Aqueous Zn-ion batteries(AZIBs)have attracted increasing attention in next-generation energy storage systems due to their high safety and economic.Unfortunately,the side reactions,dendrites and hydrogen evolution effe...Aqueous Zn-ion batteries(AZIBs)have attracted increasing attention in next-generation energy storage systems due to their high safety and economic.Unfortunately,the side reactions,dendrites and hydrogen evolution effects at the zinc anode interface in aqueous electrolytes seriously hinder the application of aqueous zinc-ion batteries.Here,we report a critical solvation strategy to achieve reversible zinc electrochemistry by introducing a small polar molecule acetonitrile to form a“catcher”to arrest active molecules(bound water molecules).The stable solvation structure of[Zn(H_(2)O)_(6)]^(2+)is capable of maintaining and completely inhibiting free water molecules.When[Zn(H_(2)O)_(6)]^(2+)is partially desolvated in the Helmholtz outer layer,the separated active molecules will be arrested by the“catcher”formed by the strong hydrogen bond N-H bond,ensuring the stable desolvation of Zn^(2+).The Zn||Zn symmetric battery can stably cycle for 2250 h at 1 mAh cm^(-2),Zn||V_(6)O_(13)full battery achieved a capacity retention rate of 99.2%after 10,000 cycles at 10 A g^(-1).This paper proposes a novel critical solvation strategy that paves the route for the construction of high-performance AZIBs.展开更多
The architectural design of redox-active organic molecules and the modulation of their electronic properties significantly influence their application in energy storage systems within aqueous environments.However,thes...The architectural design of redox-active organic molecules and the modulation of their electronic properties significantly influence their application in energy storage systems within aqueous environments.However,these organic molecules often exhibit sluggish reaction kinetics and unsatisfactory utilization of active sites,presenting significant challenges for their practical deployment as electrode materials in aqueous batteries.In this study,we have synthesized a novel organic compound(PTPZ),comprised of a centrally symmetric and fully ladder-type structure,tailored for aqueous proton storage.This unique configuration imparts the PTPZ molecule with high electron delocalization and enhanced structural stability.As an electrode material,PTPZ demonstrates a substantial proton-storage capacity of 311.9mAh g^(-1),with an active group utilization efficiency of up to 89% facilitated by an 8-electron transfer process,while maintaining a capacity retention of 92.89% after 8000 chargingdischarging cycles.Furthermore,in-situ monitoring technologies and various theoretical analyses have pinpointed the associated electrochemical processes of the PTPZ electrode,revealing exceptional redox activity,rapid proton diffusion,and efficient charge transfer.These attributes confer a significant competitive advantage to PTPZ as an anode material for high-performance proton storage devices.Consequently,this work contributes to the rational design of organic electrode materials for the advancement of rechargeable aqueous batteries.展开更多
Due to environmental protection requirements,extraction of bioactive compounds from plant materials using environment-friendly green solvents has always been a research hotspot.And great efforts of scholars have been ...Due to environmental protection requirements,extraction of bioactive compounds from plant materials using environment-friendly green solvents has always been a research hotspot.And great efforts of scholars have been made in this direction,as well as environment-friendly solvents have been used to develop many innovative extraction techniques.Ionic liquids(ILs)and deep eutectic solvents(DESs)are two kinds of typical designable green solvents,which are potential replacements for traditional volatile organic solvents used for extracting.Under the substances action of inorganic salts or polymers,ILs/DESs can form an aqueous two-phase system(ATPS),which has obvious advantages for separating natural products.This paper discussed the phase separation principle of ILs/DESs-based ATPSs and reviewed the applications in the extraction of natural active molecules in recent years,as well as to promote the development of separation of the active constituents in Chinese materia medica.展开更多
We simulate the self-assembly of active colloidal molecules from binary mixtures of spherical particles using a Brownian dynamics algorithm.These particles interact via phoretic interactions,which are determined by tw...We simulate the self-assembly of active colloidal molecules from binary mixtures of spherical particles using a Brownian dynamics algorithm.These particles interact via phoretic interactions,which are determined by two independently tunable parameters,surface activity and surface mobility.In systems composed of equal-size particles,we observe the formation of colloidal molecules with well-defined coordination numbers and spatial arrangement,which also display distinct dynamic functions,such as resting,translating,and rotating.By changing the size ratio to 2:1 between the two species,we further observe the formation of colloidal molecules with new structures arising from breaking the size symmetry.By tuning the mutual interactions between the smaller species via their surface mobility,we are able to control their spacing as well as the coordination number of the colloidal molecules.This study highlights the importance of tuning surface parameters and size asymmetry in controlling the structure and the active dynamics of colloidal molecules.展开更多
