Density functional theory investigations revealed that the pyridine-boryl radical generated in situ using 4-cyanopyridine and bis(pinacolato)diboron could be used as a bifunctional “reagent”, which ...serves as not only a pyridine precursor but also a boryl radical. With the unique reactivity of such radicals, 4-substituted pyridine derivatives could be synthesized using α,β-unsaturated ketones and 4-cyanopyridine via a novel radical addition/CC coupling mechanism. Several controlled experiments were conducted to provide supportive evidence for the proposed mechanism. In addition to enones, the scope could be extended to a wide range of boryl radical acceptors, including various aldehydes and ketones, aryl imines and alkynones. Lastly, this transformation was applied in the late-stage modification of a complicated pharmaceutical molecule.
A rapid approach has been developed for the fluorescent carbon dots (CDs) by the hydrothermal treatment of lignin in the presence of H₂O₂. The as-synthesized CDs were found to emit blue ...photoluminescence with excellent photostability. Moreover, the CDs displayed biocompatibility, low cytotoxicity, and high water solubility properties. Finally, the as-resulted CDs were demonstrated to be excellent probes for bioimaging and biosensing applications.
Substituted Hantzsch esters can act as radical reservoirs in photoredox reactions, steadily releasing a carbon radical and a hydrogen atom radical in the absence of an additional electron acceptor. ...We propose that radical release by substituted Hantzsch esters occurs via a mechanism involving an internal redox cycle. Cinnamidecinnamides, styrenes, α,β‐unsaturated acids, and diarylethenes could be alkylated smoothly with these reagents.
The debromination of vicinal dibromo compounds to generate alkenes usually requires harsh reaction conditions and the addition of catalysts. Just recently the visible‐light‐induced debromination of ...vicinal dibromo compounds emerged as a possible alternative to commonly used methods, but the substrate scope of this reaction is limited and a photocatalyst is necessary for the successful conversion of the starting compounds. A catalyst‐free visible‐light‐induced debromination of vicinal dibromo compounds with a base‐activated Hantzsch ester as photosensitizer is reported. The method has a wide substrate scope and a broad functional‐group compatibility.
Turn all the lights on! The debromination of vicinal dibromo compounds to generate alkenes usually requires harsh reaction conditions and the addition of catalysts. A mild, catalyst‐free visible‐light‐induced debromination of vicinal dibromo compounds using a base‐activated Hantzsch ester as photosensitizer is presented. This method has a wide substrate scope and tolerates a broad range of functional groups.
Elevated temperatures limit plant growth and reproduction and pose a growing threat to agriculture. Plant heat stress response is highly conserved and fine-tuned in multiple pathways. Spinach (
L.) ...is a cold tolerant but heat sensitive green leafy vegetable. In this study, heat adaptation mechanisms in a spinach sibling inbred heat-tolerant line Sp75 were investigated using physiological, proteomic, and phosphoproteomic approaches. The abundance patterns of 911 heat stress-responsive proteins, and phosphorylation level changes of 45 phosphoproteins indicated heat-induced calcium-mediated signaling, ROS homeostasis, endomembrane trafficking, and cross-membrane transport pathways, as well as more than 15 transcription regulation factors. Although photosynthesis was inhibited, diverse primary and secondary metabolic pathways were employed for defense against heat stress, such as glycolysis, pentose phosphate pathway, amino acid metabolism, fatty acid metabolism, nucleotide metabolism, vitamin metabolism, and isoprenoid biosynthesis. These data constitute a heat stress-responsive metabolic atlas in spinach, which will springboard further investigations into the sophisticated molecular mechanisms of plant heat adaptation and inform spinach molecular breeding initiatives.
Ferroptosis has emerged as a therapeutic tactic to trigger cancer cell death driven by abnormal accumulation of reactive oxygen species (ROS). However, a single ferroptosis treatment modality is ...often limited. In this work, a combination therapy of ferroptosis and immunotherapy for cancer was proposed. Specifically, a versatile nanodrug was designed for the multiple treatment of hepatocellular carcinoma (HCC) by loading dihydroartemisinin (DHA) on Fe3+-doped MnO2 nanosheets (Fe-MnO2/DHA). Firstly, Fe-MnO2/DHA was degraded by glutathione (GSH) in the tumor microenvironment (TME) to release Fe2+, Mn2+ and DHA, leading to aberrant ROS accumulation due to Fenton/Fenton-like reaction. Secondly, breakage of endoperoxide bridge from DHA was caused by Fe2+ to further induce oxidative stress. Thirdly, the depleted GSH promoted the inactivation of glutathione peroxidase 4 (GPX4), resulting in lipid peroxide (LPO) accumulation. The resulting LPO and ROS could induce ferroptosis and apoptosis of liver cancer cells. Furthermore, Fe-MnO2/DHA mediated three-pronged stimulation of oxidative stress, resulting in high levels of targeted immunogenic cell death (ICD). It could enhance the infiltration of CD4+ T and CD8+ T cells, and promote macrophage polarization. DHA also acted as an immunomodulator to inhibit regulatory T cells (Tregs) for systemic antitumor. Overall, Fe-MnO2/DHA presents a multi-modal therapy for HCC driven by ferroptosis, apoptosis and immune activation, significantly advancing synergistic cancer treatment.
