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Selective hydrogenation of alkynes to alkenes requires a catalytic site with suitable electronic properties for modulating the adsorption and conversion of alkyne, alkene as well as dihydrogen. Here, we report a complex palladium hydride, CaPdH2, featured by electron-rich [PdH2]δ- sites that are surrounded by Ca cations that interacts with C2H2 and C2H4 via σ-bonding to Pd and unusual cation-π interaction with Ca, resulting in a much weaker chemisorption than those of Pd metal catalysts. Concomitantly, the dissociation of H2 and hydrogenation of C2Hx (x = 2-4) species experience significant energy barriers over CaPdH2, which is fundamentally different from those reported Pd-based catalysts. Such a unique catalytic environment enables CaPdH2, the very first complex transition-metal hydride catalyst, to afford a high alkene selectivity for the semihydrogenation of alkynes.

Strong infectivity enables coronavirus disease 2019 (COVID-19) to rage throughout the world. Moreover, the lack of drugs with definite therapeutic effects further aggravates the spread of the pandemic. Remdesivir is one of the most promising anti-severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) drugs. However, the limited clinical effects make its therapeutic effect controversial, which may result from the poor accumulation and activation of remdesivir in the lung. Therefore, we developed lyophilized remdesivir liposomes (Rdv-lips) which can be reconstituted as liposomal aerosol for pulmonary delivery to improve the in vivo behavior of existing remdesivir cyclodextrin conclusion compound (Rdv-cyc) injections. Liposome encapsulation endowed remdesivir with much higher solubility and better biocompatibility. The in vitro liposomal aerosol characterization demonstrated that Rdv-lips possessed a mass median aerodynamic diameter of 4.118 μm and fine particle fraction (, Graphical Abstract Image, graphical abstract

Clavulanic acid (CA) is usually used together with other β‐lactam antibiotics as combination drugs to inhibit bacterial β‐lactamases, which is mainly produced from the fermentation of microorganism such as Streptomyces clavuligerus. Recently, it is still a challenge for downstream processing of low concentration and unstable CA from fermentation broth with high solid content, high viscosity, and small cell size. In this study, an integrated process was developed for simultaneous solid–liquid separation and primary purification of CA from real fermentation broth of S. clavuligerus using salting‐out extraction system (SOES). First, different SOESs were investigated, and a suitable SOES composed of ethanol/phosphate was chosen and further optimized using the pretreated fermentation broth. Then, the optimal system composed of 20% ethanol/15% K2HPO4 and 10% KH2PO4 w/w was used to direct separation of CA from untreated fermentation broth. The result showed that the partition coefficient (K) and recovery yield (Y) of CA from untreated fermentation broth were 29.13 and 96.8%, respectively. Simultaneously, the removal rates of the cells and proteins were 99.8% and 63.3%, respectively. Compared with the traditional method of membrane filtration or liquid–liquid extraction system, this developed SOES showed the advantages of simple operation, shorter operation time, lower process cost and higher recovery yield of CA. These results demonstrated that the developed SOES could be used as an attractive alternative for the downstream processing of CA from real fermentation broth.

Gas–particle partitioning of water-soluble organic compounds plays a significant role in influencing the formation, transport, and lifetime of organic aerosols in the atmosphere, but is poorly characterized. In this work, gas- and particle-phase concentrations of isoprene oxidation products (C5-alkene triols and 2-methylterols), levoglucosan, and sugar polyols were measured simultaneously at a suburban site of the western Yangtze River Delta in east China. All target polyols were primarily distributed into the particle phase (85.9 %–99.8 %). Given the uncertainties in measurements and vapor pressure predictions, a dependence of particle-phase fractions on vapor pressures cannot be determined. To explore the impact of aerosol liquid water on gas–particle partitioning of polyol tracers, three partitioning schemes (Cases 1–3) were proposed based on equilibriums of gas vs. organic and aqueous phases in aerosols. If particulate organic matter (OM) is presumed as the only absorbing phase (Case 1), the measurement-based absorptive partitioning coefficients (Kp,OMm) of isoprene oxidation products and levoglucosan were more than 10 times greater than predicted values (Kp,OMt). The agreement between Kp,OMm and Kp,OMt was substantially improved when solubility in a separate aqueous phase was included, whenever water-soluble and water-insoluble OM partitioned into separate (Case 2) or single (Case 3) liquid phases, suggesting that the partitioning of polyol tracers into the aqueous phase in aerosols should not be ignored. The measurement-based effective Henry's law coefficients (KH,em) of polyol tracers were orders of magnitude higher than their predicted values in pure water (KH,wt). Due to the moderate correlations between log⁡(KH,em/KH,wt) and molality of sulfate ions, the gap between KH,em and KH,wt of polyol tracers could not be fully parameterized by the equation defining “salting-in” effects and might be ascribed to mechanisms of reactive uptake, aqueous phase reaction, “like-dissolves-like” principle, etc. These study results also partly reveal the discrepancy between observation and modeling of organic aerosols.

To explore the effect of miR-93-mediated Wnt/β-catenin pathway on the vascular calcification (VC) of chronic renal failure (CRF). SD rats were utilized to construct CRF models and divided into Control, CRF, CRF + LV (lentiviral vector)-miR-93 and CRF + LV-Con groups. Renal tissues collected from rats were performed hematoxylin and eosin (HE) staining and Masson staining, while the abdominal aorta was dissected for alizarin red staining and Von Kossa staining. VC-related genes were determined by qRT-PCR while Wnt/β-catenin pathway-related proteins were examined by Western blotting. As compared to Control group, the serum levels of blood urea nitrogen (BUN), serum creatinine (Scr), phosphorus (P), cystatin C (Cys-C) and 24-h urea protein (24 h Upro), and the scores of renal interstitial lesion and fibrotic area in rats from CRF group were elevated, with the increased calcified area of aorta as well as the enhanced calcium content and ALP. Meanwhile, rats in the CRF group had up-regulated expression of OPN, OCN, RUNX2 and BMP-2 and down-regulated expression of miR-93. As for the expression of Wnt/β-catenin pathway, rats in the CRF group had sharp increases in the protein expression of TCF4 and β-catenin, while α-SMA was down-regulated. However, changes of the above were reversed in rats from CRF + LV-miR-93 group, and TCF4 was confirmed to be a target gene of miR-93. MiR-93, via inhibiting the activity of Wnt/β-catenin pathway by targeting TCF4, can improve the renal function of CRF rats, thereby mitigating the vascular calcification of CRF.

