Synthesis of heterointerfaces in NiO/SnO2 coated nitrogen-doped graphene for efficient lithium storage.

Currently, it remains a challenge to make comprehensive improvements to overcome the disadvantages of volume expansion, Li2O irreversibility and low conductivity of SnO2. Heterostructure construction has been investigated as an effective strategy to promote electron transfer and surface reaction kinetics, leading to high electrochemical performance. Herein, NiO/SnO2 heterojunction modified nitrogen doped graphene (NiO/SnO2@NG) anode materials were prepared using hydrothermal and carbonization techniques. Based on the excellent structural advantages, sufficiently small NiO/SnO2 heterojunction nanoparticles increase the interfacial density to promote Li2O decomposition, and the built-in electric field accelerates the charge transport rate to improve the conductivity. The three-dimensional porous graphene framework effectively mitigates volume expansion during cycling and stabilizes the reactive interface of electrode materials. The results show that the NiO/SnO2@NG mixture has high reversible specific capacity (938.8 mA h g-1 after 450 cycles at 0.1 A g-1), superior multiplicity performance (374.5 mA h g-1 at 3.0 A g-1) and long cycle life (685.3 mA h g-1 after 1000 cycles at 0.5 A g-1). Thus, this design of introducing NiO to form heterostructures with SnO2 is directly related to enhancing the electrochemical performance of lithium-ion batteries (LIBs).

Influence of formaldehyde exposure on the molecules of the NO/cGMP-cAMP signaling pathway in different brain regions of Balb/c mice.

This toxicology study was conducted to assess the impact of formaldehyde, a common air pollutant found in Chinese gymnasiums, on the brain function of athletes. In this research, a total of 24 Balb/c male mice of SPF-grade were divided into four groups, each consisting of six mice. The mice were exposed to formaldehyde at different concentrations, including 0 mg/m3, 0.5 mg/m3, 3.0 mg/m3, and 3.0 mg/m3 in combination with an injection of L-NMMA (NG-monomethyl-L-arginine), which is a nitric oxide synthase antagonist. Following a one-week test period (8 h per day, over 7 days), measurements of biomarkers related to the nitric oxide (NO)/cGMP-cAMP signaling pathway were carried out on the experimental animals post-treatment. The study found that: (1) Exposure to formaldehyde can lead to brain cell apoptosis and neurotoxicity; (2) Additionally, formaldehyde exposure was found to alter the biomarkers of the NO/cGMP-cAMP signaling pathway, with some changes being statistically significant (p < 0.05 or p < 0.01); (3) The use of L-NMMA, an antagonist of the NO/cGMP-cAMP signaling pathway, was found to prevent these biomarker changes and had a protective effect on brain cells. The study suggests that the negative impact of formaldehyde on the brain function of mice is linked to the regulation of the NO/cGMP-cAMP signaling pathway.

Target isolation of diverse sesquiterpenoid from the stems of Daphne genkwa based on molecular networking.

Guiding by LC-MS/MS analysis and the Global Natural Products Social (GNPS) Molecular Networking, three undescribed sesquiterpenoids, stedapgens A-C, and two known analogues were discovered in the barks of Daphne genkwa Sieb. et Zucc. The structures were determined by analysis of their spectroscopic data and quantum-chemical calculations. All the isolated novel compounds were tested for their acetylcholinesterase inhibitory activities with IC50 = 0.754 ± 0.059, 0.696 ± 0.026, and 0.337 ± 0.023 µg/ml. Among them, stedapgen A displayed promising inhibitory activities against AChE, and the binding sites were predicted by molecular docking.

Two pairs of bioactive cyclohexene alkaloid enantiomers from the roots of Piper nigrum.

Two pairs of cyclohexene amide alkaloid enantiomers were obtained from the root of Piper nigrum. Their plane structures were established by NMR and HRESIMS spectra. The absolute configurations of 1a/1b and 2a/2b were determined by the comparison between the experimental and calculated electronic circular dichroism (ECD) spectra. All identified compounds were tested for inhibitory effects on acetylcholinesterase (AChE) in vitro. Notably, compounds 1b and 2b showed strong inhibitory effects on AChE and the interaction between proteins and compounds was discussed by molecular docking studies.

General Approach for Two-Dimensional Rare-Earth Oxyhalides with High Gate Dielectric Performance.

