Search

As the desired sulfur host of lithium-sulfur battery, the strong polarity and fast electron migration capability are indispensable for achieving effective adsorption and conversion of lithium polysulfides (LiPSs), that is, restricting the shuttle effect. Herein a porous microdisk Ti4O7/TiN/C heterojunction with strong polar N-Ti-O covalent bonds is precisely constructed. Compared with O-Ti-O or N-Ti-N bond in single Ti4O7 or TiN, the N-Ti-O bond with stronger polarity could adsorb and bond with S and Li atoms in LiPSs, which is beneficial for LiPSs adsorption. Beside, the Ti4O7/TiN heterostructure favors the electron transfer, which could promote the conversion of LiPSs. The design strategy is to construct abundant polar N-Ti-O bonds at Ti4O7/TiN heterogeneous interface that would realize the associative process of LiPSs adsorption, trapping, and conversion, thereby restraining the shuttle effect efficiently. In the current study, as the host of the sulfur cathode, the porous microdisk TiN/Ti4O7/C heterojunction exhibits a high specific capacity of 1204.5 mAh g−1 at 0.2 C, and a high specific capacity of 616.5 mAh g−1 at an ultrahigh current density of 4 C. In addition, 86.4% and 116.9% capacity are retained over 1000 cycles at 1 C and 2 C, respectively. This strategy provides an insight into developing lithium-sulfur battery with extraordinary performance, and opens promising routes to design the next-generation electrochemical energy storage devices.

A new gold(i) self-relay catalysis consisting of a 3,3-rearrangement, Nazarov cyclization and Michael addition cascade of 1,3-enyne acetates with aurones and their derived azadienes is reported, producing functionalized cyclopentenones.

The development of stable, high-energy electrode materials for lithium ion-batteries requires an elaborate effort to optimize the active materials as well as the chemical bonds and electron/ion transport in the electrode. However, hindered by the intrinsic structure and electrochemical degradation which is attributed to the volume expansion of materials, an increase in battery safety and reliability is concerned. Here, taking silicon as an example, we propose a strategy to stabilize this anode by successive chemical bonds reconstructing the surface. In this study, silicon nanoparticles are assembled in a carbon-copper framework via a facile and scalable pyrolysis process to provide a short-range electron transfer and pulverization suppression. Dissimilar to the current carbon coating methods, with the aid of Cu-O-C, Si-O-C, and Si-C chemical bonds, silicon hybridized reduced graphene oxide (rGO) and double-faced adhesive tape derived carbon composite (Si+rGO@DFAT-C) exhibits high structural integrity and immune to delamination. Hence, it demonstrates superior capacity (1536 mAh g at 0.1 A g ), high rate capability (1126 mAh g at 2 A g ), and stable electron stability (968.1 mAh g after 200 cycles at 0.5 A g ). This study emphasizes the crucial importance of well-tailor surface chemical bond reconstruction for the anode stabilization for high-performance LIBs. −1 −1 −1 −1 −1 −1

The influence of graphite content (volume fraction, 0, 3, 6, 9, 12%) on the microstructure, mechanical properties, thermal physical properties, and wear properties of silicon carbide particle–reinf...

Coupling dual active components into one integrated catalyst as well as understanding their electronic interaction behavior on reversible oxygen electrocatalysis is central to achieving high energy-conversion efficiency for Zn-air batteries (ZABs). Herein, we demonstrate an effective couple of MnO and Co nanocrystals embedded in N-doped graphite carbon to integrate a highly efficient bifunctional catalyst (denoted as MnO/Co@NGC) toward oxygen reduction and evolution reaction (ORR/OER). MnO/Co@NGC was first successfully prepared by the one-step pyrolysis of Mn3[Co(CN)6]2·9H2O@PVP (poly(vinyl pyrrolidone)), and X-ray absorption near-edge structure analysis revealed that the charges were transferred from MnO to Co@NGC, which makes MnO more electrophilic to facilitate the initial electrochemical adsorption of OH- for improving the OER activity. As expected, the as-designed MnO/Co@NGC displays excellent bifunctional ORR/OER activity with a small overpotential gap of only 0.736 V, providing the ZABs with a high trip efficiency of 57.2% as well as excellent cycling stability. This work not only offers a bifunctional ORR/OER electrocatalyst but also further highlights the interfacial charge distribution in oxygen electrocatalysis, affording a promising approach for developing advanced energy-related materials.

Oxygen vacancies play a positive role in optimizing the physical and chemical properties of metal oxides. In this work, we demonstrated oxygen vacancy-promoted enhancement of Li-ion diffusion kinetics in Li2GeO3 nanoparticle-encapsulated carbon nanofibers (denoted as Li2GeO3-x/C) and accordingly boosted lithium storage. The introduction of the oxygen vacancies in Li2GeO3-x/C can enhance electronic conductivity and evidently decrease activation energy of Li-ion transport, thus resulting in evidently accelerated Li-ion diffusion kinetics during the lithiation/delithiation process. Thus, the Li2GeO3-x/C nanofibers exhibit an exceptionally large discharge capacity of 1460.5 mA h g-1 at 0.1 A g-1, high initial Coulombic efficiency of 81.3%, and excellent rate capability. This facile and efficient strategy could provide a reference for injecting the oxygen vacancies into other metal oxides for high-performance anode materials.

As the use time of concrete structures increases, defects such as concrete cracks, corrosion and exposure of steel bars gradually appear, resulting in additional repair of concrete structures to increase their durability and life. In this article, the effects of nano-modified polymer cement-based materials as repair material on the bending behavior of repaired concrete beams were studied. Based on the moment, deflection, strain, surface quality and cracking development monitor of repaired concrete beams, the bending behavior of repaired beams with polymer, nano-modified polymer and fibers was compared and the failure mechanism of the beams was analyzed. The results showed that the nano-modified polymer cement-based materials are helpful in improving the performance of repaired beams, manifested by the increase in the ultimate bending moment and the significant improvement in the quality of the interface between repair and matrix concrete. Compared with polymer cement-based materials, nano-modified polymer cement-based materials result in a 27% increase in ultimate bending moment of the repaired beam and a 58% increase in cracking moment, while reducing the total number of cracks by 23% and the average width of cracks by 17% in the repaired beam. This article demonstrated the availability of nanomaterials for improving the loading behavior of structural components with polymer-modified cement-based materials.

