Aqueous Zn-iodine batteries(ZIBs)face the formidable challenges towards practical implementation,including metal corrosion and rampant dendrite growth on the Zn anode side,and shuttle effect of polyiodide species from...Aqueous Zn-iodine batteries(ZIBs)face the formidable challenges towards practical implementation,including metal corrosion and rampant dendrite growth on the Zn anode side,and shuttle effect of polyiodide species from the cathode side.These challenges lead to poor cycle stability and severe self-discharge.From the fabrication and cost point of view,it is technologically more viable to deploy electrolyte engineering than electrode protection strategies.More importantly,a synchronous method for modulation of both cathode and anode is pivotal,which has been often neglected in prior studies.In this work,cationic poly(allylamine hydrochloride)(Pah^(+))is adopted as a low-cost dual-function electrolyte additive for ZIBs.We elaborate the synchronous effect by Pah^(+)in stabilizing Zn anode and immobilizing polyiodide anions.The fabricated Zn-iodine coin cell with Pah^(+)(ZnI_(2) loading:25 mg cm^(−2))stably cycles 1000 times at 1 C,and a single-layered 3.4 cm^(2) pouch cell(N/P ratio~1.5)with the same mass loading cycles over 300 times with insignificant capacity decay.展开更多
Multi-electron and multi-orbital effects play a crucial role in the interaction of strong laser fields with complex molecules.Here,multi-electron effects encompass not only electron-electron Coulomb interactions and e...Multi-electron and multi-orbital effects play a crucial role in the interaction of strong laser fields with complex molecules.Here,multi-electron effects encompass not only electron-electron Coulomb interactions and exchangecorrelation effects but also the interference between the dynamics of different electron wave packets.展开更多
Polyethylene oxide(PEO)-based solid-state polymer electrolytes(SPE)face the challenges of insufficient ionic conductivity and uncontrollable Li dendrite growth.The filler strategy can reinforce anode interface stabili...Polyethylene oxide(PEO)-based solid-state polymer electrolytes(SPE)face the challenges of insufficient ionic conductivity and uncontrollable Li dendrite growth.The filler strategy can reinforce anode interface stability,but at the cost of a large filler content(usually more than 10 wt%).This would increase the granular sensation,gravitational separation risk,and electrolyte membrane roughness with the creation of inhomogeneous Li^(+)transport channels between filler and polymer.Herein,we propose a trace filling strategy to address the above problems by introducing an amphoteric molecule L-Cysteine(LCy)as an eco-friendly and low-cost electrolyte additive.Only trace amount of LCy is required and integrated into PEO to form a homogenous,granule-less SPE with enhanced ionic conductivity and dendrite suppression capability.The ionic conductivity increases to 0.54 mS cm^(-1)at 60℃ after introducing only 1 wt%LCy.The amphotericity of LCy with basic–NH_(2)and acidic–COOH groups can promote the dissociation of Li salt and release more free Li ions through Lewis acid-base synergy,as well as the formation of multiple hydrogen bonds between PEO and LCy.The trace LCy additive swiftly leads to the formation of more ionic conductive interphases at both the anode and cathode sides.The composite SPE enables the stable cycling of Li metal for over 1400 h at 0.2 mA cm^(-2)and sustains a maximum current density up to 1.4 mA cm^(-2)in Li Li symmetric cells.The corresponding all-solid-state Li||FeF_(3)full cells exhibit a high specific capacity up to 567 mA h g^(-1)at 0.2 C and stable cycling performance for at least 700 cycles at 0.5 C with a high capacity retention.The excellent interface compatibility also guarantees the achievement of highcapacity Li-Fe-F conversion reaction even under the thin electrolyte membrane thickness and largerscale pouch cell configuration.展开更多
This study preliminarily investigates the structure-activity relationships of novel [5,6]-fused ring energetic materials derived from the 6-nitro-7-azido-pyrazol [3,4-d][1,2,3]triazine 2-oxide(ICM-103) skeleton, empha...This study preliminarily investigates the structure-activity relationships of novel [5,6]-fused ring energetic materials derived from the 6-nitro-7-azido-pyrazol [3,4-d][1,2,3]triazine 2-oxide(ICM-103) skeleton, emphasizing the role of functional group substitution in tailoring key properties such as detonation performance and mechanical sensitivity. Strategic incorporation of nitrogen-rich substituents(e.g., hydrazine, guanidine) into the 1,2,3-triazine 2-oxide framework yielded compounds with diverse performance characteristics. Notably, compound 2 demonstrates energy performance(D = 8916 m·s^(-1) and P = 36.80 GPa) comparable to RDX, yet with lower mechanical sensitivity(IS = 37 J). Theoretical calculations show that the properties of the substituents themselves and their coupling with the molecular skeleton jointly determine the key properties of the target molecules. This study provides a framework for the customized design of energetic materials by linking the chemical properties of substituents with the performance parameters of target molecules. These findings highlight the potential of local molecular structural modification driven by structure-activity relationship analysis in promoting the development of next-generation energetic materials and lay a solid foundation for future research in this field.展开更多
The tensile strain in inorganic perovskite films induced by thermal annealing is one of the primary factors contributing to the inefficiency and instability of inorganic perovskite solar cells(IPSCs),which reduces the...The tensile strain in inorganic perovskite films induced by thermal annealing is one of the primary factors contributing to the inefficiency and instability of inorganic perovskite solar cells(IPSCs),which reduces the defect formation energy.Here,a flexible molecule 5-maleimidovaleric acid(5-MVA)was introduced as a strain buffer to release the residual strain of CsPbI_(2.85)Br_(0.15)perovskite.Maleic anhydride and carboxyl groups in 5-MVA interact strongly with the uncoordinated Pb^(2+)through Lewis acid-base reaction,thus tightly“pull”the perovskite lattice.The in-between soft carbon chain increased the structural flexibility of CsPbI_(2.85)Br_(0.15)perovskite materials,which effectively relieved the intrinsic internal strain of CsPbI_(2.85)Br_(0.15),resisted the corrosion of external strain,and also reduced the formation of defects such as VIand Pb0.In addition,the introduction of 5-MVA improved crystal quality,passivated residual defects,and narrowed energy level barriers.Eventually,power conversion efficiency(PCE)of NiOxbased inverted IPSCs increased from 19.25%to 20.82%with the open-circuit voltage enhanced from 1.164 V to 1.230 V.The release of strain also improved the stability of CsPbI_(2.85)Br_(0.15)perovskite films and devices.展开更多
