Precisely constructing orbital coupling-modulated iron dinuclear site for enhanced catalytic ozonation performance.

The advancement of atomically precise dinuclear heterogeneous catalysts holds great potential in achieving efficient catalytic ozonation performance and contributes to the understanding of synergy mechanisms during reaction conditions. Herein, we demonstrate a "ship-in-a-bottle and pyrolysis" strategy that utilizes Fe2(CO)9 dinuclear-cluster to precisely construct Fe2 site, consisting of two Fe1-N3 units connected by Fe-Fe bonds and firmly bonded to N-doped carbon. Systematic characterizations and theoretical modeling reveal that the Fe-Fe coordination motif markedly reduced the devotion of the antibonding state in the Fe-O bond because of the strong orbital coupling interaction of dual Fe d-d orbitals. This facilitates O-O covalent bond cleavage of O3 and enhances binding strength with reaction intermediates (atomic oxygen species; *O and *OO), thus boosting catalytic ozonation performance. As a result, Fe dinuclear site catalyst exhibits 100% ozonation efficiency for CH3SH elimination, outperforming commercial MnO2 catalysts by 1,200-fold. This research provides insights into the atomic-level structure-activity relationship of ozonation catalysts and extends the use of dinuclear catalysts in catalytic ozonation and beyond.

MOFs Modulate Copper Trafficking in Tumor Cells for Bioorthogonal Therapy.

In situ drug synthesis using the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction has attracted considerable attention in tumor therapy because of its satisfactory effectiveness and reduced side-effects. However, the exogenous addition of copper catalysts can cause cytotoxicity and has hampered biomedical applications in vivo. Here, we design and synthesize a metal-organic framework (MOF) to mimic copper chaperone, which can selectively modulate copper trafficking for bioorthogonal synthesis with no need of exogenous addition of copper catalysts. Like copper chaperones, the prepared ZIF-8 copper chaperone mimics specifically bind copper ions through the formation of coordination bonds. Moreover, the copper is unloaded under the acidic environment due to the dissipation of the coordination interactions between metal ions and ligands. In this way, the cancer cell-targeted copper chaperone mimics can selectively transport copper ions into cells. Regulation of intracellular copper trafficking may inspire constructing bioorthogonal catalysis system with reduced metal cytotoxicity in live cells.

Ionic Current Saturation Enabled by Cation Gating Effect in Metal-Organic-Framework Membranes.

Ion transport through nanoporous two-dimensional (2D) membranes is predicted to be tunable by controlling the charging status of the membranes' planar surfaces, the behavior of which though remains to be assessed experimentally. Here we investigate ion transport through intrinsically porous membranes made of 2D metal-organic-framework layers. In the presence of certain cations, we observe a linear-to-nonlinear transition of the ionic current in response to the applied electric field, the behavior of which is analogous to the cation gating effect in the biological ion channels. Specifically, the ionic currents saturate at transmembrane voltages exceeding a few hundreds of millivolts, depending on the concentration of the gating cations. This is attributed to the binding of cations at the membranes' surfaces, tuning the charging states there and affecting the entry/exit process of translocating ions. Our work also provides 2D membranes as candidates for building nanofluidic devices with tunable transport properties.

Engineering peptide drug therapeutics through chemical conjugation and implication in clinics.

The development of peptide drugs has made tremendous progress in the past few decades because of the advancements in modification chemistry and analytical technologies. The novel-designed peptide drugs have been modified through various biochemical methods with improved diagnostic, therapeutic, and drug-delivery strategies. Researchers found it a helping hand to overcome the inherent limitations of peptides and bring continued advancements in their applications. Furthermore, the emergence of peptide-drug conjugates (PDCs)-utilizes target-oriented peptide moieties as a vehicle for cytotoxic payloads via conjugation with cleavable chemical agents, resulting in the key foundation of the new era of targeted peptide drugs. This review summarizes the various classifications of peptide drugs, suitable chemical modification strategies to improve the ADME (adsorption, distribution, metabolism, and excretion) features of peptide drugs, and recent (2015-early 2024) progress/achievements in peptide-based drug delivery systems as well as their fruitful implication in preclinical and clinical studies. Furthermore, we also summarized the brief description of other types of PDCs, including peptide-MOF conjugates and peptide-UCNP conjugates. The principal aim is to provide scattered and diversified knowledge in one place and to help researchers understand the pinching knots in the science of PDC development and progress toward a bright future of novel peptide drugs.

