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High-hardness TaN compacts with a diameter and height of 6 mm were synthesized through the phase transformation of CoSn-type into WC-type TaN under experimental conditions of high temperature and high pressure. The Vickers hardness of WC-type TaN compacts obtained at the pressure of 5 GPa and the temperature of 1873 K is found to be ~21.5 ± 1.5 GPa with a load of 3 Kg, which is comparable to that of the pure tungsten carbide compact (~20 GPa) and higher than those of ultrahigh temperature ceramics ZrB2 and HfB2 under the same load. The high hardness of WC-type TaN compacts presented in this work is attributed to the deviatoric strain and well-bonded nanograins. The synthesized WC-type TaN compacts also possess a high oxidation temperature (1072 K). These results suggest that the WC-type TaN with high hardness and high thermal stability holds great promise for industrial applications.

Fracture healing is a complex event with the involvement of many cell systems, cytokines, as well as mRNAs. Herein, we report the interactions among long noncoding RNA X-inactive specific transcript (XIST)/microRNA-135 (miR-135)/cAMP response element-binding protein 1 (CREB1) axis during fracture healing. We observed increased expression of XIST in patients with long-term unhealed fracture by microarray analysis. Subsequently, a mouse model with tibial fracture and a cell model using osteoblast-like MC3T3-E1 cells were generated. The XIST overexpression during fracture healing decreased proliferation and differentiation of MC3T3-E1 cells, while silencing of XIST facilitated MC3T3-E1 cell growth. Furthermore, miR-135 targeted CREB1 and negatively regulated its expression. XIST acted as a sponge for miR-135, thereby upregulating CREB1 and promoting the activity of the TNF-α/RANKL pathway. Transfection of miR-135 inhibitor or CREB1 overexpression blocked the stimulating effects of XIST knockdown on MC3T3-E1 cell growth. Besides, specific inhibitors of the TNF-α/RANKL pathway reversed the repressive role of XIST in cell osteogenic differentiation. All in all, these findings suggest that XIST knockdown induces the differentiation of osteoblast-like cells via regulation of the miR-135/CREB1/TNF-α/RANKL axis. XIST, as a consequence, represents an attractive therapeutic strategy to accelerate fracture healing.

Single-atom catalysts (SACs) have demonstrated excellent performances in chemoselective hydrogenation reactions. However, the employment of precious metals and/or organic solvents compromises their sustainability. Herein, we for the first time report the chemoselective hydrogenation of 3-nitrostyrene over noble-metal-free Co-N-C SAC in green solvent — compressed CO2. An interesting inverted V-curve relation is observed between the catalytic activity and CO2 pressure, where the conversion of 3-nitrostyrene reaches the maximum of 100% at 5.0 MPa CO2 (total pressure of 8.1 MPa). Meanwhile, the selectivities to 3-vinylaniline at all pressures remain high (> 99%). Phase behavior studies reveal that, in sharp contrast with the single phase which is formed at total pressure above 10.8 MPa, bi-phase composed of CO2/H2 gas-rich phase and CO2-expanded substrate liquid phase forms at total pressure of 8.1 MPa, which dramatically changes the reaction kinetics of the catalytic system. The reaction order with respect to H2 pressure decreases from ~0.5 to zero at total pressure of 8.1 MPa, suggesting the dissolved CO2 in 3-nitrostyrene greatly promotes the dissolution of H2 in the substrate, which is responsible for the high catalytic activity at the peak of the inverted V-curve.

Atomically dispersed M-N-C (M refers to transition metals) materials represent the most promising catalyst alternatives to the precious metal Pt for the electrochemical reduction of oxygen (ORR), yet the genuine active sites in M-N-C remain elusive. Here, we develop a two-step approach to fabricate Cu-N-C single-atom catalysts with a uniform and well-defined Cu2+-N4 structure that exhibits comparable activity and superior durability in comparison to Pt/C. By combining operando X-ray absorption spectroscopy with theoretical calculations, we unambiguously identify the dynamic evolution of Cu-N4 to Cu-N3 and further to HO-Cu-N2 under ORR working conditions, which concurrently occurs with reduction of Cu2+ to Cu+ and is driven by the applied potential. The increase in the Cu+/Cu2+ ratio with the reduced potential indicates that the low-coordinated Cu+-N3 is the real active site, which is further supported by DFT calculations showing the lower free energy in each elemental step of the ORR on Cu+-N3 than on Cu2+-N4. These findings provide a new understanding of the dynamic electrochemistry on M-N-C catalysts and may guide the design of more efficient low-cost catalysts.