The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycl...The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.展开更多
Colloidal molecules exhibit unique electronic,optical,and magnetic properties owing to their molecular-like configurations and coupling effects,making them promising building blocks for multifunctional materials.Howev...Colloidal molecules exhibit unique electronic,optical,and magnetic properties owing to their molecular-like configurations and coupling effects,making them promising building blocks for multifunctional materials.However,achieving precise and controllable assembly of isotropic nanoparticles with high yields remains a great challenge.In this study,we present a synergistic strategy that integrates molecular dynamics simulations with interpretable machine learning to develop a programmable assembly system based on block copolymers and DNA-functionalized nanoparticles.Our simulation results reveal that block copolymer modification facilitates stepwise control over surface phase separation and nanoparticle coassembly,thereby enhancing structural stability and efficiently suppressing disordered aggregation of atom-like nanoparticles.Furthermore,we demonstrated that precise,controllable,and programmable assembly of colloidal molecules can be achieved through rational DNA sequence design.SHapley Additive exPlanations(SHAP)analysis identified key structural descriptors that govern assembly outcomes and elucidated their underlying mechanistic roles.This work not only deepens the understanding of colloidal molecule assembly mechanisms but also lays a theoretical foundation for the rational design of functional colloidal architectures in nanomaterial science.展开更多
An in-depth understanding of the hydration mechanism of tricalcium silicate is an important basis for optimizing cement strength development.In this study,the adsorption of water molecules onto the M3-C3S(001)surface ...An in-depth understanding of the hydration mechanism of tricalcium silicate is an important basis for optimizing cement strength development.In this study,the adsorption of water molecules onto the M3-C3S(001)surface at different water coverage levels(θ=1/5,2/5,3/5,4/5,and 1)was investigated using first-principles calculations.The results demonstrate that the conclusions obtained for single water molecule adsorption cannot be fully applied to multiple water molecule adsorption.The total adsorption energies become more negative with increasing water coverage,while the average adsorption energy of each water molecule becomes more positive with increasing water coverage.The water–water interactions reduce the water–surface interactions and are responsible for the anticooperative adsorption of multiple water molecules onto M3-C_(3)S(001).The formation of Ca–OH(–Ca)bonds favors the detachment of Ca from co-valent oxygen,which reveals the significant role of dissociative adsorption.This work aims to extend the water adsorption study on M3-C3S(001)from single water molecule adsorption to multiple water molecule adsorption,providing more detailed insights into the initial water reaction on the C3S surface.展开更多
With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk che...With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk chemicals predominantly depend on conventional fossil fuel-based chemical refining processes.This dependence poses a substantial challenge to both environmental sustainability and energy resources[1].An example of this issue is the synthesis of hydroxylamine(NH2OH).展开更多
In recent years,the ternary strategy of adding a vip molecule to the active layer has been proven to be effective for improving the performance of organic solar cells(OSCs).Isomerization engineering of the vip mol...In recent years,the ternary strategy of adding a vip molecule to the active layer has been proven to be effective for improving the performance of organic solar cells(OSCs).Isomerization engineering of the vip molecule is a simple method to increase the amount of promising material,but there are only limited reports,and the structure-property relationships are still unclear.In this work,we synthesized three isomers named BTA5-F-o,BTA5-F-m,and BTA5-F-p,with different fluorine substitution positions,to study the influence of isomerization on the photovoltaic performance.After introducing them as the third components to the classic host system PM6:Y6,all three ternary devices showed improved power conversion efficiency(PCEs)compared to the binary system(PCE of 17.46%).The ternary OSCs based on BTA5-F-o achieved a champion PCE of 19.11%,while BTA5-F-m and BTA5-F-p realized PCEs of 18.65%and 18.45%,respectively.Mechanism studies have shown that the dipole moment of the BTA5-F-o end group is closer to that of the Y6 end group,despite the three isomers with almost identical energy levels and optical properties.It is indicated that the electron attraction ability of BTA5-F-o best matches that of Y6,which leads to the higher charge mobility,less charge recombination,and stronger exciton dissociation and extraction ability in the ternary blend system.This study suggests that rationally adjusting the position of substituents in the terminal group can be an effective way to construct nonfullerene vip acceptors to achieve highly efficient ternary OSCs.展开更多
Hepatocellular carcinoma(HCC)is a primary malignant tumor of the liver and one of the most common malignant tumors,as well as the third leading cause of cancer-related death.In recent years,immune checkpoint inhibitor...Hepatocellular carcinoma(HCC)is a primary malignant tumor of the liver and one of the most common malignant tumors,as well as the third leading cause of cancer-related death.In recent years,immune checkpoint inhibitors have emerged as a key strategy in cancer treatment.However,anti-programmed cell death 1/programmed death ligand 1 therapies,one of the main immunotherapeutic approaches,only elicit a response in only approximately 20%of advanced HCC.This suggests that there may be other immune checkpoints playing important roles in HCC immunotherapy.Recent studies have highlighted Signal regulatory protein alpha(SIRPα)is a phagocytic checkpoint in macrophages and other immune cells,as a promising novel therapeutic target in tumor immunotherapy.This review summarizes current progress on SIRPαin HCC and identifies key challenges for future related research.展开更多
