Fluorinated MOF-Based Hexafluoropropylene Nanotrap for Highly Efficient Purification of Octafluoropropane Electronic Specialty Gas.

High-purity octafluoropropane (C3F8) electronic specialty gas is a key chemical raw material in semiconductor and integrated circuit manufacturing industry, while selective removal of hexafluoropropylene (C3F6) impurity for C3F8 purification is essential but a challenging task. Here we report a fluorinated cage-like MOF Zn-bzc-CF3 (bzc=5-(trifluoromethyl)-1H-pyrazole-4-carboxylic acid) for C3F6/C3F8 separation. The incorporation of -CF3 groups not only provides suitable pore aperture size for highly efficient size-exclusive C3F6/C3F8 separation, but also creates hydrophobic microenvironments, endowing Zn-bz-CF3 high chemical stability. Remarkably, Zn-bzc-CF3 exhibits high C3F6 adsorption capacity while excluding C3F8, achieving ideal molecular-sieving C3F6/C3F8 separation. Breakthrough experiments show that Zn-bzc-CF3 can efficiently separate C3F6/C3F8 mixture and high-purity C3F8 (99.9 %) can be obtained.

Efficient and selective capture of thorium ions by a covalent organic framework.

The selective separation of thorium from rare earth elements and uranium is a critical part of the development and application of thorium nuclear energy in the future. To better understand the role of different N sites on the selective capture of Th(IV), we design an ionic COF named Py-TFImI-25 COF and its deionization analog named Py-TFIm-25 COF, both of which exhibit record-high separation factors ranging from 102 to 105. Py-TFIm-25 COF exhibits a significantly higher Th(IV) uptake capacity and adsorption rate than Py-TFImI-25 COF, which also outperforms the majority of previously reported adsorbents. The selective capture of Py-TFImI-25 COF and Py-TFIm-25 COF on thorium is via Th-N coordination interaction. The prioritization of Th(IV) binding at different N sites and the mechanism of selective coordination are then investigated. This work provides an in-depth insight into the relationship between structure and performance, which can provide positive feedback on the design of novel adsorbents for this field.

Step-Nucleation In Situ Self-Repair to Prepare Rollable Large-Area Ultrathin MOF Membranes.

Ultrathin membranes with ultrahigh permeance and good gas selectivity have the potential to greatly decrease separation process costs, but it requires the practical preparation of large area membranes for implementation. Metal-organic frameworks (MOFs) are very attractive for membrane gas separation applications. However, to date, the largest MOF membrane area reported in the literature is only about 100 cm2 . In the present study, a new step-nucleation in situ self-repair strategy is proposed that enables the preparation of large-area (2400 cm2 ) ultrathin and rollable MOF membranes deposited on an inexpensive flexible polymer membrane support layer for the first time, combining a polyvinyl alcohol (PVA)-metal-ion layer and a pure metal-ion layer. The main role of the pure metal-ion layer is to act as the main nucleation sites for MOF membrane growth, while the PVA-metal-ion layer acts as a slow-release metal-ion source, which supplements MOF crystal nucleation to repair any defects occurring. Membrane modules are necessary components for membrane applications, and spiral-wound modules are among the most common module formats that are widely applied in gas separation. A 4800 cm2 spiral-wound membrane module was successfully prepared, demonstrating the practical implementation of large-area MOF membranes.

Efficient Capture of Th(IV) and U(VI) by Radiation-Resistant Oxygen-Rich Ion Traps Based on a Metal-Organic Framework.