Trauma‐induced osteonecrosis of the femoral head (TIONFH) is characterized by femoral head collapse accompanied by degenerative changes of the hip. We previously reported that miR‐93‐5p expression is abnormally high in patients with TIONFH, but the role of miR‐93‐5p in the TIONFH process remains unclear. Herein, we investigated the role of miR‐93‐5p in TIONFH in a rabbit model. Bone marrow mesenchymal stem cells (BMSCs) were used for both in vivo and in vitro experiments. A rabbit model of TIONFH was injected with BMSCs transfected with miR‐93‐5p inhibitor. In addition, both an miR‐93‐5p mimic and negative control were transfected into BMSCs. Expression of miR‐93‐5p was significantly increased in the model group compared with control samples. An miR‐93‐5p inhibitor induced the expression of bone morphogenetic protein 2 (BMP‐2) and alkaline phosphatase. Furthermore, expression of osteogenesis‐related markers (BMP‐2, secreted phosphoprotein 1, RUNX family transcription factor 2 and Osterix) was higher in the miR‐93‐5p inhibitor group, as revealed by quantitative PCR and western blotting. In addition, in vitro experimentation revealed that an miR‐93‐5p mimic decreased BMP‐2 and TNF receptor superfamily member 11b expression, but increased receptor activator of nuclear factor‐kappaB ligand expression. In summary, the miR‐93‐5p inhibitor could promote osteogenic differentiation by increasing BMP‐2 expression during the development of TIONFH. Thus, miR‐93‐5p may have potential as a therapeutic target for TIONF treatment., Here, we investigated the role of miR‐93‐5p in a rabbit trauma‐induced osteonecrosis of the femoral head model and in vitro using bone marrow mesenchymal stem cells. In vivo, miR‐93‐5p expression was significantly increased in the model group, and its inhibition resulted in an increase in the level of osteogenesis‐related markers. In vitro, application of a miR‐93‐5p mimic led to a decrease in bone morphogenetic protein 2 expression. Thus, inhibition of miR‐93‐5p may promote osteogenic differentiation in trauma‐induced osteonecrosis of the femoral head.

Fine-tuning of the coordination environment of single-atom catalysts (SACs) is effective to optimize their catalytic performances, yet it remains challenging due to the vulnerability of SACs. Herein, we report a new approach to engineering the coordination environment of M-N-C (M = Fe, Co, and Ni) SACs by using glutamic acid as the N/C source and pyrolysis atmosphere as a regulator. Compared with that in N2, NH3 was able to promote the doping of N at T < 700 °C yet etch the N-species at higher temperatures, by which the M-N coordination number (CN) and the electronic structure were delicately tuned. It was found that the electron density of Ni single atoms increased with the decrease of Ni-N CN. As a consequence, the capability of Ni-N-C to dissociate H2 was greatly enhanced and a higher catalytic activity in chemoselective hydrogenation of functionalized nitroarenes was achieved. Moreover, this modulation method could be applied to other transition metals including Fe and Co. In particular, the as-synthesized Co-N-C SAC afforded a turnover frequency of 152.3 h−1 with 99% selectivity to 3-vinylaniline in the hydrogenation of 3-nitrostyrene, which was the highest ever reported thus far and was at least one order of magnitude more active than state-of-the-art noble-metal-free M-N-C catalysts, demonstrating the great potential of engineering the coordination environment of SACs.

Carbon fiber composites composed of carbon fiber and pyrolytic carbon (PyC) matrix have great potential application in the brakes of aircrafts, where the combination of high mechanical strength and excellent frictional properties are required. In this work, two-component silicon-based interlocking enhancements were designed and constructed into carbon fiber composites for boosting the mechanical and frictional properties. Specially, silicon carbide nanowires (SiCnws) and silicon nitride nanobelts (Si3N4nbs) could form interlocking architectures, where SiCnws are rooted firmly on the carbon fiber surface in the radial direction and Si3N4nbs integrate the PyC matrix with carbon fibers together via a networked shape. SiCnws-Si3N4nbs not only refine the PyC matrix but also promote the bonding of the fiber/matrix interface and the cohesion strength of the PyC matrix, thus enhancing the mechanical and frictional properties. Benefiting from the SiCnws-Si3N4nbs synergistic effect and interlocking enhancement mechanism, the interlaminar shear strength and compressive strength of carbon fiber composites increased by 88.41% and 73.40%, respectively. In addition, the friction coefficient and wear rate of carbon fiber composites decreased by 39.50% and 69.88%, respectively. This work could open up an interlocking enhancement strategy for efficiently fabricating carbon fiber composites and promoting mechanical and frictional properties that could be used in the brakes of aircrafts.

Cobalt–free perovskites Ln0.5Sr0.5Fe0.9Mo0.1O3–δ (Ln = lanthanide; LnSFM) were prepared via a sol–gel process. Pure rhombohedral phases were still not obtained for the samples (Ln = Sm and Gd) even sintered at 1300 °C. Thus, only the LaSFM, PrSFM and NdSFM compositions were assessed as IT–SOFC cathodes in terms of their thermal, electrical and electrochemical properties. Thermal expansion of the LnSFM was well compatible with that of Sm0.2Ce0.8O1.9 (SDC) electrolyte. Both conductivity and electrochemical performances of the LnSFM followed the same sequence of La > Nd > Pr. For the LaSFM, NdSFM and PrSFM cathodes, peak conductivities reached 73, 63 and 59 S·cm–1 at 650 °C; polarization resistances attained 0.211, 0.446 and 0.469 Ω·cm2 at 700 °C; peak power densities of the LnSFM cells with 300–μm–thick SDC electrolyte achieved 269, 261 and 233 mW·cm–2 at 700 °C without cell degradation for operating 100 h. By comprehensive comparison, the LaSFM is assessed as a preferred cobalt–free ceramic cathode for IT–SOFC.

Chemoselective hydrogenation of unsaturated aldehyde to unsaturated alcohol has attracted growing interests in recent years due to its widespread applications in fine chemicals. However, the hydrogenation of the C=O bond was thermodynamically and kinetically unfavorable over the hydrogenation of the C=C bond. Thus, to obtain the unsaturated alcohol from the unsaturated aldehyde is very difficult in most of the catalytic systems. In this work, ZnAl-hydrotalcite-supported cysteine-capped Au25 nanoclusters were used as the precatalysts for chemoselective hydrogenation of cinnamaldehyde to cinnamyl alcohol. The catalyst showed stable high selectivity (~ 95%) at prolonged reaction time and complete conversion of the substrate. According to the results of the control experiments, the in-situ DRIFTS of the substrate under high pressure of hydrogen and the 27Al MAS-NMR spectroscopy, we proposed that the difference of the preferential adsorption of the C=O bond to that of the C=C bond was derived from the nature of the support of the gold catalysts.

