Visible-Light-Promoted Regioselective Hydroborylation of Ketene Dithioacetals with NHC-Boranes.

NHC-boranes have been treated as a reliable source of boryl radicals. In this study, regioselective hydroborylation of ketene dithioacetals with NHC-borane was achieved under mild conditions via a visible-light-promoted radical chain process using thiophenol as a proton donor and hydrogen atom transfer. This protocol features a low-cost catalyst, good functional group tolerance, a relatively broad range of substrate scope, and good to excellent yields. Moreover, mechanism of this hydroborylation reaction was preliminarily studied.

Visible-light-promoted N-H functionalization of O-substituted hydroxamic acid with diazo esters.

Herein we report an N-H functionalization of O-substituted hydroxamic acid with diazo esters under blue LED irradiation conditions. The present transformations could be performed efficiently under mild conditions without use of catalyst, additive and N2 atmosphere. Interestingly, when THF and 1,4-dioxane were employed as the reaction solvents, an active oxonium ylide involved three-component reaction and an N-H insertion of carbene species into hydroxamate occurred, respectively.

Organic extracts in PM2.5 are the major triggers to induce ferroptosis in SH-SY5Y cells.

As a major air pollutant, PM2.5 can induce apoptosis of nerve cells, causing impairment of the learning and memory capabilities of humans and animals. Ferroptosis is a newly discovered way of programmed cell death. It is unclear whether the neurotoxicity induced by PM2.5 is related to the ferroptosis of nerve cells. In this study, we observed the changes in ferroptosis hallmarks of SH-SY5Y cells after exposure to various doses (40, 80, and 160 µg/mL PM2.5) for 24 h, exposure to 40 µg/mL PM2.5 for various times (24, 48, and 72 h), as well as exposure to various components (Po, organic extracts; Pw, water-soluble extracts; Pc, carbon core component). The results showed that PM2.5 reduced the cell viability, the content of GSH, and the activity of GSH-PX and SOD in SH-SY5Y cells with exposure dose and duration increasing. On the other hand, PM2.5 increased the content of iron, MDA, and the level of lipid ROS in SH-SY5Y cells with exposure dose and duration increasing. Additionally, PM2.5 reduced the expression levels of HO-1, NRF2, SLC7A11, and GPX4. The ferroptosis inhibitors Fer-1 and DFO significantly increase the cells viabilities and significantly reversed the changes of other above ferroptosis hallmarks. We also observed the different effects on ferroptosis hallmarks in the SH-SY5Y cells exposed to PM2.5 (160 µg/mL) and its various components (organic extracts, water-soluble extracts, and carbon core) for 24 h. We found that only the organic extracts shared similar results with PM2.5 (160 µg/mL). This study demonstrated that PM2.5 induced ferroptosis of SH-SY5Y cells, and organic extracts might be the primary component that caused ferroptosis.

Energy metabolism disorders and oxidative stress in the SH-SY5Y cells following PM2.5 air pollution exposure.

Studies have shown that PM2.5 exposure can induce neuronal apoptosis and neurobehavioral changes in animal experiments due partly to the mitochondria-mediated oxidative damage. How does it affect the mitochondrial energy metabolism as well as the neuronal damage, however, remain unclear. This study aimed to investigate the molecular processes of energy metabolism and oxidative damage induced by ambient PM2.5 exposure in SH-SY5Y cells. SH-SY5Y cells were treated with PM2.5 to establish a cytotoxicity model. A Seahorse Extracellular Flux Analyzer (XFp) was performed to evaluate the cellular mitochondrial respiratory and glycolysis after exposure to PM2.5. The dose- and time-dependent effects of PM2.5 on oxidative damage and apoptosis were analyzed. To further explore the relationship among oxidative damage, energy metabolism and apoptosis, SH-SY5Y cells were co-cultured with BHA and PM2.5 for 24 h. The results demonstrated that the basic respiration and ATP production, the typical index of mitochondrial respiration as well as glycolysis, significantly reduced in SH-SY5Y cells with dose and time dependent. At the same time, the PM2.5 could significantly decrease the cell viability and Mn-SOD activity, and increase the ROS levels and apoptosis rate as the escalation of dose and the extension of time. Importantly, the application of BHA could synchronously recover the PM2.5 induced cell energy metabolism disorder, oxidative damage, and apoptosis. It seems that the abnormal cellular energy metabolism may be caused by oxidative damage following fine particles exposure, and further led to apoptosis.

Visible-light-driven PhSSPh-catalysed regioselective hydroborylation of α,ß-unsaturated carbonyl compounds with NHC-boranes.

A photo-induced transition-metal-free regioselective hydroborylation of α,ß-unsaturated carbonyl compounds is developed. The PhSSPh reagent was employed as the photocatalyst, and NHC-BH3 was used as the boron source. This transformation shows a broad substrate scope and provides a wide range of α-borylcarbonyl molecules in good to excellent yields.

Synthesis of spirocyclic oxazole derivatives from 2-arylidene cycloalkanones and α-halohydroxamates.

Herein we disclose a facile route to spirocyclic oxazole derivatives via [3 + 2] cycloaddition reactions between 2-arylidene cycloalkanones and azaoxyallyl cations that formed in situ from α-halohydroxamates in the presence of base. This methodology was shown to lead to an efficient formation of a series of functionalized spirocyclic oxazole derivatives in good to excellent yields.

Reactive organic radical-doped Ag(I)-based coordination compounds for highly efficient antibacterial wound therapy.

Antibiotics, being critical antimicrobial agents, have been widely used for treating bacterial infections. However, prolonged use of antibiotics can induce drug resistance resulting in "superbug" that threatens human health. Therefore, developing antibiotic-free materials with intrinsic antibacterial properties is the key to the "superbug" challenge. In this study, two highly efficient metal-organic frameworks (MOFs) were successfully assembled through synergistic use of the antibacterial properties of reactive organic radicals and silver (Ag) cations. These hybrid Ag-based materials possessed radical-doped characteristics, continuously releasing Ag+, which significantly inhibited the growth of four common Gram-negative and Gram-positive human pathogens (Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, and Staphylococcus aureus), and particularly two multi-drug-resistance bacteria (MRSA and MDR-PA). Furthermore, in vivo assays indicated that the synergistic antibacterial effect of these compounds could significantly accelerate the healing rate of infected wounds in mice. Blood biochemistry and histological analyses of main organs in treated mice also exhibited negligible cytotoxicity. This study unveiled the promising potential of Ag-MOFs for anti-infective therapies and future clinical applications.