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    Principles of Design and Synthesis of Metal Derivatives from MOFs (Adv. Mater. 24/2023)
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    Abstract:
    MOF-Derived Materials Despite the instability and low electrical conductivity of metal–organic frameworks (MOFs), metal-based derivatives (MDs) retain the intricate nanostructures of MOFs while boasting improved stability and significantly higher electrical conductivities. In article number 2210166, Thibault De Villenoisy and co-workers delve into the nanostructural design of MDs, discussing various established and potential future materials, and also identifying and rationalizing design parameters with the aim to guide optimal composition and performance.
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    Rational design
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    Abstract The development of efficient phototherapeutic agents (PTA) through rational and specific principles exhibits great potential to the biomedical field. In this study, a facile and rational strategy was used to design PTA through perturbation theory. According to the theory, both the intersystem crossing rate for singlet oxygen generation and nonradiative transition for photothermal conversion efficiency can be simultaneously enhanced by the rational optimization of donor–acceptor groups, heavy atom number, and their functional positions, which can effectively decrease the energy gap between the singlet and triplet states and increase the spin‐orbit coupling constant. Finally, efficient PTA were obtained that showed excellent performance in multimode‐imaging‐guided synergetic photodynamic/photothermal therapy. This study therefore expands the intrinsic mechanism of organic PTA and should help guide the rational design of future organic PTA via perturbation theory.
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    Abstract Crystalline frameworks including primarily metal organic frameworks (MOF) and covalent organic frameworks (COF) have received much attention in the field of heterogeneous catalysts recently. Beyond providing large surface area and spatial confinement, these crystalline frameworks can be designed to either directly act as or influence the catalytic sites at molecular level. This approach offers a unique advantage to gain deeper insights of structure–activity correlations in solid materials, leading to new guiding principles for rational design of advanced solid catalysts for potential important applications related to energy and fine chemical synthesis. In this review, recent key progress achieved in designing MOF‐ and COF‐based molecular solid catalysts and the mechanistic understanding of the catalytic centers and associated reaction pathways are summarized. The state‐of‐the‐art rational design of MOF‐ and COF‐based solid catalysts in this review is grouped into seven different areas: (i) metalated linkers, (ii) metalated moieties anchored on linkers, (iii) organic moieties anchored on linkers, (iv) encapsulated single sites in pores, and (v) metal‐mode‐based active sites in MOFs. Along with this, some attention is paid to theoretical studies about the reaction mechanisms. Finally, technical challenges and possible solutions in applying these catalysts for practical applications are also presented.
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    Nanomaterials with more than one enzyme-like activity are termed multienzymic nanozymes, and they have received increasing attention in recent years and hold huge potential to be applied in diverse fields, especially for biosensing and therapeutics. Compared to single enzyme-like nanozymes, multienzymic nanozymes offer various unique advantages, including synergistic effects, cascaded reactions, and environmentally responsive selectivity. Nevertheless, along with these merits, the catalytic mechanism and rational design of multienzymic nanozymes are more complicated and elusive as compared to single-enzymic nanozymes. In this review, the multienzymic nanozymes classification scheme based on the numbers/types of activities, the internal and external factors regulating the multienzymatic activities, the rational design based on chemical, biomimetic, and computer-aided strategies, and recent progress in applications attributed to the advantages of multicatalytic activities are systematically discussed. Finally, current challenges and future perspectives regarding the development and application of multienzymatic nanozymes are suggested. This review aims to deepen the understanding and inspire the research in multienzymic nanozymes to a greater extent.
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