microRNAs (miRNAs) derived from viruses, have been detected in body fluids and are known to regulate the expression of host genes. Recent evidence indicates that SARS-CoV-2-encoded miRNAs could contribute to pulmonary...microRNAs (miRNAs) derived from viruses, have been detected in body fluids and are known to regulate the expression of host genes. Recent evidence indicates that SARS-CoV-2-encoded miRNAs could contribute to pulmonary disease. Pulmonary fibrosis is an important complication in SARS-CoV-2 infected patients, either during hospitalization or after discharge, however, the underlying mechanisms are not fully elucidated. Here, we report a SARS-CoV-2-encoded miRNA, miR-nsp3-3p, facilitates host pulmonary fibrosis by inhibiting expression of activated leukocyte cell adhesion molecule (ALCAM) and promoting epithelial-mesenchymal transition (EMT). First, we detected miR-nsp3-3p in clinical specimens and found it was remarkably increased in throat swabs and alveolar lavage fluids from severe/critical COVID-19 patients compared to control groups or mild/moderate patients. We further revealed that adeno-associated virus (AAV)-nsp3 infection can induce pulmonary fibrosis in BALB/c mice while miR-nsp3-3p antagomirs can reverse that, and ALCAM was found to be as a target gene of miR-nsp3-3p. miR-nsp3-3p overexpression can inhibit the expression of ALCAM and promote EMT of pulmonary epithelial cells. Moreover, overexpression of ALCAM can reverse the miR-nsp3-3p-induced EMT and fibrosis. These findings highlight the essential role of SARS-CoV-2-encoded miRNAs in promoting the pathological progression of lung disease, and provide novel insights into the interactions between viral miRNAs and host pathology.展开更多
Iron(Ⅱ)tetra-(1,4-dithin)-porphyrazine,(FePz(dtn)_(4))is able to activate molecule oxygen for oxygenation degradation of rhodamine B(RhB)in an extensive pH region without light excitation.Experiments indicate that th...Iron(Ⅱ)tetra-(1,4-dithin)-porphyrazine,(FePz(dtn)_(4))is able to activate molecule oxygen for oxygenation degradation of rhodamine B(RhB)in an extensive pH region without light excitation.Experiments indicate that the RhB can be degraded nearly 52%in alkaline aqueous solution,bubbling with dioxygen for seven hours in the presence of FePz(dtn)_(4)and the hydrogen peroxides as an active intermediate were determined by DPD method.The catalyst is recyclable and the catalyst activity was maintained after 10 recycles.展开更多
The activation and selective conversion of energy-related molecules is an important research area of energy chemistry.The depletion of petroleum has stimulated research activities into the utilization of non-petroleum...The activation and selective conversion of energy-related molecules is an important research area of energy chemistry.The depletion of petroleum has stimulated research activities into the utilization of non-petroleum carbon resources such as natural gas(including conventional and展开更多
To investigate whether estradiol （E2） plays a role in cell-contact-dependent regulatory mechanism of T cell activation, we studied the role of E2 in regulating gene transcription of CTLA-4, ICOS, B7-1, B7-2 and B7h ...To investigate whether estradiol （E2） plays a role in cell-contact-dependent regulatory mechanism of T cell activation, we studied the role of E2 in regulating gene transcription of CTLA-4, ICOS, B7-1, B7-2 and B7h in vitro. The splenic cells of normal female BALB/c mice were activated by ConA. Then the cells were cultured with E2 （100 pg/ml or 50 ng/ml） for 24 h or 48 h, respectively. The cell proliferation was measured by MTF assay and the expression of the co-stimulatory molecules mRNA was examined by RT-PCR analysis. We found that E2 （100 pg/ml, physiological level） stimulated the acti- vated spleen cells proliferation; inhibited CTLA-4, ICOS, TGF-β and IL-10 gene transcription; promoted B7-1 and B7-2 gene transcription. E2 （50 ng/ml, pregnant level） inhibited the proliferation of the activated splenic cells; promoted CTLA-4, B7-1, IL-10 but inhibited B7-2 and TGF-β gene transcription. Therefore, we conclude that the effects of E2 on T cell activation are partially through its regulation on the co-stimulatory molecules. The co-stimulatory molecules are crucial components of the cell-contact dependent regulatory mechanism, and E2 may regulate T cell activation by this mechanism.展开更多
Chikungunya fever(CF)is caused by an arbovirus whose manifestations are extremely diverse,and it has evolved with significant severity in recent years.The clinical signs triggered by the Chikungunya virus are similar ...Chikungunya fever(CF)is caused by an arbovirus whose manifestations are extremely diverse,and it has evolved with significant severity in recent years.The clinical signs triggered by the Chikungunya virus are similar to those of other arboviruses.Generally,fever starts abruptly and reaches high levels,followed by severe polyarthralgia and myalgia,as well as an erythematous or petechial maculopapular rash,varying in severity and extent.Around 40%to 60%of affected individuals report persistent arthralgia,which can last from months to years.The symptoms of CF mainly represent the tissue tropism of the virus rather than the immunopathogenesis triggered by the host's immune system.The main mechanisms associated with arthralgia have been linked to an increase in T helper type 17 cells and a consequent increase in receptor activator of nuclear factor kappa-Βligand and bone resorption.This review suggests that persistent arthralgia results from the presence of viral antigens post-infection and the constant activation of signaling lymphocytic activation molecule family member 7 in synovial macrophages,leading to local infiltration of CD4+T cells,which sustains the inflammatory process in the joints through the secretion of pro-inflammatory cytokines.The term"long chikungunya"was used in this review to refer to persistent arthralgia since,due to its manifestation over long periods after the end of the viral infection,this clinical condition seems to be characterized more as a sequel than as a symptom,given that there is no active infection involved.展开更多
Due to the diversity and feasibility of structural modification for organic molecules,organic-based redox flow batteries(ORFBs)have been widely investigated,especially in aqueous solution under neutral circumstance.In...Due to the diversity and feasibility of structural modification for organic molecules,organic-based redox flow batteries(ORFBs)have been widely investigated,especially in aqueous solution under neutral circumstance.In this work,a symmetric aqueous redox flow battery(SARFB)was rationally designed by employing a bipolar redox active molecule(N,N’-dimethyl-4,4-bipyridinium diiodide,MVI2)as both cathode and anode materials and combining with an anion exchange membrane.For one MVI2 flow battery,MV2+/MV·+and I-/I3-serve as the redox couples of anode and cathode,respectively.The MVI2 battery with a working voltage of 1.02 V exhibited a high voltage efficiency of 90.30%and energy efficiency of 89.44%after 450 cycles,and crossover problem was prohibited.The comparable conductivity of MVI2 water solution enabled to construct a battery even without using supporting electrolyte.Besides,the bipolar character of MVI2 battery with/without supporting electrolyte was investigated in the voltage range between-1.2 V and 1.2 V,showing excellent stable cycling stability during the polarity-reversal test.展开更多
