Ultrasound-responsive nanocarriers for cancer therapy: Physiochemical features-directed design.

Photoelectrocatalytic (PEC) hydrogen production technology combines the advantages of photocatalysis and electrocatalysis and utilizes solar energy to drive water splitting, which is a technology for sustainable energy systems. However, its low photocatalytic water splitting efficiency results in relatively small hydrogen production. And the cost-effectiveness of PEC water splitting technology and the overall solar energy conversion efficiency to hydrogen remains a great challenge. Metal-organic frameworks (MOFs) are porous materials created through the coordination of metal ions or clusters with organic bridging ligands via ligand bonds. They offer high specific surface areas, abundant metal active sites, large pore volumes, and customizable structures and compositions, making them highly favorable for applications in photoelectrocatalysis. This review discusses the advancements in photoelectrocatalytic hydrogen production technology using metal-organic frameworks (MOFs) and derivatives. It covers the principles of photoelectrocatalysis, preparation methods for MOF catalysts and strategies for performance enhancement. These strategies include improving light absorption, enhancing carrier separation efficiency, and ensuring stability. The paper also discusses the current challenges and future directions of photoelectrocatalytic water splitting technology. Overall, this review offers a thorough theoretical framework and practical insights for researchers in this field.

Recent advancements in metal-organic frameworks (MOFs) have transformed the field of bone disease treatment by offering multifunctional platforms that integrate targeted drug delivery, enhanced osteogenesis, and antibacterial properties within a single material system. This review categorizes contemporary MOFs based on their metal constituents, such as zinc, magnesium, zirconium, cobalt, calcium, iron, copper, titanium, and rare earth metals, emphasizing their distinct physicochemical properties and unique biological functionalities. Unlike traditional biomaterials, MOFs provide highly tunable pore architectures and exceptional surface areas for efficient drug encapsulation and controlled release, facilitating localized therapeutic effects with minimal invasiveness. Cutting-edge developments include one-pot synthesis methods that enable the uniform distribution of therapeutic agents and sustained release profiles, significantly improving clinical applicability. This perspective highlights the synergistic effects of MOFs combined with scaffolds, hydrogels, and implants, which promote cellular proliferation, osteogenic differentiation, and angiogenesis, thus addressing critical challenges in bone regeneration. Moreover, emerging insights into metal ion-specific mechanisms such as calcium signaling in osteogenesis, zinc-mediated angiogenesis, and the antibacterial role of copper and rare earth elements underscore the strategic design of MOFs tailored to complex bone pathologies, including osteoporosis, infections, and osteosarcoma. This comprehensive overview not only maps recent progress but also delineates future research directions to optimize MOF functionality and expedite its translation into clinical bone therapies.

With the rapid progression of cutting-edge technologies, the demand for scintillator performance has become increasingly stringent, requiring enhancements across multiple dimensions, such as radioluminescence intensity, flexibility, and stability. Metal-organic frameworks (MOFs) have emerged as a promising class of materials capable of addressing these challenges through their tunable structures and their hybrid organic-inorganic nature. Here, we report the design of a thorium-based MOF scintillator, Th-TCBPE, constructed from high-atomic-number thorium nodes, and an aggregation-induced emission (AIE)-active linker (H4TCBPE). The rigid framework effectively suppresses nonradiative decay pathways of the AIE ligand, thereby affording an exceptional photoluminescence quantum yield (PLQY) of 90.83%, far surpassing that of the free ligand (56.78%). Under X-ray excitation, Th-TCBPE achieves a remarkably low detection limit of 3.46 μGy s-1, indicative of the outstanding sensitivity to low-dose radiation. Moreover, incorporation of Th-TCBPE into a flexible poly(dimethylsiloxane) (PDMS) matrix yielded composite films capable of high-fidelity X-ray imaging with a spatial resolution of 14.91 lp mm-1. These results underscore the promise of heavy-metal-based MOFs as efficient, multifunctional scintillators, opening new avenues for next-generation radiation detection and high-resolution imaging technologies.