ZIF-8 Nanoparticle: A Valuable Tool for Improving Gene Delivery in Sperm-Mediated Gene Transfer.

Metal-organic frameworks (MOFs) are porous materials with unique characteristics that make them well-suited for drug delivery and gene therapy applications. Among the MOFs, zeolitic imidazolate framework-8 (ZIF-8) has emerged as a promising candidate for delivering exogenous DNA into cells. However, the potential of ZIF-8 as a vector for sperm-mediated gene transfer (SMGT) has not yet been thoroughly explored.This investigation aimed to explore the potential of ZIF-8 as a vector for enhancing genetic transfer and transgenesis rates by delivering exogenous DNA into sperm cells. To test this hypothesis, we employed ZIF-8 to deliver a plasmid expressing green fluorescent protein (GFP) into mouse sperm cells and evaluated the efficiency of DNA uptake. Our findings demonstrate that ZIF-8 can efficiently load and deliver exogenous DNA into mouse sperm cells, increasing GFP expression in vitro. These results suggest that ZIF-8 is a valuable tool for enhancing genetic transfer in SMGT, with important implications for developing genetically modified animals for research and commercial purposes. Additionally, our study highlights the potential of ZIF-8 as a novel class of vectors for gene delivery in reproductive biology.Overall, our study provides a foundation for further research into using ZIF-8 and other MOFs as gene delivery systems in reproductive biology and underscores the potential of these materials as promising vectors for gene therapy and drug delivery.

Engineering Platelet Membrane-Coated Bimetallic MOFs as Biodegradable Nanozymes for Efficient Antibacterial Therapy.

Nanocatalytic-based wound therapeutics present a promising strategy for generating reactive oxygen species (ROS) to antipathogen to promote wound healing. However, the full clinical potential of these nanocatalysts is limited by their low reactivity, limited targeting ability, and poor biodegradability in the wound microenvironment. Herein, a bio-organic nanozyme is developed by encapsulating a FeZn-based bimetallic organic framework (MOF) (MIL-88B-Fe/Zn) in platelet membranes (PM@MIL-88B-Fe/Zn) for antimicrobial activity during wound healing. The introduction of Zn in MIL-88B-Fe/Zn modulates the electronic structure of Fe thus accelerating the catalytic kinetics of its peroxidase-like activity to catalytically generate powerful ROS. The platelet membrane coating of MOF innovatively enhanced the interaction between nanoparticles and the biological environment, further developing bacterial-targeted therapy with excellent antibacterial activity against both gram-positive and gram-negative bacteria. Furthermore, this nanozyme markedly suppressed the levels of inflammatory cytokines and promoted angiogenesis in vivo to effectively treat skin surface wounds and accelerate wound healing. PM@MIL-88B-Fe/Zn exhibited superior biodegradability, favourable metabolism and non-toxic accumulation, eliminating concerns regarding side effects from long-term exposure. The high catalytic reactivity, excellent targeting features, and biodegradability of these nanoenzymes developed in this study provide useful insights into the design and synthesis of nanocatalysts/nanozymes for practical biomedical applications.

Bioactive Metal-Organic Frameworks as a Distinctive Platform to Diagnosis and Treat Vascular Diseases.

Vascular diseases (VDs) pose the leading threat worldwide due to high morbidity and mortality. The detection of VDs is commonly dependent on individual signs, which limits the accuracy and timeliness of therapies, especially for asymptomatic patients in clinical management. Therefore, more effective early diagnosis and lesion-targeted treatments remain a pressing clinical need. Metal-organic frameworks (MOFs) are porous crystalline materials formed by the coordination of inorganic metal ions and organic ligands. Due to their unique high specific surface area, structural flexibility, and functional versatility, MOFs are recognized as highly promising candidates for diagnostic and therapeutic applications in the field of VDs. In this review, the potential of MOFs to act as biosensors, contrast agents, artificial nanozymes, and multifunctional therapeutic agents in the diagnosis and treatment of VDs from the clinical perspective, highlighting the integration between clinical methods with MOFs is generalized. At the same time, multidisciplinary cooperation from chemistry, physics, biology, and medicine to promote the substantial commercial transformation of MOFs in tackling VDs is called for.

