A metal‐free direct trifluoromethylthiolation of sulfonium ylides with an electrophilic trifluoromethylthiolating reagent has been established, in which sulfonium salt or α‐bromoacetic ester is ...employed as sulfonium ylide precursors. This trifluoromethylthiolation enables the straightforward construction of SCF3‐substituted sulfonium ylides from a wide range of substrates, including ketones, esters, and even PEGylated substrates. Moreover, the application of this approach in large‐scale preparation and the fluorescence and fluorine‐19 magnetic resonance imaging capabilities of the product are also explored.
A solvent‐exchange approach for the preparation of solvated graphene frameworks as high‐performance anode materials for lithium‐ion batteries is reported. The mechanically strong graphene frameworks ...exhibit unique hierarchical solvated porous networks and can be directly used as electrodes with a significantly improved electrochemical performance compared to unsolvated graphene frameworks, including very high reversible capacities, excellent rate capabilities, and superior cycling stabilities.
Solvated graphene frameworks (SGFs) that were prepared through a convenient solvent‐exchange approach are binder‐free anodes for lithium‐ion batteries with significantly improved properties compared to unsolvated graphene frameworks. They exhibit ultrahigh reversible capacities, excellent rate capabilities, and superior cycling stabilities. GA=graphene aerogel.
Lignocellulosic biomass, microalgae and sewage sludge have distinct compositions and structures to each other. To understand the effect of feedstock differences on biomass liquefaction process, the ...liquefaction characteristics of rice straw (lignocellulosic biomass), Spirulina (microalgae) and sewage sludge were comparatively studied. Liquefaction experiments were performed in a 500 mL autoclave at identical conditions (623 K, 9.4–10.1 MPa and 20 min retention time). Although the content of organic materials in sewage sludge was the lowest among above three biomasses, the yield of bio-oil from sewage sludge reached up to 39.5 ± 1.16%, higher than those from rice straw (21.1 ± 0.93%) and Spirulina (34.5 ± 1.31%). Besides, the bio-oils from sewage sludge had the highest heating value (36.14 MJ/kg). However, Spirulina showed the highest conversion (79.7 ± 1.02%). GC–MS analysis results indicated that the major compounds in the bio-oil from rice straw were phenolic compounds. In case of sewage sludge and Spirulina, esters were the main compositions. The volatility distribution of hydrocarbons was evaluated by C-NPgram (Carbon-Normal Paraffin gram). It was showed that the majority of hydrocarbons from sewage sludge and Spirulina were distributed at C17 and C20, whereas they were distributed at C8 in rice straw-derived bio-oil. The types of feedstocks have a significant effect on biomass liquefaction.
•Rice straw, sewage sludge and Spirulina were liquefied at identical conditions.•Sewage sludge produced the highest bio-oil yield but the lowest conversion rate.•The composition of bio-oil from rice straw consisted mainly of phenolic compound.•The major hydrocarbons were esters in both sewage sludge and Spirulina bio-oils.•Among three bio-oils, rice straw bio-oil showed a distinct volatility distribution.
Rholling in the bicycles: A rhodium(I)‐catalyzed cycloisomerization for the synthesis of bicyclic compounds containing a cycloheptatriene ring from linear alkenynes (see scheme; ...cod=1,5‐cyclooctadiene) is proposed to proceed through 1,2‐acyloxy migration, 6 π electrocyclization, migratory insertion, and reductive elimination. The overall process can be viewed as a novel intramolecular 5+2 cycloaddition with concomitant 1,2‐acyloxy migration.
Cancer nanovaccines have attracted widespread attention by inducing potent cytotoxic T cell responses to improve immune checkpoint blockade (ICB) therapy, while the lack of co-stimulatory molecules ...limits their clinical applications. Here, a genetically engineered cancer cytomembrane nanovaccine is reported that simultaneously overexpresses co-stimulatory molecule CD40L and immune checkpoint inhibitor PD1 to elicit robust antitumor immunity for cancer immunotherapy. The CD40L and tumor antigens inherited from cancer cytomembranes effectively stimulate dendritic cell (DC)-mediated immune activation of cytotoxic T cells, while the PD1 on cancer cytomembranes significantly blocks PD1/PD-L1 signaling pathway, synergistically stimulating antitumor immune responses. Benefiting from the targeting ability of cancer cytomembranes, this nanovaccines formula shows an enhanced lymph node trafficking and retention. Compared with original cancer cytomembranes, this genetically engineered nanovaccine induces twofold DC maturation and shows satisfactory precaution efficacy in a breast tumor mouse model. This genetically engineered cytomembrane nanovaccine offers a simple, safe, and robust strategy by incorporating cytomembrane components and co-stimulatory molecules for enhanced cancer immunotherapy.
Upconversion nanoparticles (UCNPs) with superior optical and chemical features have been broadly employed for in vivo cancer imaging. Generally, UCNPs are surface modified with ligands for cancer ...active targeting. However, nanoparticles in biological fluids are known to form a long-lived “protein corona”, which covers the targeting ligands on nanoparticle surface and dramatically reduces the nanoparticle targeting capabilities. Here, for the first time, we demonstrated that by coating UCNPs with red blood cell (RBC) membranes, the resulting cell membrane-capped nanoparticles (RBC-UCNPs) adsorbed virtually no proteins when exposed to human plasma. We further observed in various scenarios that the cancer targeting ability of folic acid (FA)-functionalized nanoparticles (FA-RBC-UCNPs) was rescued by the cell membrane coating. Next, the FA-RBC-UCNPs were successfully utilized for enhanced in vivo tumor imaging. Finally, blood parameters and histology analysis suggested that no significant systematic toxicity was induced by the injection of biomimetic nanoparticles. Our method provides a new angle on the design of targeted nanoparticles for biomedical applications.