We have created a novel glutathione S-transferase π1 (gstp1) knockout (KO) zebrafish model and used it for comparative analyses of redox homeostasis and response to drugs that cause endoplasmic reticulum (ER) stress and induce the unfolded protein response (UPR). Under basal conditions, gstp1 KO larvae had higher expression of antioxidant nuclear factor erythroid 2-related factor 2 (Nrf2) accompanied by a more reduced larval environment and a status consistent with reductive stress. Compared with wild type, various UPR markers were decreased in KO larvae, but treatment with drugs that induce ER stress caused greater toxicities and increased expression of Nrf2 and UPR markers in KO. Tunicamycin and 02-{2,4-dinitro-5-[4-(N-methylamino)benzoyloxy]phenyl}1-(N,N-dimethylamino)diazen-1-ium-1,2-diolate (PABA/nitric oxide) activated inositol-requiring protein-1/X-box binding protein 1 pathways, whereas thapsigargin caused greater activation of protein kinase-like ER kinase/activating transcription factor 4/CHOP pathways. These results suggest that this teleost model is useful for predicting how GSTP regulates organismal management of oxidative/reductive stress and is a determinant of response to drug-induced ER stress and the UPR. SIGNIFICANCE STATEMENT: A new zebrafish model has been created to study the importance of glutathione S-transferase π1 in development, redox homeostasis, and response to drugs that enact cytotoxicity through endoplasmic reticulum stress and induction of the unfolded protein response.

Myofibrillar protein accounting for about 60% of total muscle proteins is expected to be a promising source of bioactive peptides. The purpose of the present study was to purify antioxidant peptides from myofibrillar protein hydrolysate of chicken breast by ultrafiltration and gel filtration chromatography, and evaluate their chemical antioxidant activities and protective effects in H2O2-stressed NIH-3T3 cells. Four major peptides were identified using nano-LC-ESI-MS/MS as ITTNPYDY, IGWSPLGSL, ITTNPYDYHY, and LRVAPEEHPTL. The sequenced peptides were synthesized and exhibited remarkable radical-scavenging ability, ORAC (108.2–133.5 μM TE per mg peptide), and FRAP (75.4–92.5 mM Fe2+ per mg peptide). Structure–activity relationship indicated that the antioxidant capacity of the peptides was more related to the presence of hydrophobic and antioxidant amino acids (including Trp, Val, Ile, Leu, Ala, Pro, Gly, Asp, His, and Tyr) in the sequences as well as their molecular structures. Moreover, they protected NIH-3T3 cells against oxidative damage through inhibiting ROS generation and lipid peroxidation. Especially, the antioxidant peptides ITTNPYDY and IGWSPLGSL significantly (p < 0.05) elevated intracellular glutathione level and antioxidant enzyme activities, and suppressed apoptosis by blocking caspase-3 activation. This work highlights that the selected peptides may serve as functional food ingredients with antioxidant and cytoprotective characteristics.

Although vanadium (V)-based sulfides have been investigated as cathodes for aqueous zinc-ion batteries (ZIBs), the performance improvement and the intrinsic zinc-ion (Zn2+) storage mechanism revelation is still challenging. Here, VS4@rGO composite with optimized morphology is designed and exhibits ultrahigh specific capacity (450 mA h g−1 at 0.5 A g−1) and high-rate capability (313.8 mA h g−1 at 10 A g−1) when applied as cathode material for aqueous ZIBs. Furthermore, the VS4@rGO cathode presents long-life cycling stability with capacity retention of ∼82% after 3500 cycles at 10 A g−1. The structural evolution, redox, and degradation mechanisms of VS4 during (dis)charge processes are further probed by in situ XRD/Raman techniques and TEM analysis. Our results indicate that the main energy storage mechanism is derived from the intercalation/deintercalation reactions in the open channels of VS4. Notably, an irreversible phase transition of VS4 into Zn3(OH)2V2O7·2H2O (ZVO) during the charging process and the further transition from ZVO to ZnV3O8 during long-term cycles are also observed, which might be the main reason leading to the capacity degradation of VS4@rGO. Our study further improves the electrochemical performance of VS4 in aqueous ZIBs through morphology design and provides new insights into the energy storage and performance degradation mechanisms of Zn2+ storage in VS4, and thus may endow the large-scale application of V-based sulfides for energy storage systems.

The genus Limonium includes important halophyte plants containing a variety of bioactive compounds of therapeutic interest. In the present work, the untargeted phytochemical profiles of both aerial part and root extracts from six Limonium species namely, L. bellidifolium, L. globuliferum, L. gmelinii, L. lilacinum, L. sinuatum and L. iconicum from Turkey were determined. Furthermore, several biological activities (in vitro antioxidant and enzyme inhibitory effects) were investigated. Overall, significant amounts of total phenolics (43.64-238.18 mg g-1) and flavonoids (1.61-129.69 mg g-1) were recorded. Particularly, the root extracts of L. gmelinii, L. iconicum and L. globuliferum showed the highest total phenolic content (204.13-238.18 mg g-1), whilst the highest total flavonoid content was recorded in the root extracts of L. gmelinii (129.69 mg g-1). Overall, the tested extracts demonstrated potent radical scavenging activities in both DPPH (2,2- diphenyl-1-picrylhydrazyl) and ABTS (3-ethylbenzothiazoline-6-sulphonic acid) (90.10-507.94 mg g-1 and 163.39-1175.34 mg g-1, respectively). However, the highest scavenging potential (p < 0.05) was displayed by the root extracts of L. iconicum. Conversely, the metal chelating ability assay revealed that L. lilacinum root extract showed the highest activity (21.03 mg g-1). Interestingly, all the extracts were found to be active inhibitors of cholinesterases (AChE (acetylcholinesterase): 4.20-5.11 mg GALAE (galantamine equivalent) per g; BChE (butyrylcholinesterase): 3.89-10.75 mg GALAE per g), amylase (0.52-1.09 mmol ACAE (acarbose equivalent) per g) and tyrosinase (119.41-155.67 mg KAE (kojic acid equivalent) per g), unlike for glucosidase (2.31-2.41 mmol ACAE per g). Taken together, these findings demonstrated a diverse chemical profiles and biological of the extracts, to be potentially considered as phytotherapeutic or functional ingredients due to their antioxidant properties and inhibition of key enzymes involved in several diseases.