Biomass-derived activated carbon has attracted much attention in electrochemical energy systems, and its great potential can be further unlocked for achieving high-performance by tuning its composi...

Although metal silicates are considered as the promising electrode materials for lithium-ion batteries, metal silicate-based materials suffer from inadequate cycling performance and dimensional unreliability evoked by the large volume changes during cycling, which hinders their practical applications. In principle, the poor electrochemical kinetics during the redox reactions of metal silicates is originated from the instinct structure. Hence, the precise and delicate ability to construct hetero-layers to tailor intercalation reaction remains elusive. Herein, a facile strategy of designing and constructing heterostructure in a cobalt-copper silicates nano-architecture (CNT@CoCuSiOx) with synergistic interaction between cobalt silicate (Co2SiO4) with copper silicate (CuSiO3) on the surface of carbon nanotubes (CNTs). Moreover, Co2SiO4/CuSiO3 heterojunction with unbalanced charge distributions that rooted from in-situ generation on CNTs by a facile one-step hydrothermal process, can efficiently tailor the electrochemical activities of Cu3+/Cu2+ and Co3+/Co2+ redox reactions by elevating transfer of electrons and delivering the heterointerface effect. The tough and conductive nanostructure of CNTs basement facilitate the ion diffusion and improve the rate capability. The heterostructure-incorporated CNT@CoCuSiOx-(2/1) exhibits not only outstanding electrochemical capacity (545 mAh g−1 at 0.1 A g−1), superior ion/electron transmission efficiency but also robust cycling performance (516 mAh g−1 after 900 cycles at 0.5 A g−1 and an excellent capacity retention rate of 95%). Beyond energy storage, our delicate methodology in manipulating the electrochemical behavior of metal silicates opens up a critical insight into rational fabrication of next-generation anodes for lithium-ion battery.

Carbon dioxide (CO2) pretreatment to concrete at the early curing ages is a feasible technique towards achieving a greener and more sustainable concrete industry. However, the carbonation efficienc...

Although transition metal silicates are recognized as high potential and attractive materials for next-generation lithium-ion batteries (LIBs) due to their efficient energy storage, earth-abundance...

Metal-organic frameworks (MOFs) have been extensively used in the fabrication of new advanced electrode materials for lithium ion batteries (LIBs). However, low-productivity and high-cost are some of the main challenges of MOF-derived electrodes. Herein, we report a simple solvothermal procedure to fabricate novel Fe4-based metal-organic clusters (Fe-MOCs) with their subsequent conversion to an S,N dual-doped carbon framework incorporating iron oxides under a N2 atmosphere (namely Fe2O3@Fe3O4-SNC). The as-prepared Fe2O3@Fe3O4-SNC composite, owing to the strong interaction between the dual-doped carbon and iron oxides, shows excellent lithium storage performance as an anode with high pseudocapacitance. Furthermore, DFT computational analyses confirm that the hybrid shows excellent adsorption ability with a low energy barrier due to strong electronic interactions between the iron oxides and S,N-doped carbon matrix. In addition, Fe2O3@Fe3O4-SNC-based LIB shows high energy and power densities at the full-cell level, confirming this synthesis strategy to be a promising approach towards MOC-derived electrode materials for their application in LIBs and beyond-lithium batteries.

Ni-modified Ag/SiO2 catalysts containing 0~3 wt.% Ni were obtained by impregnating Ni species onto Ag/SiO2 followed by calcination and reduction. The catalysts’ performance in the hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG) was tested. Ag-0.5%Ni/SiO2 showed the highest catalytic activity among these catalysts and exhibited excellent catalytic stability. The effects of the Ni content on the structure and surface chemical states of catalysts were investigated by XRF, N2-sorption, XRD, TEM, EDX-mapping, FT-IR, H2-TPR, UV–vis, and XPS. The better catalytic activity and stability of Ni-modified Ag/SiO2 (versus Ag/SiO2) are ascribed to the improved dispersion of active Ag species as well as the higher resistance to the growth of Ag particles due to the presence of Ni species.

Single-atom catalysts (SACs) have attracted much attention due to their outstanding catalytic performance in heterogeneous catalysis. Here, we report a template sacrificial method to fabricate an a...

The stereospecific design of the interface effects can optimize the electron/Li-ion migration kinetics for energy-storage materials. In this study, an electric field was introduced to silicon-based materials (C-SiOx@Si/rGO) through the rational construction of multi-heterostructures. This was achieved by manipulating the physicochemical properties at the atomic level of advanced Li-ion batteries (LIBs). The experimental and density functional theory calculations showed that the unbalanced charge distribution generated a large potential difference, which in turn induced a large-scale electric-field response with a boosted interfacial charge transfer in the composite. The as-prepared C-SiOx@Si/rGO anode showed advanced rate capability (i.e., 1579.0 and 906.5 mAh g-1 at 1000 and 8000 mA g-1, respectively) when the migration paths of the Li-ion/electrons hierarchically optimized the large electric field. Furthermore, the C-SiOx@Si/rGO composite with a high SiOx@Si mass ratio (73.5 wt %) demonstrated a significantly enhanced structural stability with a 40% volume expansion. Additionally, when coupled with the LiNi0.8Co0.1Mn0.1O2 (NCM) cathode, the NCM//C-SiOx@Si/rGO full cell delivers superior Li-ion storage properties with high reversible capacities of 157.6 and 101.4 mAh g-1 at 500 and 4000 mA g-1, respectively. Therefore, the electric-field introduction using optimized electrochemical reaction kinetics can assist in the construction of other high-performance LIB materials.

Tailings wastewater contains a large number of harmful ions which damage the hydraulic concrete structures and seriously affect the safety of water conservancy systems. This paper studied the dam concrete of a medium-sized reservoir in southeastern China which was corroded by tailings wastewater. To this end, a long-term follow-up investigation was conducted into the corrosion of the dam concrete during the period from 2013 to 2019. A multiscale analysis was also carried out on the long-term influence of the tailings wastewater on the mechanical performance and microstructure of the dam concrete. The results revealed that the corrosion by the tailings wastewater containing H+ and SO 4 2 − caused a significant decline in the mechanical performance of the dam concrete in terms of the increase in the carbonation depth and the reduction of the compressive strength. Compared to the time period from 2006 to 2013, the rate of corrosion slowed down during 2013–2019. Furthermore, the main reason for the deterioration of the dam concrete was that the attack of H+ and SO 4 2 − resulted in the dissolution erosion and expansion erosion of the dam concrete. The dissolution erosion of the concrete led to the increase in the average pore diameter, median pore diameter, and porosity of the dam concrete, while the expansion erosion improved the formation of gypsum and ettringite. Moreover, the dam concrete experienced various degrees of corrosion in different zones. Specifically, the dissolution erosion was most serious in the tidal zone, while the expansion erosion was severest in the submerged zone. Finally, this paper can provide a frame of reference for the research on the corrosion mechanism and service safety of hydraulic concrete structures eroded by various types of tailings wastewater.