The title compound, 5（R）-（1R,2S,5R）-menthoxy-4（R）-N-cyclohexylaminobutyrolactone 1, has been synthesized via the asymmetric Micheal addition reaction of 5（R）-menthoxy- 2（5H）-furanone 4 with cyclohexylamine 5...The title compound, 5（R）-（1R,2S,5R）-menthoxy-4（R）-N-cyclohexylaminobutyrolactone 1, has been synthesized via the asymmetric Micheal addition reaction of 5（R）-menthoxy- 2（5H）-furanone 4 with cyclohexylamine 5, and structurally determined by single-crystal X-ray diffraction. Crystal data： C20H36NO3, Mr = 337.49, monoclinic system, space group P21, a = 9.8677（7）, b = 9.7737（7）, c=11.0204（8） A, β= 103.7820（10）°, V= 1032.25（13） A^3, Z = 2, Dc= 1.086 g/cm^3, 2（MoKα） = 0.071073 nm,μ= 0.071 mm^-1 and F（000） = 372. The structure was refined to R = 0.0328 and wR = 0.0864 for 4203 observed reflections （I 〉 2σ（I））. The crystallographic results of molecule 1 show that the functionalized N-cyclohexylamino group is linked in the 4-position of butyrolactone to form the novel chiral optically active compound.展开更多
The title compound, 5-methoxy-butyrolacto[3,4-b]-1-N-cyclohexylaziridine 1, has been synthesized via tandem Micheal addition and intramolecular nucleophilic substitution reactions of 5-methoxy-3-bromo-2（5H）-furanone...The title compound, 5-methoxy-butyrolacto[3,4-b]-1-N-cyclohexylaziridine 1, has been synthesized via tandem Micheal addition and intramolecular nucleophilic substitution reactions of 5-methoxy-3-bromo-2（5H）-furanones 4 with primary amines 5, and structurally determined by single-crystal X-ray diffraction. Crystal data： C11H17NO3, Mr = 211.26, monoclinic system, space group P21/c, a = 17.800（3）, b = 5.3864（10）, c = 12.2571（10）A°, β = 90.449（3）°, V = 1175.1（3） A°^3, Z= 4, De= 1.194 g/cm^3, λ（MoKα） = 0.071073 nm, μ = 0.087 mm^-1 and F（000） = 456. The structure was refined to R = 0.0505 and wR = 0.1208 for 2579 observed reflections （I 〉 2σ（I））. The crystallographic results of molecule 1 show that the functionalized aziridine ring is fused with a lactone ring to form the component with [3.1.0] bicyclic skeleton.展开更多
The title compound, 2（S）,3（R）-dihydroxymethyl-N-cyclohexylaziridine 1, has been synthesized via tandem Micheal addition and internal nucleophilic substitution reactions of 5-methoxy-3-bromo-2（5H）-furanones 2 wit...The title compound, 2（S）,3（R）-dihydroxymethyl-N-cyclohexylaziridine 1, has been synthesized via tandem Micheal addition and internal nucleophilic substitution reactions of 5-methoxy-3-bromo-2（5H）-furanones 2 with cyclohexylamine 3 and subsequent reduction of intermediate 5. Its crystal structure was determined by single-crystal X-ray diffraction. Crystal data：C10H19NO2, Mr = 185.26, monoclinic system, space group P21/n, a = 8.0620（16）, b = 7.2013（14）, c= 18.555（4） A°, β= 102.30（3）°, V= 1052.5（4）A°^3, Z= 4, De= 1.169 g/cm^3, λ（MoKα） = 0.071073 nm,μ = 0.080 mm^- 1 and F（000） = 408. The structure was refined to R = 0.0439 and wR = 0.1178 for 1839 observed reflections （I 〉 2σ（I））. The crystallographic structure of 1 shows that the functionalized aziridine ring links two hyroxymethyl groups.展开更多
The title compound, spiro[ 1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]- hexane-2,2＇-3＇-（16＇-methoxyacetatyl-4＇-l-menthyloxybutyrolactone）] 1, was obtained via tandem asymmetric double Michael addition/inte...The title compound, spiro[ 1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]- hexane-2,2＇-3＇-（16＇-methoxyacetatyl-4＇-l-menthyloxybutyrolactone）] 1, was obtained via tandem asymmetric double Michael addition/internal nucleophilic substitution of the chiral synthon, 5-l-menthyloxy-3-bromo-2-（5H）-furanone 2 with methoxy α-chloroacetate as a nucleophile under mild conditions, and structurally [letermined by single-crystal X-ray diffraction. Crystal data： C31H47BrO9, Mr = 643.60, orthorhombic, space group P212121. α = 9.6564（7）, b = 14.8994（11）, c = 23.6771（17） A, V= 3406.5（4） A^3, Z = 4, Dc= 1.255 g/cm^3, 2（MoKa） = 0.71073 A,μ= 1.254 mm^-1 and F（000） = 1360. The structure was refined to R =[0.0324 and wR = 0.0737 for 5123 observed reflections （I〉 2σ（I））. The crystallographic results of molecule 1 show that the interesting reaction of 2 with methoxy α-chloroacetate, in the usual manner, gave the spiro-cyclopropane skeleton with O-linked derivative containing multiple stereogenic centers 1 rather than the expected C-linked derivative.展开更多
The title compound, spiro[1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]-hexane-2,2-3-(16-methoxyacetatyl-4-l-menthyloxybutyrolactone)] 1, was obtained via tandem asymmetric double Michael addition/internal nucleop...The title compound, spiro[1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]-hexane-2,2-3-(16-methoxyacetatyl-4-l-menthyloxybutyrolactone)] 1, was obtained via tandem asymmetric double Michael addition/internal nucleophilic substitution of the chiral synthon, 5-l-menthyloxy-3-bromo-2-(5H)-furanone 2 with methoxy α-chloroacetate as a nucleophile under mild conditions, and structurally determined by single-crystal X-ray diffraction. Crystal data: C31H47BrO9, Mr = 643.60, orthorhombic, space group P212121, a = 9.6564(7), b = 14.8994(11), c = 23.6771(17) , V = 3406.5(4) 3, Z = 4, Dc = 1.255 g/cm3, λ(MoKα) = 0.71073 , μ = 1.254 mm-1 and F(000) = 1360. The structure was refined to R = 0.0324 and wR = 0.0737 for 5123 observed reflections (I > 2σ(I)). The crystallographic results of molecule 1 show that the interesting reaction of 2 with methoxy α-chloroacetate, in the usual manner, gave the spiro-cyclopropane skeleton with O-linked derivative containing multiple stereogenic centers 1 rather than the expected C-linked derivative.展开更多
