Search

Polyradical cages are of great interest because they show very fascinating physical and chemical properties, but many challenges remain, especially for their synthesis and characterization. Herein, we present the synthesis of a polyradical cation cage 14⋅+ through post‐synthetic oxidation of a redox‐active phenothiazine‐based Pd2L4‐type coordination cage 1. It′s worth noting that 1 exhibits excellent reversible electrochemical and chemical redox activity due to the introduction of a bulky 3,5‐di‐tert‐butyl‐4‐methoxyphenyl substituent. The generation of 14⋅+ through reversible electrochemical oxidation is investigated by in situ UV/Vis‐NIR and EPR spectroelectrochemistry. Meanwhile, chemical oxidation of 1 can also produce 14⋅+ which can be reversibly reduced back to the original cage 1, and the process is monitored by EPR and NMR spectroscopies. Eventually, we succeed in the isolation and single crystal X‐ray diffraction analysis of 14⋅+, whose electronic structure and conformation are distinct to original 1. The magnetic susceptibility measurements indicate the predominantly antiferromagnetic interactions between the four phenothiazine radical cations in 14⋅+. We believe that our study including the facile synthesis methodology and in situ spectroelectrochemistry will shed some light on the synthesis and characterization of novel polyradical systems, opening more perspectives for developing functional supramolecular cages. [ABSTRACT FROM AUTHOR]

Bone marrow mesenchymal stem cells (BMSCs) -derived extracellular vesicles (EVs), especially small EVs (sEVs), were vastly reported to enable multiple restorative effects on ischemic stroke, yet the protective mechanism of blood-brain barrier (BBB) has not been fully illustrated. In the present study, we investigated the therapeutic effects and mechanism of BMSCs-derived sEVs on BBB injury after ischemic stroke. In-vivo, administering sEVs to transient middle cerebral artery occlusion (tMCAo) mice mitigated the brain infarct volume, BBB permeability and neural apoptosis, and improved the cerebral blood flow perfusion and neurological function. Simultaneously, cerebral vascular endothelial overexpressed Caveolin-1 (Cav-1) together with its strong co-localization with autophagosome protein LC3B were suppressed, and ZO-1 and Occludin expressions were enhanced, whose results were consistent with those of oxygen-glucose-deprivation/reperfusion (OGD/R)-insulted brain endothelial cells (BECs) in vitro . Furthermore, by employing Cav-1 siRNA and pcDNA3.1 transfection, Co-immunoprecipitation, cycloheximide assay, and molecular docking, it proved that brain endothelial Cav-1 was an essential upstream of autophagy activation, contributing to tight-junction proteins delegation via the autophagy-lysosomal pathway. Altogether, our study demonstrates the novel mechanism of Cav-1-dependent tight-junction proteins autophagic disruption on BBB integrity after ischemic stroke, and BMSC-sEVs treatment can reverse such hazard cascades., Competing Interests: Competing Interests: The authors have declared that no competing interest exists., (© The author(s).)

Polyradical cages are of great interest because they show very fascinating physical and chemical properties, but many challenges remain, especially for their synthesis and characterization. Herein, we present the synthesis of a polyradical cation cage 1 4 ⋅ + through post-synthetic oxidation of a redox-active phenothiazine-based Pd 2 L 4 -type coordination cage 1. It's worth noting that 1 exhibits excellent reversible electrochemical and chemical redox activity due to the introduction of a bulky 3,5-di-tert-butyl-4-methoxyphenyl substituent. The generation of 1 4 ⋅ + through reversible electrochemical oxidation is investigated by in situ UV/Vis-NIR and EPR spectroelectrochemistry. Meanwhile, chemical oxidation of 1 can also produce 1 4 ⋅ + which can be reversibly reduced back to the original cage 1, and the process is monitored by EPR and NMR spectroscopies. Eventually, we succeed in the isolation and single crystal X-ray diffraction analysis of 1 4 ⋅ + , whose electronic structure and conformation are distinct to original 1. The magnetic susceptibility measurements indicate the predominantly antiferromagnetic interactions between the four phenothiazine radical cations in 1 4 ⋅ + . We believe that our study including the facile synthesis methodology and in situ spectroelectrochemistry will shed some light on the synthesis and characterization of novel polyradical systems, opening more perspectives for developing functional supramolecular cages., (© 2024 Wiley-VCH GmbH.)