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•A simple, economical and time-saving method to prepare Fe-MnO2/DHA nanosheets.•Fe-MnO2/DHA induces ferroptosis by Fenton/Fenton-like reaction, breakage of endoperoxide bridge from DHA and inhibiting GPX4 expression.•Fe-MnO2/DHA induces immunotherapy by stimulating ICD to enhance the infiltration of CD4+ and CD8+ T cells as well as promote macrophage polarization.
Breast cancer (BC) patients who undergo surgery followed by radiotherapy and chemotherapy have limitations on physical activity which will lead to a decreased quality of life and poor physical ...fitness level. The purpose of this study was to investigate the effects of the combined exercise intervention based on internet and social media software (CEIBISMS) on postoperative breast cancer patients by evaluating their quality of life, muscle strength and cardiorespiratory capacity.
This study was a randomized control trial with an intervention period of 12 weeks. Sixty participants (30 in each group, 42-60 years old, female) were recruited through an outpatient department. Procedure of exercise in the intervention group included: via phone step-recording app, ask the individuals to complete the target number of steps within a specified period of exercise, four times per week; face-to-face remote video instruction of individuals on muscle training, three times per week; via social media apps daily push common knowledge of physical exercise BC rehabilitation. The control group received traditional treatment and rehabilitation according to daily specifications of the hospital. The primary outcome was quality of life and the secondary outcomes were muscle strength and cardiorespiratory capacity.
Experiments using a Short Form 36 showed that the CEIBISMS yielded significantly better results than traditional methods, in vitality (p = 0.009), mental health (p = 0.001) and reported health transition (p = 0.048) by week 12. The CEIBISMS resulted in significant improvement in the stand-up and sit-down chair test (p < 0.0001), arm lifting test (p = 0.017).
The CEIBISMS offered rehabilitative effects in quality of life (QOL) and muscle strength of postoperative patients with breast cancer (BC) in China.
ChiCTR-IPR-17012368 . Trial registered on 14 August, 2017.
Faced with the increasing volume of retired lithium-ion batteries (LIBs), recycling and reusing the spent graphite (SG) is of great significance for resource sustainability. Here, a facile method for ...transforming the SG into a carbon framework as well as loading Fe2O3 to form a composite anode with a sandwich structure is proposed. Taking advantage of the fact that the layer spacing of the spent graphite naturally expands, impurities and intercalants are eliminated through microwave thermal shock to produce microwave-puffed graphite (MPG) with a distinct three-dimensional structure. Based on the mechanism of microwave-induced gasification intercalation, a Fe2O3-MPG intercalation compound (Fe2O3-MPGIC) anode material was constructed by introducing iron precursors between the framework layers and subsequently converting them into Fe2O3 through annealing. The Fe2O3-MPGIC anode exhibits a high reversible capacity of 1000.6 mAh g−1 at 200 mA g−1 after 100 cycles and a good cycling stability of 504.4 mAh g−1 at 2000 mA g−1 after 500 cycles. This work can provide a reference for the feasible recycling of SG and development of high-performance anode materials for LIBs.
The rapid pace of urbanization has led to an increasing frequency of road collapses, posing a significant threat to urban traffic safety. Underground pipeline leakage stands out as the primary cause ...of such collapses. This paper presents a macroscopic analysis of the subgrade seepage erosion process caused by pipeline leakage. Model tests were conducted to investigate the formation mechanism and explore the influence of water level, water flow rate, and soil type. The study revealed that the subgrade seepage erosion caused by pipeline leakage undergoes four distinct stages: infiltration, slow erosion, rapid erosion, and erosion convergence. Soil erosion shares similarities with sand erosion in its developmental process. The water level plays a pivotal role in determining the shape and size of the eroded area caused by sand seepage erosion. The size of the erosion cavities formed during the soil seepage erosion increased along with the increase in the water flow rate. The size of the erosion cavity increased by up to 55.7% when the flow rate was increased by three times. In addition, clay soils do not undergo significant erosional damage but do produce significant settlement. The soil erosion process caused by underground leakages in pipelines was investigated using model tests in this study, which provided valuable information for researchers performing an in-depth analysis of the mechanism of roadbed cavities generated by urban underground pipeline leakage, which is critical for safeguarding people’s travel safety and decreasing social and economic losses.
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