Latest ArticlesThe efficacy of photodynamic therapy (PDT) for breast tumors is hindered by challenges such as inadequate tumor targeting, limited treatment depth, and strong oxygen dependence. Herein, a promising photosensitizer VP-B was developed to simultaneously address all the aforementioned issues for the treatment of hypoxic deep-seated breast tumors. The biotinylated photosensitizer VP-B not only exhibited precise targeting towards breast tumor tissue, but also efficiently triggered the generation of abundant 1O2 and O2−• under 690 nm red light irradiation. Indeed, the red light penetration ability enabled VP-B to achieve successful application in a mouse orthotopic breast tumor model. After intravenous administration, VP-B can selectively target tumor tissues and significantly inhibit the growth of hypoxic deep-seated tumors. Therefore, this new type Ⅰ & Ⅱ photosensitizer could boost fluorescence-guided photodynamic therapy of other hypoxic solid tumors.
Covalent organic frameworks (COFs) are crystalline porous polymeric materials composed of organic monomers connected by strong covalent bonds and offer high stability, good crystallinity, a large specific surface area, and controllable structures. COFs are widely used in the fields of adsorption and separation, catalysis, photovoltaics, and drug-delivery. The structural regulation and performance optimization of COFs can be realized through the modification of ligands and the selection of linkage methods. In which, the types of linkage are closely related to the stability and performance of COFs. In this review, nitrogen-containing linkage-bonds (NCLBs) in COFs are divided into N-containing double bonds, N-containing conjugated rings and N-containing unconjugated rings. The association between structure and performance of COFs is elaborated and the synthesis methods of COFs are systematically summarized. Moreover, the structural design, theoretical prediction and machinable application of COFs are prospected
Proteolysis-targeting chimera (PROTAC) has emerged as an efficient strategy to accurately control intracellular protein levels. However, conventional PROTACs are generally limited by nonspecific protein degradation and off-tissue side effects. Particularly, there is a lack of effective chemical tools for visualizing protein degradation. Herein, a near-infrared fluorescent and theranostic PROTAC (PRO-S-DCM) was designed for imaging the degradation of bromodomain-containing protein 4 (BRD4). PRO-S-DCM could be tumor-specifically activated and exhibited favorable imaging effects both in vitro and in vivo. PRO-S-DCM was proven to be a theranostic probe, which potently inhibited growth, invasion and migration of HeLa cells and induced cell apoptosis.
Bacterial infection, insufficient angiogenesis, and oxidative damage are generally regarded as key issues that impede wound healing, making it necessary to prepare new biomaterials to simultaneously address these problems. In this work, monodispersed CeO2@CuS nanocomposites (NCs) were successfully prepared with tannin (TA) as the reductant and linker. Due to abundant oxygen vacancies in CeO2 and the polyphenolic structure of TA, the TA-CeO2@CuS NCs exhibited a remarkable antioxidant ability to scavenge excessive reactive oxygen species (ROS), which would likely induce serious inflammation. In addition, the TA-CeO2@CuS NCs demonstrated excellent antibacterial capability with near-infrared ray (NIR) irradiation, and the released copper ions could promote the regeneration of blood vessels. These synergistic effects indicated that the synthesized TA-CeO2@CuS NCs could serve as a promising biomaterial for multimodal wound therapy.
Three monomers, namely A2, B2, and GH, were designed and synthesized. By utilizing double host-guest interactions, the monomers A2+B2+GH underwent self-assembly to form a supramolecular linear polymer (SLP) at high concentrations. Long fibers could be pulled from the concentrated SLP solution. Upon the addition of PdCl2(PhCN)2 into the SLP solution, a structural transformation occurred from SLP to a supramolecular crosslinked polymer (SCP) through metal coordination interaction. This transformation induced fluorescence quenching, test paper strips for ion detection experiment confirmed that the SLP had good detection ability for Pd2+. Furthermore, the SCP underwent a transformation into a gel when the concentration exceeded 145 mmol/L. The SCP gel demonstrated sensitivity to different stimuli, such as K+ ions and changes in temperature, accompanied by a reversible transition between sol and gel states. Additionally, rheological analyses indicated that the gel possessed favorable self-healing properties.
Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries, attributed to its high theoretical specific capacity and low electrochemical potential. However, safety concerns related to lithium dendrite-induced short circuits and suboptimal electrochemical performance have impeded the commercial viability of lithium metal batteries. Current research efforts primarily focus on altering the solvated structure of Li+ by modifying the current collector or introducing electrolyte additives to lower the nucleation barrier, expedite the desolvation process, and suppress the growth of lithium dendrites. Nevertheless, an integrated approach that combines the advantages of these two strategies remains elusive. In this study, we successfully employed metal-organic salt additives with lithophilic properties to accelerate the desolvation process, reduce the nucleation barrier of Li+, and modulate its solvated structure. This approach enhanced the inorganic compound content in the solid electrolyte interphase (SEI) on lithium foil surfaces, leading to stable Li+ deposition and stripping. Specifically, LiCu cells demonstrated excellent cycle life and Coulombic efficiency (97.28% and 98.59%, respectively) at 0.5 mA/cm2@0.5 mAh/cm2 and 1 mA/cm2@1 mAh/cm2 for 410 and 240 cycles, respectively. LiLi symmetrical cells showed no short circuit at 1 mA/cm2@1 mAh/cm2 for 1150 h, and LiLFP full cells retained 68.9% of their capacity (104.6 mAh/g) after 250 cycles at N/P (1.1:1.0) with a current density of 1 C.
Although supramolecular transformations have been emerged as a potent strategy for transitioning between various topologies, post-modification induced topological transformations have never been explored in the context of [2]catenane topologies. In this study, we present a novel supramolecular transformation between a Hopf link and a macrocycle, induced by the Diels–Alder click reaction. By strategically selecting the half-sandwich ruthenium binuclear fragment B as a rigid capping agent, we successfully integrated tetrazine moieties into the metalla[2]catenane structure. We demonstrated that the introduction of 2,5-norbornadiene (NBD) as an external stimulus allows for the transformation of the novel metalla[2]catenane, featuring reactive tetrazine sites, into the corresponding monomeric ring through post-modification for the first time. The synthetic results are corroborated by single-crystal X-ray diffraction analysis, ESI-TOF/MS, elemental analysis, and detailed solution-state NMR techniques.
A new oxidative N-heterocyclic carbene (NHC)-catalyzed high-order [7 + 3] annulation reaction of γ-indolyl phenols as 1, 7-dinucleophiles and α, β‐alkynals with the aid of Sc(OTf)3 is reported, enabling the highly regioselective access to unprecedented polyarene-fused ten-membered lactams bearing a bridged aryl-aryl-indole scaffold in moderate to good yields. This protocol demonstrates a broad substrate scope, good compatibility with substituents and complete regioselectivity, providing an organocatalytic modular synthetic strategy for creating medium-sized lactams.
Halide solid-state electrolytes (HSSEs) with excellent ionic conductivity and high voltage stability are promising for all-solid-state Li-ion batteries (ASSLBs). However, they suffer from poor processability, mechanical durability and humidity stability, hindering their large-scale applications. Here, we introduce a dry-processing fibrillation strategy using hydrophobic polytetrafluoroethylene (PTFE) binder to encapsulate Li3InCl6 (LIC) particles (the most representative HSSE). By manipulating the fibrillating process, only 0.5 wt% PTFE is sufficient to prepare free-standing LIC-PTFE (LIC-P) HSSEs. Additionally, LIC-P demonstrates excellent mechanical durability and humidity resistance. They can maintain their shapes after being exposed to humid atmosphere for 30 min, meanwhile still exhibit high ionic conductivity of > 0.2 mS/cm at 25 ℃. Consequently, the LIC-P-based ASSLBs deliver a high specific capacity of 126.6 mAh/g at 0.1 C and long cyclability of 200 cycles at 0.2 C. More importantly, the ASSLBs using moisture-exposed LIC-P can still operate properly by exhibiting a high capacity-retention of 87.7% after 100 cycles under 0.2 C. Furthermore, for the first time, we unravel the LIC interfacial morphology evolution upon cycling because the good mechanical durability enables a facile separation of LIC-P from ASSLBs after testing.
Supramolecular luminescent materials (SLMs) exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches, making them highly attractive in the field of luminescent materials. In recent years, the novel macrocyclic arenes characterized by unique electron-rich structures, ease of derivatization, tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials. The incorporation of macrocyclic arenes into SLMs leads to simple preparation process, diverse photophysical phenomena and sophisticated regulatory mechanisms, which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials. In this review, the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies, including host-guest complexes, supramolecular polymers, nanoparticles, and other assemblies. Moreover, some insights into future directions for this research area will also be offered.