Two-dimensional (2D) rare-earth oxyhalides (REOXs) with novel properties offer fascinating opportunities for fundamental research and applications. The preparation of 2D REOX nanoflakes and heterostructures is crucial for revealing their intrinsic properties and realizing high-performance devices. However, it is still a great challenge to fabricate 2D REOX using a general approach. Herein, we design a facile strategy to prepare 2D LnOCl (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy) nanoflakes using the molten salt method assisted by the substrate. A dual-driving mechanism was proposed in which the lateral growth could be guaranteed by the quasi-layered structure of LnOCl and the interaction between the nanoflakes and the substrate. Furthermore, this strategy has also been successfully applied for block-by-block epitaxial growth of diverse lateral heterostructures and superlattice. More significantly, the high performance of MoS2 field-effect transistors with LaOCl nanoflake as the gate dielectric was demonstrated, exhibiting competitive device characteristics of high on/off ratios up to 107 and low subthreshold swings down to 77.1 mV dec-1. This work offers a deep understanding of the growth of 2D REOX and heterostructures, shedding new light on the potential applications in future electronic devices.

[2 + 2]-Cycloaddition-derived cyclobutane natural products: structural diversity, sources, bioactivities, and biomimetic syntheses.

Covering: up to the end of 2021[2 + 2]-Type cyclobutane natural products are biosynthetically derived from intermolecular [2 + 2] cycloaddition or intramolecular [2 + 2] cycloaddition reactions. Due to their distinctive cyclobutane architectures, diverse biological effects, interesting formation processes, and synthetic challenges, these compounds have attracted considerable attention from scientists. In this article, the progress in research published through the end of 2021 on [2 + 2]-cycloaddition-derived cyclobutane natural products, including their structural diversity, sources, bioactivities and biomimetic syntheses, was reviewed; in addition, structural revisions were included. Emphasis was placed on the structural diversity of these interesting molecules and their biomimetic syntheses, which will provide inspiration for the total synthesis or biomimetic synthesis of more [2 + 2]-type cyclobutane natural products and further phytochemistry investigations.

Discovery of the Caged-Vibsane Norditerpenoids with Unprecedented Chemical Architectures and Exploration of Their Various Acid Tolerances.

Cyclovibsanones A-D (1-4, respectively), featuring unprecedented caged tricyclo[5.4.1.05,9]dodecane and bicyclo[4.2.1]hexane cores, were isolated from the leaves of Viburnum odoratissimum. Their structures as well as that of one chemical derivative (5), which was transformed from 2, were determined by spectroscopic data, theoretical calculations, and the ML-JDP4/MAEΔΔδ methods. In addition, compounds 1 and 2 were found to possess dissimilarities in acid tolerance during nuclear magnetic resonance (NMR) experiments. The potential mechanism was consequently postulated and further supported through NMR analysis and mechanistic calculations. Biologically, chemical derivative 5 exerted antiproliferative activity against HepG2 cells.

Two New Enantiomers of Phenylethanoid and Their Anti-Inflammatory Activities.

In this phytochemical investigation, two pairs of new phenylethanoid derivative enantiomers (1a/1b and 2a/2b), a new phenylethanoid derivative 3b, and seven known compounds (3a, 4-9) were isolated from the leaves of Picrasma quassioides. Spectroscopic techniques were used for the elucidation of their chemical structures, and the absolute configurations were determined by a comparison between the experimental and calculated ECD data, as well as the application of Snatzke's method. Compounds (1a/1b-3a/3b) were measured for their production of NO levels in LPS-induced BV-2 microglial cells. The results showed that all compounds exhibited potential inhibitory effects, and compound 1a showed stronger activity than the positive control.

Four Pairs of Neuroprotective Aryldihydronaphthalene-Type Lignanamide Enantiomers from the Herbs of Solanum lyratum.

Four pairs of aryldihydronaphthalene-type lignanamide enantiomers were isolated from Solanum lyratum (Solanaceae). The enantiomeric separation was accomplished by chiral-phase HPLC, and five undescribed compounds were elucidated. Analysis by various spectroscopy and ECD calculations, the structures of undescribed compounds were illuminated. The neuroprotective effects of all compounds were evaluated using H2 O2 -induced human neuroblastoma SH-SY5Y cells and AchE inhibition activity. Among them, compound 4 a exhibited remarkable neuroprotective effects at high concentrations of 25 and 50 µmol/L comparable to Trolox. Compound 1 a showed the highest AchE inhibition with the IC50 value of 3.06±2.40 µmol/L. Molecular docking of the three active compounds was performed and the linkage between the compounds and the active site of AchE was elucidated.