Modified potential ecological risk index (MRI) was proposed based on the potential ecological risk index (RI) and risk assessment code (RAC) by modifying an index. The modified index was relevant to ...the chemical speciation of heavy metals. Xiawan Port, a typical region contaminated by industrial production, was selected as a case study area. The total concentrations and chemical speciation of heavy metals in sediments of Xiawan Port were analyzed. The experimental data indicate that Xiawan Port is seriously polluted by heavy metals, especially by Cd. The risks of heavy metals are evaluated by RI, RAC and MRI, respectively. The resluts of MRI show that the risks of heavy metals are in the decreasing order of Cd>Pb>Cu>Zn. Comparison of results by different methods reveals that MRI integrates the characters of RI and RAC. MRI is recognized to be useful for risk managemnt of heavy metals in sediments.
The occurrence in drug resistance of chronic myeloid leukemia (CML) was accompanied by autophagy activation. Abnormal circular RNAs (circRNAs) participated in this progression. This study attempted ...to investigate the potential role of circ_0009910 in imatinib resistance of CML cells.
The expression of circ_0009910 and miR-34a-5p was measured by quantitative real-time polymerase chain reaction (qRT-PCR). The characterization of circ_0009910 was investigated using oligo (dT)18 primers, Actinomycin D and RNase R. Cell viability (IC50 value) and apoptosis were assessed by Cell Counting Kit-8 (CCK8) assay and flow cytometry assay, respectively. The relative protein expression was quantified by western blot. The relationship among miR-34a-5p, circ_0009910 and ULK1 was predicted by online bioinformatics tool, and verified by dual-luciferase reporter assay and RNA immunoprecipitation (RIP).
The expression of circ_0009910 was up-regulated in the serum of imatinib-resistance CML patients and K562/R cells, and associated with unfavorable clinicopathologic features. Circ_0009910 in K562 and K562/R cells was mainly localized in the cytoplasm. Circ_0009910 knockdown inhibited cell proliferation and autophagy, but induced apoptosis in K562/R cells. Circ_0009910 targeted miR-34a-5p to regulate ULK1. MiR-34a-5p depression rescued the effects of circ_0009910 knockdown on apoptosis and autophagy in K562/R cells.
Circ_0009910 accelerated imatinib-resistance in CML cells by modulating ULK1-induced autophagy via targeting miR-34a-5p, providing a potential target in imatinib resistance of CML.
•Circ_0009910 was highly expressed in imatinib-resistance K562 cells.•Circ_0009910 knockdown inhibited cell proliferation and autophagy, but induced apoptosis in K562/R cells.•MiR-34a-5p was a target of circ_0009910, and ULK1 was a target of miR-34a-5p.•Circ_0009910 exerted a promotion role in the resistance of CML by activating ULK1-induced autophagy via targeting miR-34a-5p.
Thermochemical liquefaction characteristics of rice husk in mixed solvent (ethanol–water) were investigated in this study. Compared with pure water or ethanol, the mixed solvent showed synergistic ...effect at a relatively lower temperature. The highest bio-oil yield was obtained at 533K in ethanol–water mixed solvent (V/V, 5:5) and found to be 21.15%. In pure water and mixed solvent treatments, the yield of bio-oil declined with reaction temperature increasing from 533K to 613K. However, with the pure ethanol as solvent, the bio-oil yield increased firstly and then decreased slightly. In addition, the effects of solid–liquid ratio and solvent filling ratio on the distribution of liquefaction products were also explored with ethanol–water mixed solvent as medium. Higher solid–liquid ratio resulted in lower bio-oil yield, while the increase of solvent filling ratio led to an increase in the bio-oil yield. The compositions of bio-oil from rice husk consisted mainly of phenolic compounds, long-chain alkanes, ketones and esters. Compared with pure water or ethanol, the relative concentration of phenolic compounds in mixed solvent run was higher and reached up to 21.22%.
•Liquefaction of rice husk in ethanol–water mixed solvent was investigated.•Under tested conditions, ethanol–water mixed solvent displayed synergistic effect.•Too high solid–liquid ratio would suppress the production of bio-oil.•Higher solvent filling ratio may result in higher yield of bio-oil.•The main components of bio-oils were saccharides and phenolic compounds.
Summary
Immune‐mediated thrombotic thrombocytopenic purpura (iTTP) is a rare and life‐threatening haematological emergency. Although therapeutic plasma exchange together with corticosteroids achieve ...successful outcomes, a considerable number of patients remain refractory to this treatment and require early initiation of intensive therapy. However, a method for the early identification of refractory iTTP is not available. To develop and validate a model for predicting the probability of refractory iTTP, a cohort of 265 consecutive iTTP patients from 17 large medical centres was retrospectively identified. The derivation cohort included 94 patients from 11 medical centres. For the validation cohort, we included 40 patients from the other six medical centres using geographical validation. An easy‐to‐use risk score system was generated, and its performance was assessed using internal and external validation cohorts. In the multivariable logistic analysis of the derivation cohort, three candidate predictors were entered into the final prediction model: age, haemoglobin and creatinine. The prediction model had an area under the curve of 0.886 (95% CI: 0.679–0.974) in the internal validation cohort and 0.862 (95% CI: 0.625–0.999) in the external validation cohort. The calibration plots showed a high agreement between the predicted and observed outcomes. In conclusion, we developed and validated a highly accurate prediction model for the early identification of refractory iTTP. It has the potential to guide tailored therapy and is a step towards more personalized medicine.
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