Defective high-entropy rocksalt oxide with enhanced metal‒oxygen covalency for electrocatalytic oxygen evolution

High‐entropy materials are emerging electrocatalysts by integrating five or more elements into one single crystallographic phase to optimize the electronic structures and geometric environments.Here,a rocksalt‐type high‐entropy oxide Mg_(0.2)Co_(0.2)Ni_(0.2)Cu_(0.2)Zn_(0.2)O(HEO)is developed as an electrocatalyst towards the oxygen evolution reaction(OER).The obtained HEO features abundant cation and oxygen vacancies originating from the lattice mismatch of neighboring metal ions,together with enlarged Co/Ni‒O covalency due to the introduction of less electronegative Mg and Zn.As a result,the HEO exhibits superior intrinsic OER activities,delivering a turnover frequency(TOF)15 and 84 folds that of CoO and NiO at 1.65 V,respectively.This study provides a mechanistic understanding of the enhanced OER on HEO and demonstrates the potential of high‐entropy strategy in developing efficient oxygen electrocatalysts by elaborately incorporating low‐cost elements with lower electronegativity.

Improving metallic lithium anode with Na PF6additive in Li PF6-carbonate electrolyte

Metallic lithium anode is widely applied to building highenergy-density batteries such as lithium–sulfur and lithium–oxygen batteries because of its high specific capacity(3860 mAh g?1)and lowest negative potential(?3.04 V vs.standard hydrogen electrode(SHE))[1,2].However,the practical applications of Li anode remain challenging[3–6].The large volume change during repeated plating/stripping of Li would cause mechanical and interfacial instability[7,8].The solid electrolyte interphase(SEI)layers on lithium surface with poor elasticity are vulnerable to crack under variable stress/strain,leading to continuous side reactions between exposed fresh Li and electrolyte[9–11].In addition,the uncontrollable nucleation and growth of Li incur the formation of dendrites,which could accelerate detrimental parasitic reactions.Because of the uneven stripping,dendritic Li may deteriorate into electrically disconnected or“dead”Li,resulting in poor Coulombic efficiency,rapid capacity decay,and short circuit risk[12–17].

Anionic formulation of electrolyte additive towards stable electrocatalytic oxygen evolution in seawater splitting

Hydrogen generation through seawater electrolysis provides a promising,attractive pathway towards the utilization of sustainable energy.However,the catalytic activity and stability of oxygen evolution anode are severely limited by the chloride-induced corrosion and competitive oxidation reactions.In this work,we demonstrate an anion-assisted performance improvement strategy by quick and universal screening of electrolyte additive via correlating Cl-repellency with the anionic properties.Particularly,the addition of phosphate ions is found to enable highly stable alkaline seawater splitting at industry-level current density(0.5 A cm^(-2))over 500 h using transition metal hydroxides as anodic electrocatalysts.In situ experiments and theoretical simulations further reveal that the dynamic anti-corrosion behaviors of surface-adsorbed phosphate ions are attributed to three factors including repelling Cl-ions without significantly blocking OH-diffusion,preventing transition metal dissolution and acting as a local pH buffer to compensate the fast OH-consumption under high current electrolysis.

Deficient Rnf43 potentiates hyperactive Kras-mediated pancreatic preneoplasia initiation and malignant transformation

