Metal-organic frameworks (MOFs) offer tunable porosity and electronic structure for advanced chemical sensing, yet most rely on single-mode transduction mechanisms that limit selectivity and sensitivity. Here, we report a metal center-engineered bimetallic Mn/Cu-BTC integrated with a micro quartz tuning fork (MQTF) transducer to achieve multidimensional (colorimetric-piezoelectric) sensing of ethylene oxide (EtO). The incorporation of Mn2+ into the Cu-BTC lattice generates abundant open coordination sites and modifies the local electronic environment, enabling synergistic EtO adsorption and tunable d-d electronic transitions. The resulting sensor exhibits a wide dynamic range (12 ppb-25 ppm), an ultra-low detection limit of 12 ppb, and very high selectivity toward EtO compared to common interferents. Comprehensive characterization (SEM, XPS, XRD, UV-Vis) confirms successful Mn incorporation and structural integrity. This work establishes a generalizable strategy for coupling metal center engineering with multidimensional transduction, advancing MOF-based hybrid devices for trace toxic gas detection and environmental safety monitoring.

Radioactive iodine isotopes generated during nuclear fission present significant challenges due to their high radioactivity, mobility, and long-term ecological hazards. Their efficient capture and safe disposal are therefore critical for nuclear waste management. The adsorption method is considered the most promising approach owing to its operational simplicity and low energy consumption. Herein, we propose a multi-strategy synergistic molecular engineering design that enhances aqueous stability through a hydrophobic sulfonylcalix[4]arene capping ligand, strengthens electrostatic adsorption for iodine via a positively charged pyridinium-functionalized endo cavity, and fine-tunes the cavity structure through conformational modification of the bridging ligands. Based on this strategy, a series of cobalt-based metal-organic cages (MOCs) with precisely tailored endo cavity configurations were successfully synthesized. Systematic investigations of their iodine adsorption behaviors in gaseous, organic, and aqueous phases revealed maximum adsorption capacity of 650.5 mg g(-1) for gaseous I-2 and 1345.2 mg g(-1) for aqueous I-3(-). Mechanistic studies indicate that gaseous adsorption primarily relies on the synergistic effect of Co2+ sites and pyridinium sites, whereas the highly efficient aqueous adsorption is mainly driven by strong electrostatic interactions between the pyridinium-functionalized cationic endo cavity and I-3(-) anions. Recirculating flow system adsorption experiments further demonstrated that this pyridinium-functionalized MOC achieves rapid and efficient capture of low-concentration I-3(-) with good resistance to ionic interference and robust cycling stability. This work provides a clear molecular model for understanding the structure-performance relationship in iodine adsorption and offers promising candidate materials for the aqueous remediation of radioactive iodine.

Metal-organic cages (MOCs), with their unique cavity structures, abundant specific surface areas, and host-guest recognition capabilities, have been consistently demonstrated as catalysts that can significantly accelerate reaction rates and enhance substrate enrichment. Notably, although research has been devoted to the application of MOC in catalysis, studies focusing on the utilization of peroxymonosulfate (PMS) activation for pollutant degradation remain relatively limited. Herein, this study presented the synthesis of a novel cobalt-based metal-organic cage, {Co4(mu 4-OCH3)(TBSC)}2L42DMFCH3OH (L = 1,3-adamantanedicarboxylic acid), Ada-MOC, and evaluate its catalytic performance in PMS activation for methylene blue (MB) degradation. The results indicated that the Ada-MOC/PMS system showed a superior MB degradation efficiency of 99.9% within 30 min, with a k app value 33 times higher than that of the PMS system. Furthermore, the Ada-MOC exhibited high stability and catalytic activity across a broad pH range and under diverse water quality conditions. Mechanistic studies revealed that nonradical pathways such as singlet oxygen (1O2) played a dominant role in the reaction process. Based on LC-TOF-MS analysis combined with DFT calculations, three potential degradation pathways for MB have been proposed. The Ada-MOC/PMS system developed in this research demonstrates considerable potential for practical application in organic wastewater remediation.

