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
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
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
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
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
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
In the current era,harvesting sustainable energy is a prime sustainable goal for the continuous growth of human civilization without any adverse effect on the surrounding atmosphere.The intermittent nature of renewabl...In the current era,harvesting sustainable energy is a prime sustainable goal for the continuous growth of human civilization without any adverse effect on the surrounding atmosphere.The intermittent nature of renewable energy resources has posed serious questions about their potential to provide a reliable flow of continuous energy.A strategic conversion of renewables to chemical energy can offer the leeway for a facile energy transduction process where renewables will be converted into chemical bonds in the first step before their need-based conversion to readily usable electricity or other forms of energy.In this context,two compatible redox couples,H2O⇌H2 and H2O⇌O2,have emerged as the prime contenders for small molecule-based energy conversion due to their natural abundance and relatively well-known chemistry.A plethora of synthetic catalysts have been designed to date that can trigger H2 production,H2 oxidation,water oxidation,and O2 reduction.Typically,all these catalysts function independently and must be assembled together for a fully functional setup that can consistently convert renewables to electric energy.This assembly will be practically more useful if bifunctional catalysts,which can execute more than one reaction,can be included.In this review,we have highlighted the evolution of two major classes of such bifunctional or Janus catalysts that can function in H2 production/water oxidation and O2 reduction/water oxidation in tandem with the application of the appropriate energy source.The specific design of such catalysts involves the strategic incorporation of dopants and lattice defects on specific metal oxide or metal phosphide templates.Such modulation of the surface morphology is key for developing active heterogeneous Janus catalysts.In this review,we have summarized the different approaches for generating and studying such Janus catalysts,as they will lay the foundation for an efficient,economical,and eco-friendly pathway for sustainable energy usage with the rational assembly of energy converting and storage devices.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, 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, 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, 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
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 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
The development of electrode materials for supercapacitors is a significant issue for future energy storage devices.In addition,the selective oxidation of sulfides to sulfoxides that serve as key intermediates for syn...The development of electrode materials for supercapacitors is a significant issue for future energy storage devices.In addition,the selective oxidation of sulfides to sulfoxides that serve as key intermediates for synthesizing medically and chemically active molecules is still a critical challenge.In this study,two novel 3D POM-based metal-organic frameworks,formulated as[Cu_(3)(bty)_(3)][BW_(12)O_(40)]·4H_(2)O(1)and[Cu_(2.5)(bty)_(5)][BW_(12)O_(40)]·7H_(2)O(2)(bty=bis(1,2,4-triazol-1-yl)ethane),were obtained via a one-step synthesis strategy by adjusting the pH value under solvothermal conditions.In compound 1,{BW_(12)}as a 2-connected node is located between 2D Cu-organic sheets to yield a novel 3D POM-based metal-organic framework.There are 1D channel structures constructed with Cu-organic sheets in compound 2.Then,{BW_(12)}as a 4-connected node merged into the orifice of the Cu-organic framework forming a glamorous 3D framework.Moreover,the 3D Cu-organic framework of 2 displays the fascinating shape of vase structures.These two compounds could be applied as electrode materials for supercapacitors with specific capacitances of 214.59 F g^(-1) and 189.17 F g^(-1) at 0.48 A g^(-1) respectively,as well as efficient heterogeneous catalysts for selective oxidation of sulfides to their corresponding sulfoxides.展开更多
Spin active molecules have been proposed for quantum computing,due to their unique advantages such as the possibility of having multiple eigenstates.Using pulse electron paramagnetic resonance,a Gd(Ⅲ)complex was thor...Spin active molecules have been proposed for quantum computing,due to their unique advantages such as the possibility of having multiple eigenstates.Using pulse electron paramagnetic resonance,a Gd(Ⅲ)complex was thoroughly investigated to demonstrate the protocol of harnessing the large spin quantum number of the rare-earth molecule and implementing a qudit.The desired anisotropy of the S=7/2 system,which makes all spin transitions addressable with an X-band spectrometer,was quantitatively determined at 10 K with a set of crystalfield parameters.The relatively long phase memory time,ca.1μs,of the oxygen-coordinated 4f spin was extended up to 16.8μs using dynamic decoupling pulse sequences.An arbitrary superposition state between each adjacent level pair was achieved by Rabi cycles with a crystal sample positioned in both perpendicular and parallel directions.Finally,a more detailed orientation mapping of the Rabi frequencies,which govern the quantum phase gate operation time,was provided based on the spin Hamiltonian.展开更多
