Modifying the Oxidative Potentials of Imines in a Dye Loaded Capsule for Photocatalytic Cyclization with Hydrogen Evolution

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(11)

Опубликована: Янв. 13, 2024

Abstract Modifying redox potential of substrates and intermediates to balance pairs steps are important stages for multistep photosynthesis but faced marked challenges. Through co‐clathration iridium photosensitizer imine substrate within one packet a metal‐organic capsule shift the potentials substrate, herein, we reported multiphoton enzymatic strategy generation heterocycles by intramolecular C−X hydrogen evolution cross‐couplings. The cage facilitated pre‐equilibrium substrate‐involving clathrate that cathodic shifts oxidation substrate‐dye‐host ternary complex configuration inversion via spatial constraints in confined space. new two photon excitation enabled precise control electron transfer between each pair (photosensitizer, capsule), endowing catalytic system proceeding smoothly with an fashion. Three kinds 2‐subsituted (−OH, −NH 2 , −SH) imines N‐aryl enamines all give corresponding cyclization products efficiently under visible light irradiation, demonstrating promising microenvironment driven thermodynamic activation host‐dye‐substrate synergistic combination photocatalytic transformations.

Язык: Английский

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Enzymatic Activation and Continuous Electrochemical Production of Methane from Dilute CO₂ Sources with a Self-Healing Capsule

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(29), С. 19951 - 19961

Опубликована: Июль 4, 2024

Converting dilute CO2 source into value-added chemicals and fuels is a promising route to reduce fossil fuel consumption greenhouse gas emission, but integrating electrocatalysis with capture still faced marked challenges. Herein, we show that self-healing metal–organic macrocycle functionalized as an electrochemical catalyst selectively produce methane from flue air the lowest applied potential so far (0.06 V vs reversible hydrogen electrode, RHE) through enzymatic activation fashion. The capsule emulates enzyme' pocket abstract one in situ-formed CO2-adduct molecule commercial amino alcohols, forming easy-to-reduce substrate-involving clathrate combine electroreduction for thorough reduction. We find system exhibited kinetics first time Michaelis–Menten mechanism reduction of maintained Faraday efficiency (FE) 74.24% selectivity over 99% continuous operation 200 h. A consecutive working lab at 50 mA·cm–2, eleven-for-one (10 h 1 healing) electrolysis manner, gives turnover number (TON) more than 10,000 within 100 integrated facilitates (ca. 13.0% CO2) 400 ppm 42.7 mL CH4 1.0 m3 air). new strategy molecular electrocatalyst manner anodic shifting potentials provided departure existing catalytic techniques.

Язык: Английский

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Revisiting the Origins of Reactivity and Selectivity in the Pd₆L₄-Cage-Catalyzed Diels–Alder Reactions: A Combined Computational and Experimental Study

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

Supramolecular metal–organic cages (MOCs) have gained attention as versatile catalytic platforms due to their self-assembled architectures and well-defined cavities, which mimic enzyme active sites enable spatial confinement. This confinement modulates the reaction pathways enhances performance. Recent studies highlight potential in various organic transformations, but factors governing MOC-catalyzed reactions remain incompletely understood. work builds on prior computational of Diels–Alder catalyzed by palladium-based MOCs, showing that common view transition-state stabilization via π–π interactions is not valid. Instead, we find between substrate ligands destabilize transition state. Additionally, theoretical regioselectivity, validated experimentally, suggest encapsulation efficiency key determining selectivity. These findings provide new insights into mechanisms reactions.

Язык: Английский

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Wavelength-selective, time-resolved, and visible-light-responsive multicolor switching systems for multistate dynamic information encryption

Chemical Engineering Journal, Год журнала: 2024, Номер 496, С. 154363 - 154363

Опубликована: Июль 28, 2024

Язык: Английский

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Modifying the Oxidative Potentials of Imines in a Dye Loaded Capsule for Photocatalytic Cyclization with Hydrogen Evolution

Angewandte Chemie, Год журнала: 2024, Номер 136(11)

Опубликована: Янв. 13, 2024

Abstract Modifying redox potential of substrates and intermediates to balance pairs steps are important stages for multistep photosynthesis but faced marked challenges. Through co‐clathration iridium photosensitizer imine substrate within one packet a metal‐organic capsule shift the potentials substrate, herein, we reported multiphoton enzymatic strategy generation heterocycles by intramolecular C−X hydrogen evolution cross‐couplings. The cage facilitated pre‐equilibrium substrate‐involving clathrate that cathodic shifts oxidation substrate‐dye‐host ternary complex configuration inversion via spatial constraints in confined space. new two photon excitation enabled precise control electron transfer between each pair (photosensitizer, capsule), endowing catalytic system proceeding smoothly with an fashion. Three kinds 2‐subsituted (−OH, −NH 2 , −SH) imines N‐aryl enamines all give corresponding cyclization products efficiently under visible light irradiation, demonstrating promising microenvironment driven thermodynamic activation host‐dye‐substrate synergistic combination photocatalytic transformations.

