Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/...Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/chemical stability.To enhance the performance of intrinsic g-CN,a supramolecular self-assembly strategy has been proposed to regulate the molecular structure of supramolecular precursors through non-covalent interactions across molecular building blocks,thereby optimizing the electronic structure of g-CN.This review provides a comprehensive overview of the recent progress in supramolecular self-assembly-derived graphitic carbon nitride(SM-CN)from both experimental and theoretical computational research in synthesis strategies,including synthesis methods and influencing factors,providing a theoretical foundation for the design of supramolecular assembly.It also discusses modification strategies,such as internal modification of the conjugated plane,interlayer optimization,and construction of heterointerfaces to improve the electronic structure of SM-CN owing to its unique layered structure.This review further summarizes the applications of SM-CN in environment and energy,including wastewater treatment,sterilization and disinfection/air purification,water splitting,H_(2)O_(2)production,organic synthesis/biomass conversion,CO_(2)reduction,photocatalytic coupling technology.Finally,perspectives and outlooks for the future development of SM-CN aim to inspire further innovation in the design and construction of high-performance SM-CN for broader applications.展开更多
Constructing nanofibers with specific therapeutic effects against cancer is a challenge.Here,we present the synthesis approach and application prospects of supramolecular nanofibers,which are based on cucurbit[8]uril(...Constructing nanofibers with specific therapeutic effects against cancer is a challenge.Here,we present the synthesis approach and application prospects of supramolecular nanofibers,which are based on cucurbit[8]uril(CB[8])as the host and terpyridine lanthanum ions metal complex as the vip,constructed by layer-by-layer self-assembly through supramolecular interaction.Moreover,nanofibers with lanthanide luminescence properties exhibit surprising pH-responsive deformation properties and antibacterial behavior.In the tumor micro-environment,the dramatic reduction in the size of the nanofibers enables specific and hierarchical release of anticancer drugs in tumor cells to exert an advanced therapeutic effect.In addition,the synergistic therapeutic efficacy was achieved by reducing the excess of Gram-positive and Gram-negative bacteria surrounding tumor cells.The novel supramolecular nanofibers with sequential drug release and combined therapeutic mode provide new guidance for the synthesis of drug carrier materials and direction for the promotion of nanomaterial-mediated cancer therapy.展开更多
Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments re...Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.展开更多
The abundant intracellular glutathione(GSH)in cancer cells severely undermines the therapeutic efficacy of different treatments due to their role in protecting cancer cells from the associated oxidative stress.Develop...The abundant intracellular glutathione(GSH)in cancer cells severely undermines the therapeutic efficacy of different treatments due to their role in protecting cancer cells from the associated oxidative stress.Developing a highly integrated system to consume GSH would help to improve the therapeutic outcomes.In this study,supramolecular prodrug self-assemblies(SPSAs)with IR825 loaded inside were developed to consume GSH via two-pronged pathways while augmenting the therapeutic potency of chemo/photothermal treatment.SPSAs were prepared using water-soluble pillar[6]arene(WP[6])as host units and H_(2)O_(2)-responsive nitrogen mustard prodrug,chlorambucil-(phenylboronic acid pinacol ester)conjugates(Cb-BE),as the vips.When SPSAs were internalized by cancer cells,the generation of quinone methide(QM)from Cb-BE and singlet oxygen(^(1)O_(2))from irradiation-activated IR825 could consume GSH in a concerted way.As such,the therapeutic efficacies of the released chlorambucil and the accompanied hyperthermia were augmented toward synergistically inhibiting tumor growth.展开更多
Molecular recognition directed self-assemblies from complementary molecular components, melamine and barbituric acid derivatives were studied by means of NMR, fluorescence, and TEM. It was found that both the process ...Molecular recognition directed self-assemblies from complementary molecular components, melamine and barbituric acid derivatives were studied by means of NMR, fluorescence, and TEM. It was found that both the process of the self-assembly and the morphologies of the result- ed self-assemblies could be mediated by modifying the structures of the molecular components used. The effect of the structures of the molecular components on the formation of the self-as- semblies was discussed in terms of intermolecular interactions.展开更多