Background:Metastasis is the main cause of tumor-associated death and mainly responsible for treatment failure of breast cancer.Autophagy accelerates tumor metastasis.In our work,we aimed to investigate the possibilit...Background:Metastasis is the main cause of tumor-associated death and mainly responsible for treatment failure of breast cancer.Autophagy accelerates tumor metastasis.In our work,we aimed to investigate the possibility of microRNAs(miRNAs)which participate in the regulation of autophagy to inhibit tumor metastasis.Methods:MiRNA array and comprehensive analysis were performed to identify miRNAs which participated in the regulation of autophagy to inhibit tumor metastasis.The expression levels of miR-3653 in breast cancer tissues and cells were detected by quantitative real-time polymerase chain reaction.In vivo and in vitro assays were conducted to determine the function of miR-3653.The target genes of miR-3653 were detected by a dual luciferase reporter activity assay and Western blot.The relationship between miR-3653 and epithelial-mesenchymal transition(EMT)was assessed by Western blot.Student’s t-test was used to analyze the difference between any two groups,and the difference among multiple groups was analyzed with one-way analysis of variance and a Bonferroni post hoc test.Results:miR-3653 was downregulated in breast cancer cells with high metastatic ability,and high expression of miR-3653 blocked autophagic flux in breast cancer cells.Clinically,low expression of miR-3653 in breast cancer tissues(0.054±0.013 vs.0.131±0.028,t=2.475,P=0.014)was positively correlated with lymph node metastasis(0.015±0.004 vs.0.078±0.020,t=2.319,P=0.023)and poor prognosis(P<0.001).miR-3653 ameliorated the malignant phenotypes of breast cancer cells,including proliferation,migration(MDA-MB-231:0.353±0.013 vs.1.000±0.038,t=16.290,P<0.001;MDA-MB-468:0.200±0.014 vs.1.000±0.043,t=17.530,P<0.001),invasion(MDA-MB-231:0.723±0.056 vs.1.000±0.035,t=4.223,P=0.013;MDA-MB-468:0.222±0.016 vs.1.000±0.019,t=31.050,P<0.001),and colony formation(MDA-MB-231:0.472±0.022 vs.1.000±0.022,t=16.620,P<0.001;MDA-MB-468:0.650±0.040 vs.1.000±0.098,t=3.297,P=0.030).The autophagy-associated genes autophagy-related gene 12(ATG12)and activating molecule in beclin 1-regulated autophagy protein 1(AMBRA1)are target genes of miR-3653.Further studies showed that miR-3653 inhibited EMT by targeting ATG12 and AMBRA1.Conclusions:Our findings suggested that miR-3653 inhibits the autophagy process by targeting ATG12 and AMBRA1,thereby inhibiting EMT,and provided a new idea and target for the metastasis of breast cancer.展开更多
Chiral butyrolacto[3,4-b]-2(S)-6(R)-1-N-akylaziridines 7 were synthesized in enantiopure form utilizing racemic 5-methoxy-3-bromo-2(5H)-furanone (5) and available amines (6) as key precursors. After highly effective r...Chiral butyrolacto[3,4-b]-2(S)-6(R)-1-N-akylaziridines 7 were synthesized in enantiopure form utilizing racemic 5-methoxy-3-bromo-2(5H)-furanone (5) and available amines (6) as key precursors. After highly effective reduction of 7, the functionalized 2(S),3(R)-dihyroxymethyl-N-alkylaziridines (8) were obtained in good yields with ≥98% ee. This is a simple and pratical method for the preparation of enantiopure aziridines which are important interme-diates in the synthesis of biologic active molecules.展开更多
Due to the coronavirus disease 2019(COVID‐19)pandemic,the development of antiviral drugs has attracted increasing attention.Clinical antiviral drugs show weak solubility,low bioavailability,adverse side effects,or on...Due to the coronavirus disease 2019(COVID‐19)pandemic,the development of antiviral drugs has attracted increasing attention.Clinical antiviral drugs show weak solubility,low bioavailability,adverse side effects,or only limited targets.With the advancement of nanotechnology and material science,biosafety nanomaterials have been constructed for drug delivery systems of antiviral disease therapy,such as liposomes,polymers,gold nanoparticles,and graphene.These nanodrug systems can either deliver synthesized antiviral drugs siRNA/miRNA and small molecular compounds,deliver bioactive large molecular drug proteins and mRNA,or show antiviral activity by themselves.Nanodelivery systems could effectively enhance the efficiency of antiviral drugs by increasing drug loading and host cell uptake with a small size and high specific surface area.This review focused on the biosafety nanomaterials used for antiviral therapy and discussed the options for the design of antiviral drugs in the future.展开更多
Aromaticity,in general,can promote a given reaction by stabilizing a transition state or a product via a mobility ofπelectrons in a cyclic structure.Similarly,such a promotion could be also achieved by destabilizing ...Aromaticity,in general,can promote a given reaction by stabilizing a transition state or a product via a mobility ofπelectrons in a cyclic structure.Similarly,such a promotion could be also achieved by destabilizing an antiaromatic reactant.However,both aromaticity and transition states cannot be directly measured in experiment.Thus,computational chemistry has been becoming a key tool to understand the aromaticity-driven reaction mechanisms.In this review,we will analyze the relationship between aromaticity and reaction mechanism to highlight the importance of density functional theory calculations and present it according to an approach via either aromatizing a transition state/product or destabilizing a reactant by antiaromaticity.Specifically,we will start with a particularly challenging example of dinitrogen activation followed by other small-molecule activation,Csingle bondF bond activation,rearrangement,as well as metathesis reactions.In addition,antiaromaticity-promoted dihydrogen activation,CO_(2)capture,and oxygen reduction reactions will be also briefly discussed.Finally,caution must be cast as the magnitude of the aromaticity in the transition states is not particularly high in most cases.Thus,a proof of an adequate electron delocalization rather than a complete ring current is recommended to support the relatively weak aromaticity in these transition states.展开更多
基金supported by the National Natural Science Foundation of China(No.52272198 and 52002122)the Project funded by China Postdoctoral Science Foundation(No.2021M690947).