Metal-organic frameworks (MOFs) are promising materials for hydrogen storage due to their high specific surface area and structural tunability. In this study, we provide the first demonstration of enhanced hydrogen storage performance in a CuBTC (also known as HKUST-1) MOF by incorporating nickel and magnesium through a combination of in situ and postmodification solvent-free mechanochemical ball milling. A comprehensive combination of structural and adsorption-desorption characterization is employed to examine and understand the impact of Ni2+ and Mg2+ divalent metal ions through in situ and postmodification methods. In general, the post-Ni-modification method achieved higher hydrogen storage capacities than in situ-Ni-modification routes. The post-Ni-modified CuBTC with 30 min milling time exhibited the highest hydrogen storage capacity of 4.2 wt % at 20 bar and 77 K, which is 31% higher than the pristine CuBTC. The substitution of Cu2+ by Ni2+ during the postmodification process increased the active metal sites and Cu+ content, thus contributing to enhanced hydrogen storage capacity. Our findings indicate that modification via a solvent-free mechanochemical route is an effective novel strategy for improving the hydrogen storage performance of MOF materials.

The functionalization of metal-organic frameworks (MOFs) enables fluorescence sensing and proton conduction, making them crucial in the fields of environmental monitoring and fuel cells. In this study, a heterometallic MOF of {[EuAg(TDA)2(H2O)]·H2O}n (1) was successfully constructed via a hydrothermal method using a thiodiglycolic acid (H2TDA) ligand and Ag+/Eu3+ ions as metal centers. The structural characterization confirmed that 1 was a three-dimensional framework and exhibited good chemical stability. The fluorescence sensing experiments showed that 1 could be used as a fluorescence sensor for identifying 2-methylhippuric acid (2-MHA) with a detection limit as low as 16.6 nM, featuring rapidity, sensitivity, anti-interference, and good recycling performance, and its potential sensing mechanism had further been analyzed. Additionally, the electrical conductivity of 1 was 1.27 × 10-3 S cm-1 at 98% relative humidity and 333 K, indicating its potential as a proton conductive material. Hence, this multifunctional heterometallic MOF demonstrates significant application potential in both optical sensors and proton conductors.

Two-dimensional metal-organic nanosheets (MONs) combine the topological and chemical versatility of metal-organic frameworks (MOFs) with the advantages of 2D materials, yet their top-down synthesis remains limited mainly to systems with labile coordination bonds. Here, we report a top-down strategy to access MONs from robust 3D MOFs via in-plane covalent bond excision using clip-off chemistry. This approach enables formation of crystalline, porous 2D layers from otherwise nonexfoliable 3D Zr-polycarboxylate frameworks, expanding the scope of accessible MON architectures. Compared to the parent MOF, the resulting MONs exhibit enhanced catalytic performance in esterification reactions, due to the improved exposure of outer active sites.

Inhibition of cyclin-dependent kinases (CDKs) offers a promising approach for selective cancer therapy by arresting aberrant cell proliferation and inducing tumor cell senescence. However, the limited efficacy and acquired resistance resulting from primarily cytostatic rather than cytotoxic effects have hindered broader clinical applications. To overcome these limitations, we propose a senescence-primed ferroptosis strategy using a metal-organic framework (MOF)-based nanoplatform (ZPG) that codelivers CDK4/6 inhibitor (palbociclib) and ferroptosis inducer (gallium ions, Ga3+) to enhance antitumor efficacy. ZPG exhibited excellent physiological stability, improved cellular uptake, and controlled drug release. In oral squamous cell carcinoma (OSCC) cells with CDK4/6 hyperactivity, palbociclib selectively blocks cell-cycle progression and induces robust senescence, leading to downregulation of antiferroptosis factors (GPX4 and GSH) and upregulation of pro-ferroptosis factors (ACSL4 and Fe2+ accumulation). Such redox reprogramming compromises cellular antioxidant defenses and promotes lipid peroxidation, thereby sensitizing senescent cells to ferroptosis. Meanwhile, Ga3+ mimics Fe3+ in protein binding and disrupts iron metabolism, further amplifying ferroptotic stress and promoting selective ferroptosis in senescent tumor cells. Leveraging ZPG for the codelivery of therapeutic agents, the synergistic mechanism resulted in markedly enhanced antitumor efficacy both in vitro and in vivo, with minimal off-target toxicity. Collectively, the ZPG-enabled senescence-primed ferroptosis strategy provides a promising and mechanistically rational approach for improving cancer therapy.