In this experiment, a liquid chromatography tandem mass spectrometry method was built to determine 15 pesticide residues in Chinese cabbage and cucumber samples based on online turbulent flow chromatography purification. After modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction, extracts were directly injected to the TLX (TurboFlow Liquid Xcalibur) system and brought to TurboFlow™ columns for on-line purification and then transferred to analytical column for further separation and analysis. TurboFlow™ columns types, transfer flow rate, and transfer time were optimized. Limits of detection and limits of quantification of the method obtained for 15 pesticide residues were ranged between 0.2–1.0 μg/kg and 0.5–2.0 μg/kg in Chinese cabbage and cucumber samples. Recoveries of pesticide residues were in range of 75.3 %–103.7 %. Matrix effects for 15 pesticides were in range of 5.6 %–106.6 %. The developed method has been successfully used for the determination of 15 pesticide residues in real samples.

The complex structures and electronic properties of alkali metals and their alloys provide a natural laboratory for studying the interelectronic interactions of metals under compression. A recent theoretical study (J. Phys. Chem. Lett. 2019, 10, 3006) predicted an interesting pressure-induced decomposition-recombination behavior of the Na2K compound over a pressure range of 10 - 500 GPa. However, a subsequent experiment (Phys. Rev. B 2020, 101, 224108) reported the formation of NaK rather than Na2K at pressures above 5.9 GPa. To address this discordance, we study the chemical stability of different stoichiometries of NaxK (x = 1/4, 1/3, 1/2, 2/3, 3/4, 4/3, 3/2 and 1 - 4) by effective structure searching method combined with first-principles calculations. Na2K is calculated to be unstable at 5 - 35 GPa due to the decomposition reaction Na2K-> NaK + Na, coinciding well with the experiment. NaK undergoes a combination-decomposition-recombination process accompanied by an opposite charge-transfer behavior between Na and K with pressure. Besides NaK, two hitherto unknown compounds NaK3 and Na3K2 are uncovered. NaK3 is a typical metallic alloy, while Na3K2 is an electride with strong interstitial electron localization., 19 pages, 4 figures, with supporting information

In this work, the solubilities of (d)- and (d,l)-penicillamine were first experimentally measured in the binary mixtures of ethanol and water. Then, the primary nucleation rate and various nucleati...

The compatibility of an amine-based foaming agent, Duomeen CTM [C12–14N(CH3)C3N(CH3)2], and crude oil on supercritical CO2 foam transport are evaluated for a carbonate reservoir with high pressure ...

Summary In this paper, we describe a laboratory investigation of a nonionic surfactant for carbon dioxide-(CO2-) foam mobility control in the East Seminole field, a heterogeneous carbonate reservoir in the Permian Basin of west Texas. A method of high-performance liquid chromatography-evaporativelight-scattering detector (HPLC-ELSD) was followed for characterizing the surfactant stability. The foam transport process was studied in the absence and the presence of East Seminole crude oil, with test results showing that strong CO2-foam forms in either a bulk-foam test or foam-flow test. An oxygen scavenger, carbohydrazide, was found effective for controlling the stability of the surfactant up to 80°C and total dissolved solid of ∼34,000 ppm. Moreover, a phosphonate scale inhibitor was investigated and found to be compatible with the oxygen scavenger to accommodate a surfactant solution in a gypsum-oversaturated reservoir brine. During the oil-fractional flow test, an emulsion appears to form, causing a noticeable pressure increase; however, emulsion generation failed to cause a significant phase plugging in the test. Also, a STARS™ (Computer Modelling Group Ltd., Calgary, Alberta, Canada) foam model was applied to obtain the foam parameters from the foam-flow experiments at steady-state conditions. The insights from laboratory experiments better enable translation of the foam technology to the field.

Cobalt − free perovskite oxide La0.5Ba0.5Fe0.95Mo0.05O3−δ (LBFMo) was investigated as the electrode of symmetric solid oxide fuel cell (S − SOFC) based on 300−um − thick La0.9Sr0.1Ga0.8Mg0.2O3−δ (LSGM) electrolyte. The electrochemical performance of the S − SOFC with LBFMo|LSGM|LBFMo configuration was evaluated using ambient air as oxidant and H2 as fuel. The maximum power density (Pmax) of the S − SOFC achieves as high as 0.96 W cm−2 at 800 °C; meanwhile, the total polarization resistance (Rpt) of the S − SOFC (including the contributions of both cathode and anode) is only ∼0.12 Ω cm2. Impedance spectra analysis indicates the polarization associated with anode plays a more rate − limiting role in the whole electrochemical reaction process of the S − SOFC. In addition, using LBFMo as symmetric electrode, the S − SOFC also exhibits good cell stability. All results indicate that the LBFMo is a very potential candidate for S − SOFC electrode.

