is challenging to develop environmentally friendly catalytic systems, especially in constructing efficient and recyclable catalysts under water or solvent-free conditions. Here, we designed two novel coordination polymers Cd–CPs and Fe–CPs to investigate their catalytic performance in water. Gratifyingly, it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions, while it was effective for the synthesis of 1,3,5-triazines through acceptorless dehydrogenative coupling strategies. The features of broad substrate, high atom efficiency, and good catalyst reusability highlight the feasibility of this transformation. In additional, we demonstrated the spindle-like structures Fe-P, derived from the Fe–CPs via phosphorylation, which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability. This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction, and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.
Fractal assembly in discrete structures, especially for artificial supramolecular species, has attracted significantly increased interest over the past two decades. In this study, we present the precisely controlled fractal expanding synthesis of a novel triangular prism supramolecule featuring Sierpiński triangular face, which was achieved through a module-intervened self-expansion strategy. The homoleptic S1 was firstly synthesized through the assembly of ligand L1 with Zn2+ ions. Based on the triangular-faced prism S1, we further introduced Sierpiński triangular faces on the section of the heteroleptic supramolecular cage S2 with an expanded inner cavity and more abundant active sites for photocatalytic properties. The topotactic architectures for both S1 and S2 were fully characterized by nuclear magnetic resonance spectroscopy, high-resolution electrospray ionization mass spectrometry, transmission electron microscopy, and atomic force microscopy. Furthermore, the enhanced photocatalytic activity of the fractal expanded S2 was performed via the superior amine oxidative efficiency over S1. This study proposes the unprecedented fractal expanding strategy for three-dimensional supramolecular species with higher complexity, potentially opening new avenues for structural regulation of artificial fractal molecules.
The Jellium closed-shell model, a cornerstone of cluster science, has long guided the design of superatoms by dictating electron-counting rules. However, its reliance on precise control of cluster composition and electron shell occupancy presents significant experimental challenges. Here, we introduce a ligation strategy that circumvents these limitations by demonstrating that the adiabatic electron affinity (AEA) of aluminum-based clusters, whether with filled or partially filled electron shells, can be dramatically enhanced through the attachment of organic Lewis acid ligands. It was evidenced that the AEA of PAl12 can be significantly increased by 2.17 eV after the ligation of two ligands, indicating a remarkable improvement in its electron-accepting ability. This approach yields superhalogen species, offering a versatile and practical means to tune the electronic properties of clusters while preserving their superatomic states, independent of shell occupancy. Remarkably, this ligand-induced modulation is not confined to naked clusters but also extends to nano-confined systems, hinting at its broader applicability. Given the indispensable role of ligands in cluster synthesis, this strategy holds promise for advancing the field of condensed-phase superatom synthesis, potentially complementing traditional electron-counting rules in a broader range of applications.
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