Self-assembly of block copolymers(BCPs)is highly intricate and is adsorbing extensive experimental and simulation efforts to reveal it for maximizing structural order and device performances.The coarse-grained(CG)mole...Self-assembly of block copolymers(BCPs)is highly intricate and is adsorbing extensive experimental and simulation efforts to reveal it for maximizing structural order and device performances.The coarse-grained(CG)molecular dynamics(MD)simulation offers a microscopic angle to view the self-assembly of BCPs.Although some molecular details are sacrificed during CG processes,this method exhibits remarkable computational efficiency.In this study,a comprehensive CG model for polystyrene-block-poly(2-vinylpyridine),PS-b-P2VP,one of the most extensively studied BCPs for its high Flory-Huggins interaction parameter,is constructed,with parameters optimized using target values derived from all-atom MD simulations.The CG model precisely coincides with various classical self-assembling morphologies observed in experimental studies,matching the theoretical phase diagrams.Moreover,the conformational asymmetry of the experimental phase diagram is also clearly revealed by our simulation results,and the phase boundaries obtained from simulations are highly consistent with experimental results.The CG model is expected to extend to simulate the self-assembly behaviors of other BCPs in addition to PS-b-P2VP,thus increasing understanding of the microphase separation of BCPs from the molecular level.展开更多
UHMWPE fibers exhibit impressive modulus and strength,but they have not reached their theoretical limits.Researchers focus on molecular weight,orientation,and crystallinity of UHMWPE,yet their contributions to mechani...UHMWPE fibers exhibit impressive modulus and strength,but they have not reached their theoretical limits.Researchers focus on molecular weight,orientation,and crystallinity of UHMWPE,yet their contributions to mechanical properties are unclear.Molecular dynamics simulations are valuable but often limited by computational constraints.Our aim is to simulate higher molecular weights to better represent real UHMWPE fibers.We used Packmol and Polyply methodologies to construct PE systems,with Polyply reproducing more reasonable properties of UHMWPE fibers.Additionally,tensile simulations showed that orientation and crystallinity greatly impact Young's modulus more than molecular weight.Energy decomposition indicated that higher molecular weights lead to covalent bonds that can withstand more energy during stretching,thus increasing breaking strength.Combining simulations with machine learning,we found that orientation has the most significant impact on Young's modulus,contributing 60%,and molecular weight plays the most crucial role in determining the breaking strength,accounting for 65%.This study provides a theoretical basis and guidelines for enhancing UHMWPE's modulus and strength.展开更多
In this work,we proposed a strategy for the hydrolysis of native corn starch after the treatment of corn starch in an ionic liquid aqueous solution,and it is an awfully“green”and simple means to obtain starch with l...In this work,we proposed a strategy for the hydrolysis of native corn starch after the treatment of corn starch in an ionic liquid aqueous solution,and it is an awfully“green”and simple means to obtain starch with low molecular weight and amorphous state.X-ray diffraction results revealed that the natural starch crystalline region was largely disrupted by ionic liquid owing to the broken intermolecular and intramolecular hydrogen bonds.After hydrolysis,the morphology of starch changed from particles of native corn starch into little pieces,and their molecular weight could be effectively regulated during the hydrolysis process,and also the hydrolyzed starch samples exhibited decreased thermal stability with the extension of hydrolysis time.This work would counsel as a powerful tool for the development of native starch in realistic applications.展开更多
The coupling reactions of methanol and long-chain alkanes(n-dodecane,n-tetradecane and n-hexadecane)over CHA-type molecular sieves were studied in a fixed bed reactor.Over SAPO-34 and SSZ-13,it was found that the indu...The coupling reactions of methanol and long-chain alkanes(n-dodecane,n-tetradecane and n-hexadecane)over CHA-type molecular sieves were studied in a fixed bed reactor.Over SAPO-34 and SSZ-13,it was found that the induction period of methanol conversion was shortened by the introduction of long-chain alkanes.However,the addition of long-chain alkanes had little influence on the product distribution.Polymethylbenzenes and the derivatives were the main retained species on spent SSZ-13 catalyst,while adamantanes were the main retained species on SAPO-34.This indicates that coking species formation was mainly related to the further transformation of long-chain alkane/methanol coupling products at acid sites of the molecular sieve.These findings provide valuable information of long chain alkanes conversion and methanol reaction behavior of induction period over small pore CHA molecular sieves.展开更多