Background:Largely due to incidental detection,asymptomatic pancreatic cystic le-sions(PCLs)have become prevalent in recent years.Among them,intraductal papillary mucinous neoplasm(IPMN)infrequently advances to pancreatic ductal adenocarcinoma(PDAC).Conservative surveillance versus surgical intervention is a difficult clinical decision for both caregivers and PCL patients.Because RNF43 loss-of-function mutations and KRAS gain-of-function mutations concur in a subset of IPMN and PDAC,their biological significance and therapeutic potential should be elucidated.Methods:Pancreatic Rnf43 knockout and Kras activated mice(Rnf43^(−/−);Kras^(G12D))were generated to evaluate their clinical significance in pancreatic pre-neoplastic initiation and malignant transformation.Results:Loss of Rnf43 potentiated the occurrence and severity of IPMN and PDAC in oncogenic Kras mice.The Wnt/β-catenin signaling pathway was activated in pan-creatic Kras^(G12D)and Rnf43 knockout mice and the PORCN inhibitor LGK974 blocked pancreatic IPMN initiation and progression to PDAC accordingly.Conclusions:Rnf43 is a tumor suppressor in the prevention of pancreatic malignant transformation.This genetically reconstituted autochthonous pancreatic Rnf43^(−/−);Kras^(G12D)preclinical cancer model recapitulates the pathological process from pancreatic cyst to cancer in humans and can be treated with inhibitors of Wnt/β-catenin signaling.Since the presence of RNF43 and KRAS mutations in IPMNs predicts future development of advanced neoplasia from PCLs,patients with these genetic anomalies warrant surveillance,surgery,and/or targeted therapeutics such as Wnt/β-catenin inhibitors.

Overexpressed PKM2 promotes macrophage phagocytosis and atherosclerosis

Background:The expression of pyruvate kinase muscle 2(PKM2)is augmented in macrophages of patients with atherosclerotic coronary artery disease.The role of PKM2 in atherosclerosis is to be determined.Methods:Global and myeloid cell-specific PKM2 knock-in mice with ApoE^(-/-)background(ApoE^(-/-),PKM2^(KI/KI)and Lyz2-cre,ApoE^(-/-),and PKM2^(flox/flox))were produced to evaluate the clinical significance of PKM2 in atherosclerosis development.Wild-type and PKM2 knock-in macrophages were isolated to assess the function of PKM2 in macrophage phagocytosis.Atherosclerotic mice were treated with PKM2 inhibitor shikonin(SKN)to evaluate the therapeutic potential of PKM2 suppression in atherosclerosis.Results:Oxidized low-density lipoprotein(oxLDL)upregulated PKM2 in macrophages.PKM2 in return promoted the uptake of oxLDL by macrophages.Overexpressed PKM2 accelerated atherosclerosis in mice.SKN blocked the progress of mouse atherosclerosis.Conclusions:PKM2 accelerates macrophage phagocytosis and atherosclerosis.Targeting PKM2 is a potential therapy for atherosclerosis.

ISAR Imaging and Cross-Range Scaling Based on Image Rotation Correlation

With the rapid advancement of technology,not only do we need to acquire a clear in-verse synthetic aperture radar(ISAR)image,but also the real size of the target on the imaging plane,so it’s particularly important for the ISAR to rescale the images.That is,the ISAR image which is in the range-Doppler domain is converted into the range-azimuth domain.Actually,the key point to solving the problem is to estimate the rotation parameters.In this paper,a new scheme to rescale the images is proposed.For the sake of solving the problem of two-dimensional image blur and target high-speed,the instantaneous range instantaneous Doppler(IRID)method is used to obtain ISAR images,and the rotation parameters are estimated by comparing the rotation correlation of the two images.Using this method,the error of the estimated rotation parameters is greatly reduced,so that the target can be rescaled accurately.The simulation results verify the ef-fectiveness of the proposed algorithm.

Screening and Verification of Genes Specifically Responding to Continuous Cropping Obstacle in Rehmannia glutinosa L.

Rehmannia glutinosa L.is one of the important medicinal crops in China.Continuous cropping obstacle severely restricts the yield and quality of R.glutinosa,but its molecular mechanism is still unclear.In this study,with widely-planted "Wen 85-5" as an experiment material,based on the digital gene expression profiling (DGE) data of previous five stress treatments (continuous cropping,phenolic acid,salt,drought and waterlogging) and the first cropping and continuous cropping treatments of R.glutinosa in five different periods (seedling period,elongation period,early expanding period,middle expanding period and later expanding period),80 candidate genes (|log 2 ratio|≥1,FDR <0.001) specifically responding to continuous cropping obstacle in R.glutinosa were screened.Functional analysis revealed that the differentially expressed genes were involved in the secretion and endocytosis of root cells,which may suggest that the recognition and absorption of allelopathic autotoxins by the roots of R.glutinosa is an important factor that restricts the development of roots in continuous cropping of R.glutinosa.In order to accurately lock genes specifically responding to continuous cropping obstacle in R.glutinosa,continuous cropping soil extract and ferulic acid and p-hydroxybenzonic acid were used to treat aseptic plantlets of R.glutinosa,respectively,and it was confirmed through qRT-PCR that the expression levels of some genes under phenolic acid treatment changed more severely than that under the continuous cropping soil extract treatment,and four key genes involved in the response of R.glutinosa to continuous cropping were finally locked.This study lays a foundation for further exploration of the molecular mechanism of continuous cropping obstacle.