Growing evidence has shown that some pharmaceutical excipients can act on drug transporters. The present study was aimed at investigating the effects of 13 commonly used excipients on the intestinal absorption of metformin (MTF) and the underlying mechanisms using Caco-2 cells and an ex vivo mouse non-everted gut sac model. First, the uptake of MTF in Caco-2 cells was markedly inhibited by nonionic excipients including Solutol HS 15, polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 80, and crospovidone. Second, transport profile studies showed that MTF was taken up via multiple cation-selective transporters, among which a novel pyrilamine-sensitive proton-coupled organic cation (H+/OC+) antiporter played a key role. Third, Solutol HS 15, polysorbate 40, and polysorbate 60 showed cis-inhibitory effects on the uptake of either pyrilamine (prototypical substrate of the pyrilamine-sensitive H+/OC+ antiporter) or 1-methyl-4-phenylpyridinium (substrate of traditional cation-selective transporters including OCTs, MATEs, PMAT, SERT, and THTR-2), indicating that their suppression on MTF uptake is due to the synergistic inhibition toward multiple influx transporters. Finally, the pH-dependent mouse intestinal absorption of MTF was significantly decreased by Solutol HS 15, polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 80, and pyrilamine. In conclusion, this study revealed that a novel transport process mediated by the pyrilamine-sensitive H+/OC+ antiporter contributes to the intestinal absorption of MTF in conjunction with the traditional cation-selective transporters. Mechanistic understanding of the interaction of excipients with cation-selective transporters can improve the formulation design and clinical application of cationic drugs.

We report a simple and efficient Pd/MgO catalyst loaded with ppm level of Pd (7.8 ppm) for semi-hydrogenation of acetylene to ethylene. The catalyst showed excellent performance with high acetylene conversion (97%), high ethylene selectivity (89%) and good stability. Moreover, the atomically dispersed Pd atoms are inactive for ethylene hydrogenation. Isotopic and FTIR results suggest that H2 dissociates at isolated Pd atoms in a heterolytic manner forming O-H bond, which may account for the high selectivity.

Nowadays, transition-metal phosphides have been reported to function well in photocatalytic water splitting and possess great potential to substitute traditional noble-metal cocatalysts in the future. Herein, p-type cobalt phosphide (CoP-Co2P) nanomaterials were synthesized by phosphating the solvothermally prepared Co(OH)2 nanoflowers at a low temperature (300 °C). Then, we combined the phosphides with commercial TiO2 through facile mechanical mixing to fabricate a useful noble-metal-free photocatalyst. The phosphating time that had an influence on the composition of phosphides was tuned, and 3 h was an ideal condition after comparison. The cobalt phosphide-modified TiO2 at the optimal weight percentage (nominal 0.5%) exhibited the highest photocatalytic hydrogen rate of approximately 824.5 μmol g-1 h-1 under simulated sunlight irradiation, which was nearly equal to 160 times that of bare TiO2 and 1.7 times that of single CoP-modified TiO2. The CoPx/TiO2 heterojunction interfaces were studied using photoluminescence (PL), time-resolved PL, and photoelectrochemical methods, which revealed that the effective charge separation and transfer accelerated by the built-in electric field of p-n junction contributed significantly to the photocatalytic performance.

Two new zirconium-based heterometal–organic frameworks, Zr3CP3–Mn (1) and Zr3CP3–Ni (2), constructed from [Cp3Zr3(μ3-O)(μ2-OH)3(IN)3] secondary building units and transition metal cations, were successfully synthesized through a one-pot method. Single-crystal X-ray diffraction analysis shows that both 1 and 2 have one-dimensional chain structures, in which [Cp3Zr3(μ3-O)(μ2-OH)3(IN)3] SBUs are connected by Mn and Ni ions. Furthermore, photoreduction of CO2 under visible light irradiation reveals that 1 and 2 have good catalytic activities to reduce CO2 into carbon monoxide and hydrogen. The CO yields of 1 and 2 were 9.30 and 5.21 mmol g−1 h−1 under one hour irradiation at 293 K, respectively. In addition, the inherent photocatalytic mechanism was studied through photochemical and electrochemical measurements. This work provides a valuable perspective for the design and synthesis of simple, low-cost MOF catalysts for photoreduction of CO2.

Two 3d–4f heterometal–organic frameworks are synthesized by a steam-assisted conversion method and are characterized by single-crystal X-ray diffraction, PXRD, IR, TG, and UV–vis spectroscopy. Compounds 1 and 2 have similar structures, in which binuclear gadolinium clusters are connected by [M(BPDC)3] (M = Ni for 1 and Co for 2) secondary building units (SBUs) and extend into 3D frameworks with pcu topologies. In addition, we have also investigated the photoreduction of CO2 under visible light. The CO yields reached 7622 μmol−1 g−1 and 11 250 μmol−1 g−1 with 1 and 2 as catalysts, respectively, and ruthenium pyridine as the photosensitizer after two hours of visible light irradiation. Both of them have high selectivity values for CO, reaching 94.85% for 1 and 94.46% for 2. Furthermore, the catalytic mechanism is proposed through a photoelectrochemical test. This study provides a feasible strategy for the design of efficient CO2 photocatalysts with a high charge separation rate.

Ferroelectricity has an excellent reversible polarization conversion behavior under an external electric field. Herein, we propose an interesting strategy to alleviate the shuttle effect of lithium-sulfur battery by utilizing ferroelectric metal-organic framework (FMOF) as a host material for the first time. Compared to other MOF with same structure but without ferroelectricity and commercial carbon black, the cathode based on FMOF exhibits a low capacity decay and high cycling stability. These results demonstrate that the polarization switching behaviors of FMOF under the discharge voltage of lithium-sulfur battery can effectively trap polysulfides by polar-polar interactions, decrease polysulfides shuttle and improve the electrochemical performance of lithium-sulfur battery.