As a key component of shale oil,petroleum fractions,and chemical products,the oxidative pyrolysis behavior of paraffin directly influences energy conversion efficiency and the direction of process optimization.A deep ...As a key component of shale oil,petroleum fractions,and chemical products,the oxidative pyrolysis behavior of paraffin directly influences energy conversion efficiency and the direction of process optimization.A deep understanding of its oxidative pyrolysis mechanism is crucial for addressing wax deposition in oil and gas extraction,enhancing product selectivity in cracking processes,and advancing novel clean fuel technologies.Traditional experimental methods face challenges in capturing transient free-radical reaction pathways at high temperatures,whereas molecular dynamics simulations offer a powerful approach to bridge the research gap in elucidating atomic-scale dynamic mechanisms.This database is constructed based on high-precision molecular dynamics simulations,comprising oxidative pyrolysis trajectory data for three paraffin models featuring different straight-chain hydrocarbon distributions within the temperature range of 2100-2500 K.The COMPASS force field was employed to optimize the initial structures,and the ReaxFF reactive force field was used to simulate the oxidative pyrolysis process.The database includes atomic trajectories,species evolution information,and reaction network analysis results for both heating and isothermal cracking processes,with a total data volume of approximately 141 GB(including 150000 atomic configuration frames).The data is stored in a hierarchical directory structure,supporting multi-scale oxidative pyrolysis mechanism studies and providing atomic-scale dynamic evidence for revealing carbon chain length effects and temperature sensitivity.展开更多
Chemotherapeutic paclitaxel(PTX) formulations are widely used in clinical cancer treatment;however, they are also associated with concomitant programmed death-ligand(PD-L1) upregulation and an immunosuppressive microe...Chemotherapeutic paclitaxel(PTX) formulations are widely used in clinical cancer treatment;however, they are also associated with concomitant programmed death-ligand(PD-L1) upregulation and an immunosuppressive microenvironment. Herein, we rationally designed carrier-free, reduction-sensitive PTX dimer self-assembling nanoprodrugs(di PC NPs), composed of a glutathione(GSH)-responsive PTX dimer prodrug(di PTX) and the PD-L1 downregulator celastrol(Cel) for combinational chemoimmunotherapy. Following intravenous administration, the di PC NPs exhibited prolonged blood circulation and preferential tumor accumulation by exploiting the enhanced permeability and retention effect. Subsequently, the elevated GSH levels in tumor cells cleaved the disulfide bonds,triggering the rapid release of PTX and Cel. The released PTX elicited potent cytotoxic effects and induced immunogenic cell death(ICD), whereas the released Cel synergistically enhanced ICD and downregulated PD-L1 expression in tumor cells. Together, these effects resulted in remarkable antitumor efficacy with exhibited a favorable safety profile within the therapeutic window in both Lewis lung carcinoma cells and B16F10 tumorbearing mice. Our findings highlight a promising strategy for highly efficient combination chemoimmunotherapy.展开更多
Peptide-based assemblies have gained increasing attention in different areas of nanotechnology,drug delivery and molecular biology.Among these,non-natural β-peptide scaffolds are particularly promising,as their progr...Peptide-based assemblies have gained increasing attention in different areas of nanotechnology,drug delivery and molecular biology.Among these,non-natural β-peptide scaffolds are particularly promising,as their programmable and diverse secondary structures,high metabolic stability and strong self-association propensity can be easily exploited to create variable constructs.We have recently demonstrated that heterochiral,acyclic β^(3)-peptides assembled into striped lamellar nanostructures that induced antibacterial activity.The process of this assembly formation could be exploited in diverse areas,however identifying oligomerisation stages,and more importantly,controlling the spontaneous process at different levels is still lacking.In this study,a set of analogues heterochiral hexameric β^(3)-peptide sequences was investigated to understand how systematic,small variations of the sequences,such as single point mutation or N-terminal chemical modification,can influence the resulting assemblies and allow the control of formed morphologies.TEM and cryo-EM combined with molecular dynamics simulation enabled the identification and differentiation of morphological stages throughout the entire multi-step process.Depending on the position of the sequence modifications,the self-assembled structures formed small oligomers,individual protofibrils,extended,flat lamellae,bundles and macroscopic clusters.These results outline how the self-assembly process of short heterochiral β-peptides can be qualitatively fine-tuned by sequence modifications,which contribute to understanding the general peptide assembly processes for their fibrillar morphologies.展开更多