Urea is an essential nitrogen fertilizer and chemical, yet its conventional synthesis relies on high temperature and pressure, with high energy consumption and carbon dioxide (CO2)emissions. Electrochemical routes that couple CO2 reduction with waste nitrogen (N)sources offer a more sustainable alternative, but performance hinges on catalyst design. Copper (Cu)-based catalysts are promising because they lower activation barriers for CO2 and nitrate (NO3 -) reduction and can be tuned by alloying, grain-boundary engineering, and coordination regulation. Modified Cu catalysts, including atoms, nanoparticles, bulk metal, and metal-organic frameworks, with tailored electronic structures and lower energy barriers for key intermediates, exhibit good catalytic performance in terms of selectivity, yield rate, and applied potential. Nonetheless, critical challenges remain in resolving reaction mechanisms, establishing structure-activity relationships, and achieving practical performance. This review provides the first comprehensive analysis of Cu-based catalysts for electrochemical urea synthesis from CO2 and waste N nitrogen sources, and evaluates how catalyst structure, electrolytes, and operating conditions govern activity and selectivity, offering guidance for future design and application of Cu-based catalysts in electrochemical urea synthesis.

Separation of propylene (C3H6) from the propylene/propane (C3H8) mixture, one of the most significant while daunting industrial separation challenges, is primarily through traditional energy-intensive cryogenic distillation. Herein, we leverage pore engineering in pillared metal-organic frameworks (MOFs) (CPL-1, coordination pillared layer, L = pyrazine) to reinforce C3H6/C3H8 separation. The MOF-embedded functional group (CPL-1-CH3, L = methylpyrazine) is suitable for sieving propylene from propane. Particularly, compared to CPL-1, CPL-1-CH3 exhibits a larger C3H6/C3H8 uptake ratio, C3H6/C3H8 adsorption selectivity, and stronger binding affinity for C3H6, as evidenced by single component adsorption isotherms and the heat of adsorption calculations. The in-depth molecular study unveils multiple supramolecular interactions that favor C3H6 over C3H8. Breakthrough experiments prove that CPL-1-CH3 could efficiently separate the C3H6/C3H8 mixture with different ratios. With its impressive adsorption difference, green synthesis method, and cost-effective production, CPL-1-CH3 holds prospective for alkene/alkane separation. This study provides deep insights to construct and develop high-powered MOF materials to address intricate chemical separation challenges.

Designing efficient and durable electrocatalysts for alkaline hydrogen evolution reaction (HER) is pivotal to a sustainable hydrogen economy. Here, we embed ultrafine RuIr alloy nanoparticles in N-doped porous carbon nanofibers (NCNFs) by electrospinning energetic metal-organic framework (MOF) precursors followed by pyrolysis. The resulting RuIr@NCNFs exhibit an overpotential as low as 22 mV at 10 mA cm-2 in 1.0 M KOH, surpassing commercial Pt/C, and exhibit negligible activity decay over 12 h of continuous operation. Combined density functional theory and spectroscopy indicate Ir → Ru charge redistribution that optimizes ΔGH * and facilitates water dissociation (Volmer), thereby accelerating the overall alkaline HER kinetics. Meanwhile, Ir incorporation mitigates Ru oxidation, enhancing long-term durability. Additionally, the N-doped porous carbon scaffold enhances electronic conductivity and mass transport, further boosting performance. This work highlights how bimetallic synergy coupled with MOF-derived carbon architectures enables highly active and robust alkaline HER catalysts with technologically relevant durability.