Co/C Nanocomposites with Tunable Condensed States Induced by Conformation-Mediated Strategy for Electromagnetic Wave Absorption.

The strategic regulation of condensed state structures in multicomponent nanomaterials has emerged as an effective approach for achieving controllable electromagnetic (EM) properties. Herein, a novel conformation-mediated strategy is proposed to manipulate the condensed states of Co and C, as well as their interaction. The conformation of polyvinylpyrrolidone molecules is adjusted using a gradient methanol/water ratio, whereby the coordination dynamic equilibrium effectively governs the deposition of metal-organic framework precursors. This process ultimately influences the combined impact of derived Co and C in the resulting Co/C nanocomposites post-pyrolysis. The experimental results show that the condensed state structure of Co/C nanocomposites transitions from agglomerate state → to biphasic compact state → to loose packing state. Benefiting from the tunable collaboration between interfacial polarization and defects polarization, and the appropriate electrical conductivity, the diphasic compact state of Co/C nanocomposites achieves an effective absorbing bandwidth of 7.12 GHz (2.1 mm) and minimum reflection loss of -32.8 dB. This study highlights the significance of condensed state manipulation in comprehensively regulating the EM wave absorption characteristics of carbon-based magnetic metal nanocomposites, encompassing factors such as conductivity loss, magnetic loss, defect polarization, and interface polarization.

Direct Electrodeposition of Electrically Conducting Ni3(HITP)2 MOF Nanostructures for Micro-Supercapacitor Integration.

Micro-supercapacitors emerge as an important electrical energy storage technology expected to play a critical role in the large-scale deployment of autonomous microdevices for health, sensing, monitoring, and other IoT applications. Electrochemical double-layer capacitive storage requires a combination of high surface area and high electronic conductivity, with these being attained only in porous or nanostructured carbons, and recently found also in conducting metal-organic frameworks (MOFs). However, techniques for conformal deposition at micro- and nanoscale of these materials are complex, costly, and hard to upscale. Herein, the study reports direct, one step non-sacrificial anodic electrochemical deposition of Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2 - Ni3(HITP)2, a porous and electrically conducting MOF. Employing this strategy enables the growth of Ni3(HITP)2 films on a variety of 2D substrates as well as on 3D nanostructured substrates to form Ni3(HITP)2 nanotubes and Pt@ Ni3(HITP)2 core-shell nanowires. Based on the optimal electrodeposition protocols, Ni3(HITP)2 films interdigitated micro-supercapacitors are fabricated and tested as a proof of concept.

High-Valence Metal Doping Induced Lattice Expansion for M-FeNi LDH toward Enhanced Urea Oxidation Electrocatalytic Activities.

The precise design of low-cost, efficient, and definite electrocatalysts is the key to sustainable renewable energy. The urea oxidation reaction (UOR) offers a promising alternative to the oxygen evolution reaction for energy-saving hydrogen generation. In this study, by tuning the lattice expansion, a series of M-FeNi layered double hydroxides (M-FeNi LDHs, M: Mo, Mn, V) with excellent UOR performance are synthesized. The hydrolytic transformation of Fe-MIL-88A is assisted by urea, Ni2+ and high-valence metals, to form a hollow M-FeNi LDH. Owing to the large atomic radius of the high-valence metal, lattice expansion is induced, and the electronic structure of the FeNi-LDH is regulated. Doping with high-valence metal is more favorable for the formation of the high-valence active species, NiOOH, for the UOR. Moreover, the hollow spindle structure promoted mass transport. Thus, the optimal Mo-FeNi LDH showed outstanding UOR electrocatalytic activity, with 1.32 V at 10 mA cm-2 . Remarkably, the Pt/C||Mo-FeNi LDH catalyst required a cell voltage of 1.38 V at 10 mA·cm-2 in urea-assisted water electrolysis. This study suggests a new direction for constructing nanostructures and modulating electronic structures, which is expected to ultimately lead to the development of a class of auxiliary electrocatalysts.

