Bioinspired Photoactive Cu-Halide Coordination Polymers for Reduction Activation and Oxygen Conversion.

Natural copper oxygenases provide fundamental principles for catalytic oxidation with kinetically inert molecular oxygen, but it remains a marked challenge to mimic both their structure and function in an entity. Inspired by the Cu enzymatic sites, herein we report two new photoactive binuclear copper-iodine- and bisbenzimidazole-comodified coordination polymers to reproduce the natural oxo-functionalization repertoire in a unique photocatalytic pathway. Under light irradiation, the Cu-halide coordination polymers effectively reduce NHP esters and complete oxygen reduction activation via photoinduced electron transfer for the aerobic oxidative coupling of hydroquinone with terminal alkynes, affording hydroxyl-functionalized ketones with high efficiency and selectivity.

KG4NH: A Comprehensive Knowledge Graph for Question Answering in Dietary Nutrition and Human Health.

It is commonly known that food nutrition is closely related to human health. The complex interactions between food nutrients and diseases, influenced by gut microbial metabolism, present challenges in systematizing and practically applying knowledge. To address this, we propose a method for extracting triples from a vast amount of literature, which is used to construct a comprehensive knowledge graph on nutrition and human health.

Photocatalytic C(sp)-H bond functionalization by Cu(I) halide cluster-mediated O activation.

Photocatalytic C-H bond activation is a challenging approach to selectively functionalize C(sp)-H bonds with dioxygen under mild conditions. Herein, by merging transition metal- and photo-catalysis, photoactive Cu(I)-halide(X) (X = Cl, Br, I) clusters are employed to effectively catalyse the selective monooxygenation and C-C oxidative cross-coupling of C(sp)-H bonds with unreactive O upon light irradiation. This modern protocol promises a photoinduced SET process between Cu(I)-clusters and O, and possibly forms Cu(II)-O˙ species for abstracting the H-atom from the C(sp)-H bond.

Binding of Dual-Function Hybridized MetalOrganic Capsules to Enzymes for Cascade Catalysis.

The combination of chemo- and biocatalysis for multistep syntheses provides attractive advantages in terms of evolvability, promiscuity, and sustainability striving for desirable catalytic performance. Through the encapsulation of flavin analogues by both NADH and heme mimics codecorated heteroleptic metalorganic capsules, herein, we report a progressive hostguest strategy to imitate cytochrome P450s catalysis for cascade oxidative coupling catalysis. Besides the construction of stable dual-function metalorganic capsules and the modification of cofactor-decorated capsules at the domain of enzymes, this supramolecular strategy involves multistage directional electron flow, affording reactive ferric peroxide species for inducing oxygenation.

A Metal-Organic Framework as a Multiphoton Excitation Regulator for the Activation of Inert C(sp )-H Bonds and Oxygen.

The activation and oxidization of inert C(sp )-H bonds into value-added chemicals affords attractively economic and ecological benefits as well as central challenge in modern chemistry. Inspired by the natural enzymatic transformation, herein, we report a new multiphoton excitation approach to activate the inert C(sp )-H bonds and oxygen by integrating the photoinduced electron transfer (PET), ligand-to-metal charge transfer (LMCT) and hydrogen atom transfer (HAT) events together into one metal-organic framework. The well-modified nicotinamide adenine dinucleotide (NAD ) mimics oxidized Ce -OEt moieties to generate Ce -OEt chromophore and its reduced state mimics NAD via PET.

A host-guest semibiological photosynthesis system coupling artificial and natural enzymes for solar alcohol splitting.

Development of a versatile, sustainable and efficient photosynthesis system that integrates intricate catalytic networks and energy modules at the same location is of considerable future value to energy transformation. In the present study, we develop a coenzyme-mediated supramolecular host-guest semibiological system that combines artificial and enzymatic catalysis for photocatalytic hydrogen evolution from alcohol dehydrogenation. This approach involves modification of the microenvironment of a dithiolene-embedded metal-organic cage to trap an organic dye and NADH molecule simultaneously, serving as a hydrogenase analogue to induce effective proton reduction inside the artificial host.

A host-guest approach to combining enzymatic and artificial catalysis for catalyzing biomimetic monooxygenation.

Direct transfer of protons and electrons between two tandem reactions is still a great challenge, because overall reaction kinetics is seriously affected by diffusion rate of the proton and electron carriers. We herein report a host-guest supramolecular strategy based on the incorporation of NADH mimics onto the surface of a metal-organic capsule to encapsulate flavin analogues for catalytic biomimetic monooxygenations in conjunction with enzymes. Coupling an artificial catalysis and a natural enzymatic catalysis in the pocket of an enzyme, this host-guest catalyst-enzyme system allows direct proton and electron transport between two catalytic processes via NADH mimics for the monooxygenation of both cyclobutanones and thioethers.

Negatively charged metal-organic hosts with cobalt dithiolene species: improving PET processes for light-driven proton reduction through host-guest electrostatic interactions.

By incorporating 1,2-benzenedithiol as a chelator to construct cobalt dithiolene species, two negatively charged redox-active metal-organic hosts were obtained. By taking advantage of electrostatic interactions, cationic Ru-based photosensitizers were constrained to improve photoinduced electron transfer processes for efficient photocatalytic proton reduction.