Encapsulation engineering of porous crystalline frameworks for delayed luminescence and circularly polarized luminescence.

Delayed luminescence (DF), including phosphorescence and thermally activated delayed fluorescence (TADF), and circularly polarized luminescence (CPL) exhibit common and broad application prospects in optoelectronic displays, biological imaging, and encryption. Thus, the combination of delayed luminescence and circularly polarized luminescence is attracting increasing attention. The encapsulation of guest emitters in various host matrices to form host-guest systems has been demonstrated to be an appealing strategy to further enhance and/or modulate their delayed luminescence and circularly polarized luminescence. Compared with conventional liquid crystals, polymers, and supramolecular matrices, porous crystalline frameworks (PCFs) including metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), zeolites and hydrogen-bonded organic frameworks (HOFs) can not only overcome shortcomings such as flexibility and disorder but also achieve the ordered encapsulation of guests and long-term stability of chiral structures, providing new promising host platforms for the development of DF and CPL. In this review, we provide a comprehensive and critical summary of the recent progress in host-guest photochemistry via the encapsulation engineering of guest emitters in PCFs, particularly focusing on delayed luminescence and circularly polarized luminescence. Initially, the general principle of phosphorescence, TADF and CPL, the combination of DF and CPL, and energy transfer processes between host and guests are introduced. Subsequently, we comprehensively discuss the critical factors affecting the encapsulation engineering of guest emitters in PCFs, such as pore structures, the confinement effect, charge and energy transfer between the host and guest, conformational dynamics, and aggregation model of guest emitters. Thereafter, we summarize the effective methods for the preparation of host-guest systems, especially single-crystal-to-single-crystal (SC-SC) transformation and epitaxial growth, which are distinct from conventional methods based on amorphous materials. Then, the recent advancements in host-guest systems based on PCFs for delayed luminescence and circularly polarized luminescence are highlighted. Finally, we present our personal insights into the challenges and future opportunities in this promising field.

Visible-light-driven photocatalytic carboxylation to aromatic carboxylic acids with CO2.

(Hetero)aromatic carboxylic acids and their derivatives attract attention due to their role in the synthesis of several biologically active molecules, active pharmaceutical ingredients, polymers, etc. Carbon dioxide (CO2) is a prime C1 source for the synthesis of aromatic carboxylic acids because of its nontoxicity, nonflammability, abundance and renewability. Owing to the thermodynamic and chemical inertness of CO2, traditional carboxylation to aromatic carboxylic acids with CO2 is always performed under harsh reaction conditions or using stoichiometric metallic reductants. Visible-light-driven carboxylation with CO2 provides an environmentally benign, mild, and high-efficiency route for the production of aromatic carboxylic acids. This review comprehensively introduces the visible-light-driven preparation of aromatic carboxylic acids through a visible-light-driven oxidative addition and reductive elimination mechanism, binding of aryl (radical) anions which are produced by photoinduced electron transfer (PET) to CO2, binding of carbon dioxide anion radicals (CO2˙-) which are formed by PET to aryl compounds, radical coupling between CO2˙- and aryl radicals, and other mechanisms. Finally, this review provides a summary and the future work direction. This article offers a theoretical guidance for efficient synthesis of aromatic carboxylic acids via photocatalysis.

A Coordination-Driven Self-Assembly and NIR Photothermal Conversion Study of Organometallic Handcuffs.

Due to their fascinating topological structures and application prospects, coordination supramolecular complexes have continuously been studied by scientists. However, the controlled construction and property study of organometallic handcuffs remains a significant and challenging research subject in the area of supramolecular chemistry. Hence, a series of tetranuclear organometallic and heterometallic handcuffs bearing different size and metal types were rationally designed and successfully synthesized by utilizing a quadridentate pyridyl ligand (tetra-(3-pyridylphenyl)ethylene) based on three Cp*Rh (Cp* = η5-C5Me5) fragments bearing specific longitudinal dimensions and conjugated planes. These results were determined with single-crystal X-ray diffraction analysis technology, ESI-MS NMR spectroscopy, etc. Importantly, the photoquenching effect of Cp* groups and the discrepancy of intermolecular π-π stacking interactions between building block and half-sandwich fragments promote markedly different photothermal conversion results. These results will further push the synthesis of topological structures and the development of photothermal conversion materials.