The strategy of incorporating earth-abundant catalytic centers into light-absorbing architectures is desirable from the viewpoint of low cost,low toxicity,and versatility for activating small molecules to produce sola...The strategy of incorporating earth-abundant catalytic centers into light-absorbing architectures is desirable from the viewpoint of low cost,low toxicity,and versatility for activating small molecules to produce solar-based fuels.Herein,we show that an Fe-quaterpyridine molecular catalyst can be anchored to a light-absorbing,crystalline,carbon nitride(PTI),to yield a molecular-catalyst/material hybrid,Fe-qpy-PTI,capable of facilitating CO_(2)reduction to CO selectively(up to∼97–98%)in aqueous solution under lowintensity light irradiation.This hybrid material leverages the ability of the Fe-qpy catalyst to bind CO_(2)upon a one-electron reduction,as achieved by transfer of excited electrons from the carbon-nitride semiconductor.At a low incident power density of only 50 mW cm^(−2),the catalytic activity of the hybrid material was measured across a range of catalyst loadings from 0.1–3.8 wt%,yielding CO rates of up to 596μmol g^(−1)h^(−1)for a 3.8 wt%loading during a 3 h experiment.Over the course of 8 h,the hybrid material attained a CO evolution rate of 608μmol g^(−1)h^(−1)and 305 turnovers for a TOF of∼38 h^(−1)and an apparent quantum yield of 2.6%.Higher light intensities provided an initial increase in activity but negatively impacted photocatalytic rates with time,with an AQY of 0.6%at 150 mW cm^(−2)and 0.4%at 250 mW cm^(−2).Transient absorption spectroscopy results showed electron survival probabilities consistent with the trends in observed product rates.Computational modeling was also used to evaluate and understand the mechanistic pathway of the high product selectivity for CO versus H2.These results thus help unveil key factors for leveraging the mechanistic understanding of molecular catalysts for CO_(2)reduction for pairing with light absorbing semiconductors and establishing optimal conditions to attain maximal rates in aqueous solution.展开更多
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 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.
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.
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.
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support provided by the Department of Science and Technology,Science and Engineering Research Board(DST-SERB)India,for the core research grant(CRG/2020/001239)DST,Indiasupported National Center of Excellence(DST/TMD/CCUS/CoE/202/IITB).
文摘In the current era,harvesting sustainable energy is a prime sustainable goal for the continuous growth of human civilization without any adverse effect on the surrounding atmosphere.The intermittent nature of renewable energy resources has posed serious questions about their potential to provide a reliable flow of continuous energy.A strategic conversion of renewables to chemical energy can offer the leeway for a facile energy transduction process where renewables will be converted into chemical bonds in the first step before their need-based conversion to readily usable electricity or other forms of energy.In this context,two compatible redox couples,H2O⇌H2 and H2O⇌O2,have emerged as the prime contenders for small molecule-based energy conversion due to their natural abundance and relatively well-known chemistry.A plethora of synthetic catalysts have been designed to date that can trigger H2 production,H2 oxidation,water oxidation,and O2 reduction.Typically,all these catalysts function independently and must be assembled together for a fully functional setup that can consistently convert renewables to electric energy.This assembly will be practically more useful if bifunctional catalysts,which can execute more than one reaction,can be included.In this review,we have highlighted the evolution of two major classes of such bifunctional or Janus catalysts that can function in H2 production/water oxidation and O2 reduction/water oxidation in tandem with the application of the appropriate energy source.The specific design of such catalysts involves the strategic incorporation of dopants and lattice defects on specific metal oxide or metal phosphide templates.Such modulation of the surface morphology is key for developing active heterogeneous Janus catalysts.In this review,we have summarized the different approaches for generating and studying such Janus catalysts,as they will lay the foundation for an efficient,economical,and eco-friendly pathway for sustainable energy usage with the rational assembly of energy converting and storage devices.
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, 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, 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, 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.
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 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financially supported by the Major Research Program of High Education of Henan Province(21B15001721B150019)+2 种基金the Joint Program for Fostering Talents of National Natural Science Foundation of China and Henan Province(U1304202)State Scholarship Fund,Henan Province Science and Technology Project(222300420523)The Scientific Research Innovation Team of Xuchang University(2022CXTD001).
文摘The development of electrode materials for supercapacitors is a significant issue for future energy storage devices.In addition,the selective oxidation of sulfides to sulfoxides that serve as key intermediates for synthesizing medically and chemically active molecules is still a critical challenge.In this study,two novel 3D POM-based metal-organic frameworks,formulated as[Cu_(3)(bty)_(3)][BW_(12)O_(40)]·4H_(2)O(1)and[Cu_(2.5)(bty)_(5)][BW_(12)O_(40)]·7H_(2)O(2)(bty=bis(1,2,4-triazol-1-yl)ethane),were obtained via a one-step synthesis strategy by adjusting the pH value under solvothermal conditions.In compound 1,{BW_(12)}as a 2-connected node is located between 2D Cu-organic sheets to yield a novel 3D POM-based metal-organic framework.There are 1D channel structures constructed with Cu-organic sheets in compound 2.Then,{BW_(12)}as a 4-connected node merged into the orifice of the Cu-organic framework forming a glamorous 3D framework.Moreover,the 3D Cu-organic framework of 2 displays the fascinating shape of vase structures.These two compounds could be applied as electrode materials for supercapacitors with specific capacitances of 214.59 F g^(-1) and 189.17 F g^(-1) at 0.48 A g^(-1) respectively,as well as efficient heterogeneous catalysts for selective oxidation of sulfides to their corresponding sulfoxides.
