Covalent organic frameworks (COFs) are a class of organic crystalline porous materials discovered in the early 21st century that have become an attractive class of emerging materials due to their high crystallinity, intrinsic porosity, structural regularity, diverse functionality, design flexibility, and outstanding stability. However, many chemical and physical properties strongly depend on the presence of metal ions in materials for advanced applications, but metal-free COFs do not have these properties and are therefore excluded from such applications. Metalated COFs formed by combining COFs with metal ions, while retaining the advantages of COFs, have additional intriguing properties and applications, and have attracted considerable attention over the past decade. This review presents all aspects of metalated COFs, from synthetic strategies to various applications, in the hope of promoting the continued development of this young field.

Metalated covalent organic frameworks: from synthetic strategies to diverse applications.

Covalent organic frameworks (COFs), as meticulously designed porous crystalline materials, have garnered significant interdisciplinary attention. Notably, extensive efforts have been directed towards creating fluorescent COFs by strategically integrating fluorophores, optimized conjugated structures, and exploring diverse topologies, utilizing luminescent mechanisms like aggregation-induced emission and intramolecular charge transfer. With stable covalent linkages, large specific surface areas, and abundant active sites, fluorescent COFs stand out as excellent candidates for sensing application. This review presents a thorough overview of chemical and biosensors based on fluorescent COFs, categorized by analytes, with a focus on recent advancements in sensing principles and performance. The review concludes by outlining challenges and opportunities in this field, aiming to guide material design for sensing applications and stimulate exploration into novel analyte implementations. 

Insights into sensing applications of fluorescent covalent organic frameworks

Nanomedicines are extensively used in cancer therapy. Covalent organic frameworks (COFs) are crystalline organic porous materials with several benefits for cancer therapy, including porosity, design flexibility, functionalizability, and biocompatibility. This review examines the use of COFs in cancer therapy from the perspective of reticular chemistry and function-oriented materials design. First, the modification sites and functionalization methods of COFs are discussed, followed by their potential as multifunctional nanoplatforms for tumor targeting, imaging, and therapy by integrating functional components. Finally, some challenges in the clinical translation of COFs are presented with the hope of promoting the development of COF-based anticancer nanomedicines and bringing COFs closer to clinical trials.

Covalent Organic Frameworks: Opportunities for Rational Materials Design in Cancer Therapy.

Adenosine triphosphate (ATP) and Fe3+ are important "signaling molecules" in living organisms, and their abnormal concentrations can be used for the early diagnosis of degenerative diseases. Therefore, the development of a sensitive and accurate fluorescent sensor is essential for detecting these signaling molecules in biological matrices. Herein, nitrogen-doped graphene quantum dots (N-GQDs) with cyan fluorescence emission were prepared by thermal cleavage of graphene oxide (GO) with N,N-dimethylformamide (DMF) as a solvent. The synergistic effect of static quenching and internal filtration enabled the selective quenching of N-GQD fluorescence by Fe3+. With the introduction of ATP, Fe3+ in the N-GQDs-Fe3+ system formed a more stable complex with ATP via the Fe-O-P bond, thus restoring the fluorescence of the N-GQDs. Fe3+ and ATP were detected in the linear ranges of 0-34 μM and 0-10 μM with the limits of detection (LOD) of 2.38 nM and 1.16 nM, respectively. In addition to monitoring Fe3+ and ATP in mouse serum and urine, the proposed method was also successfully applied for cytoplasmic imaging of 4T1 cells and in vivo imaging of freshwater shrimps. Moreover, the fluorescence and solution color change-based "AND" logic gate was successfully demonstrated in the biological matrix. Importantly, a complete sensing system was constructed by combining the N-GQDs with hydrogel kits and fluorescent flexible films. Thus, the prepared N-GQDs can be expected to serve as a valuable analytical tool for monitoring Fe3+ and ATP concentrations in biological matrices. 

Nitrogen-doped graphene quantum dot-based portable fluorescence sensor for the sensitive detection of Fe3+ and ATP with logic gate operation

One kind of driving of Cu on α - Fe 2 O 3 was successfully created for removing NO x . It brought excellent low-temperature performance, high N 2 selectivity and strong water and sulfur resistance. The concrete process was that Cu 2+ ions entered into the crystal lattice of Fe 2 O 3 , forming solid solution with Cu-O-Fe structure and further changed the property of Fe 2 O 3 . On the one hand, Cu 2+ ions adjusted the electrophilicity of Fe 3+ species, thereby facilitating the generation and adsorption of NO 2 , nitrate and nitrite species and increasing Lewis acid sites. The increase of NH 3 and NO x adsorbed species on the catalyst surface conduced to excellent low-temperature NH 3 -SCR activity. On the other hand, the regulation of Cu brought abundant lattice defects to Fe 2 O 3 which strengthened the redox ability and generated oxygen vacancy. It led to the growth of surface adsorbed oxygen, which was crucial for the “fast SCR” reaction. In-situ DRIFTS results revealed that the NH 3 on Lewis acid sites preferred to react with weakly adsorbed NO 2 through Langmuir-Hinshelwood (L-H) mechanism over the Fe-Cu composite oxide catalyst. Meanwhile, the NH 3 on Lewis acid sites was also able to react with monodentate nitrates, bidentate nitrates and nitrites through L-H reaction mechanism. This work provided a new inspiration for the construction of green and efficient catalysts to remove NO x in the practical industrial applications. • The FeCu oxides catalyst showed excellent low-temperature SCR performance. • The driving of Cu on Fe 2 O 3 facilitated NH 3 -SCR reaction. • The Cu driver promoted NO x adsorption and increased the Lewis acidity. • The NH 3 -SCR reaction over the catalyst followed “fast SCR” and L-H mechanisms. 

High-performance Fe-Cu composite oxide for selective catalytic reduction of NO with NH3: Driving of Cu on α-Fe2O3

Fluorescent Nanoscale Covalent Organic Frameworks with the Theoretically Matched Redox Potential of Fe3+/Fe2+ for Monitoring of Adenosine-5′-Triphosphate in Cells

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Fluorescent Nanoscale Covalent Organic Frameworks with the Theoretically Matched Redox Potential of Fe3+/Fe2+ for Monitoring of Adenosine-5′-Triphosphate in Cells