Herein, based on a well-stabilized Ti-MOF (IEF-11), an oxygen-rich ion trap with synergy interaction of active atoms was proposed for the removal of Th(IV) and U(VI) from aqueous solutions. Due to the high coordination number of Ti and compact framework structure, IEF-11 has excellent resistance toward ß-ray irradiation, even under 1000 kGy irradiation dosage. Meanwhile, owing to the special chelating effect of the oxygen-rich ion traps, the maximum adsorption amounts of IEF-11 for Th(IV) (pH = 3.0) and U(VI) (pH = 5.0) ions can reach 305.9 and 240.7 mg g-1, and the separation coefficients exceed 200 for Th(IV)/Nd(III), Th(IV)/Sm(III), and Th(IV)/Eu(III) and 100 for U(VI)/Eu(III), U(VI)/La(III), and U(VI)/Sr(II). Moreover, IEF-11 shows fast adsorption kinetics with an equilibrium time of ∼100 min. The adsorption amount almost remains even after four adsorption-desorption cycles. Finally, experimental and theoretical calculations indicate that Th(IV) and U(VI) ions are anchored in the ion trap in the form of chemical bonds. Meanwhile, the circular pore trap (class I trap) than the long pore trap (class II trap) is considered to be the better adsorption site. We expect that our work will provide a new insight for constructing effective adsorbents for radioactive nuclides.

Electro-Fenton mineralization of real textile wastewater by micron-sized ZVI powder anode.

The diverse compositions and complex nature of the textile wastewater make it imperative to find an economical and suitable degradation pathway. The degradation of real textile wastewater on a novel heterogeneous electro-Fenton system was carried out with a composite anode of magnetically fixed micron ZVI coupling with a Ti/RuO2-IrO2 sheet. The influences of different variables such as mZVI dosage, H2O2 amount, applied voltage and pH value on both total organic carbon and chemical oxygen demand removal efficiencies and energy consumption were investigated. The optimized parameters were simultaneously verified by using electrochemical workstation Tafel curves and Nyquist plots. The optimal operating conditions for evaluating the wastewater treatment were H2O2 dosage of 0.10 mol·L-1, applied voltage of 5.0 V, mZVI amount of 1.0 g·L-1 and initial pH value of 3.0. The high TOC and COD removal efficiencies of 92.44 and 82.84% could be achieved simultaneously in 60 min, respectively. XRD, XPS and SEM-EDS were used to investigate the interaction between the pollutant and the mZVI. GC-MS analysis was performed on untreated and treated wastewater to determine the degradation of pollutants in dyeing wastewater during the electro-Fenton process and to effectively propose a suitable degradation mechanism for this system.

Theoretical Screening of CO2 Electroreduction over MOF-808-Supported Self-Adaptive Dual-Metal-Site Pairs.

Electrochemical CO2 reduction to transportation fuels and valuable platform chemicals provides a sustainable avenue for renewable energy storage and realizes an artificially closed carbon loop. However, the rational design of highly active and selective CO2 reduction electrocatalysts remains a challenging task. Herein, a series of metal-organic framework (MOF)-supported flexible, self-adaptive dual-metal-site pairs (DMSPs) including 21 pairwise combinations of six transition metal single sites (MOF-808-EDTA-M1M2, M1/M2 = Fe, Cu, Ni, Pd, Pt, Au) for the CO2 reduction reaction (CO2RR) were theoretically screened using density functional theory calculations. Against the competitive hydrogen evolution reaction, MOF-808-EDTA-FeFe and MOF-808-EDTA-FePt were identified as the promising CO2RR electrocatalysts toward C1 and C2 products. The calculated limiting potential for CO2 electroreduction to C2H6 and C2H5OH over MOF-808-EDTA-FeFe is -0.87 V. Compared with an applied potential of -0.56 eV toward CH4 production over MOF-808-EDTA-FeFe, MOF-808-EDTA-FePt exhibits an even better activity for CO2 reduction to C1 products at a limiting potential of -0.35 V. The present work not only identifies promising candidates for highly selective CO2RR electrocatalysts leading to C1 and C2 products but also provides mechanistic insights into the dynamic nature of DMSPs for stabilizing various reaction intermediates in the CO2RR process.

Stepwise Engineering the Pore Aperture of a Cage-like MOF for the Efficient Separation of Isomeric C4 Paraffins under Humid Conditions.