Tailoring the Hydrophobic Interface of Core-Shell HKUST-1@Cu2O Nanocomposites for Efficiently Selective CO2 Electroreduction.

The electrochemical reduction of carbon dioxide (CO2) to ethylene creates a carbon-neutral approach to converting carbon dioxide into intermittent renewable electricity. Exploring efficient electrocatalysts with potentially high ethylene selectivity is extremely desirable, but still challenging. In this report, a laboratory-designed catalyst HKUST-1@Cu2O/PTFE-1 is prepared, in which the high specific surface area of the composites with improved CO2 adsorption and the abundance of active sites contribute to the increased electrocatalytic activity. Furthermore, the hydrophobic interface constructed by the hydrophobic material polytetrafluoroethylene (PTFE) effectively inhibits the occurrence of hydrogen evolution reactions, providing a significant improvement in the efficiency of CO2 electroreduction. The distinctive structures result in the remarkable hydrocarbon fuels generation with high Faraday efficiency (FE) of 67.41%, particularly for ethylene with FE of 46.08% (-1.0 V vs RHE). The superior performance of the catalyst is verified by DFT calculation with lower Gibbs free energy of the intermediate interactions with improved proton migration and selectivity to emerge the polycarbon（C2+） product. In this work, a promising and effective strategy is presented to configure MOF-based materials with tailored hydrophobic interface, high adsorption selectivity and more exposed active sites for enhancing the efficiency of the electroreduction of CO2 to C2+ products with high added value.

Recent Advances in Hierarchical Porous Engineering of MOFs and Their Derived Materials for Catalytic and Battery: Methods and Application.

Hierarchical porous materials have attracted the attention of researchers due to their enormous specific surface area, maximized active site utilization efficiency, and unique structure and properties. In this context, metal-organic frameworks (MOFs) offer a unique mix of properties that make them particularly appealing as tunable porous substrates containing highly active sites. This review focuses on recent advances in the types and synthetic strategies of hierarchical porous MOFs and their derived materials. Furthermore, it highlights the relationship between the mass diffusion and transport of hierarchical porous structures and the pore size with examples and simulations, while identifying their potential and limitations. On this basis, how the synthesis conditions affect the structure and electrochemical properties of MOFs based hierarchical porous materials with different structures is discussed, highlighting the prospects and challenges for the synthetization, as well as further scientific research and practical applications. Finally, some insights into current research and future design ideas for advanced MOFs based hierarchical porous materials are presented.

Defect-Rich Functional HfO2-x for Highly Reversible Zn Metal Anode.

Interface engineering attracted tremendous attention owing to its remarkable ability to impede dendrite growth and side reactions in aqueous zinc-ion batteries. Artificial interface layers composed of crystalline materials have been extensively employed to stabilize the Zn anode. However, the diffusion kinetics of Zn2+ in highly crystalline materials are hindered by steric effects from the lattice, thereby limiting the high-rate performance of the cell. Here, defect-rich HfO2-x polycrystals derived from metal-organic frameworks (MOFs) (D-HfO2-x) are developed to enhance the Zn deposition behavior. The discrepancy of dielectric constants between metallic Zn and HfO2 enables the building of an electrostatic shielding layer for uniform Zn deposition. More importantly, the oxygen vacancies in D-HfO2-x provide abundant active sites for Zn2+ adsorption, accelerating the kinetics of Zn2+ migration, which contributes to the preferential exposure of the Zn (002) plane during plating. Consequently, the D-HfO2-x-modified Zn anode delivers ultrastable durability of over 5000 h at 1 mA cm-2 and a low voltage hysteresis of 30 mV. The constructed defective coating provides a guarantee for the stable operation of Zn anodes, and the innovative approach of defective engineering also offers new ideas for the protection of other energy storage devices.

Nanoscale Metal-Organic Frameworks as a Photoluminescent Platform for Bioimaging and Biosensing Applications.