Catalytic Degradation of Triphenylmethane Dyes with an Iron Porphyrin Complex as a Cytochrome P450 Model.

The organic dyes used in printing and dyeing wastewater have complex components, diverse structures and strong chemical stability, which make them not suitable for treatment and difficult to degrade in the environment. Porphyrins are macromolecules with 18 π electrons formed by four pyrrole molecules connected with a methylene bridge that has a stable structure. Porphyrin combines with iron to form an active intermediate with a structure similar to the cytochrome P450 enzyme, so they are widely used in the biomimetic field. In the current study, 5,10,15,20-tetra (4-carboxyphenyl) porphine ferric chloride (III) (Fe(III)TCPP) was used as a catalyst and iodosobenzene was used as an oxidant to explore the catalytic degradation of triphenylmethane dyes, such as rhodamine B (RhB) and malachite green (MG). The results of UV-Vis spectral analysis have shown that the conversion rate of the rhodamine B was over 90% when the amount of Fe(III)TCPP was 0.027 mM and the amount of iodosobenzene was eight equivalents. When the catalyst was 0.00681 mM and the amount of the oxidant was five equivalents, the conversion rate of the malachite green reached over 95%. This work provides a feasible method for the degradation of triphenylmethane dyes.

Salt-Templated Nanoarchitectonics of CoSe2-NC Nanosheets as an Efficient Bifunctional Oxygen Electrocatalyst for Water Splitting.

Recently, the extensive research of efficient bifunctional electrocatalysts (oxygen evolution reaction (OER) and hydrogen evolution reaction (HER)) on water splitting has drawn increasing attention. Herein, a salt-template strategy is prepared to synthesize nitrogen-doped carbon nanosheets encapsulated with dispersed CoSe2 nanoparticles (CoSe2-NC NSs), while the thickness of CoSe2-NC NSs is only about 3.6 nm. Profiting from the ultrathin morphology, large surface area, and promising electrical conductivity, the CoSe2-NC NSs exhibited excellent electrocatalytic of 10 mA·cm-2 current density at small overpotentials of 247 mV for OER and 75 mV for HER. Not only does the nitrogen-doped carbon matrix effectively avoid self-aggregation of CoSe2 nanoparticles, but it also prevents the corrosion of CoSe2 from electrolytes and shows favorable durability after long-term stability tests. Furthermore, an overall water-splitting system delivers a current density of 10 mA·cm-2 at a voltage of 1.54 V with resultants being both the cathode and anode catalyst in alkaline solutions. This work provides a new way to synthesize efficient and nonprecious bifunctional electrocatalysts for water splitting.

Pseudopterosin A ameliorates ischaemia-induced brain injury by acting on Akt signalling pathway.

INTRODUCTION: Brain injury caused by ischaemic stroke is a major cause of disability and death throughout the world. The present study evaluates the neuroprotective effect of pseudopterosin A (PtA) against ischaemia-induced brain injury. MATERIAL AND METHODS: Ischaemia was induced by pMCAO model, and rats were separated in to three groups. A control group; an ischemic group receiving saline solution; and a PtA group receiving PtA (5 mg/kg, i.p.) for the period of three days, i.e. two days before surgery and after the surgery. Effect of PtA was assessed by estimating the infract volume and neurological deficits. Level of oxidative stress, inflammatory mediators, and markers of apoptosis were estimated in the brain tissues. Western blot assay and immunohistochemistry was done for the assessment of expressions of protein. RESULT: Data from the study suggest that treatment with PtA significantly decreases the infracted volume and neurological deficit score compared to the ischaemic group. Treatments with PtA attenuate the activity of antioxidant enzyme, and the level of inflammatory mediators and markers of apoptosis in the brain tissues of ischaemia-induced brain injury. Phosphorylation of FKHR, Bad, and Akt were significantly reduced in the PtA-treated group compared to the ischaemic group. CONCLUSIONS: The present study shows that pseudopterosin A attenuates neuronal injury in the pMCAO model by acting on the Akt signalling pathway.