PFKFB3 downregulation aggravates Angiotensin II-induced podocyte detachment.

Podocytes play a critical role in maintaining normal glomerular filtration, and podocyte loss from the glomerular basement membrane (GBM) initiates and worsens chronic kidney disease (CKD). However, the exact mechanism underlying podocyte loss remains unclear. Fructose-2,6-biphosphatase 3 (PFKFB3) is a bifunctional enzyme that plays crucial roles in glycolysis, cell proliferation, cell survival, and cell adhesion. This study aimed to determine the role of PFKFB3 in angiotensin II (Ang II) kidney damage. We found that mice infused with Ang II developed glomerular podocyte detachment and impaired renal function accompanied by decreased PFKFB3 expression in vivo and in vitro. Inhibition of PFKFB3 with the PFKFB3 inhibitor 3PO further aggravated podocyte loss induced by Ang II. In contrast, activating PFKFB3 with the PFKFB3 agonist meclizine alleviated the podocyte loss induced by Ang II. Mechanistically, PFKFB3 knockdown likely aggravate Ang II-induced podocyte loss by suppressing talin1 phosphorylation and integrin beta1 subunit (ITGB1) activity. Conversely, PFKFB3 overexpression protected against Ang II-induced podocyte loss. These findings suggest that Ang II leads to a decrease in podocyte adhesion by suppressing PFKFB3 expression, and indicates a potential therapeutic target for podocyte injury in CKD.

Effect of food-to-microorganisms ratio on aerobic granular sludge settleability: Microbial community, potential roles and sequential responses of extracellular proteins and polysaccharides.

The food-to-microorganism ratio (F/M) is an important parameter in wastewater biotreatment that significantly affects the granulation and settleability of aerobic granular sludge (AGS). Hence, understanding the long-term effects and internal mechanisms of F/M on AGS settling performance is essential. This study investigated the relationship between F/M and the sludge volume index (SVI) within a range of 0.23-2.50 kgCOD/(kgMLVSS·d). Thiothrix and Candidatus_Competibacter were identified as two dominant bacterial genera influencing AGS settling performance. With F/M increased from 0.27 kgCOD/(kgMLVSS·d) to 1.53 kgCOD/(kgMLVSS·d), the abundance of Thiothrix significantly increased from 0.20% to 27.02%, and the hydrophobicity of extracellular proteins (PN) decreased, which collectively reduced AGS settling performance. However, under high-F/M conditions, the gel-like polysaccharides (PS) effectively retained the granular biomass by binding to the highly abundant Thiothrix (53.65%). The progressive increment in biomass led to a concomitant reduction in F/M, resulting in the recovery of AGS settleability. In addition, two-dimensional correlation infrared spectroscopy analysis revealed the preferential responses of PN and PS to the increase and decrease of F/M, and the content and characteristics of PN and PS played important roles in granular settling. The study provides insight into the microbial composition and the potential role of extracellular polymer substances in the AGS sedimentation behavior, offering valuable theoretical support for stable AGS operation.

Two-Dimensional Wedge-Shaped Magnetic EuS: Insight into the Substrate Step-Guided Epitaxial Synthesis on Sapphire.

Rare earth chalcogenides (RECs) with novel luminescence and magnetic properties offer fascinating opportunities for fundamental research and applications. However, controllable synthesis of RECs down to the two-dimensional (2D) limit still has a great challenge. Herein, 2D wedge-shaped ferromagnetic EuS single crystals are successfully synthesized via a facile molten-salt-assisted chemical vapor deposition method on sapphire. Based on the theoretical simulations and experimental measurements, the mechanisms of aligned growth and wedge-shaped growth are systematically proposed. The wedge-shaped growth is driven by a dual-interaction mechanism, where the coupling between EuS and the substrate steps impedes the lateral growth, and the strong bonding of nonlayered EuS itself facilitates the vertical growth. Through temperature-dependent Raman and photoluminescence characterization, the nanoflakes show a large Raman temperature coefficient of -0.030 cm-1 K-1 and uncommon increasing band gap with temperature. More importantly, by low-temperature magnetic force microscopy characterization, thickness variation of the magnetic signal is revealed within one sample, indicating the great potential of the wedge-shaped nanoflake to serve as a platform for highly efficient investigation of thickness-dependent magnetic properties. This work sheds new light on 2D RECs and will offer a deep understanding of 2D wedge-shaped materials.