Immunotherapy has transformed cancer treatment,marked by the approval of numerous antibody-based drugs.However,the limitations of antibodies in pharmacokinetics including long half-lives,limited oral bioavailability a...Immunotherapy has transformed cancer treatment,marked by the approval of numerous antibody-based drugs.However,the limitations of antibodies in pharmacokinetics including long half-lives,limited oral bioavailability and immunogenicity,have prompted the pursuit of small molecule-based immunotherapy.Traditional drug discovery strategies,which focus on blocking protein activity through inhibitors,face persistent hurdles,such as reliance on accessible binding pockets,poor selectivity,and the emergence of drug resistance.Targeted protein degradation(TPD)technologies have emerged as powerful tools to address these limitations,offering significant therapeutic advantages over conventional inhibition strategies,particularly for historically "undruggable" targets.In recent years,small molecule-based protein degraders have rapidly advanced in cancer immunotherapy.In this review,we highlight recent progress in TPD-driven small-molecule drug discovery and summarize the application of these technologies in cancer immunotherapy,including degraders targeting PD-1/PD-L1,chemokine receptors,IDO1,AhR,and others.展开更多
Circularly polarized luminescence(CPL)-active materials have a wide range of technological applications.Traditionally,creating CPL-active materials relies on the use of chiral luminophores.In contrast,supramolecular a...Circularly polarized luminescence(CPL)-active materials have a wide range of technological applications.Traditionally,creating CPL-active materials relies on the use of chiral luminophores.In contrast,supramolecular assembly introduces an innovative and promising strategy for developing CPL-active materials not only from chiral luminophores but also from achiral species.This approach significantly enriches the diversity of CPL-active materials.It also offers an effective means to optimize the performance of CPL-active materials,such as enhancing the asymmetry factor|glum|.Compared to polymers,the assembly of small molecules is generally easier to control.This review systematically summarizes the recent progress and developments in CPL from small-molecule assemblies,particularly focusing on differences,merits,and demerits of three typical assembly modes.The aim is to provide valuable insights for the future development of chiroptical materials.展开更多
Enhanced mass concentrations of aromatic-derived secondary organic aerosol(SOA)are frequently observed during humid-haze events.However,the influencing mechanism of relative humidity(RH)in aromatic-derived SOA formati...Enhanced mass concentrations of aromatic-derived secondary organic aerosol(SOA)are frequently observed during humid-haze events.However,the influencing mechanism of relative humidity(RH)in aromatic-derived SOA formation remains incompletely understood.Here,the RH dependence of SOA formation in the presence of NOx was explored by a series of chamber experiments for toluene(TOL)and 1,3,5-trimethylbenzene(TMB)photooxidation.The yield of TOL SOA and TMB SOA increased by 221%and 52%with increasing RH from~8%to~70%,respectively.Analytical results from a high-resolution mass spectrometer showed that SOA constituents with high oxygen content(O/C>0.6)were more abundant in SOA formed in the~70%RH experiment.The elevated yields and O/C of SOA could be attributed to the promoted formation and particle-phase diffusivity of highly oxidized molecules.In addition,in comparison with TMB,TOL could produce more unsaturated aldehydes,which are oxidized into carboxylic acids with high O/C,leading to a more sensitive response of TOL SOA formation to the change in RH.Our work provides mechanistic insights into RH roles in aromatic SOA formation and is helpful for a better understanding of humid-haze events.展开更多
This paper provides a systematic review of Matrix-Assisted Laser Desorption/Ionization-Mass Spectrometry Imaging(MALDI-MSI),encompassing its technical principles,experimental workflows,matrix optimization strategies,a...This paper provides a systematic review of Matrix-Assisted Laser Desorption/Ionization-Mass Spectrometry Imaging(MALDI-MSI),encompassing its technical principles,experimental workflows,matrix optimization strategies,and recent advancements in plant science applications.It highlights the method's groundbreaking applications in spatial mapping of plant metabolites,dynamic hormone monitoring,and functional studies of tissue microdomains,while offering critical insights into current technical limitations and future research directions.展开更多
Organic compounds are promising electrode materials for aqueous zinc-ion batteries(AZIBs) but largely suffer from poor rate and cycling performance.This work reports that the push-pull electron effect of organic compo...Organic compounds are promising electrode materials for aqueous zinc-ion batteries(AZIBs) but largely suffer from poor rate and cycling performance.This work reports that the push-pull electron effect of organic compounds could be used to tune the electrochemical performance of AZIB s.Hexaazatriphenylene-based(HATN) small molecules with different withdrawing or donating groups were synthesized and used as electrodes for AZIBs.Compared to the hydrogen atoms and electrondonating methyl groups,the electron-withdrawing fluorine atoms endow HATN-based small molecule(HATN-6F)with a much-improved redox platform,rate performance and cycling stability.The fluorinated electrode HATN-6F potently amplifies and stabilizes the kinetics of cation co-(de)insertion reactions,concurrently enhancing the conductivity and electron affinity,resulting in improved rate performance and enhanced cycling stability.The combination of theoretical calculations and experimental characterization confirms that the fluorine-rich peripheral environment effectively modifies the distribution of conjugated electrons in HATN,enhancing its affinity for zinc ions and improving its capacity for cations zinc storage.This work demonstrates a new avenue for the design and synthesis of organic electrode with excellent electrochemical performance for ZIBs.展开更多