Lithium-sulfur (Li-S) batteries are promising candidates for next-generation energy storage devices due to their high energy density, low cost, and environmental friendliness. However, their practical application remains limited by the polysulfide shuttle effect, sulfur volume expansion, and poor electronic conductivity of S and Li2S. In this study, titanium carbide (TiC) was grown on Ti foam using chemical vapor deposition (CVD) to construct a binder-free, highly conductive, and porous TiC-Ti threedimensional (3D) framework sulfur host for enhancing the Li-S battery performance. This 3D framework combines highly porous Ti foam with the polar surface of CVDsynthesized TiC nanoflowers, enabling efficient electron and ion transport, anchoring polysulfides to mitigate the shuttle effect, and accommodating sulfur volume expansion for enhanced cycling stability. Our study demonstrated that Li-S batteries utilizing TiC-Ti 3D framework@S cathodes achieved a high initial discharge capacity of 1506 mAhg-1 at 0.1 C and maintained 93.3% of their capacity after 500 cycles at 1 C, with an exceptionally low average capacity decay of 0.01% per cycle. Additionally, the TiC-Ti 3D framework@S cathodes exhibited reduced charge transfer resistance after cycling, indicating enhanced interfacial reaction kinetics and stability. These findings confirm that the CVD-synthesized TiC-Ti 3D framework can serve as an efficient binder-free sulfur host, which provides a promising material and structural strategy for high-performance Li-S battery design.

Tungsten diselenide (WSe2) has emerged as a highly promising material for lithium/sodium-ion batteries due to its exceptional electrical and chemical properties and unique sandwich-like two-dimensional structures. In this work, we present a chemical vapor deposition approach for synthesizing densely packed vertically oriented 2H-phase WSe2 nanosheets uniformly grown on tungsten foil. As an electrode material, the as-synthesized WSe2 exhibits remarkable electrochemical performance including excellent cycling stability, high-rate capability, and superior electrochemical activity. The WSe2 nanosheets demonstrate a high reversible specific capacity of 159.3 mAh g-1 at a current density of 5 A g-1, maintaining a near-100% Coulombic efficiency over 2400 cycles. The underlying mechanism governing electrochemical performance was further investigated using first-principles density functional theory computations. These findings underscore the potential of WSe2 nanosheets as high-performance materials for next-generation LIBs.

Sorafenib (SOR) has fast-track review status due to its dual tumor-inhibitory mechanism, but its clinical use is limited by severe side effects. This study aimed to develop a new nanocarrier to encapsulate SOR, leveraging the rise of nanomaterials in drug delivery. A coordination molecular container (CoTPE) was synthesized through the self-assembly of 4 '-(1,2,2-triphenylvinyl)-[1,1 '-biphenyl]-3,5-dicarboxylic acid as a bridging ligand with Co(II) and sulfonyl-bridged calix[4]arene. The resultant structure, comprising a cylindrical internal cavity and four bowl-like external cavities, was characterized by single-crystal X-ray diffraction. Spectroscopic titration further validated the ability of the molecular container to encapsulate SOR, exhibiting pH-sensitive, controlled-release behavior. Subsequent in vitro and in vivo assessments revealed that CoTPE displayed favorable biocompatibility and enhanced tumor-suppressing efficacy relative to free SOR. This study not only introduces a promising strategy for the targeted delivery of SOR in liver cancer therapy but also expands the utility of innovative supramolecular materials and molecular containers in biomedical and pharmaceutical applications.

Arthritis, characterized by inflammatory lesions in the joints and surrounding tissues, significantly affects patients' mobility, functional capacity, and overall quality of life. Key pathological features in the progression of arthritis include synovitis and subchondral bone resorption. A critical component of effective arthritis management is the inhibition of synovial macrophages-mediated inflammation and osteoclasts (OCs)-driven bone resorption. Herein, we present the development of a novel supramolecular coordination container, MgNSPH, which possesses inherent reactive oxygen species (ROS)-scavenging and bioimaging capabilities. Based upon the elevated expression levels of Chi3l1 and CD44 in inflamed synovial tissues, the Chi3l1 inhibitor K284-6111 (K284) was encapsulated within the cavity of MgNSPH for synergistic anti-inflammation and anti-ROS, while hyaluronic acid (HA) was incorporated as a targeting moiety into the outer layer of K284@MgNSPH, resulting in the formation of a pioneering supramolecular nanotherapeutic system, K284@MgNSPH-HA. K284@MgNSPH-HA demonstrated significant capability in ROS scavenging and effectively attenuated macrophage-mediated inflammatory responses through the inhibition of the nuclear factor (NF)-kappa B and MAPK signaling pathways. Additionally, K284@MgNSPH-HA significantly inhibited receptor activator of nuclear factor-kappa B ligand (RANKL)induced OC differentiation and function. In vivo assessments revealed that K284@MgNSPH-HA exhibited prolonged retention within the inflamed temporomandibular joint (TMJ) of rat models, targeting inflammatory macrophages to mitigate synovitis, thus protecting the structural integrity of condylar cartilage and subchondral bone. Anyway, this innovative supramolecular-nano theranostic system marks the successful integration of supramolecular coordination container with nano fabrication, which holds promise for the early diagnosis and enhanced treatment of arthritis and related inflammatory diseases.