Systematic design and self-assembly of metal-organic polyhedra with predictable configuration has been a long-standing challenge in crystal engineering due to the difficulty of finding suitable building units. Herein, we are focused on a concave polyoxovanadate cluster [V6O6(OCH3)9(SO4)4]5- that can be generated in situ under the exact reaction conditions. Based on this cluster, a potential trivalent molecular building block [V6O6(OCH3)9(SO4)(CO2)3]2- can be obtained by the bridging-ligand-substitution strategy that possesses appropriate angle information for the design of molecular cubes. Utilizing the face-directed assembly of the trivalent molecular building block and a diverse set of tetratopic carboxylate linkers, a series of metal-organic cubes VMOC-1 to VMOC-5 with the same topology but different functionalities and dimensions are designed and constructed. The inclusion study made with VMOC-3 as an example has shown that they are potential molecular receptors and can selectively capture size-matching polycyclic aromatic hydrocarbon guest molecules.

The abundance of docosahexaenoic acid (DHA) in phospholipids in the brain and retina has generated interest to search for its role in mediating neurological functions. Besides the source of many oxylipins with pro-resolving properties, DHA also undergoes peroxidation, producing 4-hydroxyhexenal (4-HHE), although its function remains elusive. Despite wide dietary consumption, whether supplementation of DHA may alter the peroxidation products and their relationship to phospholipid species in brain and other body organs have not been explored sufficiently. In this study, adult mice were administered a control or DHA-enriched diet for three weeks, and phospholipid species and peroxidation products were examined in brain, heart and plasma. Results demonstrated that this dietary regimen increased (n-3) and decreased (n-6) species to different extent in all major phospholipid classes (PC, dPE, PE-pl, PI and PS) examined. Besides changes in phospholipid species, DHA-enriched diet also showed substantial increases in 4-HHE in brain, heart and plasma. Among different brain regions, the hippocampus responded to the DHA-enriched diet showing significant increase in 4-HHE. Considering the pro- and anti-inflammatory pathways mediated by the (n-6) and (n-3) polyunsaturated fatty acids, unveiling the ability for DHA-enriched diet to alter phospholipid species and lipid peroxidation products in the brain and in different body organs may be an important step forward towards understanding the mechanism(s) for this (n-3) fatty acid on health and diseases.

Two short-term summer cruises were performed in the vicinity of Rizhao Port, western Yellow Sea, to investigate summer water stratification and the phenomenon of marine sediment acidification. Results show that water stratification has formed as early as in May. The chemoclines of dissolved oxygen (DO) and pH usually occur deeper than the thermocline. Sometimes the chemoclines of DO and pH occur synchronously at the same depths, but sometimes they do not synchronize. Above the chemocline DO fluctuates markedly and maintains at a high level or even oversaturation in daytime, suggesting the far-field impact of vessel propulsion. Below the chemocline it invariably remains at a low and stable level and slowly drops downward. The pH values of surface sediments vary in the range of 6.3–7.6. A conspicuous sediment acidification is observed along the navigation region. This phenomenon is chiefly attributed to the intermittent disruption of summer stratification by shipping activity along the shipping channel and waterways. Water stratification precludes the penetration of DO down to the bottom sediments on fair ocean status, and maintains anoxia below the sediment–water interface, whereas the abrupt DO increase driven by propeller agitating is nearly restricted in the navigation area. Therefore, the aeration effect accelerating oxidation of reducing substances and organic matter is primarily responsible for enhanced acid accumulation in surface sediments. In addition, the suspension effect is identified by the negative offsets of zero point on pH–mV diagram. Most of the measured points are scattered correspondingly on three distinct regression lines, with similar slopes but different negative offsets of pH 6.53, 6.87, and 6.99, respectively. Their geographical distribution suggests that this effect has a positive relationship with the intensity of anthropogenic disturbance. Although the suspension effect is caused by the adsorption of charged particles at the pH glass electrode interface (Yang et al. in Part Sci Technol 7:139–152, 1989), its various intensity observed in practice may also reflect the inherent distinction of depositional environments in physicochemical conditions.

Three nanosized zirconium-based molecular capsules (Zr-MCs) constructed from trinuclear zirconocene building blocks and linear carboxylate ligands, namely, {[Cp3Zr3(μ3-O)(μ2-OH)3]2(BDC)3}·Cl2(DMA)(H2O) (Zr-MC-1), {[Cp3Zr3(μ3-O)(μ2-OH)3]2(SDC)3}·Cl2(DMF)2.5 (Zr-MC-2), and {[Cp3Zr3(μ3-O)(μ2-OH)3]2(ADA)3}·Cl2(DMF)2 (Zr-MC-3) (H2BDC = 1,4-benzenedicarboxylic acid; H2SDC = 4,4-stilbenedicarboxylic acid; H2ADA = azobenzene-4,4-dicarboxylic acid), have been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, powder X-ray diffraction, IR spectroscopy, and thermogravimetric analysis. Additionally, Zr-MC-2 can serve as a promising selective sensor for Fe3+. Meanwhile, the absorption ability of Zr-MC-1 and Zr-MC-3 toward iodine was investigated.

A matrix metalloproteinases (MMPs) triggered multifunctional micellar system loading traditional chemotherapeutic agent paclitaxel (PTX) and marimastat (MATT), an inhibition of matrix metalloproteinases, was established to prevent tumor growth and metastasis. The micelles were self-assembled by the conjugate synthesized with an MMPs sensitive peptide as the bridge between PTX and poly(ethylene glycol) (PEG). 4T1 cell line derived from a murine breast tumor was selected as the cell model due to its high metastasis. The cytotoxicity assay and cell apoptosis analysis revealed that the sensitive micelles increased the toxicity and cell apoptosis compared with the insensitive micelles. In addition, this system also exhibited high penetration ability in tumor spheroids and significant invasion inhibition with the method of Transwell invasion assay. In the BALB/c mice bearing 4T1 tumors, this system inhibited the growth of the metastatic tumor and prevented the incidence of lung metastasis with low systemic toxicity. And the expression of MMP-2 and MMP-9, which are important in the process of tumor metastasis, was down-regulated. Generally, the data obtained from the in vitro and in vivo studies confirmed that the codelivery of PTX and MATT by the MMPs sensitive micelles achieved not only significant antitumor effect but also obvious inhibition effect of tumor metastasis, which are the leading cause of cancer deaths. This functional particle system may provide a promising strategy for metastatic breast cancer therapy.