The separation of isomeric C4 paraffins is an important task in the petrochemical industry, while current adsorbents undergo a trade-off relationship between selectivity and adsorption capacity. In this work, the pore aperture of a cage-like Zn-bzc (bzc=pyrazole-4-carboxylic acid) is tuned by the stepwise installation methyl groups on its narrow aperture to achieve both molecular-sieving separation and high n-C4 H10 uptake. Notably, the resulting Zn-bzc-2CH3 (bzc-2CH3 =3,5-dimethylpyrazole-4-carboxylic acid) can sensitively capture n-C4 H10 and exclude iso-C4 H10 , affording molecular-sieving for n-C4 H10 /iso-C4 H10 separation and high n-C4 H10 adsorption capacity (54.3 cm3 g-1 ). Breakthrough tests prove n-C4 H10 /iso-C4 H10 can be efficiently separated and high-purity iso-C4 H10 (99.99 %) can be collected. Importantly, the hydrophobic microenvironment created by the introduced methyl groups greatly improves the stability of Zn-bzc and significantly eliminates the negative effect of water vapor on gas separation under humid conditions, indicating Zn-bzc-2CH3 is a new benchmark adsorbent for n-C4 H10 /iso-C4 H10 separation.

Two New C19 -Diterpenoid Alkaloids from Delphinium shawurense.

Shawurenine C (1a) and D (1b), a new pair of regioisomeric C19 -diterpenoid alkaloids, and five known C19 -diterpenoid alkaloids (2-6) were isolated from the aerial part of Delphinium shawurense W. T. Wang. The chemical structures of new compounds were established based on spectroscopic analyses: HR-ESI-MS, and 1D, 2D NMR spectroscopic data. The anti-inflammatory and cytotoxic activities of these diterpenoid alkaloids were also evaluated.

A national survey on how to improve traditional Chinese medicine learning internationally: Perceptions from both teachers and students.

Background: With the increasing popularity of traditional Chinese medicine (TCM) by the global community, how to teach basic knowledge of TCM to international students and improve the teaching quality are important issues for teachers of TCM. The present study was to analyze the perceptions from both students and teachers on how to improve TCM learning internationally. Methods: A cross-sectional national survey was conducted at 23 universities/colleges across China. A structured, self-reported on-line questionnaire was administered to 34 Chinese teachers who taught TCM course in English and to 1016 international undergraduates who were enrolled in the TCM course in China between 2017 and 2021. Results: Thirty-three (97.1%) teachers and 900 (88.6%) undergraduates agreed Chinese culture should be fully integrated into TCM courses. All teachers and 944 (92.9%) undergraduates thought that TCM had important significance in the clinical practice. All teachers and 995 (97.9%) undergraduates agreed that modern research of TCM is valuable. Thirty-three (97.1%) teachers and 959 (94.4%) undergraduates thought comparing traditional medicine in different countries with TCM can help the students better understand TCM. Thirty-two (94.1%) teachers and 962 (94.7%) undergraduates agreed on the use of practical teaching method with case reports. From the perceptions of the undergraduates, the top three beneficial learning styles were practice (34.3%), teacher's lectures (32.5%), case studies (10.4%). The first choice of learning mode was attending to face-to-face teaching (82.3%). The top three interesting contents were acupuncture (75.5%), Chinese herbal medicine (63.8%), and massage (55.0%). Conclusion: To improve TCM learning among international undergraduates majoring in conventional medicine, integration of Chinese culture into TCM course, comparison of traditional medicine in different countries with TCM, application of the teaching method with case reports, and emphasization of clinical practice as well as modern research on TCM should be fully considered.

Combined Skeleton and Spatial Rigidification of AIEgens in 2D Covalent Organic Frameworks for Boosted Fluorescence Emission and Sensing of Antibiotics.

AIEgens show relatively weak fluorescence performance owing to the existence of π-π interlayer accumulation, molecular layer planarization, and intramolecular rotation in aggregation-induced emission (AIE) molecules, which limit its application scope. Herein, we put forward a combined skeleton and spatial rigidification method to boost the fluorescence emission efficiency of AIEgens. As a proof-of-concept experiment, two highly fluorescent covalent organic frameworks (COFs) were designed and constructed by the Knoevenagel condensation reaction. The experimental results show that the combined skeleton and spatial rigidification endowed excellent fluorescence emission for the resulting F-COF-2 by destruction of the π-π interlayer accumulation, interference of the molecular layer planarization, and restriction of the intramolecular rotation of the AIEgen unit. F-COF-2 displayed highly sensitive and selective NFT and NZF detection. Particularly, the Ksv value and limit of detection of F-COF-2 toward NFT were estimated to be 9.12 × 105 M-1 and 3.35 ppb, respectively, which surpassed all the reported crystalline porous fluorescent materials. The mechanism study proved that its outstanding fluorescence detection property was ascribed to the formation of a nonfluorescent complex induced by hydrogen bond interactions and electron transfer between F-COF-2 and NFT and NZF. This work not only proposes a combined skeleton and spatial rigidification strategy to improve the fluorescence efficiency of AIE molecules but also develops a sensor with high fluorescence efficiency, high chemical stability, and highly efficient detection of antibiotics.