The tracking of nanomedicines in their concentration and location inside living systems has a pivotal effect on the understanding of the biological processes, early-stage diagnosis, and therapeutic monitoring of diseases. Nanoscale metal-organic frameworks (nano MOFs) possess high surface areas, definite structure, regulated optical properties, rich functionalized sites, and good biocompatibility that allow them to excel in a wide range of biomedical applications. Controllable syntheses and functionalization endow nano MOFs with better properties as imaging agents and sensing units for the diagnosis and treatment of diseases. This minireview summarizes the tunable synthesis strategies of nano MOFs with controllable size, shape, and regulated luminescent performance, and pinpoints their recent advanced applications as optical elements in bioimaging and biosensing. The current limitations and future development directions of nano MOF-contained materials in bioimaging and biosensing applications are also discussed, aiming to expand the biological applications of nano MOF-based nanomedicine and facilitate their production or clinical translation.

Multifunctional MoCx Hybrid Polyimide Aerogel with Modified Porous Defect Engineering for Highly Efficient Electromagnetic Wave Absorption.

Traditional electromagnetic absorbing materials (EWAMs) are usually single functions and can easily affect their performance in diverse application scenarios. Effective integration of EWAMs into multiple function components is a valuable strategy to achieve maximum absorption and multifunction performance while maintaining their indispensable physical and chemical properties. In this work, the polyoxometalates (POMs) serving as "guests" are embedded within the Co-MOFs to construct 3d/4d-bimetallic based crystalline precursors of dielectric/magnetic synergistic system. The proper pyrolysis temperature induced the homogeneously distributed metallic Co and MoCx hetero-units into carbon matrix with modified porous defect engineering to enhance electromagnetic wave (EW). Owing to the brilliant synergistic effect of polarization, magnetic loss, and impedance matching, the superior RLmin of -47.72 dB at 11.76 GHz at the thickness of 2.0 mm and a wide adequate absorption bandwidth (EAB) of 4.58 GHz (7.44-12.02 GHz) covered the whole X-band at the thickness of 2.5 mm for η-MoC/Co@NC-800 are observed. More importantly, the resulting MoCx hybrid polyimide (MCP) aerogel exhibits desirable properties such as structural robustness, nonflammability, excellent thermal insulation, and self-cleaning capabilities that are comparable to those of commercially available products. This work offers inspiration and strategy for creating multipurpose microwave absorbers with intricate structural designs.

Optimization of Carbon-Defect Engineering to Boost Catalytic Ozonation Efficiency of Single Fe─N4 Coordination Motif.

Carbon-defect engineering in single-atom metal-nitrogen-carbon (M─N─C) catalysts by straightforward and robust strategy, enhancing their catalytic activity for volatile organic compounds, and uncovering the carbon vacancy-catalytic activity relationship are meaningful but challenging. In this study, an iron-nitrogen-carbon (Fe─N─C) catalyst is intentionally designed through a carbon-thermal-diffusion strategy, exposing extensively the carbon-defective Fe─N4 sites within a micro-mesoporous carbon matrix. The optimization of Fe─N4 sites results in exceptional catalytic ozonation efficiency, surpassing that of intact Fe─N4 sites and commercial MnO2 by 10 and 312 times, respectively. Theoretical calculations and experimental data demonstrated that carbon-defect engineering induces selective cleavage of C─N bond neighboring the Fe─N4 motif. This induces an increase in non-uniform charges and Fermi density, leading to elevated energy levels at the center of Fe d-band. Compared to the intact atomic configuration, carbon-defective Fe─N4 site is more activated to strengthen the interaction with O3 and weaken the O─O bond, thereby reducing the barriers for highly active surface atomic oxygen (*O/*OO), ultimately achieving efficient oxidation of CH3SH and its intermediates. This research not only offers a viable approach to enhance the catalytic ozonation activity of M─N─C but also advances the fundamental comprehension of how periphery carbon environment influences the characteristics and efficacy of M─N4 sites.

MOFs and MOF-Based Composites as Next-Generation Materials for Wound Healing and Dressings.