ME-344 is a second-generation cytotoxic isoflavone with anticancer activity promulgated through interference with mitochondrial functions. Using a click chemistry version of the drug together with affinity-enriched mass spectrometry, voltage-dependent anion channels (VDACs) 1 and 2 were identified as drug targets. To determine the importance of VDAC1 or 2 to cytotoxicity, we used lung cancer cells that were either sensitive (H460) or intrinsically resistant (H596) to the drug. In H460 cells, depletion of VDAC1 and VDAC2 by small interfering RNA impacted ME-344 effects by diminishing generation of reactive oxygen species (ROS), preventing mitochondrial membrane potential dissipation, and moderating ME-344-induced cytotoxicity and mitochondrial-mediated apoptosis. Mechanistically, VDAC1 and VDAC2 knockdown prevented ME-344-induced apoptosis by inhibiting Bax mitochondrial translocation and cytochrome c release as well as apoptosis in these H460 cells. We conclude that VDAC1 and 2, as mediators of the response to oxidative stress, have roles in modulating ROS generation, Bax translocation, and cytochrome c release during mitochondrial-mediated apoptosis caused by ME-344. SIGNIFICANCE STATEMENT: Dissecting preclinical drug mechanisms are of significance in development of a drug toward eventual Food and Drug Administration approval.

To improve the surface bioactivity of carbon/carbon composites, functionalized carbon nanotube-gelatin-Zn doped hydroxyapatite (FIC-GL-ZnH) composite coatings were fabricated on carbon/carbon compo...

In recent years, the damage caused by soil nematodes has become increasingly serious; however, the varieties and structures of the nematicides available on the market are deficient. Fluopyram, a succinate dehydrogenase inhibitor (SDHI) fungicide developed by Bayer AG in Germany, has been widely used in the prevention and control of soil nematodes due to its high efficiency and novel mechanism of action. In this paper, two series of novel target compounds were designed and synthesized with nematicidal and fungicidal fluopyram as the molecular skeleton in order to introduce sulfide and sulfone substructures. The structures were identified and characterized by 1H nuclear magnetic resonance (NMR), 13C NMR, and high-resolution mass spectrometer (HRMS). The bioassays revealed that most of the compounds showed excellent nematicidal activities at 200 µg·mL−1 in comparison with fluopyram, while the nematode mortality rate dropped sharply at 100 µg·mL−1, except for compounds I-11 and II-6. In terms of fungicidal activity, compound I-9 was discovered to have an excellent inhibitory rate, and a molecular docking simulation was performed that can provide important guidance for the design and exploration of efficient fungicidal lead compounds.

A self-helix structure Si3N4 nanobelts reinforced hydroxyapatite (HSN/HA) coating has been synthesised on carbon/carbon composites by a combination method of catalyst-assisted pyrolysis of polymeri...

One-dimensional (1D) hollow-structured nanomaterials with desirable compositions have aroused huge attention in the field of electrochemical energy storage. In the present study, 1D hierarchical cobalt hexacyanoferrate (CoHCF) microtubes were initially fabricated using a facile self-templated method with the electrospun polyacrylonitrile (PAN)-cobalt acetate (Co(Ac)2) as templates. After the chemical reaction was performed between the templates and a potassium ferricyanide solution, the core-shell PAN-Co(Ac)2@CoHCF nanofibers were successfully fabricated. Subsequently, the CoHCF microtubes were finally obtained via the selective dissolution of the PAN-Co(Ac)2 cores. Benefiting from the unique structural characteristic, the CoHCF microtubes electrode exhibited prominent electrochemical characteristics in Na2SO4 aqueous electrolyte, including a high specific capacitance of 281.8 F g−1 (at 1 A g−1), and good rate capability as well as long cycling stability (93% capacitance retention after 5000 cycles). The hybrid supercapacitor assembled with CoHCF microtubes and activated carbon (AC) as the positive and negative electrodes, respectively, exhibited a high energy density of 43.89 W h kg−1, a power density of 27.78 kW kg−1, as well as a long cycle life. Note that this versatile self templated synthetic strategy could be extended to fabricate other 1D hollow Prussian blue (PB) or its analogues (PBA) with controllable composition, which have a potential application in a range of fields.

There is now increasing evidence which suggests a key role for osteoblast apoptosis in the pathogenesis of postmenopausal osteoporosis. Here, we evaluated the role and mechanism of proteasome 26S subunit, ATPase (PSMC) 6, a protein that is highly expressed in bone. Gene expression pattern had been extracted based on database of Gene Expression Omnibus (GEO). GEO2R was employed for analyses, while the DAVID database was adopted to further analyze the gene ontology (GO) as well as Kyoto Encyclopedia of Genomes pathway (KEGG) enrichment. Then, the Search Tool Retrieval of Interacting Genes (STRING) was utilized to carry out interaction regulatory network for the top 200 differentially expressed genes (DEGs). A key gene, called PSMC6, was identified by Cytoscape 3.6.0. The OVX osteoporosis model was established in female C57BL/6 mice by full bilateral ovariectomy. According to our findings, PSMC6 gene knockout would elevate bone mineral density (BMD) and the phosphorylation level of PI3K protein and increased the protein level of cleaved caspase-3/-9 in OVX osteoporosis mice. Further, MTT, bromodeoxyuridine, and flow cytometry assays revealed that PSMC6 inhibition promoted the progression of cell cycle and cell proliferation, whereas, PSMC6 overexpression promoted the apoptosis and inhibited cell cycle progression and cell proliferation in vitro. Besides, we found that PI3K activation significantly decreased PSMC6-induced osteoblast apoptosis and promoted cell proliferation through regulating the protein levels of p53, cyclinD1, and cleaved caspase-3/9. In conclusion, PSMC6 aggravated the degree of OVX-induced osteoporosis by inhibiting the PI3K/AKT signal transduction pathway, thereby promoting the apoptosis of osteoblasts.

