Electrosynthesis of hydrogen peroxide (H2O2) in the acidic environment could largely prevent its decomposition to water, but efficient catalysts that constitute entirely earth‐abundant elements are ...lacking. Here we report the experimental demonstration of narrowing the interlayer gap of metallic cobalt diselenide (CoSe2), which creates high‐performance catalyst to selectively drive two‐electron oxygen reduction toward H2O2 in an acidic electrolyte. The enhancement of the interlayer coupling between CoSe2 atomic layers offers a favorable surface electronic structure that weakens the critical *OOH adsorption, promoting the energetics for H2O2 production. Consequently, on the strongly coupled CoSe2 catalyst, we achieved Faradaic efficiency of 96.7 %, current density of 50.04 milliamperes per square centimeter, and product rate of 30.60 mg cm−2 h−1. Moreover, this catalyst shows no sign of degradation when operating at −63 milliamperes per square centimeter over 100 hours.
A strategy that narrows the interlayer distance of cobalt diselenide (CoSe2) is reported, which enables strong coupling between CoSe2 monolayers. The strongly coupled CoSe2 can catalyze electrosynthesis of H2O2 in acidic media efficiently, which yields Faradaic efficiency of 96.7 %, current density of 50.04 mA cm−2, and product rate of 30.60 mg cm−2 h−1, outperforming all catalysts reported previously in acidic environments.
The enantioselective construction of C-CF
R (R: alkyl or fluoroalkyl) bonds has attracted the attention of synthetic chemists because of the importance of chiral fluorinated compounds in life and ...materials sciences. Catalytic asymmetric fluoroalkylation has mainly been realized under organocatalysis and Lewis acid catalysis, with substrates limited to carbonyl compounds. Few examples using transition-metal catalysis exist, owing to side reactions including decomposition and isomerization of fluoroalkylating reagents. Herein we report umpolung asymmetric difluoroallylation of hydrazones with 3-bromo-3,3-difluoropropene (BDFP) under palladium catalysis. Difluoroallylation products having quaternary chiral carbon centers are afforded in good yields with high α/γ- and enantioselectivities. The usefulness of the reaction products is demonstrated and an inner-sphere mechanism of the reaction is proposed. The use of chiral N-heterocyclic carbene as ligand is the key for the selectivities as well as the productivity of the reaction.
Although the Turing structures, or stationary reaction‐diffusion patterns, have received increasing attention in biology and chemistry, making such unusual patterns on inorganic solids is ...fundamentally challenging. We report a simple cation exchange approach to produce Turing‐type Ag2Se on CoSe2 nanobelts relied on diffusion‐driven instability. The resultant Turing‐type Ag2Se‐CoSe2 material is highly effective to catalyze the oxygen evolution reaction (OER) in alkaline electrolytes with an 84.5 % anodic energy efficiency. Electrochemical measurements show that the intrinsic OER activity correlates linearly with the length of Ag2Se‐CoSe2 interfaces, determining that such Turing‐type interfaces are more active sites for OER. Combing X‐ray absorption and computational simulations, we ascribe the excellent OER performance to the optimized adsorption energies for critical oxygen‐containing intermediates at the unconventional interfaces.
A novel Turing‐type Ag2Se‐CoSe2 structure has been synthesized, which possesses rich Ag2Se‐CoSe2 interfaces, exhibiting a 221 mV overpotential at a current density of 10 mA cm−2 in 0.1 M KOH electrolyte with a high anodic energy efficiency of 84.5 %.
DNA 5-hydroxymethylcytosine (5hmC) modification is known to be associated with gene transcription and frequently used as a mark to investigate dynamic DNA methylation conversion during mammalian ...development and in human diseases. However, the lack of genome-wide 5hmC profiles in different human tissue types impedes drawing generalized conclusions about how 5hmC is implicated in transcription activity and tissue specificity. To meet this need, we describe the development of a 5hmC tissue map by characterizing the genomic distributions of 5hmC in 19 human tissues derived from ten organ systems. Subsequent sequencing results enabled the identification of genome-wide 5hmC distributions that uniquely separates samples by tissue type. Further comparison of the 5hmC profiles with transcriptomes and histone modifications revealed that 5hmC is preferentially enriched on tissue-specific gene bodies and enhancers. Taken together, the results provide an extensive 5hmC map across diverse human tissue types that suggests a potential role of 5hmC in tissue-specific development; as well as a resource to facilitate future studies of DNA demethylation in pathogenesis and the development of 5hmC as biomarkers.