文摘Aqueous Zn-ion batteries(AZIBs)have attracted increasing attention in next-generation energy storage systems due to their high safety and economic.Unfortunately,the side reactions,dendrites and hydrogen evolution effects at the zinc anode interface in aqueous electrolytes seriously hinder the application of aqueous zinc-ion batteries.Here,we report a critical solvation strategy to achieve reversible zinc electrochemistry by introducing a small polar molecule acetonitrile to form a“catcher”to arrest active molecules(bound water molecules).The stable solvation structure of[Zn(H_(2)O)_(6)]^(2+)is capable of maintaining and completely inhibiting free water molecules.When[Zn(H_(2)O)_(6)]^(2+)is partially desolvated in the Helmholtz outer layer,the separated active molecules will be arrested by the“catcher”formed by the strong hydrogen bond N-H bond,ensuring the stable desolvation of Zn^(2+).The Zn||Zn symmetric battery can stably cycle for 2250 h at 1 mAh cm^(-2),Zn||V_(6)O_(13)full battery achieved a capacity retention rate of 99.2%after 10,000 cycles at 10 A g^(-1).This paper proposes a novel critical solvation strategy that paves the route for the construction of high-performance AZIBs.
基金National Natural Science Foundation of China,Grant/Award Numbers:22279166,52002157National Institute of Education,Singapore,under its Academic Research Fund,Grant/Award Numbers:RI 1/21 EAH,RI 3/23 EAH+1 种基金China Postdoctoral Science Foundation,Grant/Award Numbers:2022M711686,2023M741471Postgraduate Research&Practice Innovation Program of Jiangsu Province,Grant/Award Number:SJCX24_2512。
文摘The architectural design of redox-active organic molecules and the modulation of their electronic properties significantly influence their application in energy storage systems within aqueous environments.However,these organic molecules often exhibit sluggish reaction kinetics and unsatisfactory utilization of active sites,presenting significant challenges for their practical deployment as electrode materials in aqueous batteries.In this study,we have synthesized a novel organic compound(PTPZ),comprised of a centrally symmetric and fully ladder-type structure,tailored for aqueous proton storage.This unique configuration imparts the PTPZ molecule with high electron delocalization and enhanced structural stability.As an electrode material,PTPZ demonstrates a substantial proton-storage capacity of 311.9mAh g^(-1),with an active group utilization efficiency of up to 89% facilitated by an 8-electron transfer process,while maintaining a capacity retention of 92.89% after 8000 chargingdischarging cycles.Furthermore,in-situ monitoring technologies and various theoretical analyses have pinpointed the associated electrochemical processes of the PTPZ electrode,revealing exceptional redox activity,rapid proton diffusion,and efficient charge transfer.These attributes confer a significant competitive advantage to PTPZ as an anode material for high-performance proton storage devices.Consequently,this work contributes to the rational design of organic electrode materials for the advancement of rechargeable aqueous batteries.
基金supported by National Natural Science Foundation of China(No.21864012)Jishou University National and Local United Engineering Laboratory of Integrative Utilization of Eucommia ulmoides open item(No.DZL201801)Natural Science Innovation Project of Jishou University(No.Jdy20049)。
文摘Due to environmental protection requirements,extraction of bioactive compounds from plant materials using environment-friendly green solvents has always been a research hotspot.And great efforts of scholars have been made in this direction,as well as environment-friendly solvents have been used to develop many innovative extraction techniques.Ionic liquids(ILs)and deep eutectic solvents(DESs)are two kinds of typical designable green solvents,which are potential replacements for traditional volatile organic solvents used for extracting.Under the substances action of inorganic salts or polymers,ILs/DESs can form an aqueous two-phase system(ATPS),which has obvious advantages for separating natural products.This paper discussed the phase separation principle of ILs/DESs-based ATPSs and reviewed the applications in the extraction of natural active molecules in recent years,as well as to promote the development of separation of the active constituents in Chinese materia medica.
基金the Innovation Program of Guangdong Provincial Department of Education,China(Grant No.2019KTSCX148)the Science and Technology Innovation Commission of Shenzhen(Grant No.JCYJ20170818141727254).
文摘We simulate the self-assembly of active colloidal molecules from binary mixtures of spherical particles using a Brownian dynamics algorithm.These particles interact via phoretic interactions,which are determined by two independently tunable parameters,surface activity and surface mobility.In systems composed of equal-size particles,we observe the formation of colloidal molecules with well-defined coordination numbers and spatial arrangement,which also display distinct dynamic functions,such as resting,translating,and rotating.By changing the size ratio to 2:1 between the two species,we further observe the formation of colloidal molecules with new structures arising from breaking the size symmetry.By tuning the mutual interactions between the smaller species via their surface mobility,we are able to control their spacing as well as the coordination number of the colloidal molecules.This study highlights the importance of tuning surface parameters and size asymmetry in controlling the structure and the active dynamics of colloidal molecules.
基金supported by the National Natural Science Foundations of China(82372342)the Clinical Diagnosis and Treatment New Technology Project of Jinling Hospital(No.22LCZLXJS40).
