Mechanistic study of visible light-driven CdS or g-C₃N₄-catalyzed C–H direct trifluoromethylation of (hetero)arenes using CF₃SO₂Na as the trifluoromethyl source

The mild and sustainable methods for C–H direct trifluoromethylation of (hetero)arenes without any base or strong oxidants are in extremely high demand. Here, we report that the photo-generated electron-hole pairs of classical semiconductors (CdS or g-C3N4) under visible light excitation are effective to drive C–H trifluoromethylation of (hetero)arenes with stable and inexpensive CF3SO2Na as the trifluoromethyl (TFM) source via radical pathway. Either CdS or g-C3N4 propagated reaction can efficiently transform CF3SO2Na to [rad]CF3 radical and further afford the desired benzotrifluoride derivatives in moderate to good yields. After visible light initiated photocatalytic process, the key elements (such as F, S and C) derived from the starting TFM source of CF3SO2Na exhibited differential chemical forms as compared to those in other oxidative reactions. The photogenerated electron was trapped by chemisorbed O2 on photocatalysts to form superoxide radical anion (O2[rad]−) which will further attack [rad]CF3 radical with the generation of inorganic product F− and CO2. This resulted in a low utilization efficiency of [rad]CF3 (&lt;50%). When nitro aromatic compounds and CF3SO2Na served as the starting materials in inert atmosphere, the photoexcited electrons can be directed to reduce the nitro group to amino group rather than being trapped by O2. Meanwhile, the photogenerated holes oxidize SO2CF3− into [rad]CF3. Both the photogenerated electrons and holes were engaged in reductive and oxidative paths, respectively. The desired product, trifluoromethylated aniline, was obtained successfully via one-pot free-radical synthesis.</p

Ambient fine particulate pollution and daily morbidity of stroke in Chengdu, China.

INTRODUCTION:Association has been reported between ambient fine particulate matter (PM) and adverse outcomes of cerebrovascular events. However, it remains unclear that whether short-term exposure to PM relates to stroke and the lag of health effects. This triggers us to examine the relationship between PM and population stroke morbidity in Chengdu. METHODS:The daily average concentration of atmospheric pollutants and meteorological factors and daily morbidity of stroke in Chengdu (2013-2015) were collected. Based on time series analysis-generalized additive models (GAM), single-pollutant, two-pollutant and multi-pollutant model were established. The effects of atmospheric PM2.5 (defined as PM less than 2.5μm in aerodynamic diameter), PMc(defined as PM less than 10μm and more than 2.5μm in aerodynamic diameter) and PM10 (defined as PM less than 10μm in aerodynamic diameter) concentration on the daily mortality of stroke were analyzed, respectively. RESULTS:The three-year mean concentrations of PM2.5, PMc and PM10 for air pollutants were 75.9, 43.9 and 119.7 μg/m3, respectively. PM2.5 on the current day (lag0) and with a moving average of 0-1 days were significantly associated with the increasing risk of stroke morbidity, and PM2.5 with a lag of 0-1 days had greater association, whereas for PMc and PM10 there were no significant association observed. In our study, every 10μg/m3 increase of PM2.5 was associated with 0.69% percent change in stroke morbidity (95%CI: 0.01~1.38). For females, every 10μg/m3 increase of PM2.5 contributes to 0.80% percent change of onset. And for the group of age less than 65, we observed 0.78% higher risk every 10μg/m3 increase of PM2.5. CONCLUSIONS:These findings suggest that short-term exposure to PM2.5 within 1 day is associated with the onset of stroke, and the younger people (age<65) and females are more sensitive than older people and males

Icariin promotes bone marrow mesenchymal stem cells osteogenic differentiation via the mTOR/autophagy pathway to improve ketogenic diet-associated osteoporosis

Abstract Background Icariin, a traditional Chinese medicine, has demonstrated anti-osteoporotic properties in ovariectomized mice. However, its effectiveness in preventing bone loss induced by ketogenic diet (KD), which mimics osteoporosis in human, remains unexplored. This study aims to investigate icariin’s impact on KD-induced bone loss in mice. Methods Thirty mice were divided into: sham, KD, and KD + icariin groups. Post a 12-week intervention, evaluation including bone microstructures, serum concentrations of tartrate-resistant acid phosphatase (TRAP) and bone-specific alkaline phosphatase (ALP), and femoral tissue expression levels of osteocalcin (OCN) and TRAP. The expression levels of mammalian target of rapamycin (mTOR), ALP, peroxisome proliferator-activated receptor gamma (PPAR-γ), phosphorylated mTOR (p-mTOR), and the autophagy adaptor protein (p62) were also analyzed. Alizarin granule deposition and cellular ALP levels were measured following the induction of bone marrow mesenchymal stem cells (BMSCs) into osteogenesis. Results The study found that KD significantly impaired BMSCs' osteogenic differentiation, leading to bone loss. Icariin notably increased bone mass, stimulated osteogenesis, and reduced cancellous bone loss. In the KD + icariin group, measures such as bone tissue density (TMD), bone volume fraction (BV/TV), trabecular number (Tb.N), and trabecular thickness (Tb.Th) were significantly higher than in the KD group. Additionally, bone trabecular separation (Tb.Sp) was markedly lower in the KD + icariin group. Moreover, icariin increased OCN and ALP levels while suppressing PPAR-γ, TRAP, p62, and p-mTOR. In cellular studies, icariin encouraged osteogenic development in BMSCs under KD conditions. Conclusions Icariin effectively counteracts bone thinning and improves bone microstructure. Its mechanism likely involves stimulating BMSCs osteogenic differentiation and inhibiting bone resorption, potentially through mTOR downregulation. These findings suggest icariin's potential as an alternative treatment for KD-induced bone loss