Platelet endothelial cell adhesion molecule-1 (PECAM-1 or CD31) is a well-known marker of endothelial cells and a key factor for adhesion and accumulation of platelets. CD31 plays roles in cell ...proliferation, apoptosis, migration, and cellular immunity. CD31 is also expressed on tumor cells, such as breast cancer cells and non-Hodgkin's lymphomas, and contributes to tumor cell invasion. Here, our experiments show that CD31 promotes metastasis by inducing the epithelial–mesenchymal transition in hepatocellular carcinoma by up-regulating integrin β1 via the FAK/Akt signaling pathway.
•CD31 is expressed on tumor cells of hepatocellular carcinoma and is correlated with a reduced OS and DFS.•CD31 promotes tumor metastasis in hepatocellular carcinoma by inducing epithelial–mesenchymal transition.•The ITGB1-FAK-Akt signaling pathway is critical for CD31 to induce epithelial–mesenchymal transition.•The CD31 positive tumor cells form a new subgroup of HCC and may provide a new insight into abnormal differentiation of HCC cells.
Purpose
Previous studies have indicated that transient receptor potential (TRP) channels can influence cancer development. The TRPC subfamily consists of seven subtypes, TRPC1 − TRPC7. Interestingly, ...the expression levels of TRPC1 have been shown to be totally different in different breast cancer cell lines. Nevertheless, the underlying mechanism remains unknown. In this study, we explore the significance of TRPC1 expression in breast cancer.
Methods
Immunohistochemical TRPC1 staining was performed in 278 samples. TRPC1 expression in different breast tissues were examined. Then, the influence of TRPC1 on migration, invasion and proliferation was explored. We analyzed the protein of TRPC1 by Western blot to prove which pathway may be involved in. Finally, we use online database to predict the prognosis of TRPC1 in breast cancer.
Results
Through immunohistochemistry and in vitro experiments, we found that the expression level of TRPC1 was higher in breast cancer cells as compared with that in normal breast epithelial cells. Moreover, the expression level of TRPC1 was different between estrogen receptor-positive (ER +) and -negative (ER −) breast cancer. It was shown that TRPC1 inhibited MCF7 cell proliferation, migration, and invasion in vitro. Western blotting revealed that TRPC1 inhibited the PI3K/AKT pathway and epithelium−mesenchymal transformation, leading to subsequent inhibition of cell proliferation and metastasis. In luminal A and luminal B patients, those with high TRPC1 expression had a better prognosis. On the contrary, in basal-like and triple-negative breast cancer (TNBC) subtypes, patients with high-TRPC1 expression had a worse prognosis.
Conclusions
We confirmed that TRPC1 was high expression in breast cancer. Overexpression of TRPC1 inhibits proliferation and migration of ER + breast cancer and gives a better prognosis by inhibiting PI3K/AKT pathway activation. TRPC1 may be an independent prognostic predictor in breast cancer patients.
Recent findings have shown that lncRNA dysregulation is involved in many cancers, including osteosarcoma (OS). In a previous study, we reported a novel lncRNA, ODRUL, that could promote doxorubicin ...resistance in OS. We now report the function and underlying mechanism of ODRUL in regulating OS progression. We show that ODRUL is upregulated in OS tissues and cell lines and correlates with poor prognosis. ODRUL knockdown significantly inhibits OS cell proliferation, migration, invasion, and tumor growth in vitro and in vivo by decreasing matrix metalloproteinase (MMP) expression. A microarray screen combined with online database analysis showed that miR-3182 is upregulated and MMP2 is downregulated in sh-ODRUL-expressing MG63 cells and that miR-3182 harbors potential binding sites for ODRUL and the 3′ UTR of MMP2 mRNA. In addition, miR-3182 expression and function are inversely correlated with ODRUL expression in vitro and in vivo. A luciferase reporter assay demonstrated that ODRUL could directly interact with miR-3182 and upregulate MMP2 expression via its competing endogenous RNA activity on miR-3182 at the posttranscriptional level. Taken together, our study has elucidated the role of oncogenic ODRUL in OS progression and may provide a new target in OS therapy.
ODRUL is upregulated in osteosarcoma, correlates with poor prognosis, and promotes osteosarcoma progression in vitro and in vivo. ODRUL regulates MMP2 expression through competitively binding to miR-3182, whose expression and function inversely correlate with that of ODRUL. In conclusion, ODRUL contributes to osteosarcoma progression through the miR-3182/MMP2 axis.
On 3 January 2019, the Chang'e‐4 (CE‐4) touched down on the Von Karman crater located inside the South Pole‐Aitken Basin, providing for the first time the opportunity for in situ measurements of the ...lunar regolith at the farside of the Moon. The CE‐4 ground penetrating radar reveals that fine‐grained regolith, coarse impact ejecta, and fractured bedrocks lie beneath the exploration path of the Yutu‐2 rover. The variations of regolith permittivity with depth and the radargrams indicate that the CE‐4 site has a fine‐grained regolith layer thickness of 11.1 m, which is about 1.3–3 times higher than the in situ measurement results at the Apollo and Chang'e‐3 (CE‐3) sites except for Apollo 16, possibly due to a faster weathering rate of ejecta deposits compared with coherent basalt substrates. The penetration depth of CE‐4 is about 2.85 times (in terms of round‐way delay) deeper than CE‐3, probably due to the differences in abundances of ilmenite and rocks in the regolith.