文摘microRNAs (miRNAs) derived from viruses, have been detected in body fluids and are known to regulate the expression of host genes. Recent evidence indicates that SARS-CoV-2-encoded miRNAs could contribute to pulmonary disease. Pulmonary fibrosis is an important complication in SARS-CoV-2 infected patients, either during hospitalization or after discharge, however, the underlying mechanisms are not fully elucidated. Here, we report a SARS-CoV-2-encoded miRNA, miR-nsp3-3p, facilitates host pulmonary fibrosis by inhibiting expression of activated leukocyte cell adhesion molecule (ALCAM) and promoting epithelial-mesenchymal transition (EMT). First, we detected miR-nsp3-3p in clinical specimens and found it was remarkably increased in throat swabs and alveolar lavage fluids from severe/critical COVID-19 patients compared to control groups or mild/moderate patients. We further revealed that adeno-associated virus (AAV)-nsp3 infection can induce pulmonary fibrosis in BALB/c mice while miR-nsp3-3p antagomirs can reverse that, and ALCAM was found to be as a target gene of miR-nsp3-3p. miR-nsp3-3p overexpression can inhibit the expression of ALCAM and promote EMT of pulmonary epithelial cells. Moreover, overexpression of ALCAM can reverse the miR-nsp3-3p-induced EMT and fibrosis. These findings highlight the essential role of SARS-CoV-2-encoded miRNAs in promoting the pathological progression of lung disease, and provide novel insights into the interactions between viral miRNAs and host pathology.
基金supported by the NNSFC(No.29771025),(No.20377053)The Nine-five National Key Project of China(29833090)The Hubei Province Foundation of China(No.2003ABA071).
文摘Iron(Ⅱ)tetra-(1,4-dithin)-porphyrazine,(FePz(dtn)_(4))is able to activate molecule oxygen for oxygenation degradation of rhodamine B(RhB)in an extensive pH region without light excitation.Experiments indicate that the RhB can be degraded nearly 52%in alkaline aqueous solution,bubbling with dioxygen for seven hours in the presence of FePz(dtn)_(4)and the hydrogen peroxides as an active intermediate were determined by DPD method.The catalyst is recyclable and the catalyst activity was maintained after 10 recycles.
文摘The activation and selective conversion of energy-related molecules is an important research area of energy chemistry.The depletion of petroleum has stimulated research activities into the utilization of non-petroleum carbon resources such as natural gas(including conventional and
文摘To investigate whether estradiol （E2） plays a role in cell-contact-dependent regulatory mechanism of T cell activation, we studied the role of E2 in regulating gene transcription of CTLA-4, ICOS, B7-1, B7-2 and B7h in vitro. The splenic cells of normal female BALB/c mice were activated by ConA. Then the cells were cultured with E2 （100 pg/ml or 50 ng/ml） for 24 h or 48 h, respectively. The cell proliferation was measured by MTF assay and the expression of the co-stimulatory molecules mRNA was examined by RT-PCR analysis. We found that E2 （100 pg/ml, physiological level） stimulated the acti- vated spleen cells proliferation; inhibited CTLA-4, ICOS, TGF-β and IL-10 gene transcription; promoted B7-1 and B7-2 gene transcription. E2 （50 ng/ml, pregnant level） inhibited the proliferation of the activated splenic cells; promoted CTLA-4, B7-1, IL-10 but inhibited B7-2 and TGF-β gene transcription. Therefore, we conclude that the effects of E2 on T cell activation are partially through its regulation on the co-stimulatory molecules. The co-stimulatory molecules are crucial components of the cell-contact dependent regulatory mechanism, and E2 may regulate T cell activation by this mechanism.
文摘Chikungunya fever(CF)is caused by an arbovirus whose manifestations are extremely diverse,and it has evolved with significant severity in recent years.The clinical signs triggered by the Chikungunya virus are similar to those of other arboviruses.Generally,fever starts abruptly and reaches high levels,followed by severe polyarthralgia and myalgia,as well as an erythematous or petechial maculopapular rash,varying in severity and extent.Around 40%to 60%of affected individuals report persistent arthralgia,which can last from months to years.The symptoms of CF mainly represent the tissue tropism of the virus rather than the immunopathogenesis triggered by the host's immune system.The main mechanisms associated with arthralgia have been linked to an increase in T helper type 17 cells and a consequent increase in receptor activator of nuclear factor kappa-Βligand and bone resorption.This review suggests that persistent arthralgia results from the presence of viral antigens post-infection and the constant activation of signaling lymphocytic activation molecule family member 7 in synovial macrophages,leading to local infiltration of CD4+T cells,which sustains the inflammatory process in the joints through the secretion of pro-inflammatory cytokines.The term"long chikungunya"was used in this review to refer to persistent arthralgia since,due to its manifestation over long periods after the end of the viral infection,this clinical condition seems to be characterized more as a sequel than as a symptom,given that there is no active infection involved.
基金supported by the National Key R&D Program of China(Nos.2016YFA0202500 and 2016YFB0901502)the National Natural Science Foundation of China(NSFC,Nos.21673243,51771094 and 21805141)the Ministry of Education(MOE)of China(No.B12015)and Tianjin High-Tech(No.18JCZDJC31500)。
文摘Due to the diversity and feasibility of structural modification for organic molecules,organic-based redox flow batteries(ORFBs)have been widely investigated,especially in aqueous solution under neutral circumstance.In this work,a symmetric aqueous redox flow battery(SARFB)was rationally designed by employing a bipolar redox active molecule(N,N’-dimethyl-4,4-bipyridinium diiodide,MVI2)as both cathode and anode materials and combining with an anion exchange membrane.For one MVI2 flow battery,MV2+/MV·+and I-/I3-serve as the redox couples of anode and cathode,respectively.The MVI2 battery with a working voltage of 1.02 V exhibited a high voltage efficiency of 90.30%and energy efficiency of 89.44%after 450 cycles,and crossover problem was prohibited.The comparable conductivity of MVI2 water solution enabled to construct a battery even without using supporting electrolyte.Besides,the bipolar character of MVI2 battery with/without supporting electrolyte was investigated in the voltage range between-1.2 V and 1.2 V,showing excellent stable cycling stability during the polarity-reversal test.