Ultra-high molecular weight polyethylene(UHMWPE)is a key material for marine applications owing to its outstanding self-lubrication and corrosion resistance.However,its long-term performance is compromised by plastic ...Ultra-high molecular weight polyethylene(UHMWPE)is a key material for marine applications owing to its outstanding self-lubrication and corrosion resistance.However,its long-term performance is compromised by plastic deformation in seawater.In this study,we performed a comparative analysis of the UHMWPE dynamics under seawater and water conditions to investigate the plastic deformation of UHMWPE induced by seawater.The results show that the plastic deformation of UHMWPE is amplified in seawater relative to the water conditions.Under thin fluid conditions,frictional interfaces exhibit a higher interfacial friction force and interaction energy in seawater than in water.Compared to freely diffused water molecules,hydrated ions occupy larger interchain spaces within polyethylene.Furthermore,the diffusion of hydrated ions weakens the interchain interactions,promoting more severe polyethylene chain rearrangement and accelerating seawater-induced plastic deformation in UHMWPE during friction.Furthermore,the diffused seawater accelerated the disentangling of the polyethylene chains and enhanced the orderly orientation distribution of polyethylene.Compared to free water molecules,the water molecules of hydrated ions exhibit enhanced attraction to free-flowing water molecules,thereby accelerating seawater flow across submerged UHMWPE surfaces.This flow enhancement promotes surface polyethylene chain mobility in seawater.展开更多
Control over charge transport in molecular–scale devices requires a deep understanding of how minute structural changes influence electronic properties.Here,we demonstrate dual transport regimes in tunnel junctions o...Control over charge transport in molecular–scale devices requires a deep understanding of how minute structural changes influence electronic properties.Here,we demonstrate dual transport regimes in tunnel junctions of n-alk-1-yne(CnA)molecules with gold electrodes driven by conformational bifurcation—the emergence of two nearly isoenergetic(planar and skewed)molecular conformers(dihedral anglesα=180°andα≈65°at the alkyne terminus in the gas phase).Although the energy differences are small,these subtle conformational differences manifest as distinct transport behaviors,uncovered through unsupervised machine learning,which identified two junction groups:“short”and“long”chains,with distinct attenuation factors(β_(short)≈1.0 vs.β_(long)≈0.74)and contact conductances(G_(c,short)≈200μS vs.G_(c,long)≈8μS).This dramatic impact of the dihedral angle exceeds the impact of the inter-ring twist angle in biphenyl-based junctions and rivals changes induced by switching from gold to platinum electrodes or from monothiol to dithiol anchors in oligoacene and oligophenylene junctions.X-ray photoelectron spectroscopy(XPS)confirmed this bifurcation,linking the“short”and“long”groups to planar and skewed conformers,with dihedrals remarkably agreeing with the gas-phase values.This work establishes conformational bifurcation as a promising route for designing programmable nanotransport properties through anchor-group control.展开更多
The structural principles of traditional Chinese mortise-and-tenon joints have inspired breakthroughs in supramolecular engineering.Nevertheless,substantial challenges remain in constructing nanoscale supramolecular a...The structural principles of traditional Chinese mortise-and-tenon joints have inspired breakthroughs in supramolecular engineering.Nevertheless,substantial challenges remain in constructing nanoscale supramolecular architectures with precisely controlled giant dimensions.Herein,we report a precision-guided synthetic strategy for constructing giant 2D and 3D supramolecular architectures with rhomboidal motifs,which was achieved through a dovetail joint strategy.Initial assembly of bis-mortise ligand L1 with dovetail tenon ligand L2 in the presence of Cd^(2+)ions yielded the fundamental bis-rhombic supramolecule R1.Subsequent structural elaboration of the dovetail tenon motif enabled the development of multitopic ligands L3 and L4,which facilitated the construction of expanded architectures of the giant bis-propeller supramolecule R2 and tris-propeller supramolecule R3.The synthesized supramolecules R1-R3 were fully characterized multidimensional NMR spectroscopy,electrospray ionization mass spectrometry(ESI-MS),traveling wave ion mobility mass spectrometry(TWIM-MS),transmission electron microscopy(TEM),and atomic force microscopy(AFM).This work develops an innovative dovetail-joint assembly strategy for constructing rigid giant supramolecular architectures,establishing a new paradigm for precision engineering of complex 3D molecular systems.展开更多