Unveiling Secondary-Ion-Promoted Catalytic Properties of Cu-SSZ-13 Zeolites for Selective Catalytic Reduction of NOx.

The incorporation of secondary metal ions into Cu-exchanged SSZ-13 zeolites could improve their catalytic properties in selective catalytic reduction of NOx with ammonia (NH3-SCR), but their essential roles remain unclear at the molecular level. Herein, a series of Cu-Sm-SSZ-13 zeolites have been prepared by ion-exchanging Sm ions followed by Cu ions, which exhibit superior NH3-SCR performance. The NO conversion of Cu-Sm-SSZ-13 is nearly 10% higher than that of conventional Cu-SSZ-13 (175-250 °C) after hydrothermal ageing, showing an enhanced low-temperature activity. The Sm ions are found to occupy the six-membered rings (6MRs) of SSZ-13 by X-ray diffraction Rietveld refinement and aberration-corrected scanning transmission electron microscopy. The Sm ions at 6MRs can facilitate the formation of more active [ZCu2+(OH)]+ ions at 8MRs, as revealed by temperature-programmed reduction of hydrogen. X-ray photoelectron spectroscopy and density functional theory (DFT) calculations indicate that there exists electron transfer from Sm3+ to [ZCu2+(OH)]+ ions, which promotes the activity of [ZCu2+(OH)]+ ions by decreasing the activation energy of the formation of intermediates (NH4NO2 and H2NNO). Meanwhile, the electrostatic interaction between Sm3+ and [ZCu2+(OH)]+ results in a high-reaction energy barrier for transforming [ZCu2+(OH)]+ ions into inactive CuOx species, thus enhancing the stability of [ZCu2+(OH)]+ ions. The influence of the ion-exchanging sequence of Sm and Cu ions into SSZ-13 is further investigated by combining both experiments and theoretical calculations. This work provides a mechanistic insight of secondary ions in regulating the distribution, activity, and stability of Cu active sites, which is helpful for the design of high-performance Cu-SSZ-13 catalysts for the NH3-SCR reaction.

Effects of Ruanmailing in Blocking Early Stages of Atherosclerosis by TNF-α Regulation via Kir2.1.

Objective: Ruanmailing oral solution consists of 16 herbs, has anti-lipid peroxidation activity, protects vascular endothelial cells, and improves vascular elasticity. It is an effective drug for the treatment of atherosclerosis (AS). The objective of this study was to investigate the mechanism underlying the antiatherosclerotic effects of Ruanmailing oral solution. Methods: Macrophages were isolated, cultured, and divided into the macrophage control; macrophage foam cell; and low-, medium-, and high-concentration Ruanmailing groups. Cell proliferation was analyzed by cell counting kit-8 (CCK-8) assay, and the expression levels of inward-rectifier potassium ion channel 2.1 (Kir2.1) and tumor necrosis factor (TNF)-α were detected by reverse transcription-polymerase chain reaction (RT-PCR) and Western blot analyses. Results: CCK-8 assay results showed that the tested concentrations of Ruanmailing solution did not affect macrophage proliferation. RT-PCR and Western blot assays indicated that TNF-α expression increased significantly with the formation of macrophage foam cells (P < 0.05). In addition, significant decreases in Kir2.1 and TNF-α expression were observed following treatment with various concentrations of Ruanmailing (P < 0.05). Conclusion: Based on the results, Ruanmailing affects macrophage foam cell formation by regulating Kir2.1 expression, which in turn reduces TNF-α expression and exerts antiatherosclerotic effects. These findings provide a scientific basis for the use of traditional Chinese medicine for AS treatment.