基金Supported by the National Natural Science Foundation of China (No. 29672004)
文摘The title compound, 5（R）-（1R,2S,5R）-menthoxy-4（R）-N-cyclohexylaminobutyrolactone 1, has been synthesized via the asymmetric Micheal addition reaction of 5（R）-menthoxy- 2（5H）-furanone 4 with cyclohexylamine 5, and structurally determined by single-crystal X-ray diffraction. Crystal data： C20H36NO3, Mr = 337.49, monoclinic system, space group P21, a = 9.8677（7）, b = 9.7737（7）, c=11.0204（8） A, β= 103.7820（10）°, V= 1032.25（13） A^3, Z = 2, Dc= 1.086 g/cm^3, 2（MoKα） = 0.071073 nm,μ= 0.071 mm^-1 and F（000） = 372. The structure was refined to R = 0.0328 and wR = 0.0864 for 4203 observed reflections （I 〉 2σ（I））. The crystallographic results of molecule 1 show that the functionalized N-cyclohexylamino group is linked in the 4-position of butyrolactone to form the novel chiral optically active compound.
基金Supported by the National Natural Science Foundation of China (No. 29672004)
文摘The title compound, 5-methoxy-butyrolacto[3,4-b]-1-N-cyclohexylaziridine 1, has been synthesized via tandem Micheal addition and intramolecular nucleophilic substitution reactions of 5-methoxy-3-bromo-2（5H）-furanones 4 with primary amines 5, and structurally determined by single-crystal X-ray diffraction. Crystal data： C11H17NO3, Mr = 211.26, monoclinic system, space group P21/c, a = 17.800（3）, b = 5.3864（10）, c = 12.2571（10）A°, β = 90.449（3）°, V = 1175.1（3） A°^3, Z= 4, De= 1.194 g/cm^3, λ（MoKα） = 0.071073 nm, μ = 0.087 mm^-1 and F（000） = 456. The structure was refined to R = 0.0505 and wR = 0.1208 for 2579 observed reflections （I 〉 2σ（I））. The crystallographic results of molecule 1 show that the functionalized aziridine ring is fused with a lactone ring to form the component with [3.1.0] bicyclic skeleton.
基金Supported by the National Natural Science Foundation of China (No. 29672004)
文摘The title compound, 2（S）,3（R）-dihydroxymethyl-N-cyclohexylaziridine 1, has been synthesized via tandem Micheal addition and internal nucleophilic substitution reactions of 5-methoxy-3-bromo-2（5H）-furanones 2 with cyclohexylamine 3 and subsequent reduction of intermediate 5. Its crystal structure was determined by single-crystal X-ray diffraction. Crystal data：C10H19NO2, Mr = 185.26, monoclinic system, space group P21/n, a = 8.0620（16）, b = 7.2013（14）, c= 18.555（4） A°, β= 102.30（3）°, V= 1052.5（4）A°^3, Z= 4, De= 1.169 g/cm^3, λ（MoKα） = 0.071073 nm,μ = 0.080 mm^- 1 and F（000） = 408. The structure was refined to R = 0.0439 and wR = 0.1178 for 1839 observed reflections （I 〉 2σ（I））. The crystallographic structure of 1 shows that the functionalized aziridine ring links two hyroxymethyl groups.
基金Supported by the National Natural Science Foundation of China (No. 29672004)
文摘The title compound, spiro[ 1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]- hexane-2,2＇-3＇-（16＇-methoxyacetatyl-4＇-l-menthyloxybutyrolactone）] 1, was obtained via tandem asymmetric double Michael addition/internal nucleophilic substitution of the chiral synthon, 5-l-menthyloxy-3-bromo-2-（5H）-furanone 2 with methoxy α-chloroacetate as a nucleophile under mild conditions, and structurally [letermined by single-crystal X-ray diffraction. Crystal data： C31H47BrO9, Mr = 643.60, orthorhombic, space group P212121. α = 9.6564（7）, b = 14.8994（11）, c = 23.6771（17） A, V= 3406.5（4） A^3, Z = 4, Dc= 1.255 g/cm^3, 2（MoKa） = 0.71073 A,μ= 1.254 mm^-1 and F（000） = 1360. The structure was refined to R =[0.0324 and wR = 0.0737 for 5123 observed reflections （I〉 2σ（I））. The crystallographic results of molecule 1 show that the interesting reaction of 2 with methoxy α-chloroacetate, in the usual manner, gave the spiro-cyclopropane skeleton with O-linked derivative containing multiple stereogenic centers 1 rather than the expected C-linked derivative.
文摘The title compound, spiro[1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]-hexane-2,2-3-(16-methoxyacetatyl-4-l-menthyloxybutyrolactone)] 1, was obtained via tandem asymmetric double Michael addition/internal nucleophilic substitution of the chiral synthon, 5-l-menthyloxy-3-bromo-2-(5H)-furanone 2 with methoxy α-chloroacetate as a nucleophile under mild conditions, and structurally determined by single-crystal X-ray diffraction. Crystal data: C31H47BrO9, Mr = 643.60, orthorhombic, space group P212121, a = 9.6564(7), b = 14.8994(11), c = 23.6771(17) , V = 3406.5(4) 3, Z = 4, Dc = 1.255 g/cm3, λ(MoKα) = 0.71073 , μ = 1.254 mm-1 and F(000) = 1360. The structure was refined to R = 0.0324 and wR = 0.0737 for 5123 observed reflections (I > 2σ(I)). The crystallographic results of molecule 1 show that the interesting reaction of 2 with methoxy α-chloroacetate, in the usual manner, gave the spiro-cyclopropane skeleton with O-linked derivative containing multiple stereogenic centers 1 rather than the expected C-linked derivative.