Lysine-targeting reversible covalent inhibitors,particularly salicylaldehyde-based compounds such as the Food and Drug Administration(FDA)-approved drug Voxelotor,exhibit significant therapeutic potential but are limi...Lysine-targeting reversible covalent inhibitors,particularly salicylaldehyde-based compounds such as the Food and Drug Administration(FDA)-approved drug Voxelotor,exhibit significant therapeutic potential but are limited by challenges including instability and off-target effects.To overcome these limitations in kinase inhibitor A5,we devised a pH-responsive prodrug strategy by masking its reactive aldehyde group with an acid-labile hydrazone linkage and enhancing intracellular delivery through conjugation with FK506.The optimized prodrug demonstrated robust antitumor efficacy in K562 tumor-bearing mice.Furthermore,the incorporation of the photosensitizer chlorin e6(Ce6)led to the formation of self-assembled nanoparticles(AKNP),which not only improved physiological stability and prolonged tumor retention but also enabled light-triggered release of A5 in conjunction with photodynamic therapy(PDT).Our study thus presents a promising prodrug self-assembly strategy that combines the on-demand release of a novel lysine-targeting,reversible covalent kinase inhibitor with PDT in clinical cancer therapy.展开更多
Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.H...Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.Herein,we propose a self-assembly chemical strategy into the LCHEs induced by ordered nanostructure of zwitterionic co-solutes for highly efficient and ultrastable zinc(Zn)metal batteries.Through the systematic screening of six zwitterionic compounds,3-(decyldimethylammonio)propanesulfonate salt(C_(10))with the decyl chain and zwitterions was determined as an optimum to construct quasi-spherical aggregates with a periodic length of 3.77 nm,as confirmed by comprehensive synchronous small-angle X-ray scattering,Guinier,pair distance distribution function,Porod,and other spectroscopic characterizations and molecular dynamic simulation.In particularly,this self-assembled structure in electrolyte environments was attributed to increasing the proportion of both contact and aggregated ion pairs for the formation of LHCEs as well as to providing fast and selective Zn^(2+)conducting channels and uniform solid electrolyte interfaces for facilitated charge transfer kinetics.Moreover,the preferential adsorption of the self-assembled C_(10)on the Zn(002)surface modulated the electrical double layer to suppress hydrogen evolution and corrosion reactions.Consequently,the Zn‖Zn symmetric cells in Zn(OTf)_(2)/C_(10)electrolytes showed long-term plating/stripping behaviors over 2800 h at 1 mA cm^(-2)and 1 mAh cm^(-2)as well as over 1200 h even at 5 mA cm^(-2)and 5 mAh cm^(-2)with a very high depth of discharge of 42.7%.Furthermore,the ZnllVO_(2)/CNT full cells in Zn(OTf)_(2)/C_(10)electrolytes delivered a record-high capacity of 8.10 mAh cm^(-2)at an ultrahigh cathode mass loading of 50 mg cm^(-2)after 150 cycles.展开更多
Sustainability and scalability remain critical hurdles for the commercialization of organic solar cells(OSCs).However,addressing both poses challenge.Herein,we introduce a simple yet effective strategy utilizing 3,5-d...Sustainability and scalability remain critical hurdles for the commercialization of organic solar cells(OSCs).However,addressing both poses challenge.Herein,we introduce a simple yet effective strategy utilizing 3,5-dichloropyridine(PDCC)as a solid additive to fine-tune the self-assembly behavior of Y-series non-fullerene acceptors(NFAs)to tackle the upscaling limitations in green-solvent-processed OSCs.PDCC predominantly interacts with Y-series NFAs,facilitating molecular crystallization and thereby driving the self-assembly of Y-series NFAs during film-forming dynamics,leading to more uniform active layers with improved molecular packing and reduced charge recombination.As a result,PDCC-driven self-assembly strategy enables high-performance OSCs with a power conversion efficiency(PCE)of 20.47%.When translated to sustainable fabrication,this strategy significantly boosts the PCE of large-area green-solvent-processed OSC modules(19.3 cm^(2))from 13.87%to 15.79%,ranking it among the best-performing green-solvent-processed large-area OSC modules(>18 cm^(2)).Beyond its impact on PCE enhancement,PDCC serves as a multifunctional additive to improve long-term stability and exhibits strong universality across multiple material systems.This work establishes a promising approach for advancing sustainable and scalable OSCs,paving the way for their commercialization.展开更多