Coordination cages with well-defined nano-cavities are a particularly attractive class of synthetic supramolecular assemblies capable of catalytically mediating chemical transformations. However, examples of coordination cages with multiple intrinsically catalytic centers suitable for promoting various reactions are relatively rare. Herein, we describe a new approach to designing coordination cages that demonstrate practically useful catalytic activity for one-pot sequential reactions. Our strategy focuses on modulating the exo- and endo-cavities by introducing a pyridine-based dicarboxylate linker with an asymmetric coordination pattern. The coordination cage (Co-PYDC) provides dual active regions, including multiple exo cavities containing coordinatively labile Co(II) sites and one large endo cavity with multiple built-in μ3-H2O Brönsted acidic centers, which proved key to promoting a tandem sequence of epoxidation of olefin followed by aminolysis of epoxides. The present work provides a new paradigm for the design of multifunctional and synthetically useful supramolecular catalysts suitable for practical applications.

Lithiumu2013sulfur (Liu2013S) batteries are promising candidates for next-generation energy storage devices due to their high energy density, low cost, and environmental friendliness. However, their practical application remains limited by the polysulfide shuttle effect, sulfur volume expansion, and poor electronic conductivity of S and Li2S. In this study, titanium carbide (TiC) was grown on Ti foam using chemical vapor deposition (CVD) to construct a binder-free, highly conductive, and porous TiC-Ti three-dimensional (3D) framework sulfur host for enhancing the Liu2013S battery performance. This 3D framework combines highly porous Ti foam with the polar surface of CVD-synthesized TiC nanoflowers, enabling efficient electron and ion transport, anchoring polysulfides to mitigate the shuttle effect, and accommodating sulfur volume expansion for enhanced cycling stability. Our study demonstrated that Liu2013S batteries utilizing TiC-Ti 3D framework@S cathodes achieved a high initial discharge capacity of 1506 mAhu00B7gu22121 at 0.1 C and maintained 93.3% of their capacity after 500 cycles at 1 C, with an exceptionally low average capacity decay of 0.01% per cycle. Additionally, the TiC-Ti 3D framework@S cathodes exhibited reduced charge transfer resistance after cycling, indicating enhanced interfacial reaction kinetics and stability. These findings confirm that the CVD-synthesized TiC-Ti 3D framework can serve as an efficient binder-free sulfur host, which provides a promising material and structural strategy for high-performance Liu2013S battery design.

Coordination cages sustained by metal–ligand interactions feature polyhedral architectures and well-defined hollow structures, which have attracted significant attention in recent years due to a variety of structure-guided promising applications. Sulfonylcalix[4]arenes-based coordination cages, termed metal–organic supercontainers (MOSCs), that possess unique multi-pore architectures containing an endo cavity and multiple exo cavities, are emerging as a new family of coordination cages. The well-defined built-in multiple binding domains of MOSCs allow the efficient encapsulation of guest molecules, especially for drug delivery. Here, we critically discuss the design strategy, and, most importantly, the recent advances in research surrounding cavity-specified host–guest chemistry and biomedical applications of MOSCs.