Urinary mutagenicity reflects systemic exposure to complex mixtures of genotoxic/carcinogenic agents and is linked to tumor development. Coal combustion emissions (CCE) and diesel engine exhaust (DEE) are associated with cancers of the lung and other sites, but their influence on urinary mutagenicity is unclear. We investigated associations between exposure to CCE or DEE and urinary mutagenicity. In two separate cross-sectional studies of nonsmokers, organic extracts of urine were evaluated for mutagenicity levels using strain YG1041 in the Salmonella (Ames) mutagenicity assay. First, we compared levels among 10 female bituminous (smoky) coal users from Laibin, Xuanwei, China, and 10 female anthracite (smokeless) coal users. We estimated exposure-response relationships using indoor air concentrations of two carcinogens in CCE relevant to lung cancer, 5-methylchrysene (5MC), and benzo[a]pyrene (B[a]P). Second, we compared levels among 20 highly exposed male diesel factory workers and 15 unexposed male controls; we evaluated exposure-response relationships using elemental carbon (EC) as a DEE-surrogate. Age-adjusted linear regression was used to estimate associations. Laibin smoky coal users had significantly higher average urinary mutagenicity levels compared to smokeless coal users (28.4 ± 14.0 SD vs. 0.9 ± 2.8 SD rev/ml-eq, p = 2 × 10-5 ) and a significant exposure-response relationship with 5MC (p = 7 × 10-4 ). DEE-exposed workers had significantly higher urinary mutagenicity levels compared to unexposed controls (13.0 ± 10.1 SD vs. 5.6 ± 4.4 SD rev/ml-eq, p = .02) and a significant exposure-response relationship with EC (p-trend = 2 × 10-3 ). Exposure to CCE and DEE is associated with urinary mutagenicity, suggesting systemic exposure to mutagens, potentially contributing to cancer risk and development at various sites.

A novel strategy was proposed for preparing micro-scale monodisperses nitrifying bacteria (NB) encapsulated Ca-Alg@CaCO3 colloidosomes by exploiting capillary microfluidic device, as an attempt to treat ammonium-nitrogen wastewater in an environment-friendly, efficient and repeatable manner based on the aqueous two-phase (ATPS) system. By complying with the spatial confined urease mediate biomineralization reactions, ATPS droplets (Dextran in Polyethylene glycol) containing urease, NB regent and alginate were used as templates to prepare 500 μm Ca-Alg@CaCO3 colloidosomes with 16.48 Mpa mechanical strength. The activity of NB encapsulated in the colloidosomes was high. The simulated wastewater treated with the colloidosomes achieved a high removal rate even at harsh temperature and pH value. In both simulated and real wastewater treatment, prolonged reuse times (216 h) with high removal rate (＞90%, after being applied 72 h) were obtained by using Ca-Alg@CaCO3 colloidosomes, as compared with that (96 h) by using general alginate microbeads.

Both hydrogen peroxide (H2O2, H) and ischemia/reperfusion (I/R) can damage cardiomyocytes, which was inhibited by propofol (P). The present research was designed to examine whether propofol can reduce myocardial I/R injury by activating protein kinase C (PKC)/nuclear factor erythroid-2-related factor 2 (NRF2) pathway in H9C2 cells and rat Langendorff models. H9C2 cells were disposed of no reagents (C), H2O2 for 24 h (H), propofol for 1 h before H2O2 (H+P), and chelerythrine (CHE, PKC inhibitor) for 1 h before propofol and H2O2 (H+P+CHE). N = 3. The PKC gene of H9C2 was knocked down by siRNA and overexpressed by phorbol 12-myristate 13-acetate (PMA, PKC agonist). The cell viability and the expressions of PKC, NRF2, or heme oxygenase-1(HO-1) were evaluated. Propofol significantly reduced H9C2 cell mortality induced by H2O2, and significantly increased NRF2 nuclear location and HO-1 expression, which were restrained by siRNA knockout of PKC and promoted by PMA. Rat hearts were treated with KrebsHenseleit solution for 120 min (C), with (I/R+P) or without (I/R) propofol for 20 min before stopping perfusion for 30 min and reperfusion for 60 min, and CHE for 10 min before treated with propofol. N = 6. The levels of lactate dehydrogenase (LDH), superoxide dismutase (SOD), and creatine kinase-MB (CK-MB) in perfusion fluid and antioxidant enzymes in the myocardium were assessed. I/R, which increased LDH and CK-MB expression and reduced SOD expression, boosted the pathological damage and infarcts of the myocardium after reperfusion. However, propofol restrained all these effects, an activity that was antagonized by CHE. The results suggest that propofol pretreatment protects against I/R injury by activating of PKC/NRF2 pathway.

Background: Drugs that interfere with microtubule dynamics are used widely in cancer chemotherapy. Microtubules are composed of αβ-tubulin heterodimers, and the colchicine binding site of tubulin is an important pocket for designing tubulin polymerization inhibitors. We have previously designed and synthesized a series of colchicine binding site inhibitors (CBSIs). However, these compounds showed no anticancer activity in vivo. Then, we have used a deconstruction approach to obtain a new derivative MT189, which showed in vivo anticancer activity. Methods: We crystallized a protein complex including two tubulins, one stathmin-like domain of RB3 and one tubulin tyrosine ligase, and soaked MT189 into the crystals. We collected the diffraction data and determined the tubulin-MT189 structure to 2.8 Å. Results: Here, we report the crystal structure of tubulin complexed with MT189, elucidate how the small-molecular agent binds to tubulin and inhibits microtubule assembly, and explain previous results of the structure-activity-relationship studies. Conclusion: The tubulin-MT189 complex structure reveals the interactions between this agent and tubulin and provides insights into the design of new derivatives targeting the colchicine binding site.