Doped organic crystals possess wide application potential in the fields of scintillators and maser gain medium. However, the growth of doped organic single crystals with bulk size and high quality ...

Furfural is one of the most important biomass-derived chemicals. Its large-scale availability calls for the exploration of new transformation methods for further valorization. Here we report on the direct, one-step conversion of furfural into 1,4-pentanediols (1,4-PeDs) using a combination of Amberlyst-15 and Ru-FeOx/AC catalysts. It is interesting to find that the introduction of a suitable amount of FeOx results in a great improvement in the dispersion of Ru and a decrease in the Lewis acidity. Both XPS and H2-TPR show that there is electron transfer from Ru to Fe, and the electronic interaction facilitates the reduction of both Ru and Fe species. When used in combination with Amberlyst-15, the Ru-6.3FeOx/AC catalyst afforded the best performance with a 1,4-PeD yield of 86%; by contrast, Ru/AC free of FeOx only gave levulinic acid as the major product, demonstrating the key role of the acid/metal balance in the one-pot conversion of furfural to 1,4-PeD. Moreover, such a dual catalyst exhibited excellent durability within 175 h time-on-stream.

Bio-based primary diamines are important building blocks for sustainable bio-polymers, but their synthesis remains challenging due to the high susceptibility to polymerization. Herein, we have developed a new strategy to suppress the polymerization by employing a more nucleophilic alkylamine to scavenge the dialdehyde and a Co/ZrO2 catalyst to regulate the trans-imination and hydrogenation activity. With this strategy, 2,5-bis(aminomethyl)furan (BAMF), a promising monomer for the production of new polyamides and polyureas, is successfully synthesized via the reductive amination of biomass-derived 2,5-diformylfuran (DFF) under a H2 and NH3 atmosphere with an unprecedentedly high selectivity up to 95%. This strategy is applicable to the reductive amination of other biomass-derived dialdehydes, thus paving a new way to bio-based diamine monomers.

Direct assembling 2D zeolitic imidazolate frameworks-derived (ZIFs)-derived Ni-Co oxide on Ni foam (NixCo3−xO4/Ni foam) is a very attractive way to obtain high performance for electrochemical energy storage device. In this work, the highly optimized NixCo3−xO4/Ni foam was prepared via facile co-precipitation, ion-exchange method and subsequently composited with rGO, acting as binder-less electrode for high properties hybrid supercapacitors. As electrode materials, the pure Co3O4/Ni foam shows 94.40 C g−1 (209.78 F g−1) at 1 A g−1, while the highly optimized NixCo3−xO4/Ni foam exhibits a high capacity of 870.3 C g−1 (1934F g−1) at 1 A g−1. Compared with NixCo3−xO4/Ni foam, the reduced graphene oxides (rGO) modified NixCo3−xO4/Ni foam electrodes possess a porous conductive structure, displaying more superior capacity of 1440.99 C g−1 (3202.22F g−1) at 1 A g−1 and a higher cycling stability of 76.10% retention value after 1000 cycles. Subsequently, the NixCo3−xO4/rGO/Ni foam electrodes were assembled as a hybrid supercapacitor, exhibiting a maximum energy density of 36.31 Wh kg−1, a maximum power density of 8000 W kg−1 and a good cycling stability of 76.29% retention value after 3000 cycles. The NixCo3−xO4/rGO/Ni foam also could light the blue LED device. Thereby, it is proved that NixCo3−xO4/rGO/Ni foam is a promising materials for hybrid supercapacitors.

In the present study, a total of 12 extracts of Rhinanthus angustifolius subsp. grandiflorus, an understudied hemiparasitic species, were obtained using different extraction techniques, namely, homogenizer-assisted extraction (HAE), maceration (MAC), soxhlet (SOX), infusion, and solvents (ethyl acetate, methanol, ethanol, and water), and were evaluated for their in vitro antioxidant and enzyme-inhibiting properties. Additionally, untargeted profiling based on high-resolution mass spectrometry targeted different phytochemical classes, namely, polyphenols, terpenoids, and alkaloids. The highest total phenolic and flavonoid contents were detected using methanol as the extraction solvent. Multivariate statistics following the untargeted profiling revealed that the extraction solvent had a hierarchically higher impact than the extraction method when considering the recovery of bioactive compounds. The methanolic extracts displayed the highest radical-scavenging antioxidant capacity, as provided by CUPRAC and FRAP assays. On the other hand, the water extracts (MAC and HAE) and the infusion extract showed the highest activity as metal chelators (25.66–27.51 mg EDTAE/g). Similarly, the water extract obtained by HAE and the infusion extract revealed the highest phosphomolybdenum activity (3.92 ± 0.14 and 3.71 ± 0.01 mmol TE/g, respectively). The different extracts also exhibited different enzyme inhibition potentials. For instance, HAE and MAC ethanolic extracts inhibited only α-amylase (0.69 ± 0.01 and 0.70 ± 0.01 mmol ACAE/g), while all the other extracts showed a dual inhibition against both carbohydrate-hydrolyzing enzymes tested (i.e., α-amylase: 0.07–0.69 mmol ACAE/g, α-glucosidase: 0.03–1.30 mmol ACAE/g). Nevertheless, the other extracts inhibited acetyl-, butyryl-cholinesterases, or both, MAC–water extract displayed no inhibition against the enzymes. Additionally, all the studied extracts were found to inhibit tyrosinase, ranging from 10.62 to 52.80 mg KAE/g. In general, the water extracts showed weaker inhibition towards the enzymes than the other extracts. This study demonstrated that R. angustifolius is an excellent source of natural antioxidants and enzyme inhibitors that could be further investigated and exploited for pharmaceutical purposes.