Using cumulative quantum mechanics(CQM)and the method of generalized mathematical transfer(MGMT),we analytically study quantum nanometer cumulative-dissipative structures(CDS)and the forces arising within them,which f...Using cumulative quantum mechanics(CQM)and the method of generalized mathematical transfer(MGMT),we analytically study quantum nanometer cumulative-dissipative structures(CDS)and the forces arising within them,which focus nanostructures into regular,fractalized systems—cumulative-dissipative standing hydrogen-like excitons(atoms,molecules,lines,surfaces)and flickering crystals we discovered for the first time.(1)We demonstrate the formation of Vysikaylo standing excitons on permittivity[ε(r)]inhomogeneities in diamond in the nanoscale regions of foreign atoms.(2)For the first time,we solve the problem of measuringε(r)profiles in inhomogeneous nanoscale structures using Raman spectra(RS)[with an accuracy of up to 99.9%forε(r)and a step of up to 0.3 nm depending on the distance from the impurity atom(boron)].(3)Using our theory of Vysikaylo standing excitons,we explain the experimental observation of the degeneracy of electron spectra in standing excitons with respect to the principal quantum number n and n−1/2.By comparing the theory and experimental observations of RS in diamonds doped with boron,we solve the problem(that we formulated previously)between the de Broglie hypothesis and the classical new quantum mechanics of Dirac(which limits the-functions,or prohibits symmetric de Broglie half-waves in spherically and cylindrically symmetric quantum resonators)in favor of the de Broglie hypothesis.Based on the works of Wannier and Mott,we refine the definition of the permittivity of nanocrystals as a coefficient in electric potentials[U(r)→ε(r)U(r)]rather than electric fields[D(r)=ε(r)E(r)].We construct the most complete theory of the chemical doping of crystals(using the example of group IV crystals doped with group III and V atoms).For the first time,we raise the question of the quantum cleaning of crystals or the accumulation of dopant atoms.展开更多
An electrostatic trap for polar molecules is proposed. Loading and trapping of polar molecules can be realized by applying different voltages to the two electrodes of the trap. For ND3 molecular beams centered at -10 ...An electrostatic trap for polar molecules is proposed. Loading and trapping of polar molecules can be realized by applying different voltages to the two electrodes of the trap. For ND3 molecular beams centered at -10 m/s, a high loading efficiency of -67% can be obtained, as confirmed by our Monte Carlo simulations. The volume of our trap is as large as ,-3.6 cm3, suitable for study of the adiabatic cooling of trapped molecules. Our simulations indicate that trapped ND3 molecules can be cooled from -23.3 mK to 1.47 mK by reducing the trapping voltages on the electrodes from 50.0 kV to 1.00 kV.展开更多
Acceptor-donor-acceptor(A-D-A)type molecules,of which the novel non-fused azacyclic end-group pyrazoli-nones were modified with chlorine substitution on the phenyl ring,were synthesized.The non-fused azacyclic end-gro...Acceptor-donor-acceptor(A-D-A)type molecules,of which the novel non-fused azacyclic end-group pyrazoli-nones were modified with chlorine substitution on the phenyl ring,were synthesized.The non-fused azacyclic end-group py-razolinones have the advantages of simple synthesis steps,low cost and environmental friendliness,compared to the classical end-group dicyanomethyleneindianone.The properties of the synthesized A-D-A type molecules with non-fused azacyclic end groups were characterized by theoretical calculation,UV-vis absorption,cyclic voltammetry,X-ray diffraction and space charge limited current.It is shown that the strong UV-vis absorptions of the synthesized A-D-A type molecules are located in the wavelength range of 500~700 nm,with a moderate band gap of nearly 1.7 eV.At the same time,the influence of end-group chlorination on the properties of A-D-A type molecules was compared and explored.It is proven that this kind of A-D-A type molecule with non-fused azacyclic end groups has the potential to be applied as interfacial modified layer of the active layer in perovskite solar cell devices.展开更多
CRISPR-based tran-scription regulators(CRISPR-TRs)have revolutionized the field of synthetic biol-ogy by enabling tar-geted activation or repression of any de-sired gene.However,the majority of exist-ing inducible CRI...CRISPR-based tran-scription regulators(CRISPR-TRs)have revolutionized the field of synthetic biol-ogy by enabling tar-geted activation or repression of any de-sired gene.However,the majority of exist-ing inducible CRISPR-TRs are limited by their dependence on specific sequences,which restricts their flex-ibility and controllability in genetic engineering applications.In this study,we proposed a novel strategy to construct sequence-independent inducible CRISPR-TRs,which is achieved by the design of stem loop 2 in the single guide RNA(sgRNA).Under this strategy,by utiliz-ing toehold-mediated strand displacement(TMSD)reactions between small endogenous molecules(miR-20a and TK1 mRNA)and bridge RNA(bRNA)to link bRNA with sgRNA,we achieved synergistic transcriptional activation of VP64 and p65-HSF1 in response to en-dogenous molecules.To enable response to exogenous molecules,we added response se-quences and bRNA sequences to the 5'end of sgRNA to block sgRNA activity,and achieved activation of sgRNA by shearing the response sequence,called sequential unlimited interlock-ing(SUI).Compared with conventional sequence-restricted interlocking(spacer-blocking hairpin(SBH)),the transcriptional activation ratio between response and non-response to the Cas6A protein using our approach was increased by 2.28-fold.Our work presents a modular and versatile framework for endogenous and exogenous molecule-responsive CRISPR-TRs in mammalian cells,without limitations imposed by sequence dependence.展开更多
基金supported by the financial support from the National Research Foundation,Singapore,under its Singapore-China Joint Flagship Project(Clean Energy).