In recent years, there has been growing interest in developing innovative materials and therapeutic strategies to enhance wound healing outcomes, especially for chronic wounds and antimicrobial resistance. Metal-organic frameworks (MOFs) represent a promising class of materials for next-generation wound healing and dressings. Their high surface area, pore structures, stimuli-responsiveness, antibacterial properties, biocompatibility, and potential for combination therapies make them suitable for complex wound care challenges. MOF-based composites promote cell proliferation, angiogenesis, and matrix synthesis, acting as carriers for bioactive molecules and promoting tissue regeneration. They also have stimuli-responsivity, enabling photothermal therapies for skin cancer and infections. Herein, a critical analysis of the current state of research on MOFs and MOF-based composites for wound healing and dressings is provided, offering valuable insights into the potential applications, challenges, and future directions in this field. This literature review has targeted the multifunctionality nature of MOFs in wound-disease therapy and healing from different aspects and discussed the most recent advancements made in the field. In this context, the potential reader will find how the MOFs contributed to this field to yield more effective, functional, and innovative dressings and how they lead to the next generation of biomaterials for skin therapy and regeneration.

Strategies for the Preparation of Single-Atom Catalysts Using Low-Dimensional Metal-Organic Frameworks.

As single-atom catalysts are important energy materials, their preparation and synthesis methods have become particularly important. The unique structures of low-dimensional metal-organic frameworks and their derivatives provide various strategies for preparing single-atom catalysts. This paper summarizes various strategies for the preparation of single-atom catalysts based on low-dimensional metal-organic frameworks and their derivatives.

Universal Strategy for Metal-Organic Framework Growth: From Cascading-Functional Films to MOF-on-MOFs.

Transformation of metal-organic framework (MOF) particles into thin films is urgently needed for the persistent development of well-applicable devices, and recently emerging functional-integrated hybrid frameworks. Although some flexible polymers and exclusive modification approaches have been proposed, the additive-free and widely applicable strategy has not been reported, hampering the deep investigation of the structure-performance relationship. A universal strategy for the in situ growth of large-area and continuous MOF films with controllable microstructures is introduced, through the modification of multi-scale and multi-structure substrates with poly(4-vinylpyridine) as the anchor to capture metal ions via Coulomb attraction. Based on the clarified structure-adsorption-separation mechanisms, the customized devices fabricated by in situ growth can achieve highly selective adsorption and excellently synergetic separation of various industrially relevant isomers. In addition, this strategy is also feasible for the construction of MOF-on-MOFs with varied lattice parameters. This strategy is easy to implement and will be widely applicable to the surface growth of diverse MOFs on desired substrates, and provides a new concept for developing hybrid MOFs integrating with customized functionalities.

Constructing Metal-Organic Framework Films with Adjustable Electronic Properties on Hematite Photoanode for Boosting Photogenerated Carrier Transport.

Hematite (α-Fe2O3) has become a research hotspot in the field of photoelectrochemical water splitting (PEC-WS), but the low photogenerated carrier separation efficiency limits further application. The electronic structure regulation, such as element doping and organic functional groups with different electrical properties, is applied to alleviate the problems of poor electrical conductivity, interface defects, and band mismatch. Herein, α-Fe2O3 photoanodes are modified to regulate their electric structures and improve photogenerated carrier transport by the bimetallic metal-organic frameworks (MOFs), which are constructed with Fe/Ni and terephthalate (BDC) with 2-substitution of different organic functional groups (─H, ─Br, ─NO2 and ─NH2). The α-Fe2O3 photoanode loaded with FeNi-NH2BDC MOF catalyst exhibits the optimal photocurrent density (2 mA cm-2) at 1.23 VRHE, which is 2.33 times that of the pure α-Fe2O3 photoanode. The detailed PEC analyses demonstrate that the bimetallic synergistic effect between Fe and Ni can improve the conductivity and inhibit the photogenerated carrier recombination of α-Fe2O3 photoanodes. The ─NH2 group as an electron-donor group can effectively regulate the electron distribution and band structure of α-Fe2O3 photoanodes to prolong the lifetime of photogenerated holes, which facilitates photogenerated carrier transport and further enhances the PEC-WS performance of α-Fe2O3 photoanode.