The co-delivery of chemotherapeutic agents and immune modulators to their targets remains to be a great challenge for nanocarriers. Here, we developed a hybrid thermosensitive nanoparticle (TMNP) which could co-deliver paclitaxel-loaded transferrin (PTX@TF) and marimastat-loaded thermosensitive liposomes (MMST/LTSLs) for the dual targeting of cancer cells and the microenvironment. TMNPs could rapidly release the two payloads triggered by the hyperthermia treatment at the site of tumor. The released PTX@TF entered cancer cells via transferrin-receptor-mediated endocytosis and inhibited the survival of tumor cells. MMST was intelligently employed as an immunomodulator to improve immunotherapy by inhibiting matrix metalloproteinases to reduce chemokine degradation and recruit T cells. The TMNPs promoted the tumor infiltration of CD3+ T cells by 2-fold, including memory/effector CD8+ T cells (4.2-fold) and CD4+ (1.7-fold), but not regulatory T cells. Our in vivo anti-tumor experiment suggested that TMNPs possessed the highest tumor growth inhibitory rate (80.86%) compared with the control group. We demonstrated that the nanoplatform could effectively inhibit the growth of tumors and enhance T cell recruitment through the co-delivery of paclitaxel and marimastat, which could be a promising strategy for the combination of chemotherapy and immunotherapy for cancer treatment.

TNF stimulation generates pro-survival signals through activation of NF-κB that restrict the build-in death signaling triggered by TNF. The competition between TNF-induced survival and death signals ultimately determines the fate of a cell. Here, we report the identification of Bclaf1 as a novel component of the anti-apoptotic program of TNF. Bclaf1 depletion in multiple cells sensitizes cells to TNF-induced apoptosis but not to necroptosis. Bclaf1 exerts its anti-apoptotic function by promoting the transcription of CFLAR, a caspase 8 antagonist, downstream of NF-κB activation. Bclaf1 binds to the p50 subunit of NF-κB, which is required for Bclaf1 to stimulate CFLAR transcription. Finally, in Bclaf1 siRNA administered mice, TNF-induced small intestine injury is much more severe than in control mice with aggravated signs of apoptosis and pyroptosis. These results suggest Bclaf1 is a key regulator in TNF-induced apoptosis, both in vitro and in vivo.

Scope The intestinal epithelium is nourished by various nutrients and subjected to persistent and widespread feed-derived mycotoxin stress. l-Carnosine (LC) possesses robust antioxidant activity; however, its role in protecting intestinal mucosa against deoxynivalenol (DON) is still unclear. Methods and results In this study, 300 mg kg-1 BW LC and 3 mg kg-1 BW DON are orally administered to mice either alone or in combination for 10 days to investigate the role of LC in protecting the intestine against DON. This study found that LC alleviates the growth retardation of mice and repairs the damaged jejunal structure and barrier functions under DON exposure. LC rescues the intestinal stem cells (ISCs), increases the growth advantage in enteroids derived from jejunal crypts of mice in each group ex vivo, improves the proliferation and apoptosis of intestinal cells, and promotes ISC differentiation into absorptive cells, goblet cells, and Paneth cells. Furthermore, LC activates Nrf2 signaling by binding to Keap1 to reverse the striking DON-induced increase in ROS levels. Conclusion The study findings unveil that LC potentiates the antioxidant capacity of ISCs by regulating the Keap1/Nrf2 signaling pathway, which contributes to the intestinal epithelial regeneration response to DON insult.

Extracellular DNA (eDNA) is widely present in soil, with potential ecological impacts. Metal cations are naturally present on the surface of soil clay minerals, although the adsorption mechanism of eDNA on clay minerals saturated with metal cations is still not fully understood. The research investigated the adsorption of eDNA, using salmon sperm DNA as a representative, on metal cation (Na+, Ca2+, and Fe3+)-saturated montmorillonites (Mt). Metal cation-saturated Mt have higher adsorption capacities for DNA. Compared with Mt (3500 mg⋅kg−1), the amounts of DNA adsorption on metal cation-saturated Mt (pH = 7.0) were increased by 0.74–5.38 times, and followed the descending order of Fe-Mt > Na-Mt > Ca-Mt > Mt. A temperature of 25 °C was found to be more suitable than 15 and 35 °C for DNA adsorption, while an increasing pH value (3.0–9.0) reduced DNA adsorption on Mt and metal cation-saturated Mt. Microscopic and spectroscopic analyses, together with a model computation technique, confirmed that metal cations saturated on the surface of Mt work like a “cation bridge” linking oxygen atoms in the phosphate groups of DNA and the negatively charged moieties of Mt, which were predominantly bound through electrostatic forces, thus, facilitating DNA adsorption at pH > 5. The results of this investigation provide valuable insight into eDNA adsorption on soil clay minerals and the transport and fate of eDNA in the natural soil environment.

A $4\times4$ high-gain substrate integrated cavity (SIC) antenna array using multilayered low-temperature cofired ceramic (LTCC) technology is proposed and designed for $W$ -band applications. The TM211 mode of the SIC is utilized. Two parasitic patches are introduced on the top surface of the SIC to adjust the aperture electromagnetic field distribution of the TM211 mode in the cavity for obtaining a high-gain broadside radiation pattern. A bow tie shape is adopted for the parasitic patches to improve the matching characteristic of the SIC. The SIC is modified to a stepped flared shape to improve the gain characteristic of the antenna element. Subsequently, a two-layer low-loss substrate integrated waveguide (SIW) feeding network is designed for the $4\times4$ antenna array on the basis of the proposed high-gain SIC radiating element. The proposed antenna array shows a wide measured bandwidth of 17.48% from 81.45 to 97.05 GHz at $\vert \textrm {S}_{11} \vert dB and a measured gain of up to 20.3 dBi.