文摘Aqueous Zn-iodine batteries(ZIBs)face the formidable challenges towards practical implementation,including metal corrosion and rampant dendrite growth on the Zn anode side,and shuttle effect of polyiodide species from the cathode side.These challenges lead to poor cycle stability and severe self-discharge.From the fabrication and cost point of view,it is technologically more viable to deploy electrolyte engineering than electrode protection strategies.More importantly,a synchronous method for modulation of both cathode and anode is pivotal,which has been often neglected in prior studies.In this work,cationic poly(allylamine hydrochloride)(Pah^(+))is adopted as a low-cost dual-function electrolyte additive for ZIBs.We elaborate the synchronous effect by Pah^(+)in stabilizing Zn anode and immobilizing polyiodide anions.The fabricated Zn-iodine coin cell with Pah^(+)(ZnI_(2) loading:25 mg cm^(−2))stably cycles 1000 times at 1 C,and a single-layered 3.4 cm^(2) pouch cell(N/P ratio~1.5)with the same mass loading cycles over 300 times with insignificant capacity decay.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFE0134200)the National Natural Science Foundation of China(Grant No.12204214)+1 种基金the Fundamental Research Funds for the Central Universities(Grant No.GK202207012)QCYRCXM-2022-241。
文摘Multi-electron and multi-orbital effects play a crucial role in the interaction of strong laser fields with complex molecules.Here,multi-electron effects encompass not only electron-electron Coulomb interactions and exchangecorrelation effects but also the interference between the dynamics of different electron wave packets.
基金supported by National Natural Science Foundation of China(52372249 and 52102329)the support from the Program of Shanghai Academic Research Leader(21XD1424400)。
文摘Polyethylene oxide(PEO)-based solid-state polymer electrolytes(SPE)face the challenges of insufficient ionic conductivity and uncontrollable Li dendrite growth.The filler strategy can reinforce anode interface stability,but at the cost of a large filler content(usually more than 10 wt%).This would increase the granular sensation,gravitational separation risk,and electrolyte membrane roughness with the creation of inhomogeneous Li^(+)transport channels between filler and polymer.Herein,we propose a trace filling strategy to address the above problems by introducing an amphoteric molecule L-Cysteine(LCy)as an eco-friendly and low-cost electrolyte additive.Only trace amount of LCy is required and integrated into PEO to form a homogenous,granule-less SPE with enhanced ionic conductivity and dendrite suppression capability.The ionic conductivity increases to 0.54 mS cm^(-1)at 60℃ after introducing only 1 wt%LCy.The amphotericity of LCy with basic–NH_(2)and acidic–COOH groups can promote the dissociation of Li salt and release more free Li ions through Lewis acid-base synergy,as well as the formation of multiple hydrogen bonds between PEO and LCy.The trace LCy additive swiftly leads to the formation of more ionic conductive interphases at both the anode and cathode sides.The composite SPE enables the stable cycling of Li metal for over 1400 h at 0.2 mA cm^(-2)and sustains a maximum current density up to 1.4 mA cm^(-2)in Li Li symmetric cells.The corresponding all-solid-state Li||FeF_(3)full cells exhibit a high specific capacity up to 567 mA h g^(-1)at 0.2 C and stable cycling performance for at least 700 cycles at 0.5 C with a high capacity retention.The excellent interface compatibility also guarantees the achievement of highcapacity Li-Fe-F conversion reaction even under the thin electrolyte membrane thickness and largerscale pouch cell configuration.
基金financial support from the National Natural Science Foundation of China (Grant No.22375190)。
文摘This study preliminarily investigates the structure-activity relationships of novel [5,6]-fused ring energetic materials derived from the 6-nitro-7-azido-pyrazol [3,4-d][1,2,3]triazine 2-oxide(ICM-103) skeleton, emphasizing the role of functional group substitution in tailoring key properties such as detonation performance and mechanical sensitivity. Strategic incorporation of nitrogen-rich substituents(e.g., hydrazine, guanidine) into the 1,2,3-triazine 2-oxide framework yielded compounds with diverse performance characteristics. Notably, compound 2 demonstrates energy performance(D = 8916 m·s^(-1) and P = 36.80 GPa) comparable to RDX, yet with lower mechanical sensitivity(IS = 37 J). Theoretical calculations show that the properties of the substituents themselves and their coupling with the molecular skeleton jointly determine the key properties of the target molecules. This study provides a framework for the customized design of energetic materials by linking the chemical properties of substituents with the performance parameters of target molecules. These findings highlight the potential of local molecular structural modification driven by structure-activity relationship analysis in promoting the development of next-generation energetic materials and lay a solid foundation for future research in this field.
基金financial support of National Key Research and Development Program of China(Grant No.2022YFB04200302)joint funds of National Natural Science Foundation of China(Grant No.62104115)+5 种基金National Natural Science Foundation of China(Grant No.U21A2072)Overseas Expertise Introduction Project for Discipline Innovation of Higher Education of China(Grant No.B16027)Key R&D Program of Hebei Province(No.19214301D)Yunnan Provincial Science and Technology Project at Southwest United Graduate School(No.202302A0370009)Haihe Laboratory of Sustainable Chemical TransformationsFundamental Research Funds for the Central Universities,Nankai University。
文摘The tensile strain in inorganic perovskite films induced by thermal annealing is one of the primary factors contributing to the inefficiency and instability of inorganic perovskite solar cells(IPSCs),which reduces the defect formation energy.Here,a flexible molecule 5-maleimidovaleric acid(5-MVA)was introduced as a strain buffer to release the residual strain of CsPbI_(2.85)Br_(0.15)perovskite.Maleic anhydride and carboxyl groups in 5-MVA interact strongly with the uncoordinated Pb^(2+)through Lewis acid-base reaction,thus tightly“pull”the perovskite lattice.The in-between soft carbon chain increased the structural flexibility of CsPbI_(2.85)Br_(0.15)perovskite materials,which effectively relieved the intrinsic internal strain of CsPbI_(2.85)Br_(0.15),resisted the corrosion of external strain,and also reduced the formation of defects such as VIand Pb0.In addition,the introduction of 5-MVA improved crystal quality,passivated residual defects,and narrowed energy level barriers.Eventually,power conversion efficiency(PCE)of NiOxbased inverted IPSCs increased from 19.25%to 20.82%with the open-circuit voltage enhanced from 1.164 V to 1.230 V.The release of strain also improved the stability of CsPbI_(2.85)Br_(0.15)perovskite films and devices.