Indoor carbon dioxide (CO2) levels in enclosed spaces frequently exceed the recommended limit of 1000 ppm, creating a strong demand for sorbents that can efficiently capture dilute CO2. Amine-functionalized metal-organic frameworks (MOFs) are promising in this regard due to their strong CO2 affinity, but their long-term stability is compromised by competitive water binding and amine loss. In this work, Mg2(hob) [hob4- = 5,5'-(hydrazine-1,2-diylidenebis(methanylylidene))bis(2-oxidobenzoate)] was employed as a platform and functionalized with propylene-linked diamines, which offer higher thermal stability and reduced volatility under humid conditions compared to ethylene-linked analogues. Among the series, Mg2(hob) functionalized with N-methyl-1,3-propanediamine (mpn-MOF) showed the highest CO2 uptake (10.3 wt % at 1000 ppm and 25 °C), together with a pronounced low-pressure cooperative adsorption step. To further improve water resistance and enable practical shaping, Mg2(hob) was blended with poly(vinylidene fluoride) (PVDF) to fabricate bead-shaped composites containing 15, 25, and 35 wt % PVDF, followed by postsynthetic mpn functionalization. Notably, mpn-MOF@PVDF25 retained most of its CO2 uptake after 15 days at 40% relative humidity. This demonstrates a practical approach that combines propylene-linked diamine functionalization with hydrophobic polymer shaping to achieve long-term indoor CO2 capture.

Efficient oxygen reduction reaction (ORR) catalysts are pivotal for advancing clean energy technologies, such as fuel cells and metal-air batteries. Metalloporphyrins and metallocorroles, inspired by biological systems, represent promising molecular catalysts for the ORR due to their tunable structures and redox properties. This review systematically explores recent progress made in developing metalloporphyrin- and metallocorrole-based catalysts for the ORR, spanning from fundamental molecular design to advanced material engineering. We first introduce the fundamentals of the ORR and its significance. The discussion then delves into molecular catalysis, covering both homogeneous and heterogeneous catalytic systems. For heterogeneous systems, in addition to directly loading molecular catalysts on electrode materials through physical adsorption, we discuss covalent grafting of molecular catalysts on carbon supports (e.g., carbon nanotubes, graphene, and carbon black) and other support materials (e.g., metal oxides and gold electrodes). Moreover, the other focus of this review is placed on elucidating structure-property relationships, particularly on analyzing the effect of substituents, trans axial ligands, proton relay groups, electrostatic effects, and binuclear structures on the ORR mechanism and performance. Furthermore, the integration of these molecular catalysts into structured porous materials, including metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), and porous organic polymers (POPs), is discussed, highlighting how material design enhances catalytic activity, stability, and electron/proton transport. Finally, this review summarizes key achievements, identifies current challenges, and offers perspectives on future research directions for developing next-generation, high-performance ORR catalysts based on metalloporphyrins and metallocorroles. This work aims to provide valuable insights for the rational design of efficient and durable metalloporphyrin- and metallocorrole-based ORR catalysts and for the development of molecule-based functional materials for the future application of molecular electrocatalysis.

Conductive metal-organic frameworks (c-MOFs), composed of metal nodes and redox-active ligands, have attracted growing interest due to the coexistence of porosity and charge transport. Notably, their electrical performance is closely related to the packing and ligand oxidation state within the framework, which has rarely been explored. Typical divalent metal nodes favor saturated intralayer square-planar coordination to ligands in a single oxidation state, thereby predetermining the framework topology. Here, we report a packing and topology control strategy, achieved by tuning the ligand oxidation state and grounded in lanthanides (e.g., Gd) versatile coordination chemistry. Diffuse reflectance spectroscopy and single-crystal transport measurements reveal that, at low temperature, coordination of Gd3+ with 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) in a lower mixed oxidation state (-4 and -5) yields a more ordered porous packing (Gd1.5HHTP) with superior electronic transport performance. In contrast, at elevated temperature, the ligand adopts a higher oxidation state (-3), and coordination with Gd3+ yields a densely packed structure with local coordination disorder (GdHHTP), resulting in a markedly reduced electrical conductivity. This study demonstrates ligand-oxidation-state tuning provides an effective strategy for the precise control of structural order and charge transport in c-MOFs, laying a theoretical foundation for the rational design of materials with tunable electronic properties.