Impact of Bile Duct Tumor Thrombus on the Long-Term Surgical Outcomes of Hepatocellular Carcinoma Patients: A Propensity Score Matching Analysis.

BACKGROUND: Hepatectomy with tumor thrombectomy is the preferred treatment option for hepatocellular carcinoma (HCC) patients with bile duct tumor thrombus (BDTT); however, the impact of BDTT on their prognosis is unclear. OBJECTIVE: We aimed to investigate the long-term surgical outcomes of HCC patients with BDTT. METHODS: The data of HCC patients with and without BDTT who underwent hepatectomy were retrospectively reviewed and the long-term outcomes were compared. For propensity score matching (PSM) analysis, patients were matched in a 1:1 ratio. Subgroup analysis was conducted according to the American Joint Committee on Cancer (AJCC) staging system. RESULTS: Before PSM, HCC patients with BDTT had more advanced tumor stages and adverse clinicopathological features. Recurrence-free survival (RFS) and overall survival (OS) were significantly higher in the non-BDTT group before PSM (RFS, p < 0.001; OS, p < 0.001), while after PSM, the BDTT group had significantly poorer RFS (p = 0.025). There was no difference in OS between the groups (p = 0.588). Subgroup analysis showed that RFS and OS in AJCC stage I-II patients were significantly poorer in the BDTT group; no differences were found in the AJCC stage III group before or after PSM. When the presence of BDTT was recommended to increase the AJCC staging system by one stage in AJCC stage I-II patients, the predictive ability for RFS and OS was higher. CONCLUSIONS: BDTT was associated with significantly poorer long-term surgical outcomes in AJCC stage I-II patients. A modified AJCC staging system including BDTT status in stage I-II might have a better prognostic ability.

Role of the Rigid Host Structure in Narrow-Band Green Emission of Eu2+ in Rb2Na2(Li3SiO4)4: Insights into Electron-Phonon Coupling.

Eu2+-activated alkali-lithosilicate phosphors exhibit narrow-band emissions that are attractive to high color-rendition and wide color-gamut displays. The microscopic mechanism behind the small emission bandwidth is not presently understood. Here, we report an explicit calculation of the vibronic process occurring in the narrow-band green emission of Rb2Na2[Li3SiO4]4:Eu2+. We show that due to the high rigidity of the host material, the structural strain induced by the localized Eu2+ 4f-5d excitation is distributed among the atoms far beyond the first coordination shell and hence reduces the local structural relaxation around Eu2+. The emission bandshape is thus mainly controlled by the coupling of the electronic transition with the phonon modes associated with motions of host constituent atoms, which was further validated by the good agreement of the calculated bandshape with the experiment. The results provide insights into the generation of narrow-band emission and improve our knowledge on electron-phonon coupling of 4f-5d transitions in phosphors.

Silver-catalyzed C-3 arylthiodifluoromethylation and aryloxydifluoromethylation of coumarins.

A facile silver-catalyzed oxidative decarboxylation of arylthiodifluoroacetic acids or aryloxydifluoroacetic acids with coumarins/quinoxalin-2(1H)-ones was developed. This transformation provided a series of C-3 aryloxydifluoromethylated or arylthiodifluoromethylated coumarins/quinoxalin-2(1H)-ones containing various functional groups in moderate to good yields, featuring good functional group tolerance, easily accessible starting materials and operational simplicity.

A new precursor to diversify BCN architectures with enhanced electromagnetic wave absorption.

Hexagonal BCN (h-BCN) is considered to be a promising dielectric ceramic material with a hybrid B-C-N structure and an electromagnetic wave (EMW) absorbing material with tenable properties. H-BCN bulk and microtube architectures are simultaneously synthesized by precursor pyrolysis method using BCl3, aniline (AN) and diethylenetriamine (DETA) as the raw material. By analyzing its electromagnetic parameters, the effective absorption bandwidth of the sample cracking at 900 °C with the proportion of raw materials (DETA:AN = 1:1) can be up to 7.2 GHz, and the minimum reflection loss can reach -43.6 dB at 7.92 GHz with a thickness of 3.5 mm. Moreover, the EMW absorbing property of the ceramic can be tuned by adjusting the ratio of monomers, pyrolysis temperature, and cooling rates.

Highly Oxidized Germacranolides from Elephantopus tomentosus and the Configurational Revision of Some Previously Reported Analogues.