文摘The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.
基金financially supported by the National Natural Science Foundation of China(Nos.92477118 and 22173045)the Postgraduate Research and Practice Innovation Program of Jiangsu Province(No.KYCX25_0188)。
文摘Colloidal molecules exhibit unique electronic,optical,and magnetic properties owing to their molecular-like configurations and coupling effects,making them promising building blocks for multifunctional materials.However,achieving precise and controllable assembly of isotropic nanoparticles with high yields remains a great challenge.In this study,we present a synergistic strategy that integrates molecular dynamics simulations with interpretable machine learning to develop a programmable assembly system based on block copolymers and DNA-functionalized nanoparticles.Our simulation results reveal that block copolymer modification facilitates stepwise control over surface phase separation and nanoparticle coassembly,thereby enhancing structural stability and efficiently suppressing disordered aggregation of atom-like nanoparticles.Furthermore,we demonstrated that precise,controllable,and programmable assembly of colloidal molecules can be achieved through rational DNA sequence design.SHapley Additive exPlanations(SHAP)analysis identified key structural descriptors that govern assembly outcomes and elucidated their underlying mechanistic roles.This work not only deepens the understanding of colloidal molecule assembly mechanisms but also lays a theoretical foundation for the rational design of functional colloidal architectures in nanomaterial science.
基金supported by the Young Elite Scientists Sponsorship Program by CAST(No.2023QNRC001)Natural Science Foundation of Hunan Province,China(No.2024JJ2074)supported in part by the High Performance Computing Center of Central South University,China and the Pawsey Supercomputing Centre with funding from the Australian Government and the Government of Western Australia.
文摘An in-depth understanding of the hydration mechanism of tricalcium silicate is an important basis for optimizing cement strength development.In this study,the adsorption of water molecules onto the M3-C3S(001)surface at different water coverage levels(θ=1/5,2/5,3/5,4/5,and 1)was investigated using first-principles calculations.The results demonstrate that the conclusions obtained for single water molecule adsorption cannot be fully applied to multiple water molecule adsorption.The total adsorption energies become more negative with increasing water coverage,while the average adsorption energy of each water molecule becomes more positive with increasing water coverage.The water–water interactions reduce the water–surface interactions and are responsible for the anticooperative adsorption of multiple water molecules onto M3-C_(3)S(001).The formation of Ca–OH(–Ca)bonds favors the detachment of Ca from co-valent oxygen,which reveals the significant role of dissociative adsorption.This work aims to extend the water adsorption study on M3-C3S(001)from single water molecule adsorption to multiple water molecule adsorption,providing more detailed insights into the initial water reaction on the C3S surface.
基金supported by the National Natural Science Foundation of China(Nos.22175174 and 52332007).
文摘With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk chemicals predominantly depend on conventional fossil fuel-based chemical refining processes.This dependence poses a substantial challenge to both environmental sustainability and energy resources[1].An example of this issue is the synthesis of hydroxylamine(NH2OH).
基金support from the National Natural Science Foundation of China(62204146,52303259)the Start-up Grant of Henan University of Technology(2023BS035)。
文摘In recent years,the ternary strategy of adding a vip molecule to the active layer has been proven to be effective for improving the performance of organic solar cells(OSCs).Isomerization engineering of the vip molecule is a simple method to increase the amount of promising material,but there are only limited reports,and the structure-property relationships are still unclear.In this work,we synthesized three isomers named BTA5-F-o,BTA5-F-m,and BTA5-F-p,with different fluorine substitution positions,to study the influence of isomerization on the photovoltaic performance.After introducing them as the third components to the classic host system PM6:Y6,all three ternary devices showed improved power conversion efficiency(PCEs)compared to the binary system(PCE of 17.46%).The ternary OSCs based on BTA5-F-o achieved a champion PCE of 19.11%,while BTA5-F-m and BTA5-F-p realized PCEs of 18.65%and 18.45%,respectively.Mechanism studies have shown that the dipole moment of the BTA5-F-o end group is closer to that of the Y6 end group,despite the three isomers with almost identical energy levels and optical properties.It is indicated that the electron attraction ability of BTA5-F-o best matches that of Y6,which leads to the higher charge mobility,less charge recombination,and stronger exciton dissociation and extraction ability in the ternary blend system.This study suggests that rationally adjusting the position of substituents in the terminal group can be an effective way to construct nonfullerene vip acceptors to achieve highly efficient ternary OSCs.
基金Supported by the National Key Sci-Tech Special Project of China,No.2018ZX10302207the Beijing Natural Science Foundation,No.7222191+3 种基金the Beijing Natural Science Foundation,No.7244426the Fundamental Research Funds for the Central Universities,Peking University,No.PKU2024XGK005the Peking University Medicine Seed Fund for Interdisciplinary Research,No.BMU2021MX007 and No.BMU2022MX001Fundamental Research Funds for the Central Universities,Peking University People’s Hospital Scientific Research Development Funds,No.RDY2020-06 and No.RDJ2022-14.