The rapid advancement of flexible electronics technology has placed higher demands on the structural design and performance regulation of elastic materials.Cellulosic elastomers,with their biodegradability,renewabilit...The rapid advancement of flexible electronics technology has placed higher demands on the structural design and performance regulation of elastic materials.Cellulosic elastomers,with their biodegradability,renewability,and tunability,emerge as ideal candidate materials.Entropy-driven self-as sembly promotes the spontaneous formation of ordered structures,serving as a crucial pathway for optimizing cellulose elastomer properties.However,the structure-property relationship between the self-assembled ordered structures of cellulose elastomers and their mechanical and electrical properties remains insufficiently explored.It hinders the expansion of their applications in electronic devices.This paper systematically reviews the structure-property regulation mechanisms of self-assembled cellulosic elastomers from an entropy-driven perspective.It elucidates the application principles and performance optimization strategies for mechanical energy harvesting and self-powered sensing,while also exploring the challenges and prospects for performance enhancement.This work provides a reference for the development of self-assembled cellulosic elastomers in the field of energy devices.展开更多
The transforming growth factor-β(TGF-β)and bone morphogenetic protein(BMP)signaling pathways are pivotal regulators of cellular processes,playing indispensable roles in embryogenesis,postnatal development,and tissue...The transforming growth factor-β(TGF-β)and bone morphogenetic protein(BMP)signaling pathways are pivotal regulators of cellular processes,playing indispensable roles in embryogenesis,postnatal development,and tissue homeostasis.These pathways are particularly critical within the skeletal system,as they coordinate osteogenesis,chondrogenesis,and bone remodeling through intricate molecular mechanisms.TGF-β/BMP signaling is primarily transduced via canonical Smad-dependent pathways(e.g.,ligands,receptors,and intracellular Smads)and the non-canonical Smad-independent(e.g.,p38 mitogen-activated protein kinase,MAPK)cascade.Both pathways converge on master transcriptional regulators,including Runx2 and Osterix,and their precise coordination is indispensable for skeletal development,maintenance,and repair.The dysregulation of TGF-β/BMP signaling contributes to a spectrum of skeletal dysplasia and bone pathologies.Advances in molecular genetics,particularly gene-targeting strategies and transgenic mouse models,have deepened our understanding of the spatiotemporal control of TGF-β/BMP signaling in bone and cartilage development.Moreover,emerging research underscores extensive crosstalk between TGF-β/BMP and other critical pathways,such as Wnt/β-catenin,mitogen-activated protein kinase(MAPK),parathyroid hormone(PTH)/PTH-related protein(PTHrP),fibroblast growth factors(FGF),Hedgehog,Notch,insulin-like growth factors(IGF)/insulin-like growth factors receptor(IGFR),Mammalian target of rapamycin(mTOR),and autophagy,forming an integrated regulatory network that ensures skeletal integrity.Our review synthesizes the current knowledge on the molecular components,regulatory mechanisms,and functional integration of TGF-β/BMP signaling in skeletal biology,with an emphasis on its roles in development,regeneration,and disease.By elucidating the molecular underpinnings of TGF-β/BMP pathways and their contextual interactions,we aim to highlight translational opportunities and novel therapeutic strategies for treating skeletal disorders.展开更多
基金supported by the National Natural Science Foundation of China(NSFC No.52271228)the Natural Science Foundation of Shaanxi Province(No.2023-JC-ZD-21)the Doctoral Dissertation Innovation Fund of Xi'an University of Technology(No.101-252072301)。
文摘Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/chemical stability.To enhance the performance of intrinsic g-CN,a supramolecular self-assembly strategy has been proposed to regulate the molecular structure of supramolecular precursors through non-covalent interactions across molecular building blocks,thereby optimizing the electronic structure of g-CN.This review provides a comprehensive overview of the recent progress in supramolecular self-assembly-derived graphitic carbon nitride(SM-CN)from both experimental and theoretical computational research in synthesis strategies,including synthesis methods and influencing factors,providing a theoretical foundation for the design of supramolecular assembly.It also discusses modification strategies,such as internal modification of the conjugated plane,interlayer optimization,and construction of heterointerfaces to improve the electronic structure of SM-CN owing to its unique layered structure.This review further summarizes the applications of SM-CN in environment and energy,including wastewater treatment,sterilization and disinfection/air purification,water splitting,H_(2)O_(2)production,organic synthesis/biomass conversion,CO_(2)reduction,photocatalytic coupling technology.Finally,perspectives and outlooks for the future development of SM-CN aim to inspire further innovation in the design and construction of high-performance SM-CN for broader applications.