Electrocatalytic water electrolysis is intrinsically limited by the slow kinetics of the oxygen evolution reaction (OER) at the anodic electrode. The development of highly active and stable catalysts for the OER is both essential and challenging. In this work, we employed porous metal-organic frameworks (MOFs) to synthesize Ru-etched MOF-derived CuCoO2 nanocrystals used as an OER catalyst. The electrochemical test results revealed that the Ru-etched CuCoO2 electrode (Ni@CCORu-3) synthesized via a 3h RuCl3-etching reaction exhibits superior catalytic activity (η10=368.4mV, Tafel slope=81.2mV dec-1) in 1.0M KOH electrolyte. After an 18h OER stability test, the Ni@CCORu-3 exhibited excellent stability with a minimal overpotential degradation of approximately 30mV. This enhancement in OER activity can be attributed to the improved specific surface area and pore structure of the MOF-derived CCORu-3 catalyst, resulting from RuCl3 etching. Furthermore, the electron distribution on the catalyst surface is modulated by Ru species loaded onto the surface. X-Ray photoelectron spectroscopy (XPS) and ultraviolet-visible-near infrared (UV-Vis-NIR) absorption spectra results revealed that RuCl3 etching increases the proportion of active sites and narrows the bandgap of CuCoO2, thereby accelerating electron transfer rates during the OER process and optimizing catalytic activity. This study may provide a novel insight into enhancing the OER performance of CuCoO2 catalysts derived from MOFs.

Metal-organic frameworks (MOFs) are promising electrocatalysts for the oxygen evolution reaction (OER), owing to their high surface areas, tailorable structures, and numerous potential active sites. Herein, we investigate the impact of flow velocity within microchannels on the crystallization rate and internal structures of Co-MOF-74 via an air-liquid segmented flow method. We demonstrate that a higher flow velocity enhances the frequency of collisions between the metal ions and the organic linkers, yielding Co-MOF-74 samples with improved crystallinity, and unique voids. Specifically, the A-Co-MOF-74-8v synthesized at high flow velocity, exhibits a smaller particle size, developed internal voids, and abundant accessible electroactive sites. These features facilitate efficient mass transport and gas release during electrolysis, leading to significantly enhanced electrocatalytic OER performance. In 1M KOH, A-Co-MOF-74-8v achieves a low overpotential of 310mV at 10mAcm-2, which is 42mV lower than that of the solvothermally synthesized counterpart (ST-Co-MOF-74). This work provides key mechanistic insights and design principles for engineering highly efficient MOF-based electrocatalysts under precisely controlled microfluidic conditions.

Conventional pesticide formulations often exhibit poor utilization efficiency, rapid photodegradation, and ecological persistence, which severely limit their field efficacy. Herein, we report a dual pH/light stimuli-responsive delivery system based on magnesium-doped zirconium-porphyrin metal-organic frameworks (MOFs) for the targeted control of rice sheath blight (Rhizoctonia solani). The trifluoroacetic acid-mediated synthesis yielded uniform PCN-222 nanoparticles (⁓140nm), while subsequent Mg2+ doping and polydopamine-assisted prochloraz (Pro) encapsulation produced functional PCN-222(Mg)@Pro@PDA architectures with high loading capacity (21.08%) and mesoporous structure. Mg-N coordination modulated the porphyrinic electronic configuration, facilitating charge separation and enhancing light-driven reactive oxygen species generation. The formulation exhibited first-order release kinetics, with accelerated liberation (74.1% after 24h) under acidic microenvironments (pH 5.0). Compared to the commercial Pro-EC, the nanoformulation achieved a 23% reduction in leaf contact angle, approximately 3.1-fold improvement in rainfastness, and 38.5% lower EC₅₀ against R. solani. Biosafety evaluations revealed higher zebrafish LC₅₀ (4.08mg L⁻¹) and > 95% rice germination, confirming reduced ecotoxicity and phytotoxicity. This study presents a sustainable nano-agrochemical strategy that integrates precise pathogen control with environmental protection, offering a promising direction for the next generation of intelligent pesticide delivery systems.