文摘Hepatocellular carcinoma(HCC)is a primary malignant tumor of the liver and one of the most common malignant tumors,as well as the third leading cause of cancer-related death.In recent years,immune checkpoint inhibitors have emerged as a key strategy in cancer treatment.However,anti-programmed cell death 1/programmed death ligand 1 therapies,one of the main immunotherapeutic approaches,only elicit a response in only approximately 20%of advanced HCC.This suggests that there may be other immune checkpoints playing important roles in HCC immunotherapy.Recent studies have highlighted Signal regulatory protein alpha(SIRPα)is a phagocytic checkpoint in macrophages and other immune cells,as a promising novel therapeutic target in tumor immunotherapy.This review summarizes current progress on SIRPαin HCC and identifies key challenges for future related research.
基金supported by the National Natural Science Foundation of China(No.82173668,82373706).
文摘Immunotherapy has transformed cancer treatment,marked by the approval of numerous antibody-based drugs.However,the limitations of antibodies in pharmacokinetics including long half-lives,limited oral bioavailability and immunogenicity,have prompted the pursuit of small molecule-based immunotherapy.Traditional drug discovery strategies,which focus on blocking protein activity through inhibitors,face persistent hurdles,such as reliance on accessible binding pockets,poor selectivity,and the emergence of drug resistance.Targeted protein degradation(TPD)technologies have emerged as powerful tools to address these limitations,offering significant therapeutic advantages over conventional inhibition strategies,particularly for historically "undruggable" targets.In recent years,small molecule-based protein degraders have rapidly advanced in cancer immunotherapy.In this review,we highlight recent progress in TPD-driven small-molecule drug discovery and summarize the application of these technologies in cancer immunotherapy,including degraders targeting PD-1/PD-L1,chemokine receptors,IDO1,AhR,and others.
基金support from the National Natural Science Foundation of China(52473192)。
文摘Circularly polarized luminescence(CPL)-active materials have a wide range of technological applications.Traditionally,creating CPL-active materials relies on the use of chiral luminophores.In contrast,supramolecular assembly introduces an innovative and promising strategy for developing CPL-active materials not only from chiral luminophores but also from achiral species.This approach significantly enriches the diversity of CPL-active materials.It also offers an effective means to optimize the performance of CPL-active materials,such as enhancing the asymmetry factor|glum|.Compared to polymers,the assembly of small molecules is generally easier to control.This review systematically summarizes the recent progress and developments in CPL from small-molecule assemblies,particularly focusing on differences,merits,and demerits of three typical assembly modes.The aim is to provide valuable insights for the future development of chiroptical materials.
基金supported by the National Key Research and Development Program of China (Grant No. 2023YFC3706203)the National Natural Science Foundation of China (Grant Nos. 91644214, 22361162668, and 22406109)+1 种基金the China Postdoctoral Science Foundation (Grant No. 2024M751797)Shandong Postdoctoral Science Foundation (SDCX-ZG-202400178)
文摘Enhanced mass concentrations of aromatic-derived secondary organic aerosol(SOA)are frequently observed during humid-haze events.However,the influencing mechanism of relative humidity(RH)in aromatic-derived SOA formation remains incompletely understood.Here,the RH dependence of SOA formation in the presence of NOx was explored by a series of chamber experiments for toluene(TOL)and 1,3,5-trimethylbenzene(TMB)photooxidation.The yield of TOL SOA and TMB SOA increased by 221%and 52%with increasing RH from~8%to~70%,respectively.Analytical results from a high-resolution mass spectrometer showed that SOA constituents with high oxygen content(O/C>0.6)were more abundant in SOA formed in the~70%RH experiment.The elevated yields and O/C of SOA could be attributed to the promoted formation and particle-phase diffusivity of highly oxidized molecules.In addition,in comparison with TMB,TOL could produce more unsaturated aldehydes,which are oxidized into carboxylic acids with high O/C,leading to a more sensitive response of TOL SOA formation to the change in RH.Our work provides mechanistic insights into RH roles in aromatic SOA formation and is helpful for a better understanding of humid-haze events.
文摘This paper provides a systematic review of Matrix-Assisted Laser Desorption/Ionization-Mass Spectrometry Imaging(MALDI-MSI),encompassing its technical principles,experimental workflows,matrix optimization strategies,and recent advancements in plant science applications.It highlights the method's groundbreaking applications in spatial mapping of plant metabolites,dynamic hormone monitoring,and functional studies of tissue microdomains,while offering critical insights into current technical limitations and future research directions.
基金financially supported by the Guangdong-Hong Kong-Macao Joint Innovation Fund(No.2024A0505040001)Basic Research Project of the Science and Technology Innovation Commission of Shenzhen(No.JCYJ20220818100418040)+2 种基金the National Natural Science Foundation of China(Nos.92372114,21875097 and 22409216)the Guangdong Basic and Applied Basic Research(No.2023A1515010035)the Jiangyin-SUSTech Innovation Fund(No.OR2404014)
文摘Organic compounds are promising electrode materials for aqueous zinc-ion batteries(AZIBs) but largely suffer from poor rate and cycling performance.This work reports that the push-pull electron effect of organic compounds could be used to tune the electrochemical performance of AZIB s.Hexaazatriphenylene-based(HATN) small molecules with different withdrawing or donating groups were synthesized and used as electrodes for AZIBs.Compared to the hydrogen atoms and electrondonating methyl groups,the electron-withdrawing fluorine atoms endow HATN-based small molecule(HATN-6F)with a much-improved redox platform,rate performance and cycling stability.The fluorinated electrode HATN-6F potently amplifies and stabilizes the kinetics of cation co-(de)insertion reactions,concurrently enhancing the conductivity and electron affinity,resulting in improved rate performance and enhanced cycling stability.The combination of theoretical calculations and experimental characterization confirms that the fluorine-rich peripheral environment effectively modifies the distribution of conjugated electrons in HATN,enhancing its affinity for zinc ions and improving its capacity for cations zinc storage.This work demonstrates a new avenue for the design and synthesis of organic electrode with excellent electrochemical performance for ZIBs.