Phosphotungstic Acid Catalyzed Conjugate Addition of Indoles with α,β-Enones

A new facile, efficient and very mild entry to the synthesis of 3-（1H-indol-3-yl）-1, 3-diarylpropan-l-ones is presented. The procedure utilizes phosphotungstic acid （5 mol%） as a catalyst for the Michael addition of indole to α,β-unsaturated ketones in good yield in acetonitrile as solvent.

Synthesis of a Series New 4, 5-Dihydro-3, 5-Diphenyl -1 -（4-PhenyI-Thiazole-2-yl）-Pyrazole Derivatives

A series of novel pyrazoles compounds were synthesized by the reaction of five kinds of substitute α-bromoacetophenone with pyrazole intermediates which was prepared by the reaction of chalcones and thiosemicarbazones. This method has some advantages such as mild reaction condition, easy operation and higher yield. All the compounds were confirmed by elemental analysis, IR and 1H NMR.

Oncogenic β-catenin-driven liver cancer is susceptible to methotrexate-mediated disruption of nucleotide synthesis

Background:Liver cancer is largely resistant to chemotherapy.This study aimed to identify the effective chemotherapeutics forβ-catenin-activated liver cancer which is caused by gain-of-function mutation of catenin beta 1(CTNNB1),the most frequently altered proto-oncogene in hepatic neoplasms.Methods:Constitutiveβ-catenin-activated mouse embryonic fibroblasts(MEFs)were established by deleting exon 3(β-catenin^(Δ(ex3)/+)),the most common mutation site in CTNNB1 gene.A screening of 12 widely used chemotherapy drugs was conducted for the ones that selectively inhibitedβ-catenin^(Δ(ex3)/+)but not for wild-type MEFs.Untargeted metabolomics was carried out to examine the alterations of metabolites in nucleotide synthesis.The efficacy and selectivity of methotrexate(MTX)onβ-catenin-activated human liver cancer cells were determined in vitro.Immuno-deficient nude mice subcutaneously inoculated withβ-catenin wild-type or mutant liver cancer cells and hepatitis B virus(HBV);β-catenin^(lox(ex3)/+)mice were used,respectively,to evaluate the efficacy of MTX in the treatment ofβ-catenin mutant liver cancer.Results:MTX was identified and validated as a preferential agent against the proliferation and tumor formation ofβ-catenin-activated cells.Boosted nucleotide synthesis was the major metabolic aberration inβ-catenin-active cells,and this alteration was also the target of MTX.Moreover,MTX abrogated hepatocarcinogenesis of HBV;β-catenin^(lox(ex3)/+)mice,which stimulated concurrent Ctnnb1-activated mutation and HBV infection in liver cancer.Conclusion:MTX is a promising chemotherapeutic agent forβ-catenin hyperactive liver cancer.Since repurposing MTX has the advantages of lower risk,shorter timelines,and less investment in drug discovery and development,a clinical trial is warranted to test its efficacy in the treatment ofβ-catenin mutant liver cancer.

mTOR/miR-145-regulated exosomal GOLM1 promotes hepatocellular carcinoma through augmented GSK-3b/MMPs

Golgi membrane protein 1(GOLM1/GP73)is a serum marker of hepatocellular carcinoma(HCC).We have previously shown that mTOR promoted tumorigenesis of HCC through stimulating GOLM1 expression.In this study,we demonstrated that the mammalian target of rapamycin(mTOR)was a negative regulator of microRNA-145(miR-145)expression.miR-145 inhibited GOLM1 expression by targeting a coding sequence of GOLM1 gene.GOLM1 and miR-145 were inversely correlated in human HCC tissues.GOLM1-enriched exosomes activated the glycogen synthase kinase-3β/matrix metalloproteinases(GSK-3β/MMPs)signaling axis of recipient cells and accelerated cell proliferation and migration.In contrast,miR-145 suppressed tumorigenesis and metastasis.We suggest that mTOR/miR-145/GOLM1 signaling pathway should be targeted for HCC treatment.