Electrochemical nitrate removal by magnetically immobilized nZVI anode on ammonia-oxidizing plate of RuO2-IrO2/Ti.

Ammonium as the major reduction intermediate has always been the limitation of nitrate reduction by cathodic reduction or nano zero-valent iron (nZVI). In this work, we report the electrochemical nitrate removal by magnetically immobilized nZVI anode on RuO2-IrO2/Ti plate with ammonia-oxidizing function. This system shows maximum nitrate removal efficiency of 94.6% and nitrogen selectivity up to 72.8% at pH of 3.0, and it has also high nitrate removal efficiency (90.2%) and nitrogen selectivity (70.6%) near neutral medium (pH = 6). As the increase of the applied anodic potentials, both nitrate removal efficiency (from 27.2% to 94.6%) and nitrogen selectivity (70.4%-72.8%) increase. The incorpration of RuO2-IrO2/Ti plate with ammonia-oxidizing function on the nZVI anode enhances the nitrate reduction. The dosage of nZVI on RuO2-IrO2/Ti plate (from 0.2 g to 0.6 g) has a slight effect (the variance is no more than 10.0%) on the removal performance. Cyclic voltammetry, Tafel analysis and electrochemical impedance spectroscopy (EIS) were further used to investigate the reaction mechanisms occurring on the nZVI surfaces in terms of CV curve area, corrosion voltage, corrosion current density and charge-transfer resistance. In conclusion, high nitrate removal performance of magnetically immobilized nZVI anode coupled with RuO2-IrO2/Ti plate may guide the design of improved electrochemical reduction by nZVI-based anode for practical nitrate remediation.

MAFLD Criteria May Overlook a Subtype of Patient with Steatohepatitis and Significant Fibrosis.

INTRODUCTION: Metabolic associated fatty liver disease (MAFLD) is a novel concept for fatty liver disease. Different from non-alcoholic fatty liver disease (NAFLD), the diagnosis of MAFLD requires the presence of metabolic risks. This study aimed to characterize patients with liver steatosis but without metabolic risks (non-MR-steatosis) which may not be diagnosed by MAFLD criteria. METHODS: Consecutive patients who underwent biopsy were included in this study. The clinic-pathological characteristics of non-MR-steatosis, NAFLD and MAFLD were compared. RESULTS: A total of 1217 cases were included. There were 426 (35.00%) cases with MAFLD, 585 (48.07%) with NAFLD and 168 (13.80%) with non-MR-steatosis. The majority of the cases were infected with HBV (93.26%). The age and metabolic profiles were highest in MAFLD and lowest in non-MR-steatosis. The body mass index (BMI) level was also lowest in non-MR-steatosis (20.78 ± 1.54 kg/m2). The ALT and AST levels of the non-MR-steatosis group were not statistically different from those of MAFLD or NAFLD groups (p > 0.05). Histologically, there was no significant difference in the degrees of inflammation and fibrosis among the three groups. The severity of steatosis in non-MR-steatosis group was lower than MAFLD or NAFLD groups (p < 0.05). These results were consistent in both HBV and non-HBV subgroups. CONCLUSION: MAFLD criteria may overlook some steatotic patients without metabolic risks, who may also have steatohepatitis and significant fibrosis.

Efficient separation of vitamins mixture in aqueous solution using a stable zirconium-based metal-organic framework.

High-efficiency separation of niacin (NIA) and nicotinamide (NIC) still faces large challenge up to date. In this work, a stable zirconium-based metal-organic framework (DUT-67) was used to adsorb and separate NIA and NIC in aqueous solutions. The adsorption capacities for NIA and NIC at the concentration ratio of 1:1 were 110.2 mg g-1 and 11.2 mg g-1, respectively. Further study indicates that low ratio of NIA/ NIC is in favor of the separation. High temperature can restrain the adsorptions of NIA and NIC but promote the separation. Besides, DUT-67 can be well regenerated via a simple method. Mechanism analysis indicates that electrostatic interaction plays a critical role in the separation of these vitamins.