Coordination cages with intrinsic enzyme-like activity are a class of promising catalysts for improving the efficiency of organic reactions. We present herein a viable strategy to conveniently construct multimetallic active sites into a coordination cage via self-assembly of a pre-formed sulfonylcalix[4]arene-based tetranuclear copper(II) precursor and an amino-functionalized dicarboxylate linker. The cage exhibits a “defective”, partially open cylindrical structure and features coordinatively labile dimetallic Cu(II) sites. Modulated by this unique inner cavity environment, promising catalytic activity toward selective oxidation of primary alcohols to carboxylic acids at room temperature is achieved. Mechanistic studies reveal that the coordinatively labile dimetallic Cu(II) sites can efficiently capture and activate the substrate and oxidant to catalyze the reaction, while the confined nano-cavity environment modulates substrate binding and enhances the catalytic turnover. This study provides a new approach to designing biomimetic multifunctional coordination cages and environmentally friendly supramolecular catalysts.

Rationale: Inflammatory macrophages and osteoclasts (OCs) play critical roles in joint inflammation, which feature the excessive production of reactive oxygen species (ROS), resulting in synovial inflammation and bone erosion. Scavenging ROS, especially by modulating mitochondrial metabolic activity, could be a desirable strategy for the management of inflammatory joints. This study aimed to develop a mitochondria-targeted supramolecular drug delivery system with exogenous and endogenous ROS-scavenging activities for the treatment of joint inflammation. Methods: In this study, we utilized a zinc-based metal-organic supercontainer (MOSC) as a proton sponge and electron reservoir with outstanding proton binding capacity, extracellular ROS-scavenging ability, and biocompatibility to establish an efficient supramolecular nanocarrier for endo/lysosomal escape and mitochondrial targeting. 4-Octyl itaconate (4-OI), an itaconate derivative, served as the loaded guest for the construction of a synergistic therapeutic system for inflammatory macrophages and OCs. Results: After the effective encapsulation of 4-OI, 4-OI@Zn-NH-pyr not only exhibited potent ROS-scavenging capacity, but also reduced ROS production by mediating mitochondrial respiration in inflammatory macrophages. Regarding its anti-inflammatory efficacy, 4-OI@Zn-NH-pyr ameliorated the inflammatory reaction by activating nuclear factor erythroid 2-related factor 2 (Nrf2), thus increasing the production of antioxidants, apart from the inhibition of NF-κB pathways. Additionally, receptor activator of nuclear factor-κB ligand (RANKL)-induced osteoclast differentiation and function was remarkably suppressed by 4-OI@Zn-NH-pyr. Consistent with in vitro observations, 4-OI@Zn-NH-pyr efficiently inhibited synovial inflammation and subchondral bone destruction in an acute arthritis model. Conclusion: By using MOSCs that are highly reactive to ROS as drug-loaded matrices for the first time, this study provides an avenue for the management of severe joint inflammation by designing synergistic supramolecular drug-delivery systems with subcellular targeting and ROS-scavenging capacity.

Efficient methods to sequester the radioactive iodine element are urgently needed in the nuclear and environmental industries. Nanoporous solid adsorbents based on container molecules are particularly suited for achieving iodine sequestration due to their uniquely tunable intrinsic and extrinsic porous structure. In the present work, we describe the design and synthesis of two new coordination containers based on a sulfonylcalixarene precursor and naphthalene-1,8-dicarboxylate linker and demonstrate their promising application for iodine adsorption and release. We show that, in addition to the more common C-Hmiddotmiddotmiddot pi hydrogen bonding and hydrophobic interactions, another less appreciated type of noncovalent interaction, namely, a dual Brmiddotmiddotmiddot pi binding motif, can be introduced through the modification of the dicarboxylate linker with a bromine substituent to strengthen the crystal packing and maintain the solid-state porosity of the molecular containers. These synthetic coordination containers not only exhibit an excellent adsorption capacity for iodine vapor at a solid-gas interface but also show an effective iodine capture ability from a hexane solution through a solid-liquid interface. Importantly, the adsorption of iodine by these porous molecular solids displays remarkable reversibility and recyclability, indicating their promising practical utility for iodine capture and release.