The human placenta is an important organ that forms a barrier where maternal and fetal exchange takes place. The placenta transport iodine to the fetal circulation by transfer of maternal iodine and deiodination of thyroid hormones (THs). The aim of the study was to examine the distribution of iodine and thyroid hormone transporters in the maternal and fetal sides of human-term placenta. A cross-sectional study was performed at the First Affiliated Hospital of China Medical University. Placental samples (maternal and fetal surfaces) were collected from 113 healthy-term pregnant women. The iodine content; the concentration of thyroxine (T4), triiodothyronine (T3), and reverse T3 (rT3); and the enzyme activity of placental type 2 iodothyronine deiodinase (D2) and D3 were examined. The mRNA and protein localization/expression of iodine and thyroid hormone transporters in the placenta were also studied. We also analyzed the association between expression level of Na+/I- symporter (NIS), thyroid hormone transporter protein, D3 activity in maternal and fetal surfaces of placenta with iodine content, and thyroid hormone levels. Iodine levels in placental samples from the maternal side were significantly higher than those in samples from the fetal side. T3 and T4 expression in fetal placenta was significantly lower than in maternal placenta. D3 activity in the fetal side of the placentas was significantly higher than that in the maternal side. The mRNA and protein expression of monocarboxylate transporters 8 (MCT8), L-amino acid transporters 1 (LAT1), organic anion transporting polypeptides 4A1 (OATP4A1), and TH binding protein transthyretin (TTR) were significantly increased in maternal side, while the NIS expression was higher in fetal side of human-term placenta. In conclusion, the enzymatic deiodination of thyroid hormones forms a barrier which reduces transplacental passage of the hormones and that the maternal part of the placenta is the primary factor in the mechanism regulating the hormonal transfer.

Atomically dispersed metal-N-C structures are efficient active sites for catalyzing benzene oxidation reaction (BOR). However, the roles of N and C atoms are still unclear. We report a polymerization-regulated pyrolysis strategy for synthesizing single-atom Fe-based catalysts, and present a systematic study on the coordination effect of Fe-NxCy catalytic sites in BOR. The special coordination environment of single-atom Fe sites brings a surprising discovery: Fe atoms anchored by four-coordinating N atoms exhibit the highest BOR performance with benzene conversion of 78.4% and phenol selectivity of 100%. Upon replacing coordinated N atoms by one or two C atoms, the BOR activities decrease gradually. Theoretical calculations demonstrate the coordination pattern influences not only the structure and electronic features, but also the catalytic reaction pathway and the formation of key oxidative species. The increase of Fe-N coordination number facilitates the generation and activation of the crucial intermediate O=Fe=O species, thereby enhancing the BOR activity., Atomically dispersed metal-N-C are efficient active site for benzene oxidation but the roles of N and C atoms are still unclear. Here the authors report a highly-active single-atom Fe-based benzene oxidation catalyst and provide deep insights into the structure-activity relationship at atomic level.

Solid-phase speciation and porewater chemistry measured by the diffusive gradients in thin films (DGT) technique were used to understand the diagenesis of sulfur (S), iron (Fe), and phosphorus (P) in sediments of Jiaozhou Bay (China), which has been impacted by multiple anthropogenic perturbations. Despite water eutrophication, sediments of the bay are low in organic carbon and sulfide, but high in unsulfidized Fe(II). Dissimilatory iron reduction (DIR) prevails in sediments of the bay, and there is no evidence for responses of S and Fe diagenesis to the water eutrophication, which is largely attributable to unique depositional and diagenetic regimes in association with multiple anthropogenic perturbations. Good coupling of porewater Fe2+ and P in the porewaters suggests that P mobilization is driven mainly by DIR. Low Fe2+/P ratios in porewaters imply that oxidative regeneration of Fe oxides within the upper sediments is incapable of efficiently scavenging upward diffusing P.

The bromodomain and extra-terminal domain (BET) family of proteins, especially bromodomain-containing protein 4 (BRD4), has emerged as exciting anti-tumor targets due to their important roles in epigenetic regulation. Therefore, the discovery of BET inhibitors with promising anti-tumor efficacy will provide a novel approach to epigenetic anticancer therapy. Recently, we discovered the new BET inhibitor compound 171, which is derived from a polo-like kinase 1 (PLK1)-BRD4 dual inhibitor based on our previous research. Compound 171 was found to maintain BET inhibition ability without PLK1 inhibition, and there was no selectivity among BET family members. The in vitro and in vivo results both indicated that the overall anti-tumor activity of compound 171 was improved compared with the (+)-JQ-1 or OTX-015 BET inhibitors. Furthermore, we found that compound 171 could regulate the expression of cell cycle-regulating proteins including c-Myc and p21 and induce cell cycle arrest in the G0/G1 phase. However, compound 171 only has a quite limited effect on apoptosis, in considering that apoptosis was only observed at doses greater than 50 μM. To determine the mechanisms underlying cell death, proliferation activity assay was conducted. The results showed that compound 171 induced clear anti-proliferative effects at doses that no obvious apoptosis was induced, which indicated that the cell cycle arresting effect contributed mostly to its anti-tumor activity. The result of this study revealed the anti-tumor mechanism of compound 171, and laid a foundation for the combination therapy in clinical practice, if compound 171 or its series compounds become drug candidates in the future.

Despite significant advances in the development of highly efficient and robust oxygen evolution reaction (OER) electrocatalysts to replace noble-metal catalysts, commercializing OER catalysts with high catalytic activity for sustainable development still remains a great challenge. Especially, transition-metal Fe-based OER catalysts, despite their earth-abundant, cost-efficient, and environmentally benign superiorities over Co- and Ni-based materials, have received relatively insufficient attention because of their poor apparent OER activities. Herein, by rational design, we report Ni-modified pyrite (FeS2) spheres with yolk-shell structure that could serve as pre-electrocatalyst precursors to induce a highly active nickel-iron oxyhydroxide via in situ electrochemical topological transformation under the OER process. Notably, as confirmed by the results of X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations, Ni doping could effectively regulate the intrinsic electronic structure of FeS2 to realize a semiconductor-to-semimetal transition, which endows FeS2 with dramatically improved conductivity and water adsorption ability, providing prequisites for subsequent topological transformation. Moreover, systematic post-characterizations further reveal that the optimal Ni-FeS2-0.5 sample completely converts to amorphous Ni-doped FeOOH via an in situ electrochemical transformation with yolk-shell structure well-preserved under the OER conditions. The electronic structure modulation combined with electrochemical topotactic transformation strategies well stimulate the reactive Fe sites in Ni-FeS2-0.5, which show impressively low overpotentials of 250 and 326 mV to drive the current densities ( j) of 10 and 100 mA cm-2, respectively, and a Tafel slope as small as 34 mV dec-1 for the OER process. When assembled as a water electrolyzer for the overall water splitting, Ni-FeS2-0.5 can display a low voltage of 1.55 V to drive a current density of 10 mA cm-2, outperforming most of the transition-metal-based bifunctional electrocatalysts to date. This work may provide new insight into the rational design of other high-performance Fe-based OER electrocatalysts and inspire the exploration of cost-effective, ecofriendly electrocatalysts to meet the demand for future sustainable development.