基金supported by the National Natural Science Foundation of China(No.82273919)Natural Science Foundation of Heilongjiang Province(No.LH2024H013)China Postdoctoral Science Foundation(No.2022MD723781).
文摘Constructing nanofibers with specific therapeutic effects against cancer is a challenge.Here,we present the synthesis approach and application prospects of supramolecular nanofibers,which are based on cucurbit[8]uril(CB[8])as the host and terpyridine lanthanum ions metal complex as the vip,constructed by layer-by-layer self-assembly through supramolecular interaction.Moreover,nanofibers with lanthanide luminescence properties exhibit surprising pH-responsive deformation properties and antibacterial behavior.In the tumor micro-environment,the dramatic reduction in the size of the nanofibers enables specific and hierarchical release of anticancer drugs in tumor cells to exert an advanced therapeutic effect.In addition,the synergistic therapeutic efficacy was achieved by reducing the excess of Gram-positive and Gram-negative bacteria surrounding tumor cells.The novel supramolecular nanofibers with sequential drug release and combined therapeutic mode provide new guidance for the synthesis of drug carrier materials and direction for the promotion of nanomaterial-mediated cancer therapy.
基金the National Natural Science Foundation of China(No.21921003 for Z.T.L.and 22201293 for S.B.Y.)Shanghai Sailing Program(No.22YF1458300 for S.B.Y.)for financial support。
文摘Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
基金This work was supported by the National Natural Science Foundation of China(Nos.21801162,22277011,and 22107019)National Key Research&Development Program of China(No.2020YFA0210800)+1 种基金National Science Basic Research Plan in Shaanxi Province of China(No.2023-JC-QN-0150)the Major Project of Science and Technology of Fujian Province(No.2020HZ06006).
文摘The abundant intracellular glutathione(GSH)in cancer cells severely undermines the therapeutic efficacy of different treatments due to their role in protecting cancer cells from the associated oxidative stress.Developing a highly integrated system to consume GSH would help to improve the therapeutic outcomes.In this study,supramolecular prodrug self-assemblies(SPSAs)with IR825 loaded inside were developed to consume GSH via two-pronged pathways while augmenting the therapeutic potency of chemo/photothermal treatment.SPSAs were prepared using water-soluble pillar[6]arene(WP[6])as host units and H_(2)O_(2)-responsive nitrogen mustard prodrug,chlorambucil-(phenylboronic acid pinacol ester)conjugates(Cb-BE),as the vips.When SPSAs were internalized by cancer cells,the generation of quinone methide(QM)from Cb-BE and singlet oxygen(^(1)O_(2))from irradiation-activated IR825 could consume GSH in a concerted way.As such,the therapeutic efficacies of the released chlorambucil and the accompanied hyperthermia were augmented toward synergistically inhibiting tumor growth.
基金the National Natural Science Foundation of China.
文摘Molecular recognition directed self-assemblies from complementary molecular components, melamine and barbituric acid derivatives were studied by means of NMR, fluorescence, and TEM. It was found that both the process of the self-assembly and the morphologies of the result- ed self-assemblies could be mediated by modifying the structures of the molecular components used. The effect of the structures of the molecular components on the formation of the self-as- semblies was discussed in terms of intermolecular interactions.
基金supported by the National Natural Science Foundation of China(22438005,22108117).
文摘Self-assembly of block copolymers(BCPs)is highly intricate and is adsorbing extensive experimental and simulation efforts to reveal it for maximizing structural order and device performances.The coarse-grained(CG)molecular dynamics(MD)simulation offers a microscopic angle to view the self-assembly of BCPs.Although some molecular details are sacrificed during CG processes,this method exhibits remarkable computational efficiency.In this study,a comprehensive CG model for polystyrene-block-poly(2-vinylpyridine),PS-b-P2VP,one of the most extensively studied BCPs for its high Flory-Huggins interaction parameter,is constructed,with parameters optimized using target values derived from all-atom MD simulations.The CG model precisely coincides with various classical self-assembling morphologies observed in experimental studies,matching the theoretical phase diagrams.Moreover,the conformational asymmetry of the experimental phase diagram is also clearly revealed by our simulation results,and the phase boundaries obtained from simulations are highly consistent with experimental results.The CG model is expected to extend to simulate the self-assembly behaviors of other BCPs in addition to PS-b-P2VP,thus increasing understanding of the microphase separation of BCPs from the molecular level.