Plain Language Summary
CE‐4 is the first craft in history to land on the lunar farside. Its rover is equipped with a ground‐penetrating radar (GPR), the same as the one mounted on the CE‐3 rover, which uses pulses of electromagnetic energy to reveal the subsurface structure and properties, especially useful to study the lunar soil layer (“regolith”) that mantles most of the lunar surface. The results from the GPR show that the thickness of the regolith at the CE‐4 site is 1.3–3 times higher than the in situ measurements at the Apollo 11,12,14,15, 17, and CE‐3 sites even though the ages of the surfaces of Apollo 11 and Apollo 17 are thought to be comparable with that of the CE‐4 site. It implies a faster regolith growth speed at the CE‐4 site. The mineral mix of the surface materials at the CE‐4 site is different from that at the CE‐3: this results in less radar signal attenuation, thus increasing the detection limit up to the depth of 35 m, 2.85 times deeper than the CE‐3.
Key Points
The LPR measurements at the CE‐4 landing site reveal that the shallow structure comprises of fine‐grained regolith, coarse impact ejecta, and fractured bedrocks
The CE‐4 landing site has a thicker regolith layer (~11 m) compared with the CE‐3, hinting at a longer weathering history
A lower abundance of ilmenite and rocks in the regolith at the CE‐4 site allows 2.85 times the penetration depth compared with CE‐3 site
The construction of axially chiral N-heterobiaryls is of great interest as a result of their occurrence in organocatalysts, chiral ligands, natural products, and biologically active molecules. ...Despite remarkable achievements in this area, strategies for the preparation of new classes of axially chiral N-heterobiaryls remain to be further explored. Herein, we report the enantioselective synthesis of axially chiral arylquinolizones through an intramolecular atroposelective cycloisomerization. The reaction proceeds via the Brønsted acid-enhanced dearomatization of pyridine by a copper catalyst that allows for the formation of the desired products in excellent yields and enantioselectivities. The utility of this methodology is illustrated by a synthesis on gram scale production and transformation of the products into chiral thiourea catalysts. Mechanistic studies demonstrate that Brønsted acid plays a significant role in promoting the reactivity of the reaction, while both the steric and electronic effects of aryl substituents in substrate play a role in controlling the stereoselectivity.
White hepatopancreas syndrome has recently emerged in Chinese mitten crab (Eriocheir sinensis) aquaculture, causing considerable economic loss. The hepatopancreas color of diseased crabs becomes ...gradually lighter, turning from yellow to yellow‐white to white. Therefore, this study was conducted to investigate the changes in nutrient composition in three edible parts (hepatopancreas, ovaries, and muscle) of adult females with different colored hepatopancreases. Three groups were assessed in this study, including a yellow hepatopancreas group (control, L * = 63.92, a * = 22.14, b * = 60.95), a yellow‐white hepatopancreas group (YWHG, L * = 65.06, a * = 22.35, b * = 57.80), and a white hepatopancreas group (WHG, L * = 65.72, a * = 10.70, b * = 30.52). No statistically significant differences in average weight, tissue indices, and total edible yield were observed among the three crab groups (P >0.05). The moisture content of the hepatopancreases and ovaries in WHG was 56.12% and 9.23% higher than the control values (P <0.05), whereas hepatopancreas crude fat and ovary crude protein levels were 62.23% and 11.45% lower than the control values (P < 0.05). The total carbohydrate levels of the three edible tissues were significantly higher and the crude protein content of ovaries was significantly lower in YWHG (P < 0.05). Most amino acid levels in the WHG muscle and ovaries were significantly lower than the control (P < 0.05). Moreover, the hepatopancreas levels of total polyunsaturated fatty acids (PUFA) and n‐6PUFA in WHG were 24.88% and 31.83% lower than in control group, whereas the hepatopancreas levels of total PUFA and n‐6PUFA in YWHG were also 21.88% and 23.20% lower compared to the controls (P < 0.05). Overall, the growth and the edible parts were not affected in YWHG and WHG. Moreover, YWHG crabs exhibited few effects on nutritional value; however, the fatty acid composition of crabs was significantly changed. In contrast, WHG crabs exhibited poor nutritional quality. Nonetheless, the consumption of crabs with yellow‐white or white hepatopancreases is not recommended since the animal also referred to as diseased crabs.
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