Single-ionic conducting electrolytes are important for the improvement of lithium metal batteries with high energy density and safety. Herein, we propose a new strategy to anchor a large anionic group on the skeleton of metal-organic frameworks (MOFs) and achieve preeminent single-ionic conducting electrolytes. Utilizing a postsynthetic modification method, the trifluoromethanesulfonyl group is covalently coordinated to the amino groups of the UiO-66-NH2 framework. Such a single-ionic conducting solid-state electrolyte (SSE) has a high ionic conductivity (2.07 × 10-4 S cm-1 at 25 °C), a low activation energy of 0.31 eV, a wide electrochemical window up to 4.52 V, as well as a high Li+ transference number of 0.84. Simultaneously, it can effectively inhibit the formation of lithium dendrite. Solid-state batteries assembled with LiFePO4 as the cathode exhibit outstanding rate performance and cyclic stability, especially for low-temperature Li-metal batteries at 0 °C with trace amounts of propylene carbonate as wetting agents. More importantly, the corresponding all-solid-state batteries based on an MOF-based SSE also have nearly 100% Coulombic efficiency at different current densities.

Three nanoscale Nb/W mixed-addendum polyoxometalates, Cs14K4[(Si4W36Nb12O156)Cu(H2O)2]·47H2O, Cs10K8[(Si4W36Nb12O156)Zn(H2O)2]·28H2O, and Cs16[(H2Si4W36Nb12O156)Cd(H2O)2]·75H2O involving [SiNb3W9O40]7− fundamental building unit, have been synthesized, which all show photocatalytic hydrogen evolution activities. Furthermore, molecules 1, 2, and 3 are stable in the photocatalytic hydrogen evolution system. The embedding transition-metal cations into Nb/W mixed-addendum POMs can improve the photocatalytic H2 evolution activity.

Glycosyltransferases (GTs) are found in a wide variety of organisms, where they are involved in maintaining cell metabolism through glycosylation reactions. Glycosyltransferases transfer activated sugar from donor molecules to a variety of acceptors, this can alter the hydrophilic properties, stability, and chemical properties as well as subcellular location and biological activity of the acceptors. Many compounds that are modified by glycosylation are important sources of drug molecules. However, natural products contain only small amounts of glycosylated compounds, and it is very difficult to extract and purify these compounds. Furthermore, during the chemical synthesis of glycosylated compounds, the raw material reagents and generated by-products tend to cause environmental pollution, and it is not possible to achieve glycosylation at the particular acceptor sites. Recently, GTs have garnered interest among researchers. Therefore, here we review the current structural studies and biotechnological applications of plant GTs that would provide useful information for glycosylation engineering and bioactive glycoside production.

Glutamate (Glu) is a critical nutritional regulator of intestinal epithelial homeostasis. In addition, intestinal stem cells (ISCs) at crypt bases are known to play important roles in maintaining the renewal and homeostasis of the intestinal epithelium, and the aspects of communication between Glu and ISCs are still unknown. Here, we identify Glu and mammalian target of rapamycin complex 1 (mTORC1) as essential regulators of ISC expansion. The results showed that extracellular Glu promoted ISC expansion, indicated by increased intestinal organoid forming efficiency and budding efficiency as well as cell proliferation marker Ki67 immunofluorescence and differentiation marker Keratin 20 (KRT20) expression. Moreover, the insulin receptor (IR) mediating phosphorylation of the insulin receptor substrate (IRS) and downstream signaling phosphoinositide 3-kinase (PI3K)/protein kinase B (Akt) pathway was involved in this response in ISCs. As expected, Glu-induced mTORC1 signaling activation was observed in the intestinal porcine enterocyte cell line (IPEC-J2), and Glu activated the PI3K/Akt/mTORC1 pathway. Accordingly, PI3K inhibition partially suppressed Glu-induced mTORC1 activation. In addition, Glu increased the phosphorylation levels of IR and IRS, and inhibiting IR downregulated the IRS/PI3K/Akt pathway. Collectively, our findings first indicate that extracellular Glu activates mTORC1 via the IR/IRS/PI3K/Akt pathway and stimulates ISC expansion, providing a new perspective for regulating the growth and health of the intestinal epithelium.

Estrogens are of environmental concern because disruptive effect on biological functions at levels as low as ng/L. Wastewater treatment plant effluent is a significant source of estrogens in aquatic environment. Ferric ions (Fe3+)-saturated montmorillonite has been shown to effectively remove 17β-estradiol (βE2), a common estrogen, from pure water by catalyzing formation of insoluble βE2 oligomers on mineral surfaces. We investigated the effects of reaction temperature, dissolved organic matter, pH, and common cations, on Fe3+-saturated montmorillonite-surface catalyzed βE2 polymerization, and the removal of this estrogen from three different secondary wastewater effluents with more complicated matrixes. Highest βE2 removal occurred at near neutral pH and it increased with increasing treatment temperatures. Presence of common cations in the water did not affect the reaction efficiency. Dissolved organic matter at 15 mg C/L slightly lowered the βE2 removal efficiency as compared to that in pure water. Regardless of the source of wastewater effluents, βE2 removal efficiency of ∼40% was achieved using the dosage of Fe3+-saturated montmorillonite similar to that tested for the aqueous phases with simpler matrix. Doubling this dosage resulted in removal of ∼80% of βE2 from a tested secondary wastewater effluent within 30 min reaction. For wastewater with complex matrixes at the commonly reported βE2 levels which are magnitudes lower than the tested concentration in our study, this dosage would provide sufficient available reaction sites for the surface-catalyzed βE2 polymerization. This study demonstrated that Fe3+-saturated montmorillonite is a promising material for effective removal of phenolic estrogen compounds from domestic wastewater effluents.

Design and synthesis of metal-organic polyhedra (MOPs) with targeted geometries from predetermined secondary building units (SBUs) is a long-standing challenge in chemistry and material science. Theoretical prediction shows that there are 6 possible polyhedra from the 3-coordinated, 4-coordinated octahedron ((3,4)-c octahedron) to (3,5)-c icosahedron with minimal transitivity (simplest possible). Except for one missing polyhedron (mtr) due to the unfavorable angles, we report five MOPs based on these structures, including an octahedral (3,4)-c VMOP-21 (rdo), an icosahedral (3,5)-c VMOP-25 (trc), and three intermediate derived trinodal (3,4,5)-c VMOP-22-24 (ghm, hmg, xum). Remarkably, all these MOPs obey the minimal transitivity principle and are consistent with geometrical predictions.