Understanding the dynamical reconstruction mechanisms of the active phase in metal-organic frameworks (MOFs) during the course of oxygen evolution reaction (OER) is central to the development of efficient and durable OER catalysts, but remains elusive till present. Herein, a spatiotemporally decoupled reconstruction strategy is pioneered to engineer a dual-metal-node MOF ([Fe3O(hbdc)3][Ni2(trz)3]) catalyst (hbdc: 2-hydroxyterephthalic acid, trz: 1,2,4-triazole), in which orbitally coupled pore-microenvironments drive time-phased kinetic reconstruction of the spatially separated Fe/Ni metal nodes, creating a foundational platform to lay bare the mechanisms governing the reconstruction processes and the cross-scale kinetic. Furthermore, a multimodal operando diagnostic platform is developed that integrates in situ X-ray absorption spectroscopy (XAS), in situ Raman spectroscopy, and real-time reaction kinetics tracing, to decipher the MOF atomic-to-mesoscale reconstruction kinetics from the Fe-centered active phase to the NiFe-centered more active phase. Crucially, the purpose-partitioned pore architecture synergizes the interplay between the Fe─Ni nodes, while the self-adaptive defects, bond relaxation, and structural regeneration collectively modulate the kinetic behavior, leading to the pronounced OER activity enhancement. This work establishes a structural dynamics tracking methodology that can integrate multi-scale characterization techniques and provide deep insights into the reconstruction mechanisms, thus filling the critical gap in understanding structure-activity relationships under operando conditions.

Herein, we report a high-performance humidity sensor based on oxygen-vacancy-rich CeLaCuO integrated with a porous Ni-BTC metal-organic framework (MOF). Compared with the single CeLaCuO and Ni-BTC sensors, the CeLaCuO/Ni-BTC composite sensor exhibits a higher response value (24% @ 32% relative humidity (RH)), lower hysteresis (0.465%RH), faster response/recovery time (24.5/47.8 s), and enhanced long-term stability (<2.6% over 60 days). Moreover, it achieves a high sensitivity of S ≈ 1.35/%RH with excellent linearity (R2 = 0.9868) across 11-63% RH and demonstrates a very low temperature cross-sensitivity between 25 and 100 °C (<0.35%). These improved performance properties are attributed to abundant oxygen vacancies (Ov) in the CeLaCuO structure that provide active sites for water adsorption and H+/H3O+ species generation for fast ionic conduction. The high-surface-area Ni-BTC framework enhances water uptake and facilitates efficient charge transfer at the oxide-MOF interface. The lab-fabricated composite sensor also demonstrates real-world applicability in a microclimate chamber for monitoring the microclimate surrounding the Fragaria ananassa (strawberry) plant, where lower humidity (<60%) can cause plant stress and reduce yield. The proposed sensor placed on the plant shows a good response for various humidity levels at 43%, 51%, and 63% RHs, respectively. Moreover, the results show that, at 63% RH, plants exhibited optimal transpiration, allowing efficient water and nutrient uptake, resulting in healthy leaf morphology with minimal stress. Thus, the proposed sensors hold strong potential as next-generation real-time humidity sensors with practical applications in agriculture, smart greenhouses, environmental monitoring, and indoor climate control.

Separation and enrichment of active components in Toddalia asiatica (L.) Lam.by carboxylated chitosan-modified magnetic metal-organic frameworks.