Recent studies in the agronomic field indicate that the exogenous application of polyphenols can provide tolerance against various stresses in plants. However, the molecular processes underlying stress mitigation remain unclear, and little is known about the impact of exogenously applied phenolics, especially in combination with salinity. In this work, the impacts of exogenously applied chlorogenic acid (CA), hesperidin (HES), and their combination (HES + CA) have been investigated in lettuce (Lactuca sativa L.) through untargeted metabolomics to evaluate mitigation effects against salinity. Growth parameters, physiological measurements, leaf relative water content, and osmotic potential as well as gas exchange parameters were also measured. As expected, salinity produced a significant decline in the physiological and biochemical parameters of lettuce. However, the treatments with exogenous phenolics, particularly HES and HES + CA, allowed lettuce to cope with salt stress condition. Interestingly, the treatments triggered a broad metabolic reprogramming that involved secondary metabolism and small molecules such as electron carriers, enzyme cofactors, and vitamins. Under salinity conditions, CA and HES + CA distinctively elicited secondary metabolism, nitrogen-containing compounds, osmoprotectants, and polyamines.

The use of plant biostimulants contributes to more sustainable and environmentally friendly farming techniques and offers a sustainable alternative to mitigate the adverse effects of stress. Protein hydrolysate-based biostimulants have been described to promote plant growth and reduce the negative effect of abiotic stresses in different crops. However, limited information is available about their mechanism of action, how plants perceive their application, and which metabolic pathways are activating. Here we used a multi-trait high-throughput screening approach based on simple RGB imaging and combined with untargeted metabolomics to screen and unravel the mode of action/mechanism of protein hydrolysates in Arabidopsis plants grown in optimal and in salt-stress conditions (0, 75, or 150 mM NaCl). Eleven protein hydrolysates from different protein sources were used as priming agents in Arabidopsis seeds in three different concentrations (0.001, 0.01, or 0.1 μl ml–1). Growth and development-related traits as early seedling establishment, growth response under stress and photosynthetic performance of the plants were dynamically scored throughout and at the end of the growth period. To effectively classify the functional properties of the 11 products a Plant Biostimulant Characterization (PBC) index was used, which helped to characterize the activity of a protein hydrolysate based on its ability to promote plant growth and mitigate stress, and to categorize the products as plant growth promoters, growth inhibitors and/or stress alleviator. Out of 11 products, two were identified as highly effective growth regulators and stress alleviators because they showed a PBC index always above 0.51. Using the untargeted metabolomics approach, we showed that plants primed with these best performing biostimulants had reduced contents of stress-related molecules (such as flavonoids and terpenoids, and some degradation/conjugation compounds of phytohormones such as cytokinins, auxins, gibberellins, etc.), which alleviated the salt stress response-related growth inhibition.

Single-atom catalysts (SACs) have emerged as a frontier in heterogeneous catalysis due to the well-defined active site structure and the maximized metal atom utilization. Nevertheless, the robustness of SACs remains a critical concern for practical applications. Herein, we report a highly active, selective and robust Ru SAC which was synthesized by pyrolysis of ruthenium acetylacetonate and N/C precursors at 900 °C in N2 followed by treatment at 800 °C in NH3. The resultant Ru1-N3 structure exhibits moderate capability for hydrogen activation even in excess NH3, which enables the effective modulation between transimination and hydrogenation activity in the reductive amination of aldehydes/ketones towards primary amines. As a consequence, it shows superior amine productivity, unrivalled resistance against CO and sulfur, and unexpectedly high stability under harsh hydrotreating conditions compared to most SACs and nanocatalysts. This SAC strategy will open an avenue towards the rational design of highly selective and robust catalysts for other demanding transformations., Single-atom catalyst (SAC) has emerged as a frontier in heterogeneous catalysis yet its robustness remains a critical concern. Here, a highly active, selective and robust Ru1-N3 SAC is explored for a challenging reaction, reductive amination of aldehydes/ketones for synthesis of primary amines.

Lupin seeds can represent a valuable source of phenolics and other antioxidant compounds. In this work, a comprehensive analysis of the phytochemical profile was performed on seeds from three Lupinus species, including one cultivar (Lupinus albus) and two wild accessions (Lupinus cossentinii and Lupinus luteus), collected from the northern region of Tunisia. Untargeted metabolomic profiling allowed to identify 249 compounds, with a great abundance of phenolics and alkaloids. In this regard, the species L. cossentinii showed the highest phenolic content, being 6.54 mg/g DW, followed by L. luteus (1.60 mg/g DW) and L. albus (1.14 mg/g DW). The in vitro antioxidant capacity measured by the ABTS assay on seed extracts ranged from 4.67 to 17.58 mg trolox equivalents (TE)/g, recording the highest values for L. albus and the lowest for L. luteus. The DPPH radical scavenging activity ranged from 0.39 to 3.50 mg TE/g. FRAP values varied between 4.11 and 5.75 mg TE/g. CUPRAC values for lupin seeds ranged from 7.20 to 8.95 mg TE/g, recording the highest for L. cossentinii. The results of phosphomolybdenum assay and metal chelation showed similarity between the three species of Lupinus. The acetylcholinesterase (AChE) inhibition activity was detected in each methanolic extract analyzed with similar results. Regarding the butyrylcholinesterase (BChE) enzyme, it was weakly inhibited by the Lupinus extracts, in particular, the highest activity values were recorded for L. albus (1.74 mg GALAE/g). Overall, our results showed that L. cossentinii was the most abundant source of polyphenols, consisting mainly in tyrosol equivalents (5.82 mg/g DW). Finally, significant correlations were outlined between the phenolic compounds and the in vitro biological activity measured, particularly when considering flavones, phenolic acids and lower-molecular-weight phenolics.