Extracellular DNA in the environment may play important roles in genetic diversity and biological evolution. However, the influence of environmental persistent organic contaminants such as organochlorinated pesticides (e.g., hexachlorocyclohexanes [HCHs]) on the enzymatic degradation of extracellular DNA has not been elucidated. In this study, we observed expedited enzymatic degradation of extracellular DNA in the presence of α-HCH, β-HCH and γ-HCH. The HCH-expedited DNA degradation was not due to increased deoxyribonuclease I (DNase I) activity. Our spectroscopic and computational results indicate that HCHs bound to DNA bases (most likely guanine) via Van der Waals forces and halogen bonds. This binding increased the helicity and accumulation of DNA base pairs, leading to a more compact DNA structure that exposed more sites susceptible to DNase I and thus expedited DNA degradation. This study provided insight into the genotoxicity and ecotoxicity of pesticides and improved our understanding of DNA persistence in contaminated environments., Chao Qin, Bing Yang et al. show that organochlorinated pesticides as environmentally persistent organic contaminants enhance the degradation of extracellular DNA by making it more accessible to DNase I. This study provides insight into the persistence of DNA in contaminated environments.

One-dimensional MoO3 /MoS2 hybrid composites were synthesized by hydrothermal synthesis, and flexible MoO3 /MoS2 /PVDF nanocomposites could be prepared in a controlled fashion by combining the MoO3 /MoS2 composites with polyvinylidene fluoride (PVDF) matrix. The MoO3 /MoS2 /PVDF hybrids with a low filler content (20 wt %) exhibited distinct microwave absorption properties in the range of 2-18 GHz. The minimum reflection loss can reach -38.5 dB at 8.7 GHz, and the reflection loss was less than -10 dB in the frequency range from 3.03-11.02 GHz with an absorber thickness of 2.0-5.0 mm. The MoO3 /MoS2 /PVDF nanocomposites exhibited better absorption properties than pure MoO3 and MoS2 . The possible microwave absorption mechanism was also discussed in detail.

The objective of this research is to study the taste masking efficiency of Amberlite IRP88 in sildenafil citrate chewable tablets. Amberlite IPR88 was complexed with sildenafil citrate using the batch method. Formulation with sildenafil citrate/Amberlite IPR88 in a ratio of 2:1 by weight showed higher Drug complexation efficiency and drug-loaded, and furthermore the results from SEM, DSC, XRD, and FT-IR of selected complex indicated that the salt bridge between sildenafil and citrate was replaced by salt bridge between NH groups of sildenafil and the sulfonate group of the resin. Different chewable tablets containing the complex were prepared with various ingredients as well. Then, dissolution tests, in vivo performance assessment as well as palatability evaluation of chewable tablets were performed. The dissolution behaviors, in vivo performances and taste profiles of the prepared chewable tablets with lactose monohydrate, CMC-Na were similar to those of Nipatra Chewable Tablets, which was one of selling sildenafil citrate chewable tablet. Overall, the pH-dependent process of ion exchange by weak cationic resins opens a promising approach to mask the bitter taste of cationic drug for oral fast disintegrating formulation such as sildenafil citrate.

In areas with high exposure to pathogen contaminated water and lack the economic means for water treatment, low cost and convenient point-of-use drinking water disinfection materials/devices are essential. Using a simple craft paper making method, Fe3+-saturated montmorillonite impregnated filter paper was constructed to filter live Escherichia coli (E. coli)-spiked water. The Scanning Electron Microscopic images of the E. coli cells in contact with the Fe3+-saturated montmorillonite impregnated filter paper showed: 1) Fe3+-saturated montmorillonite particles were uniformly coated on the cellulose paper fiber, creating large mineral surface for cell contact; and 2) E. coli cell membrane was dehydrated and damaged, resulting cell deactivation upon contacting with the Fe3+-saturated montmorillonite particles impregnated in the paper. The E. coli cells passing through the Fe3+-saturated montmorillonite impregnated filter paper were not viable as further confirmed by the microfluidic dielectrophoresis analysis. They remained non-viable at room temperature even after 5 days, as shown by the results from both the Colony Counting test and the Colilert test. More than 99.5% deactivation efficiency was achieved when the ratio of the volume of the E. coli contaminated water to the mass of Fe3+-saturated montmorillonite was maintained at

Metal-organic polyhedra (MOPs) are promising candidates for many potential applications; however, their use as photocatalysts for hydrogen production has yet to be developed. Herein, the photocatalytic performance of a water-stable Zr-MOP, ZrT-1-NH2 , was evaluated, for the first time, through photocatalytic hydrogen evolution under visible-light irradiation. ZrT-1-NH2 shows clearly enhanced photocatalytic activity (510.42 μmol g-1 h-1 ) for hydrogen production, in comparison with that of other homogeneous crystalline materials. If platinum nanoparticles were introduced into the photocatalytic system, the hydrogen production efficiency of ZrT-1-NH2 could be further improved. For ZrT-1-NH2 , the conspicuous improvement in photocatalysis can be attributed to efficient electron-hole separation, targeted electron transfer, and excellent recombination suppression. Furthermore, ZrT-1-NH2 shows excellent stability during photocatalytic hydrogen evolution over five continuous runs. This work illustrates that MOP-based photocatalysts hold promise for broad applications in the domain of clean energy.