文摘Using cumulative quantum mechanics(CQM)and the method of generalized mathematical transfer(MGMT),we analytically study quantum nanometer cumulative-dissipative structures(CDS)and the forces arising within them,which focus nanostructures into regular,fractalized systems—cumulative-dissipative standing hydrogen-like excitons(atoms,molecules,lines,surfaces)and flickering crystals we discovered for the first time.(1)We demonstrate the formation of Vysikaylo standing excitons on permittivity[ε(r)]inhomogeneities in diamond in the nanoscale regions of foreign atoms.(2)For the first time,we solve the problem of measuringε(r)profiles in inhomogeneous nanoscale structures using Raman spectra(RS)[with an accuracy of up to 99.9%forε(r)and a step of up to 0.3 nm depending on the distance from the impurity atom(boron)].(3)Using our theory of Vysikaylo standing excitons,we explain the experimental observation of the degeneracy of electron spectra in standing excitons with respect to the principal quantum number n and n−1/2.By comparing the theory and experimental observations of RS in diamonds doped with boron,we solve the problem(that we formulated previously)between the de Broglie hypothesis and the classical new quantum mechanics of Dirac(which limits the-functions,or prohibits symmetric de Broglie half-waves in spherically and cylindrically symmetric quantum resonators)in favor of the de Broglie hypothesis.Based on the works of Wannier and Mott,we refine the definition of the permittivity of nanocrystals as a coefficient in electric potentials[U(r)→ε(r)U(r)]rather than electric fields[D(r)=ε(r)E(r)].We construct the most complete theory of the chemical doping of crystals(using the example of group IV crystals doped with group III and V atoms).For the first time,we raise the question of the quantum cleaning of crystals or the accumulation of dopant atoms.
基金supported by the National Natural Science Foundation of China(Grant Nos.10674047,10804031,10904037,10974055,11034002,and 11274114)the National Key Basic Research and Development Program of China(Grant Nos.2006CB921604 and 2011CB921602)+1 种基金the Basic Key Program of Shanghai Municipality,China(Grant No.07JC14017)the Shanghai Leading Academic Discipline Project,China(Grant No.B408)
文摘An electrostatic trap for polar molecules is proposed. Loading and trapping of polar molecules can be realized by applying different voltages to the two electrodes of the trap. For ND3 molecular beams centered at -10 m/s, a high loading efficiency of -67% can be obtained, as confirmed by our Monte Carlo simulations. The volume of our trap is as large as ,-3.6 cm3, suitable for study of the adiabatic cooling of trapped molecules. Our simulations indicate that trapped ND3 molecules can be cooled from -23.3 mK to 1.47 mK by reducing the trapping voltages on the electrodes from 50.0 kV to 1.00 kV.
文摘Acceptor-donor-acceptor(A-D-A)type molecules,of which the novel non-fused azacyclic end-group pyrazoli-nones were modified with chlorine substitution on the phenyl ring,were synthesized.The non-fused azacyclic end-group py-razolinones have the advantages of simple synthesis steps,low cost and environmental friendliness,compared to the classical end-group dicyanomethyleneindianone.The properties of the synthesized A-D-A type molecules with non-fused azacyclic end groups were characterized by theoretical calculation,UV-vis absorption,cyclic voltammetry,X-ray diffraction and space charge limited current.It is shown that the strong UV-vis absorptions of the synthesized A-D-A type molecules are located in the wavelength range of 500~700 nm,with a moderate band gap of nearly 1.7 eV.At the same time,the influence of end-group chlorination on the properties of A-D-A type molecules was compared and explored.It is proven that this kind of A-D-A type molecule with non-fused azacyclic end groups has the potential to be applied as interfacial modified layer of the active layer in perovskite solar cell devices.
基金supported by the National Natural Science Foundation of China(No.22073090,No.21991132,No.52021002)the National Key R&D Program of China(No.2020YFA0710700)the Funds of Youth Innovation Promotion Association,and the Fundamental Research Funds for the Central Universities(WK3450000009).
文摘CRISPR-based tran-scription regulators(CRISPR-TRs)have revolutionized the field of synthetic biol-ogy by enabling tar-geted activation or repression of any de-sired gene.However,the majority of exist-ing inducible CRISPR-TRs are limited by their dependence on specific sequences,which restricts their flex-ibility and controllability in genetic engineering applications.In this study,we proposed a novel strategy to construct sequence-independent inducible CRISPR-TRs,which is achieved by the design of stem loop 2 in the single guide RNA(sgRNA).Under this strategy,by utiliz-ing toehold-mediated strand displacement(TMSD)reactions between small endogenous molecules(miR-20a and TK1 mRNA)and bridge RNA(bRNA)to link bRNA with sgRNA,we achieved synergistic transcriptional activation of VP64 and p65-HSF1 in response to en-dogenous molecules.To enable response to exogenous molecules,we added response se-quences and bRNA sequences to the 5'end of sgRNA to block sgRNA activity,and achieved activation of sgRNA by shearing the response sequence,called sequential unlimited interlock-ing(SUI).Compared with conventional sequence-restricted interlocking(spacer-blocking hairpin(SBH)),the transcriptional activation ratio between response and non-response to the Cas6A protein using our approach was increased by 2.28-fold.Our work presents a modular and versatile framework for endogenous and exogenous molecule-responsive CRISPR-TRs in mammalian cells,without limitations imposed by sequence dependence.