The Electrochemical Tuning of Transition Metal-Based Materials for Electrocatalysis

The development of clean and sustainable energy depends largely on electrocatalysis-driven technologies.Because of this,tremendous efforts have been devoted to the search for efficient electrocatalysts to reduce the overpotential and increase the selectivity of electrochemical reactions.Of the various approaches,electrochemical tuning is seen as a promising tech-nique to controllably tune the properties of catalytic materials under mild conditions.Based on this,this review will present representative electrochemical tuning methodologies involving insertion and conversion reactions in batteries as well as in situ electrode modulation during electrocatalysis processes.This review will first provide an introduction of electrochemi-cal tuning strategies from the perspective of reactions and devices.Subsequently,this review will present comprehensive discussions on recent advancements in the modulation of various electrocatalyst properties,including electronic structure,crystalline phase,lattice strain and dimensional size,all of which significantly impact corresponding intrinsic activity and active site exposure.This review will also highlight the merits,challenges and issues of electrochemical tuning and propose promising directions in the exploration of corresponding methods in the design and enhancement of electrocatalysts for future energy applications.

Electrodeposition of Pt-Decorated Ni(OH)_(2)/CeO_(2) Hybrid as Superior Bifunctional Electrocatalyst for Water Splitting

The facile synthesis of highly active and stable bifunctional electrocatalysts to catalyze water splitting is attractive but challenging.Herein,we report the electrodeposition of Pt-decorated Ni(OH)_(2)/CeO_(2)(PNC)hybrid as an efficient and robust bifunctional electrocatalyst.The graphite-supported PNC catalyst delivers superior hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activities over the benchmark Pt/C and RuO_(2),respectively.For overall water electrolysis,the PNC hybrid only requires a cell voltage of 1.45V at 10mAcm-2 and sustains over 85 h at 1000mAcm^(-2).The remarkable HER/OER performances are attributed to the superhydrophilicity and multiple effects of PNC,in which Ni(OH)_(2)and CeO_(2)accelerate HER on Pt due to promoted water dissociation and strong electronic interaction,while the electron-pulling Ce cations facilitate the generation of high-valence Ni OER-active species.These results suggest the promising application of PNC for H2 production from water electrolysis.

Ni_(3)S_(2)@NiFePx electrode with dual-anion-modulated layer for efficient and stable oxygen evolution

The rational construction of high-performance and stable electrocatalyst for oxygen evolution reaction(OER)is a prerequisite for efficient water electrolysis.Herein,we develop a broccoli-like Ni_(3)S_(2)@NiFeP_(x)(Ni_(3)S_(2)@NFP)catalyst on nickel foam(NF)via a sequential two-step layer-by-layer assembly electrodeposition method.X-ray diffraction,in situ Raman and Fourier-transform infrared spectra have mutually validated the element segregation and phase refusion during OER condition.The reconstruction of double layer Ni_(3)S_(2)@NFP facilitates the formation of the active(oxy)hydroxides,which is modulated by the dual anionic layer with mixed sulfate and phosphate ions.As a result,the obtained Ni_(3)S_(2)@NFP electrode exhibits low overpotential(329 mV)and long-term durability(∼500 h)for OER at current density of 500mA/cm^(2).Moreover,the self-supported Ni_(3)S_(2)@NFP can act as an efficient and durable anode in alkaline anion exchange membrane water electrolysis device(AEMWE).This work provides a facile and scaled-up strategy to construct self-supported electrocatalyst and emphasizes the crucial role of anions in pre-catalyst reconstruction and enhancing OER performance.