The photoreduction of carbon dioxide (CO2) into a valuable energy gas (CO and H2) is an efficient approach to address the fossil fuel crisis and mitigate the global warming effect. The development of effective photocatalysts for CO2 reduction is still desirable and challenging. Herein, two novel polyoxometalate-based hybrids with multinuclear cobalt clusters, [Co2.67(SiW12O40)(H2O)4(Htrz)4]·Cl1.33 (Htrz = 1,2,4-triazole) (1) with a binuclear cobalt cluster and [Co3(SiW12O40)(H2O)3(Htrz)6Cl]·Cl·6H2O (2) with a trinuclear cobalt cluster, were synthesized under hydrothermal conditions. Both of them were characterized by single-crystal X-ray diffractions, PXRD, IR, TG and UV–vis spectra. Compound 1 exhibited a 3D structure with 4-connected [SiW12O40] and 3-connected [Co2(Htrz)3(H2O)3] secondary building units (SBUs). The 1D chain of compound 2 was constructed from [SiW12O40] and [Co3(Htrz)6(H2O)3Cl] SBUs. Furthermore, the photoreduction of CO2 under visible light by the two cobalt-based POMs was investigated using [Ru(bpy)3]Cl2·6H2O as a photosensitizer. The CO yields of compounds 1 and 2 were 15 705 and 18 501 μmol g−1 for the CO2 photocatalytic reduction under three hour irradiation at 293 K, respectively. The difference in the photocatalytic performance of 1 and 2 was explained by comparing the energy of the valence band, band gaps and conduction band. The results showed that the photocatalysts incorporated with multinuclear Co clusters could effectively improve photocatalytic activities, thus providing a valuable view to design high performance and cost-acceptable molecular catalysts for CO2 photoreduction.

Lateral gene transfer (LGT) promotes the proliferation of antibiotic resistance genes (ARGs). However, the lateral transfer efficiency of ARGs in the natural environment is little known. This study explored the lateral transfer of ARG-carrying plasmids to Escherichia coli (i.e., transformation) in the presence of metal oxide nanoparticles (MONPs). The presence of ZnO, Al2O3 and TiO2 nanoparticles (ZnONPs, Al2O3NPs and TiO2NPs, respectively) at concentrations of less than 50 mg L−1 inhibited the lateral transfer of pUC19 plasmid carrying the ampicillin resistance gene into E. coli DH5α in a decreasing degree of Al2O3NP > ZnONP > TiO2NP. The suppressed lateral ARG transfer was not due to the dissolution of metal ions from MONPs, but rather was caused by the binding of MONPs with the phosphate groups and bases of pUC19, as supported by microscopic, spectroscopic and computational evidence. The amount of plasmids bound to MONPs showed a significant negative correlation with the efficiency of ARG transfer, likely because plasmids and MONPs formed aggregates that were blocked out of E. coli cells, thus inhibiting the ARG lateral transfer. Our results provided new insight into the effect of MONPs on the lateral transfer of ARGs and improved our understanding of the ecological risks of plasmid-borne ARGs at the molecular and cellular level.

A rational synthetic strategy to construct two supramolecular isomers based on polyoxovanadate organic polyhedra with tetrahedral symmetries is presented. VMOP-α, a low-temperature product, has an extremely large cell volume (470 842 A3 ), which is one of the top three for well-defined MOPs. The corner-to-corner packing of tetrahedra leads to a quite low density of 0.174 g cm-3 with 1D channels (ca. 5.4 nm). The effective pore volume is up to 93.6 % of cell volume, nearly the largest found in MOPs. For the high-temperature outcome, VMOP-β, the cell volume is only 15 513 A3 . The packing mode of tetrahedra is corner-to-face, giving rise to a high-density architecture (1.324 g cm-3 ; channel 0.8 nm). Supramolecular structural transformation between VMOP-α and VMOP-β can be reversibly achieved by temperature-induced solvent-mediated transformation. These findings give a good opportunity for understanding 3D supramolecular aggregation and crystal growth based on large molecular tectonics.

Pyrethroids may be related to male reproductive system damage. However, the results of many previous studies are contradictory and uncertain. Therefore, a systematic review and a meta-analysis were performed to assess the relationship between pyrethroid exposure and male reproductive system damage. A total of 72 articles were identified, among which 57 were selected for meta-analysis, and 15 were selected for qualitative analysis. Pyrethroid exposure affected sperm count (SMD= -2.0424; 95% CI, -2.4699 to -1.6149), sperm motility (SMD=-3.606; 95% CI, -4.5172 to -2.6948), sperm morphology (SMD=2.686; 95% CI, 1.9744 to 3.3976), testis weight (SMD=-1.1591; 95% CI, -1.6145 to -0.7038), epididymal weight (SMD=-1.1576; 95% CI, -1.7455 to -0.5697), and serum testosterone level (SMD=-1.9194; 95% CI, -2.4589 to -1.3798) in the studies of rats. We found that gestational and lactational exposure to pyrethroids can reduce sperm count (SMD=1.8469; 95% CI, -2.9010 to -0.7927), sperm motility (SMD=-2.7151; 95% CI, -3.9574 to -1.4728), testis weight (SMD=-1.4361; 95% CI, -1.8873 to -0.9848), and epididymal weight (SMD=-0.6639; 95% CI, -0.9544 to -0.3733) of F1 offspring. Exposure to pyrethroids can increase malondialdehyde (SMD=3.3451; 95% CI 1.9914 to 4.6988) oxide in testes and can reduce the activities of glutathione (SMD=-2.075; 95% CI -3.0651 to -1.0848), superoxide dismutase (SMD=-2.4856; 95% CI -3.9612 to -1.0100), and catalase (SMD=-2.7564; 95% CI -3.9788 to -1.5340). Pyrethroid exposure and oxidative stress could damage male sperm quality. Gestational and lactational pyrethroid exposure affects the reproductive system of F1 offspring.