Despite a significant advancement in preparing metastable materials, one common problem is the strict and precious reaction conditions due to their metastable structures. Herein, we achieved the preparation of high-temperature stabilized metastable α-MoC1-x by mounting zinc atoms into its lattice structure. Such a structural construction could suppress the phase transformation from α-MoC1-x to β-Mo2 C through restricting the displacement of Mo atoms upon increased temperature. The resultant metastable α-MoC1-x can be stabilized up to 1000 °C and this stability temperature is the highest for the metastable α-MoC1-x so far. Synchrotron X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) confirm the structure of Zn-mounted α-MoC1-x . Density functional theory (DFT) calculations reveal that the introduction of the Zn atoms in the lattice structure of α-MoC1-x could significantly decrease the energy difference (ΔE) between α-MoC1-x and β-Mo2 C, thus effectively suppressing the phase transformation from α-MoC1-x to β-Mo2 C and accordingly maintaining the high-temperature stability of α-MoC1-x . This novel strategy can be used as a universal method to be extended to synthesize metastable α-MoC1-x from different precursors or other mounted elements. Moreover, the optimal product exhibits excellent lithium storage performances in terms of the cycling stability and rate performance.

Background and objectives: Dexmedetomidine has demonstrated protective effects against lung injury in vitro. Here, we investigated whether dexmedetomidine preconditioning protected against lung injury in hemorrhagic shock rats. Methods: Male Sprague-Dawley rats were randomly divided into four groups (n = 8): control group, hemorrhagic shock group, 5 ug.kg−1 dexmedetomidine (DEX1) group, and 10 ug.kg−1 dexmedetomidine (DEX2) group. Saline or dexmedetomidine were administered over 20 min. 30 min after injection, hemorrhage was initiated in the hemorrhagic shock, DEX1 and DEX2 group. Four hours after resuscitation, protein and cellular content in bronchoalveolar lavage fluid, and the lung histopathology were measured. The malondialdehyde, superoxide dismutase, Bcl-2, Bax and caspase-3 were also tested in the lung tissue. Results: Compare with hemorrhagic shock group, 5 ug.kg−1 dexmedetomidine pretreatment reduced the apoptosis (2.25 ± 0.24 vs. 4.12 ± 0.42%, p 0.05). Conclusion: Dexmedetomidine preconditioning has a protective effect against lung injury caused by hemorrhagic shock in rats. The potential mechanisms involved are the inhibition of cell death and improvement of antioxidation. But did not show a dose-dependent effect. Resumo: Justificativa e objetivos: Dexmedetomidina demonstrou efeitos protetores contra a lesão pulmonar in vitro. Neste estudo, investigamos se o pré-condicionamento com dexmedetomidina protege contra a lesão pulmonar em ratos com choque hemorrágico. Métodos: Ratos machos, Sprague-Dawley, foram aleatoriamente divididos em quatro grupos (n = 8): grupo controle, grupo com choque hemorrágico, grupo com 5 μg.kg−1 de dexmedetomidina (DEX1) e grupo com 10 μg.kg−1 de dexmedetomidina (DEX2). Solução salina ou dexmedetomidina foi administrada durante 20 minutos. Trinta minutos após a injeção, a hemorragia foi iniciada nos grupos choque hemorrágico, DEX1 e DEX2. Quatro horas após a ressuscitação, a proteína e o conteúdo celular no lavado broncoalveolar e a histopatologia pulmonar foram medidos. Malondialdeído, superóxido dismutase, Bcl-2, Bax e caspase-3 também foram testados no tecido pulmonar. Resultados: Na comparação com o grupo choque hemorrágico, o pré-tratamento com 5 ug.kg−1 de dexmedetomidina reduziu a apoptose (2,25 ± 0,24 vs. 4,12 ± 0,42%, p 0,05). Conclusão: O pré-condicionamento com dexmedetomidina tem um efeito protetor contra a lesão pulmonar causada por choque hemorrágico em ratos. Os potenciais mecanismos envolvidos são a inibição da morte celular e a melhora da antioxidação. Porém, não mostrou um efeito dose-dependente. Keywords: Dexmedetomidine, Hemorrhagic shock, Preconditioning, Lung injury, Rat, Palavras-chave: Dexmedetomidina, Choque hemorrágico, Pré-condicionamento, Lesão pulmonar, Rato

Inspired by steaming bread, a novel three dimensional N and S co-doped reduced graphene oxide (3D NS-rGO) foam is fabricated via a gas foaming method similar to steaming bread procedure, in which (NH4)2S2O3 is selected as the foaming agent as well as N and S source. Such cross-linked 3D structure not only has the high specific surface area also enable more transport channels for electrons/ions transport. Furthermore, introducing of N and S-containing functional groups creates lattice defects in graphene, which provides more active sites where the Faradaic pseudocapacitance occurs. Consequently, the electrochemical test of 3D NS-rGO sample in a three-electrode system demonstrates a high specific capacity of 306.3 F g−1 at 1 A g−1, two times higher than that of rGO prepared at the same temperature. Moreover, 3D NS-rGO sample reveals the superb cycling stability with less than 2% capacitance loss after 10,000 cycles and it exhibits potential application for high performance supercapacitors.

Atomic interface engineering can endow electrode materials with fascinating properties by tailoring their physicochemical behaviors, which will unlock great potential for achieving high-performance...