Norditerpenoid alkaloids from Delphinium pseudoaemulans C. Y. Yang et B. Wang.

Eight previously undescribed norditerpenoid alkaloids, pseudophnines A-D, pseudorenines A-B, and pseudonidines A-B, together with ten known norditerpenoid alkaloids, tianshanisine E, sharwuphinine B, potanisine A, lycoctonine, delbruline, isondelpheline, delavaines A-B, and shawurenines A-B were isolated from the whole plant of Delphinium pseudoaemulans C. Y. Yang et B. Wang. Their structures were established on the basis of spectroscopic analyses, including HR-ESI-MS, 1D and 2D NMR analysis. Additionally, no cytotoxicity was observed against A549 and HeLa cancer cells of these diterpenoid alkaloids when evaluated in vitro using the MTT method.

The effect of sintering process on lithium ionic conductivity of Li6.4Al0.2La3Zr2O12 garnet produced by solid-state synthesis.

Recently, solid-state electrolyte lithium lanthanum zirconium oxide garnet (Li7La3Zr2O12, LLZO) has attracted great attention due to its high room temperature conductivity of lithium ions and stability against lithium metal electrodes. The Al-doped cubic garnet Li6.4Al0.2La3Zr2O12 was synthesized by a conventional solid-state method at different sintering temperatures. The influence of the sintering process on the structure and ionic conductivity was investigated by X-ray diffraction, electrochemical impedance spectroscopy, and scanning electron microscopy. The results showed that Li vaporization and relative density were affected by the sintering process. The synergistic effects of Li concentration and relative density determined the Li+ ionic conductivity. Compared with the relative density, the Li concentration plays a more important role in determining the ionic conductivity via the solid-state method.

Linkage between human population and trace elements in soils of the Pearl River Delta: Implications for source identification and risk assessment.

The human population is both an emitter and receptor of metals. This study aims to clarify how the relationship of metals and metalloids to human populations influences their source characterization and health risk, based on metal concentrations in 298 soil samples in the Pearl River Delta (PRD) and the corresponding zip-code level population. Nickel (Ni), copper (Cu), zinc (Zn), cadmium (Cd), mercury (Hg), and lead (Pb), but not chromium (Cr) and arsenic (As), were significantly correlated with population (p<0.01), suggesting potential anthropogenic sources. A principal component analysis (PCA) revealed three factors (i.e., F1, F2, and F3) contributing to metal levels in the PRD: (1) metal transport from rivers (F1), which explained the high levels of Cr, Ni, Cu, Zn, As, and Cd in downstream areas; (2) industrial sources (F2), mainly contributing to Ni, Cu, Zn, Cd, Hg, and Pb; and (3) natural and agricultural sources (F3), mainly contributing to As and Pb. F2 was significantly correlated with population, while F3 was not, indicating that an analysis of the correlation with population could be used to identify industrial sources of metals. Compared with directly calculated risks, the population-weighted non-carcinogenic and carcinogenic risks were increased by 4.2-4.9% and 7.7-9.2%, respectively. A unit increase in the concentration of industrial metals led to higher extra risks than a corresponding increase in natural metals due to the proximity to human populations.

Fluoride-induced apoptosis and expressions of caspase proteins in the kidney of carp (Cyprinus carpio).

The study was conducted to investigate oxidative stress, apoptosis, and protein expressions of caspase-3, 8, and 9 in kidney of the carp juveniles exposed to 0, 40, 80, 120, and 160 mg L(-1) of fluoride (in the form of NaF) for 90 days. The results showed that dose- and time-dependent decrease of SOD and GSH and dose- and time-dependent increase of MDA were observed in the carp juveniles, which suggested that fluoride induced oxidative damage accompanied with morphological changes and significant apoptosis in fish exposed to fluoride, especially in the higher doses. Fluoride exposure also significantly elevated the protein expressions of caspase-3, 8, and 9. In conclusion, these results indicate that chronic exposure to fluoride causes oxidative stress, damages the kidney structure, and results in renal apoptosis by caspase-dependent pathway.