Purpose To investigate the effect of 20(S)-ginsenoside Rh2 (Rh2) on anti HepG2 liver cancer cells and HepG2 cell-derived xenograft tumors, and explore the underlying mechanisms. Materials and methods The activity of total HDACs and HAT were assessed with a HDACs colorimetric kit. Expression of HDAC1, HDAC2, HDAC6, p-ERK, ERK, p-P38, P38, p-JNK and JNK proteins was tested by Western blotting.H3K9 and H3K14 proteins were also checked by immunofluorescence, changes in cell cycle distribution with flow cytometry, cell apoptosis with annexin V-FTIC/PI double staining. Activity of Renilla luciferase (HIF) was detected using the Luciferase Reporter Assay system reagent. Gene expression for CyclinD1, Bcl-2, Bax, HIF, IL-1, IL-6, IL-10 and TNF-α was tested by q-PCR. Expression levels of CD31 and Ki-67 was tested by immunohistochemical staining. Results Total HDAC activity was decreased and total histone acetyltransferase (HAT)activity was increased in a time-dependent manner. Expression of HDAC1 and p-JNK proteins was significantly increased, expression levels of p-ERK was decreased. H3K9 and H3K14 fluorescence protein were increased. Flow cytometric analysis of the cell cycle revealed that the percentage of cells in the G0/G1 phase in the treatment group(64.35±1.36%) was significantly increased compared with the untreated group(61.61±1.23%).The apoptotic rate of the HepG2 group was 10.03±1.92%, which increased to 17.87±1.67% in the treatment group. Expression levels of the transcription factor HIF were also increased in HepG2 cells following induction by Rh2. Expression of CyclinD1 and Bcl-2 at the genetic level was significantly decreased, while expression levels of Bax, HIF, IL-1, IL-6, IL-10 and TNF-α was increased. In vivo, the expression levels of both CD31 and Ki-67 proteins were significantly down-regulated in the treatment group compared with the control group. Conclusions The effects of Rh2 were suggested to occur through the inhibition of total HDAC activity, which subsequently induced MAPK signaling and down-regulated the expression of HIF. .

Gas-particle partitioning of water-soluble organic compounds plays a significant role in the formation and source apportionment of organic aerosols, but is poorly characterized. In this work, gas- and particle-phase concentrations of isoprene oxidation products (C5-alkene triols and 2-methylterols), levoglucosan, and sugar polyols were measured simultaneously at a suburban site of the western Yangtze River Delta in east China. All target polyols were primarily distributed into the particle phase (85.9–99.8 %), and their average particle-phase fractions were not strictly dependent on vapor pressures. Moreover, the measurement-based partitioning coefficients (Kp,OM) of isoprene oxidation products and levoglucosan were 102 to 104 times larger than their predicted Kp,OM based on the equilibrium absorptive partitioning model. These are likely attributed to the hygroscopic properties of polyol tracers and high aerosol liquid water (ALW) concentrations (~20 µg m−3) of the study location. Due to the large gaps (up to 107) between measurement-based effective Henry's law coefficients (KH,e) and predicted values in pure water (KH,w), the gas-particle partitioning of polyol tracers could not be depicted using Henry's law alone either. The regressions of log (KH,w/KH,e) versus molality of major water-soluble components in ALW indicated that sulfate ions (salting-in effect) and water-soluble organic carbon can promote the partitioning of polyol tracers into the aqueous phase. These results suggest a partitioning mechanism of enhanced aqueous-phase uptake for polyol tracers, which partly reveals the discrepancy between observation and modeling of secondary organic aerosols.

Xiaotao Su,1 Shaohua Chen,2 Hongyu Lu,1 Haoyu Li,3 Chao Qin1 1Department of Neurology, The First Affiliated Hospital of Guangxi Medical University, Nanning, 530021, People’s Republic of China; 2Department of Urology, The First Affiliated Hospital of Guangxi Medical University, Nanning, 530021, People’s Republic of China; 3Department of Ophthalmology, The First Affiliated Hospital of Guangxi Medical University, Nanning, 530021, People’s Republic of ChinaCorrespondence: Haoyu LiDepartment of Ophthalmology, The First Affiliated Hospital of Guangxi Medical University, 6 Shuangyong Road, Nanning, 530021, People’s Republic of ChinaEmail med.dr.lihy@gmail.comChao QinDepartment of Neurology, The First Affiliated Hospital of Guangxi Medical University, 6 Shuangyong Road, Nanning, 530021, People’s Republic of ChinaEmail mdqc2019@126.comBackground: Glioblastoma (GBM) is the most prevalent malignant tumor of the central nervous system (CNS). However, current GBM treatments are ineffective, signifying the great importance of exploring new therapeutic targets. Curcumin has been found to be a natural compound with an anticancer potential. However, its targets and mechanisms in GBM are still unclear.Methods: Differentially expressed genes (DEGs) were screened from the GBM dataset in the GEO database and intersected with the target genes of curcumin to select potential target genes. Subsequently, survival analysis was performed with the GEPIA database to confirm the effect of target genes on the prognosis of GBM, and functional enrichment analysis was performed using the DAVID database. In vitro, CCK-8 assay was used to screen the appropriate concentration of curcumin; scratch and transwell invasion assays were used to evaluate the effect of curcumin on the migration and invasion abilities of GBM cells. Furthermore, RT-qPCR and Western blotting were used to detect changes in target genes and flow cytometry was used to assess the apoptosis level.Results: A total of 16 target genes of curcumin and GBM were obtained, among which ENO1, MMP2, and PRKD2 significantly affected the prognosis (P < 0.05). We further selected ENO1 for functional enrichment analysis and found that it was enriched in the glycolytic pathway. Meanwhile, in vitro experiments showed that curcumin could inhibit the migration and invasion of U251 cells and promote apoptosis (P < 0.05).Conclusion: ENO1 could be a possible target for curcumin in the suppression of GBM cells.Keywords: glioblastoma, curcumin, ENO1, migration, apoptosis, computational biology

High-fat diet (HFD) decreases insulin sensitivity. How high-fat diet causes insulin resistance is largely unknown. Here, we show that lean mice become insulin resistant after being administered exosomes isolated from the feces of obese mice fed a HFD or from patients with type II diabetes. HFD altered the lipid composition of exosomes from predominantly phosphatidylethanolamine (PE) in exosomes from lean animals (L-Exo) to phosphatidylcholine (PC) in exosomes from obese animals (H-Exo). Mechanistically, we show that intestinal H-Exo is taken up by macrophages and hepatocytes, leading to inhibition of the insulin signaling pathway. Moreover, exosome-derived PC binds to and activates AhR, leading to inhibition of the expression of genes essential for activation of the insulin signaling pathway, including IRS-2, and its downstream genes PI3K and Akt. Together, our results reveal HFD-induced exosomes as potential contributors to the development of insulin resistance. Intestinal exosomes thus have potential as broad therapeutic targets., High-fat diet plays a role in development of insulin resistance. Here, the authors report a mechanism that underlies the development of diet induced insulin resistance through the activation of an aryl hydrocarbon receptor mediated signalling pathway in the liver by faecal exosomes derived from intestinal cells.