The purpose of this study was to propose a lifetime prediction model of aging natural gas polyethylene (PE) pipeline with various internal pressures by thermal-oxidative aging (TOA) test and oxidative induction time (OIT) test. By using a pressured natural gas PE80 pipe under the condition similar to actual urban natural gas working condition, an improved TOA experimental set-up was built, and had been used for accelerated TOA test of pressured PE pipes at different test temperatures. By using dynamic curve linearization method and based on Arrhenius fit of the data, an empirical lifetime prediction model of thermal oxidative aging law for PE pipes was developed to extrapolate lifetime of PE80 pipes with internal pressures. The results show that under the test internal pressure of 0.1 MPa, 0.2 MPa, 0.3 MPa, and 0.4 MPa, the lifetimes of aging PE gas pipes with internal pressure are 14%, 24.5%, 36.1%, and 41.6% shorter than those without internal pressure.

Sluggish Li-ion diffusion kinetics and low initial coulombic efficiency (CE) are two big issues to be urgently solved for the MoO2 anode. Herein, we achieve significantly improved Li-ion diffusion kinetics and reversibility of Li2O in a MoO2 anode by elaborately constructing oxygen vacancies and atomic-level spatial distribution of a Ni catalyst, therefore evidently boosting its rate behavior and initial CE. The oxygen vacancy and highly distributed metallic Ni modulation is achieved by finely controlling the annealing time. The density functional theory (DFT) calculations reveal that the creation of oxygen vacancies results in unbalanced charge distribution within MoO2, thus inducing a foreign coulomb force to boost the Li-ion transfer. Furthermore, the metallic Ni in Ni/MoO2−δ can perform as an effective catalyst to ensure the fully reversible conversion of the as-formed Li2O, thereby increasing the initial CE. Benefiting from this multiscale coordinated design, Ni/MoO2−δ displays high discharge capacity (1630.9 mA h g−1 at 0.2 A g−1), large initial CE (83.7%), and excellent rate capability, and outperforms most of the previously reported MoO2-based anodes. Such a design concept not only brings MoO2 one big step closer to practical application, but also can be extended to guide the design of other anode materials with high theoretical capacity.

Ca/ZrCu/ZSM-5 catalysts containing different Zr contents were prepared by incipient wetness impregnation. The catalysts were tested for the selective catalytic reduction (SCR) of NOx with ammonia and characterized by N2-BET, N2O titration, XRD, NH3-TPD, H2-TPR, and XPS techniques. In the temperature range of 100–170 °C, after calcium impregnation, NOx conversion over the Cu/ZSM-5 catalyst decreased by 11.3–24.3%, while that over Zr0.10/Cu/ZSM-5 only decreased by 3.8–12.2%. The improvement of the calcium poisoning resistance of the ZrCu/ZSM-5 catalyst is mainly attributed to an increase in the dispersion and the surface concentration of Cu. Moreover, the addition of zirconium promotes the reduction of CuO by decreasing the interaction between CuO and CaO, which also contributes to the improvement of resistance to CaO poisoning. The apparent activation energy and turnover frequency for the SCR reaction over the Ca/ZrxCu/ZSM-5 catalysts were calculated and discussed.

A robust Pickering emulsion stabilized by lipase-immobilized alginate gel microparticles with a coating of silanized titania nanoparticles is developed for biphasic biocatalysis. The good recyclability and high stability of the proposed interfacial catalysis system have been verified, retaining about 90% of relative enzyme activity in 10 catalytic cycles with operation for 240 h. Meanwhile the Pickering emulsions remain stable during a storage time of one year. The green system can be widely applied to construct powerful platforms for enzyme or microorganism-driven interfacial catalysis.

Li4Ti5O12 (LTO)-carbon (C)-reduced graphene oxide (rGO) microspheres are synthesized via in situ supramolecular self-assembly, combined with spray drying and high-temperature calcination. Dopamine can polymerize on the surface of Ti(OH)4 and form polydopamine, through which graphene oxide(GO) connects with Ti(OH)4 uniformly and tightly to form a homogeneous supramolecular sol system. During the high-temperature calcination, polydopamine is carbonized to carbon to connect LTO with rGO, so that the aggregation of rGO is inhibited, and small-sized LTO particles are obtained. The scanning electron microscopy (SEM) image shows that in the as-prepared LTO-C-rGO microspheres, LTO particles with diameters of ∼50 nm remained homogeneous and wrapped in a three-dimensional network built by the rGO nanosheets. Electrochemical measurements show that the LTO-C-rGO anode exhibits a high reversible capacity of 184 mAh g–1 at 1 C and a high capacity retention of 94.5% after 500 cycles at 20 C. The above excellent electroc...

B-type natriuretic peptide (BNP) binds to its two cognate receptors NPRA and NPRC, encoded by Npr1 and Npr3, respectively, with equal potency and both are expressed in the spinal cord. Moreover, natriuretic peptides (NP) signal through the inhibitory cGMP pathway, raising the question of how BNP may transmit itch information. We report that Npr3 is highly restricted to laminae I-II of the dorsal horn, and partially overlaps with neuromedin B receptor (NMBR) that encodes histaminergic itch. Functional studies indicate that NPRC is required for itch evoked by histamine but not chloroquine (CQ), a nonhistaminergic pruritogen. Importantly, BNP significantly facilitates scratching behaviors mediated by NMB, but not gastrin releasing peptide (GRP) that encodes nonhistaminergic itch. Consistently, BNP evoked Ca2+ response in NMBR/NPRC HEK 293 cells and BNP-saporin that ablated both Npr1 and Npr3 neurons impaired histamine-, but not CQ-evoked, itch. These results reveal a previously unknown mechanism by which BNP changes its inhibitory mode of action to the facilitation of itch through a novel NPRC-NMBR cross-talk. Our studies suggest that neuropeptides encode histaminergic and nonhistaminergic itch not only through distinct modes but also in synergy.