Highly oxidized germacranolides are mainly found in the genus Elephantopus, contain a characteristic ten-membered molecular core that is highly flexible, and exhibit potential cytotoxic properties. However, their configurations were assigned ambiguously in previous reports due to spectroscopic observation of macrocyclic systems. Herein, 17 highly oxidized germacranolides, including 12 new germacranolides (1-12), were isolated from Elephantopus tomentosus. Their structures were characterized by spectroscopic data analysis combined with X-ray crystallography and ECD calculations, and it was possible to propose configurational revisions of five previously reported analogues (13-17). Cytotoxic activities for 1-17 against two hepatocellular carcinoma cell lines (HepG2 and Hep3B) were tested, and compounds 1-10 and 13-16 generated IC50 values of 2.2-9.8 µM. Furthermore, the observed cytotoxic activity of 1 was determined as being mediated by inducing the apoptosis of HepG2 and Hep3B cells via mitochondrial dysfunction.

Semisynthesis and Non-Small-Cell Lung Cancer Cytotoxicity Evaluation of Germacrane-Type Sesquiterpene Lactones from Elephantopus scaber.

Two series of germacrane-type sesquiterpene lactones were produced by semisynthetic modulation of scaberol C, which was prepared by a standard chemical transformation from an Elephantopus scaber extract. Their inhibition activities against non-small-cell lung cancer cells were screened, and preliminary structure-activity relationships were also established. Among them, monomeric analog 1u and dimeric analog 3d exhibited superior anti-non-small-cell lung cancer cytotoxic potencies with IC50 values of 4.3 and 0.7 µM against A549 cells, respectively, and were more active than cisplatin and the standard sesquiterpene lactones, parthenolide and scabertopin. Further studies revealed that compounds 1u and 3d cause G2/M phase arrest and induce apoptosis through the activation of mitochondrial pathways in A549 cells. Collectively, the results obtained suggest that compounds 1u and 3d are promising anti-non-small-cell lung cancer lead compounds.

Chamaejasmenin E from Stellera chamaejasme induces apoptosis of hepatocellular carcinoma cells by targeting c-Met in vitro and in vivo.

Hepatocellular carcinoma (HCC), the most prevalent liver cancer, is considered one of the most lethal malignancies with a dismal outcome. There is an urgent need to find novel therapeutic approaches to treat HCC. At present, natural products have served as a valuable source for drug discovery. Here, we obtained five known biflavones from the root of Stellera chamaejasme and evaluated their activities against HCC Hep3B cells in vitro. Chamaejasmenin E (CE) exhibited the strongest inhibitory effect among these biflavones. Furthermore, we found that CE could suppress the cell proliferation and colony formation, as well as the migration ability of HCC cells, but there was no significant toxicity on normal liver cells. Additionally, CE induced mitochondrial dysfunction and oxidative stress, eventually leading to cellular apoptosis. Mechanistically, the potential target of CE was predicted by database screening, showing that the compound might exert an inhibitory effect by targeting at c-Met. Next, this result was confirmed by molecular docking, cellular thermal shift assay (CETSA), as well as RT-PCR and Western blot analysis. Meanwhile, CE also reduced the downstream proteins of c-Met in HCC cells. In concordance with above results, CE is efficacious and non-toxic in tumor xenograft model. Taken together, our findings revealed an underlying tumor-suppressive mechanism of CE, which provided a foundation for identifying the target of biflavones.

UV-guided isolation of enantiomeric polyacetylenes from Bupleurum scorzonerifolium Willd. with inhibitory effects against LPS-induced NO release in BV-2 microglial cells.

UV-guided fractionation led to the isolation of thirteen new polyacetylenes (1-13) from the roots of Bupleurum scorzonerifolium Willd. All polyacetylenes were analyzed as racemates since the lack of optical activity and Cotton effects in the ECD spectra. The sequent chiral-phase HPLC resolution successfully gave twelve pairs of enantiomers 1a/1b and 3a/3b-13a/13b. Their structures were elucidated based on the HRESIMS and NMR data analyses. The absolute configurations were determined by the combination of Snatzke's method, electronic circular dichroism calculations, and single-crystal X-ray diffraction. Using Griess methods and MTT assays, polyacetylenes 1a, 3a, 4a/4b-12a/12b, and 13a displayed inhibitory activities against LPS-induced NO release in BV-2 microglial cells.