Cydonia oblonga Mill., normally known as the quince fruit, has been widely used in agro-food industries mainly to produce jams and jellies. However, other parts of the plants are still underutilized and not completely assessed for their nutraceutical profile. Therefore, in this work, the polyphenolic profile of C. oblonga was investigated using an untargeted metabolomics approach based on high-resolution mass spectrometry. Several compounds were identified in the different parts of the plants, including flavonoids (i.e., anthocyanins, flavones, flavan-3-ols, and flavonols), phenolic acids (both hydroxycinnamics and hydroxybenzoics), low-molecular-weight phenolics (tyrosol equivalents), lignans, and stilbenes. Overall, C. oblonga leaves showed the highest in vitro antioxidant potential, as revealed by 2,2-difenil-1-picrylhydrazyl (DPPH), 2,2′-Azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS), ferric reducing antioxidant power (FRAP), and cupric ion reducing antioxidant capacity (CUPRAC) assays, being 189.5, 285.6, 158.9, and 348.8 mg Trolox Equivalent/g, respectively. The enzymes acetyl- and butyryl-cholinesterases were both inhibited by the different plant parts of C. oblonga, with stems showing the higher inhibitory potential. Interestingly, the fruit extracts were the only parts inhibiting the α-glucosidase, with a value of 1.36 mmol acarbose equivalents (ACAE)/g. On the other hand, strong tyrosinase inhibition was found for stems and leaves, being 72.11 and 68.32 mg Kojic acid Equivalent/g, respectively. Finally, a high number of significant (0.05 &lt, p &lt, 0.01) correlations were outlined between phenolics (mainly anthocyanins, flava-3-ols, and tyrosol equivalents) and the different biological assays. Taken together, our findings suggest a potential exploitation of C. oblonga leaves and stems for the food, pharmaceutical, and cosmetic industries.

Mesenchymal stem cells (MSCs) are previously found to have potential capacity to differentiate into osteocytes when exposed to specific stimuli. However, the detailed molecular mechanism during this progress remains largely unknown. In the current study, we characterized the lncRNA NKILA as a crucial positive regulator for osteogenesis of MSCs. NKILA attenuation significantly inhibits the calcium deposition and alkaline phosphatase activity of MSCs. More interestingly, we defined that NKILA is functionally involved in the regulation of RXFP1/PI3K‐AKT and NF‐κB signalling. Knockdown of NKILA dramatically down‐regulates the expression of RXFP1 and then reduces the activity of AKT, a downstream regulator of RXFP1 signalling which is widely accepted as an activator of osteogenesis. Moreover, we identify NF‐κB as another critical regulator implicated in NKILA‐mediated osteogenic differentiation. Inhibition of NF‐κB can induce the expression of RUNX2, a master transcription factor of osteogenesis, in a HDAC2‐mediated deacetylation manner. Thus, this study illustrates the regulatory function of NKILA in osteogenesis through distinct signalling pathways, therefore providing a new insight into searching for new molecular targets for bone tissue repair and regeneration.

Groundwater treatment sludge is an industrial waste that is massively produced from groundwater treatment plants. Conventional methods for treatment of this sludge, such as discharge into deep wells or the sea, or disposal at landfills, are not environmentally sustainable. Here, we demonstrate an alternative strategy to recycle the sludge by preparing a magnetic maghemite adsorbent via a one-step hydrothermal method with NaOH solution as the only solvent. With this method, the weakly magnetized sludge, which contained 33.2% iron (Fe) and other impurities (e.g., silicon (Si), aluminum (Al), and manganese (Mn)), was converted to magnetic adsorbent (MA) with the dissolution of Si/Al oxides (e.g., quartz and albite) into the liquid fraction. At a NaOH concentration of 2 mol·L−1, approximately 18.1% of the ferrihydrite in the Fe oxides of the sludge was converted into 11.2% maghemite and 6.9% hematite after the hydrothermal treatment. MA2 (i.e., MA produced by a 2 mol·L−1 NaOH concentration) exhibited a good magnetic response of 8.2 emu·g−1 (1 emu = 10−3 A·m2), and a desirable surface site concentration of 0.75 mmol·g−1. The synthesized MA2 was used to adsorb the cationic pollutant tetracycline (TC). The adsorption kinetics of TC onto MA2 fitted well with a pseudo-second-order model, and the adsorption isotherms complied well with the Langmuir model. The maximum adsorption capacity of MA2 for TC was 362.3 mg·g−1, and the main mechanism for TC adsorption was cationic exchange. This study is the first to demonstrate the preparation of an MA from recycled sludge without a reductant and/or exogenous Fe source. The prepared adsorbent can be used as a low-cost adsorbent with high capacity for TC sorption in the treatment of TC-containing wastewater. Keywords: Groundwater treatment sludge, Maghemite, Cationic exchange, Adsorption, Tetracycline