G-quadruplexes (G4s) are DNA or RNA structures formed by guanine-rich repeating sequences. Recently, G4s have become a highly attractive therapeutic target for BRCA-deficient cancers. Here, we show that a substituted quinolone amide compound, MTR-106, stabilizes DNA G-quadruplexes in vitro. MTR-106 displayed significant antiproliferative activity in homologous recombination repair (HR)-deficient and PARP inhibitor (PARPi)-resistant cancer cells. Moreover, MTR-106 increased DNA damage and promoted cell cycle arrest and apoptosis to inhibit cell growth. Importantly, its oral and i.v. administration significantly impaired tumor growth in BRCA-deficient xenograft mouse models. However, MTR-106 showed modest activity against talazoparib-resistant xenograft models. In rats, the drug rapidly distributes to tissues within 5 min, and its average concentrations were 12-fold higher in the tissues than in the plasma. Overall, we identified MTR-106 as a novel G-quadruplex stabilizer with high tissue distribution, and it may serve as a potential anticancer agent.

The presence of the phenol gossypol has severely limited the utilization of cottonseed meal and oil in the food and animal feed industries. Highly efficient means of biodegradation of gossypol and an understanding of the cytotoxicity of its degradation products remain outside current knowledge and are of universal interest. In this work, we showed for the first time that laccase can catalyze the intramolecular annulation of the aldehyde and hydroxyl groups of gossypol for the o-semiquinone radical and originate the released ·OH radical. It was further found that the oxidation of aldehyde groups significantly decreases reproductive toxicity and hepatotoxicity. These results indicate a novel detoxification pathway for gossypol and reveal the crucial role played by radical species in cyclization. This discovery could facilitate the development of safe, convenient, and low-cost industrial methods for the detoxification of cotton protein and oil resources.

Disruption of extravillous trophoblast (EVT) migration and invasion is considered to be responsible for pathological placentation in preeclampsia (PE). Cyclin G2 (CCNG2) is an atypical cyclin that inhibits cell cycle progression. However, its biological function and underlying molecular mechanism in PE are poorly understood. In this study, clinical data demonstrated that CCNG2 was significantly upregulated in PE placenta and associated with invasive EVT dysfunction. Additionally, Ccng2 knockout led to an attenuation of PE-like symptoms in the PE mouse model produced via treatment with NG-nitro-L-arginine methyl ester (L-NAME). In vitro, CCNG2 inhibited the migration, invasion, and endothelial-like network formation of human trophoblast cell line HTR8/SVneo. Mechanically, CCNG2 suppressed JNK-dependent Wnt/PCP signaling and its downstream indicators including epithelial-to-mesenchymal transition (EMT) markers and matrix metalloproteinases (MMPs) via promoting the polyubiquitination degradation of dishevelled 2 (Dvl2) protein in HTR8/SVneo cells. We also discovered that the E3 ligase Ring finger protein 123 (RNF123), as a novel CCNG2 target among HTR8/SVneo cells, interacted with Dvl2 and participated in CCNG2-induced polyubiquitination degradation of Dvl2. Moreover, we verified that the treatment of HTR8/SVneo cells with RNF123-specific siRNA improved polyubiquitination-induced degradation of Dvl2 and the activity of Wnt/PCP-JNK signaling mediated by CCNG2. Taken together, our results reveal that the CCNG2/RNF123/Dvl2/JNK axis may be involved in the pathogenesis and progression of PE through trophoblastic cell function modulation, thus probably providing us with new therapeutic strategies for PE treatment.

A facile method was developed to produce porous alginate beads (PABs) with a controllable interconnected porous structure with aqueous two phase (ATPS) emulsions as template for 3D cell culture. ATPS emulsions, containing two biocompatible immiscible aqueous phases of cell/dextran (Dex) mixture and alginate (Alg)/polyethylene glycol (PEG) mixture and stabilized by mPEG-BSA particles, were introduced to form PABs. The pore size of PABs could be controlled by changing the emulsification frequency and the volume ratio between the ATPS emulsions and PEG-Alg solution. Moreover, cells could be directly encapsulated in the interconnected pores due to the excellent biocompatibility of ATPS. HeLa and human liver cancer cells encapsulated in the PABs present stronger cell activity (>95 %), proliferation, and enhanced functions compared with the cells encapsulated in general alginate beads (GABs). It is believed that the PABs is a promising microcarriers for 3D cell culture in vitro.

Enterovirus A71 (EV-A71) is a causative agent of hand, foot and mouth disease and occasionally causes death in children. Its infectivity and pathogenesis, however, remain to be better understood. Three sulfonated azo dyes, including acid red 88 (Ar88), were identified to enhance the infectivity of EV-A71, especially isolates with VP1-98K, 145E (-KE), by mainly promoting viral genome release in vitro. Enzymatic removal of sulfated glycosaminoglycans (GAGs) or knockout of xylosyltransferase II (XT2) responsible for biosynthesis of sulfated GAGs weakened the Ar88 enhanced EV-A71 infection. Ar88 is proposed to prevent the -KE variants from being trapped by sulfated GAGs at acidic pH and to facilitate the viral interaction with uncoating factors for genome release in endosomes. The results suggest dual roles of sulfated GAGs as attachment factors and as decoys during host interaction of EV-A71 and caution that these artificial dyes in our environment can enhance viral infection.

Background: Adult T-cell acute lymphoblastic leukemia (T-ALL) is a rare hematological malignancy and significantly linked to poor outcomes. Early T-cell precursor (ETP) leukemia is a unique subtype of T-ALL. The aim of this study is to compare the differences between ETP and non-ETP ALLs in China.Methods: We retrospectively analyzed the records of 122 adult T-ALL patients diagnosed and treated at our center between January 2014 and June 2019. All the patients enrolled were categorized into ETP and non-ETP ALL by immunophenotype, and further statistical analyses about clinical data and prognostic factors were performed.Results: Among the 122 cases, the male-to-female ratio was 2.8:1, and the median age is 29 (range, 16–82) years. Except for 10 patients with insufficient immunophenotyping results, 47.3% (53/112) are ETP and 52.7% (59/112) are non-ETP. Compared with non-ETP patients, ETP-ALL patients had lower white blood cell counts and lactate dehydrogenase levels, while they were older and had higher platelet counts and fibrinogen levels (all p < 0.05). Complete remission (CR) was achieved in 68.0% (83/122) of patients, 64.2 and 76.3% in ETP and non-ETP, respectively (p = 0.160). In total, 44.6% (37/83) of patients relapsed. Allogeneic stem cell transplantation (allo-SCT) was successfully performed in 36.1% (44/122) of patients, of which 79.5% (35/44) were in CR1. With a median follow-up of 9.1 (range, 0.5–70.3) months, the estimated 2-year overall survival (OS) and relapse-free survival (RFS) rates for the cohort were 38.0 ± 5.1 and 39.1 ± 6.3%, respectively. In the ETP group, the 2-year OS rate was 40.7 ± 8.2% and the RFS rate was 47.2 ± 10.7%, while in the non-ETP group, the 2-year OS rate was 37.9 ± 7.0% and the RFS rate was 39.2 ± 8.3% (both p > 0.05). In the landmark analysis of CR1 patients who had a survival of more than 6 months, the allo-SCT group had significantly better survival outcomes than the chemotherapy group, and the 2-year OS rates and RFS rates were 80.1 ± 7.3 vs. 28.4 ± 8.4% and 68.9 ± 8.8 vs. 12.8 ± 7.2%, respectively (both p < 0.0001). A multivariate analysis suggests that allo-SCT acts as an independent prognostic factor for both OS and RFS.Conclusions: Our results revealed that ETP accounted for a high proportion of T-ALL in Chinese. There are no CR rates and prognosis differences between ETP and non-ETP. Allo-SCT in CR1 can significantly improve patients' survival.