基金National Natural Science Foundation of China(No.81872398)Chinese Academy of Medical Sciences(CAMS)Innovation Fund for Medical Sciences(CIFMS)(No.2021-I2M-1-014)
文摘Background:Metastasis is the main cause of tumor-associated death and mainly responsible for treatment failure of breast cancer.Autophagy accelerates tumor metastasis.In our work,we aimed to investigate the possibility of microRNAs(miRNAs)which participate in the regulation of autophagy to inhibit tumor metastasis.Methods:MiRNA array and comprehensive analysis were performed to identify miRNAs which participated in the regulation of autophagy to inhibit tumor metastasis.The expression levels of miR-3653 in breast cancer tissues and cells were detected by quantitative real-time polymerase chain reaction.In vivo and in vitro assays were conducted to determine the function of miR-3653.The target genes of miR-3653 were detected by a dual luciferase reporter activity assay and Western blot.The relationship between miR-3653 and epithelial-mesenchymal transition(EMT)was assessed by Western blot.Student’s t-test was used to analyze the difference between any two groups,and the difference among multiple groups was analyzed with one-way analysis of variance and a Bonferroni post hoc test.Results:miR-3653 was downregulated in breast cancer cells with high metastatic ability,and high expression of miR-3653 blocked autophagic flux in breast cancer cells.Clinically,low expression of miR-3653 in breast cancer tissues(0.054±0.013 vs.0.131±0.028,t=2.475,P=0.014)was positively correlated with lymph node metastasis(0.015±0.004 vs.0.078±0.020,t=2.319,P=0.023)and poor prognosis(P<0.001).miR-3653 ameliorated the malignant phenotypes of breast cancer cells,including proliferation,migration(MDA-MB-231:0.353±0.013 vs.1.000±0.038,t=16.290,P<0.001;MDA-MB-468:0.200±0.014 vs.1.000±0.043,t=17.530,P<0.001),invasion(MDA-MB-231:0.723±0.056 vs.1.000±0.035,t=4.223,P=0.013;MDA-MB-468:0.222±0.016 vs.1.000±0.019,t=31.050,P<0.001),and colony formation(MDA-MB-231:0.472±0.022 vs.1.000±0.022,t=16.620,P<0.001;MDA-MB-468:0.650±0.040 vs.1.000±0.098,t=3.297,P=0.030).The autophagy-associated genes autophagy-related gene 12(ATG12)and activating molecule in beclin 1-regulated autophagy protein 1(AMBRA1)are target genes of miR-3653.Further studies showed that miR-3653 inhibited EMT by targeting ATG12 and AMBRA1.Conclusions:Our findings suggested that miR-3653 inhibits the autophagy process by targeting ATG12 and AMBRA1,thereby inhibiting EMT,and provided a new idea and target for the metastasis of breast cancer.
基金by the National Natural Science Foundation of China (No. 29672004).
文摘Chiral butyrolacto[3,4-b]-2(S)-6(R)-1-N-akylaziridines 7 were synthesized in enantiopure form utilizing racemic 5-methoxy-3-bromo-2(5H)-furanone (5) and available amines (6) as key precursors. After highly effective reduction of 7, the functionalized 2(S),3(R)-dihyroxymethyl-N-alkylaziridines (8) were obtained in good yields with ≥98% ee. This is a simple and pratical method for the preparation of enantiopure aziridines which are important interme-diates in the synthesis of biologic active molecules.
基金supported by the National Key Research&Development Program of China(No.2021YFA1201000)the Government Guided Local Science and Technology Development Fund Projects of Hebei Province(No.216Z2403G)+2 种基金Natural Science Foundation of Hebei Province(No.B2019201449,H2019201466)the Priority Strategy Project of the Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education(ts2020003)the Hebei Province“Three Three Three Talents Program”(A202003001).
文摘Due to the coronavirus disease 2019(COVID‐19)pandemic,the development of antiviral drugs has attracted increasing attention.Clinical antiviral drugs show weak solubility,low bioavailability,adverse side effects,or only limited targets.With the advancement of nanotechnology and material science,biosafety nanomaterials have been constructed for drug delivery systems of antiviral disease therapy,such as liposomes,polymers,gold nanoparticles,and graphene.These nanodrug systems can either deliver synthesized antiviral drugs siRNA/miRNA and small molecular compounds,deliver bioactive large molecular drug proteins and mRNA,or show antiviral activity by themselves.Nanodelivery systems could effectively enhance the efficiency of antiviral drugs by increasing drug loading and host cell uptake with a small size and high specific surface area.This review focused on the biosafety nanomaterials used for antiviral therapy and discussed the options for the design of antiviral drugs in the future.
基金the National Natural Science Foundation of China(22073079,22025105 and 21873079)the Ministry of Education of China(H20200504)+2 种基金the Top-Notch Young Talents Program of China is gratefully acknowledgedM.S.thanks the Ministerio de Ciencia e Innovación of Spain(project PID2020-113711GB-I00)the Generalitat de Catalunya(project 2017SGR39).
文摘Aromaticity,in general,can promote a given reaction by stabilizing a transition state or a product via a mobility ofπelectrons in a cyclic structure.Similarly,such a promotion could be also achieved by destabilizing an antiaromatic reactant.However,both aromaticity and transition states cannot be directly measured in experiment.Thus,computational chemistry has been becoming a key tool to understand the aromaticity-driven reaction mechanisms.In this review,we will analyze the relationship between aromaticity and reaction mechanism to highlight the importance of density functional theory calculations and present it according to an approach via either aromatizing a transition state/product or destabilizing a reactant by antiaromaticity.Specifically,we will start with a particularly challenging example of dinitrogen activation followed by other small-molecule activation,Csingle bondF bond activation,rearrangement,as well as metathesis reactions.In addition,antiaromaticity-promoted dihydrogen activation,CO_(2)capture,and oxygen reduction reactions will be also briefly discussed.Finally,caution must be cast as the magnitude of the aromaticity in the transition states is not particularly high in most cases.Thus,a proof of an adequate electron delocalization rather than a complete ring current is recommended to support the relatively weak aromaticity in these transition states.