Язык: Английский

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A supramolecular photosensitizer based on triphenylamine and pyrazine with aggregation-induced emission properties for high-efficiency photooxidation reactions

Journal of Colloid and Interface Science, Год журнала: 2024, Номер 665, С. 871 - 878

Опубликована: Март 30, 2024

Язык: Английский

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Reserving Electrons in Cofactor Decorated Coordination Capsules for Biomimetic Electrosynthesis of α-Hydroxy/amino Esters

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 24, 2024

Sustainable electricity-to-chemical conversion via the utilization of artificial catalysts inspired by redox biological systems holds great significance for catalyzing synthesis. Herein, we develop a biomimetic electrosynthesis strategy mediated nicotinamide adenine dinucleotide (NADH) mimic-containing coordination capsule efficiently producing α-hydroxy/amino esters. The saturated metal centers worked as an electron relay to consecutively accept single electrons while donating two NAD

Язык: Английский

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The marriage of porous cages and metal clusters for advanced catalysis

Materials Chemistry Frontiers, Год журнала: 2023, Номер 7(21), С. 5355 - 5376

Опубликована: Янв. 1, 2023

This review summaries the latest advances in synthetic strategies and characterization techniques of cage-encapsulated metal clusters. We highlight advantages that emerge from synergistic combination porous cages clusters catalytic applications.

Язык: Английский

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Covalent Immobilization of Yeast Alcohol Dehydrogenase on an Amine-Functionalized Polymeric Resin Enhances Stability for Furfural Hydrogenation to Furfuryl Alcohol Using Ethanol as the Terminal Reductant

Industrial & Engineering Chemistry Research, Год журнала: 2023, Номер 62(43), С. 17604 - 17615

Опубликована: Окт. 22, 2023

Biocatalytic processes could be highly beneficial for valorizing biomass-derived chemicals to support a circular bioeconomy. Intrinsic stability-related challenges with enzymes have often been remediated using enzyme immobilization techniques that enhance the enzymes' stability by reducing inhibition and facilitating recycling reuse. A covalent bonding strategy glutaraldehyde as cross-linker on primary amine-functionalized polymeric resin was utilized in this study immobilizing yeast alcohol dehydrogenase (YADH) coupled ethanol oxidation furfural reduction. It demonstrated capping of residual amine moieties critical avoiding yield loss during reaction, is competent reagent. Fourier transform infrared spectroscopy, thermogravimetric analysis, nitrogen physisorption, scanning electron microscopy studies confirmed successful functionalization YADH immobilization. activity 94% retention after 20 cycles. Fed-batch repeated-batch experiments over 48 h excellent reusability, three times higher longevity, four substrate consumption immobilized toward catalysis ethanol-dependent reduction furfuryl compared soluble YADH. The effects internal external mass transport limitations immobilized-enzyme-catalyzed reaction were also investigated mitigated through process design.

Язык: Английский

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Redox Triggers Guest Release and Uptake Across a Series of Azopyridine‐Based Metal–Organic Capsules

Advanced Materials, Год журнала: 2023, Номер 35(42)

Опубликована: Июль 18, 2023

Precise control over guest release and recapture using external stimuli is a valuable goal, potentially enabling new modes of chemical purification. Including redox moieties within the ligand cores molecular capsules to trigger uptake guests has proved effective, but this technique limited certain guests. Herein, construction series novel metal-organic from ditopic, tritopic, tetratopic ligands demonstrated, all which contain redox-active azo groups coordinated FeII centers. Compared their iminopyridine-based analogs, class azopyridine-based possesses larger cavities, capable encapsulating more voluminous Upon reduction capsules, are released may then be re-encapsulated when regenerated by oxidation. Since centers on arms, they modular can attached variety afford varying predictable architectures. This method thus shows promise as generalized approach for designing redox-controlled systems.

Язык: Английский

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