基金supported by the National Basic Research Program of China(2017YFA0204903 and 2018YFA0306003)National Natural Science Foundation of China(21822301 and 51802346)Beijing Academy of Quantum Information Sciences(Y18G23).
文摘Spin active molecules have been proposed for quantum computing,due to their unique advantages such as the possibility of having multiple eigenstates.Using pulse electron paramagnetic resonance,a Gd(Ⅲ)complex was thoroughly investigated to demonstrate the protocol of harnessing the large spin quantum number of the rare-earth molecule and implementing a qudit.The desired anisotropy of the S=7/2 system,which makes all spin transitions addressable with an X-band spectrometer,was quantitatively determined at 10 K with a set of crystalfield parameters.The relatively long phase memory time,ca.1μs,of the oxygen-coordinated 4f spin was extended up to 16.8μs using dynamic decoupling pulse sequences.An arbitrary superposition state between each adjacent level pair was achieved by Rabi cycles with a crystal sample positioned in both perpendicular and parallel directions.Finally,a more detailed orientation mapping of the Rabi frequencies,which govern the quantum phase gate operation time,was provided based on the spin Hamiltonian.
基金supported as part of the Center for Hybrid Approaches in Solar Energy to Liquid Fuels(CHASE),an Energy Innovation Hub funded by the U.SDepartment of Energy,Office of Science,Office of Basic Energy Sciences under Award Number DE-SC0021173+5 种基金Research efforts were performed in part at the Molecular Education,Technology and Research Innovation Center(METRIC)at NC State University and performed in part at the Analytical Instrumentation Facility(AIF)at North Carolina State University,which is supported by the State of North Carolina and the National Science Foundation(award number ECCS-2025064)The AIF is a member of the North Carolina Research Triangle Nanotechnology Network(RTNN),a site in the National Nanotechnology Coordinated Infrastructure(NNCI)This work used the High-Performance Research Computing FASTER cluster at Texas A&M University through allocation CHE240107 from the Advanced Cyberinfrastructure Coordination Ecosystem:Services&Support(ACCESS)program,81 which is supported by U.S.National Science Foundation grants#2138259,#2138286,#2138307,#2137603,and#2138296Additional efforts were performed at the University of North Carolina’s Chapel Hill Analytical and Nanofabrication Laboratory,CHANL,a member of the North Carolina Research Triangle Nanotechnology Network,RTNN,which is supported by the National Science Foundation,Grant ECCS-2025064,as part of the National Nanotechnology Coordinated Infrastructure,NNCIThe authors thank the University of North Carolina’s Department of Chemistry NMR Core Laboratory for the use of their NMR spectrometers,particularly the instrument funded under the National Science Foundation Grant No.CHE-1828183The authors thank the University of North Carolina’s Department of Chemistry Mass Spectrometry Core Laboratory for the use of their mass spectrometer funded by the National Science Foundation under Grant No.CHE-1726291.
文摘The strategy of incorporating earth-abundant catalytic centers into light-absorbing architectures is desirable from the viewpoint of low cost,low toxicity,and versatility for activating small molecules to produce solar-based fuels.Herein,we show that an Fe-quaterpyridine molecular catalyst can be anchored to a light-absorbing,crystalline,carbon nitride(PTI),to yield a molecular-catalyst/material hybrid,Fe-qpy-PTI,capable of facilitating CO_(2)reduction to CO selectively(up to∼97–98%)in aqueous solution under lowintensity light irradiation.This hybrid material leverages the ability of the Fe-qpy catalyst to bind CO_(2)upon a one-electron reduction,as achieved by transfer of excited electrons from the carbon-nitride semiconductor.At a low incident power density of only 50 mW cm^(−2),the catalytic activity of the hybrid material was measured across a range of catalyst loadings from 0.1–3.8 wt%,yielding CO rates of up to 596μmol g^(−1)h^(−1)for a 3.8 wt%loading during a 3 h experiment.Over the course of 8 h,the hybrid material attained a CO evolution rate of 608μmol g^(−1)h^(−1)and 305 turnovers for a TOF of∼38 h^(−1)and an apparent quantum yield of 2.6%.Higher light intensities provided an initial increase in activity but negatively impacted photocatalytic rates with time,with an AQY of 0.6%at 150 mW cm^(−2)and 0.4%at 250 mW cm^(−2).Transient absorption spectroscopy results showed electron survival probabilities consistent with the trends in observed product rates.Computational modeling was also used to evaluate and understand the mechanistic pathway of the high product selectivity for CO versus H2.These results thus help unveil key factors for leveraging the mechanistic understanding of molecular catalysts for CO_(2)reduction for pairing with light absorbing semiconductors and establishing optimal conditions to attain maximal rates in aqueous solution.