The application of a coordination container in biomedicine is hindered by single binding domains and unsatisfactory biostability and biocompatibility. Herein, we designed a sulfonylcalix[4]arene-based decahexanuclear zinc(II) coordination container employing a flexible tetracarboxylate ligand as a linker and utilized it as a novel drug delivery system. The coordination container consisting of one endo and four exo cavities provides multiple binding domains for efficient encapsulation of drug molecules as clearly revealed by systematic host-guest studies using NMR techniques of 1H NMR titration experiments and 2D NOESY and diffusion-ordered NMR spectroscopy studies. Incorporation of a flexible p-phenylene-bis(methanamino) spacer into the container via the carboxylate linker allowed a stepwise drug loading process through sequential binding at endo and exo cavities, as well as enabling pH-responsive stepwise drug release. The drug-loaded coordination container not only exhibits excellent biostability and biocompatibility but also provides encouraging therapeutic efficiency toward inflammatory macrophages as revealed by in vitro studies. The novel strategy for engineering the endo cavity of a coordination container provides a new approach to achieving controlled drug delivery and opens up new opportunities for designing novel functional supramolecular materials.

As one of the most complicated joint structures, temporomandibular joint (TMJ) is susceptible to inflammatory reaction caused by osteoarthritis, rheumatoid arthritis and so on. The treatment for TMJ inflammation is still challenging due to the rapid clearance and lack of selectivity of traditional medication. Herein, we design a novel discrete sulfonylcalix[4]arene-based magnesium(II) coordination container, MgDHIA, which features satisfactory biocompatibility, appropriate molecular size and multiple binding domains. MgDHIA is capable of selectively encapsulating rapamycin (RAPA) in the endo cavity and folic acid (FA) in the exo cavities to form the co-loaded system RAPA-FA@MgDHIA, which exhibits outstanding activated macrophages targeting, stepwise releasing and cellular uptake behaviors. For therapeutic aspect, the RAPA-FA@MgDHIA reprograms the phenotype of polarized macrophages, specifically, transforming the pro-inflammatory M1 macrophages to anti-inflammatory M2 phenotype by inhibiting NF-kB pathway. The in vivo studies also demonstrate that the RAPA-FA@MgDHIA presents higher accumulation in inflamed synovial tissues, protecting the articular cartilage and subchondral bone structures by alleviating synovial inflammation. Anyway, we first evaluate the application of coordination container-based nanomedicine in treatment of inflammatory TMJ, demonstrating that the drug and targeting agents co-loaded coordination container remarkably boosts the therapeutic efficacy of traditional medication, thus providing a promising approach for anti-inflammatory treatment in joints.

Hydrophobic ions can generate considerable interference to ion detection in a complex analyte with membrane-based ion-selective sensors, due to the hydrophobic interaction. In this paper, we demonstrate that the interference from the hydrophobic interaction to the sensors can be significantly reduced by incorporating hydrophilic polyethylene glycol (PEG) into the membrane. The sensor is a silicon nanowire field-effect transistor (SiNWFET) with its surface functionalized with an ionophore-doped mixed-matrix membrane (MMM), where the ionophore is either a commercial Na-ionophore III or a novel synthetic metal-organic supercontainer. The incorporation of PEG suppresses the partitioning of hydrophobic ions into the MMM and thus reduces their interference to the detection of target ions. This is evidenced with an improvement in selectivity for Na+ detection in the presence of interfering methylene blue (MB+) ion by more than an order of magnitude. It further enables detection of Na+ and MB+ using a SiNWFET sensor array in a multiplexed manner with controlled susceptivity to cross-interference and a greatly expanded dynamic range.

We demonstrate a highly sensitive and selective sensing platform for the electrochemical detection of Hg2+ in aqueous media. A graphene oxide (GO) and silver nanowire (AgNW) nanocomposites modified platinum (Pt) electrode has been applied to determine Hg2+ by using square-wave anodic stripping voltammetry (SWASV). The synergistic effect of graphene oxide and conductive AgNW greatly facilitates faster electron transport and sensing behavior for Hg2+. Under the optimum conditions, the sensor shows a high sensitivity of similar to 0.29 mu A/nM and a linear response in the range 1-70 nM toward Hg2+. The detection limit of the GO-AgNW nanocomposites modified electrode toward Hg2+ is similar to 0.1 nM, which is significantly less than the safety limit defined by the World Health Organization. The sensor has an excellent selective response to Hg2+ against other interfering heavy metal ions such as Pb2+, Cd2+, Cu2+, Na+, and Ag+. In addition, the sensor exhibits a high repeatability and reproducibility. The sensor is employed for the detection of Hg2+ in tap water samples with an outstanding performance, suggesting it is a very promising platform for on-site monitoring of Hg2+ in water.