UL16-binding protein 1(ULBP1) has been reported to inhibit trophoblast invasion through the modification of secretion functions of uNK cells in the previous study, but its mechanisms remain unclear. In this study, we investigated the related mechanism by which upregulated ULBP1 expression impaired trophoblast invasion. We found that conditioned media with ULBP1 increased autophagy in HTR-8/SVneo, and anti-TNF-α-neutralizing antibody rescued the autophagy caused by the conditioned medium. We further found TNF-α induced autophagy in trophoblast cells in a dose-dependent way and accompanied by a decreased activity of nuclear factor-kappa B (NF-κB). Inhibition of NF-κB activation by chemical inhibitor augmented these autophagic responses to TNF-α in the cells. In addition, interruption NF-κB caused a significant decrease in HTR-8/SVneo invasion and enhanced the inhibition effect of TNF-α on HTR-8/SVneo invasion. Taken together, these findings suggest that TNF-α is able to regulate autophagic activity via suppressing NF-κB, which might be the mechanism related to ULBP1 in preeclampsia pathogenesis.

Inflammatory reaction is the crux in various clinical critical diseases including decompression sickness (DCS). Ulinastatin (UTI), a potent anti-inflammatory agent, has been used clinically, including as a substitution for steroids. This study aimed to explore the potential effects of UTI upon DCS in a rabbit model. Eighty-eight rabbits were subjected to simulated diving to 6 atmospheres absolute (ATA) for 60 min with 2.5-minute decompression. Three doses of UTI (15/7.5/3.75 × 105 U/kg) or saline were intravenously administered immediately following decompression. Circulating bubbles were monitored for 3 h following decompression and DCS signs were evaluated for 24 h. Blood was sampled 8 times during 72 h after decompression for inflammatory, endothelial, oxidative and routine blood indices. Lung tissues were also sampled for evaluating endothelial function. Another six rabbits were used as Normal controls. In the high dose UTI group the mortality, general morbidity and incidence of severe DCS was decreased from 31.25 to 9.38% (P = 0.030), 84.38 to 62.50% (P = 0.048) and 46.88 to 21.88% (P = 0.035), respectively. The high dose of UTI significantly postponed the occurrence of DCS (P = 0.030) and prolonged survival time (P = 0.009) compared with the Saline group, and significantly ameliorated inflammation responses, endothelial injuries and oxidative damage. The results strongly suggest the benefit of UTI on DCS, especially for severe cases. Large doses are needed to achieve significant effects. UTI may be a potential ideal pharmacological candidate for the treatment of severe DCS.

Purpose Patients with diabetes are vulnerable to myocardial I/R (ischaemia/reperfusion) injury, but are not responsive to IPO (ischaemic post-conditioning). We hypothesized that decreased cardiac Adiponectin (APN) is responsible for the loss of diabetic heart sensitivity to IPO cardioprotecton. Methods Diabetic rats were subjected to I/R injury (30 min of LAD occlusion followed by 120 min of reperfusion). Myocardial infarct area was determined by TTC staining. Cardiac function was monitored by a microcatheter. ANP, 15-F2t-isoprostane, nitrotyrosine and MDA were measured by assay kits. Levels of p-Akt, total-Akt and GAPDH were determined by Western Blot. Results Diabetic rats subjected to myocardial IR exhibited severe myocardial infarction and oxidative stress injury, lower APN in the plasma and cardiac p-Akt expression ( P

Exposure to diesel engine exhaust (DEE) was associated with various adverse health effects including lung cancer. Particle size distribution and profiles of organic compounds in both particle and gas phases of DEE that could provide valuable insights into related health effects were measured in a diesel engine testing workshop. Concentrations of urinary 6 mono-hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) in 137 DEE-exposed workers and 127 non-DEE-exposed workers were determined. Benchmark dose method was applied to estimate lower limit of benchmark dose (BMDL) of urinary OH-PAHs most specific to DEE exposure for previously reported cancer biomarkers. We found that 84.3% of diesel exhaust particles were ultrafine particles. Indeno[123-cd]pyrene and phenanthrene were the most abundant carcinogenic and noncarcinogenic PAHs in the particle phase of DEE, respectively. Principal component analysis demonstrated that urinary hydroxyphenanthrene (OHPhe) had highest loading value on principal component (PC) representative of DEE exposure and lowest loading value on PC representative of smoking status. BMDLs of urinary OHPhe from best-fitting models for cancer biomarkers including micronucleus and 1,N6-ethenodeoxyadenosine were 1.08 μg/g creatinine and 2.82 μg/g creatinine, respectively. These results provided basis for understanding DEE exposure induced health effects and potential threshold for regulating DEE levels in an occupational setting.

Emerging evidence has supported that TAZ (transcriptional co-activator with PDZ binding motif), one transcription co-activator in Hippo signaling pathway, plays an oncogenic role in liver carcinogenesis. Targeting TAZ could be a potential therapeutic approach for liver cancer patients. In the current study, we aim to determine whether diosgenin could be an inhibitor of TAZ in liver cancer cells. We found that diosgenin inhibited the expression of TAZ in liver cancer cells. Moreover, we found that diosgenin inhibited cell growth, induced apoptosis, suppressed cell migration and invasion in part via inhibition of TAZ in liver cancer cells. Our study provides the evidence to support that diosgenin could be a potential agent for treating human liver cancer.