基金financially supported by the National Natural Science Foundation of China(Nos.52303298 and 52233002)。
文摘UHMWPE fibers exhibit impressive modulus and strength,but they have not reached their theoretical limits.Researchers focus on molecular weight,orientation,and crystallinity of UHMWPE,yet their contributions to mechanical properties are unclear.Molecular dynamics simulations are valuable but often limited by computational constraints.Our aim is to simulate higher molecular weights to better represent real UHMWPE fibers.We used Packmol and Polyply methodologies to construct PE systems,with Polyply reproducing more reasonable properties of UHMWPE fibers.Additionally,tensile simulations showed that orientation and crystallinity greatly impact Young's modulus more than molecular weight.Energy decomposition indicated that higher molecular weights lead to covalent bonds that can withstand more energy during stretching,thus increasing breaking strength.Combining simulations with machine learning,we found that orientation has the most significant impact on Young's modulus,contributing 60%,and molecular weight plays the most crucial role in determining the breaking strength,accounting for 65%.This study provides a theoretical basis and guidelines for enhancing UHMWPE's modulus and strength.
文摘In this work,we proposed a strategy for the hydrolysis of native corn starch after the treatment of corn starch in an ionic liquid aqueous solution,and it is an awfully“green”and simple means to obtain starch with low molecular weight and amorphous state.X-ray diffraction results revealed that the natural starch crystalline region was largely disrupted by ionic liquid owing to the broken intermolecular and intramolecular hydrogen bonds.After hydrolysis,the morphology of starch changed from particles of native corn starch into little pieces,and their molecular weight could be effectively regulated during the hydrolysis process,and also the hydrolyzed starch samples exhibited decreased thermal stability with the extension of hydrolysis time.This work would counsel as a powerful tool for the development of native starch in realistic applications.
基金Supported by National Natural Science Foundation of China(21991093)。
文摘The coupling reactions of methanol and long-chain alkanes(n-dodecane,n-tetradecane and n-hexadecane)over CHA-type molecular sieves were studied in a fixed bed reactor.Over SAPO-34 and SSZ-13,it was found that the induction period of methanol conversion was shortened by the introduction of long-chain alkanes.However,the addition of long-chain alkanes had little influence on the product distribution.Polymethylbenzenes and the derivatives were the main retained species on spent SSZ-13 catalyst,while adamantanes were the main retained species on SAPO-34.This indicates that coking species formation was mainly related to the further transformation of long-chain alkane/methanol coupling products at acid sites of the molecular sieve.These findings provide valuable information of long chain alkanes conversion and methanol reaction behavior of induction period over small pore CHA molecular sieves.
基金Supported by Natural Science Foundation of Shanxi Province (202203021221219)Research on the Construction of Scientific and Technological Innovation Think Tank of Shanxi Association for Science and Technology (KXKT202542)Planning Project under Commerce Statistical Society of China (2025STY122)。
文摘As a key component of shale oil,petroleum fractions,and chemical products,the oxidative pyrolysis behavior of paraffin directly influences energy conversion efficiency and the direction of process optimization.A deep understanding of its oxidative pyrolysis mechanism is crucial for addressing wax deposition in oil and gas extraction,enhancing product selectivity in cracking processes,and advancing novel clean fuel technologies.Traditional experimental methods face challenges in capturing transient free-radical reaction pathways at high temperatures,whereas molecular dynamics simulations offer a powerful approach to bridge the research gap in elucidating atomic-scale dynamic mechanisms.This database is constructed based on high-precision molecular dynamics simulations,comprising oxidative pyrolysis trajectory data for three paraffin models featuring different straight-chain hydrocarbon distributions within the temperature range of 2100-2500 K.The COMPASS force field was employed to optimize the initial structures,and the ReaxFF reactive force field was used to simulate the oxidative pyrolysis process.The database includes atomic trajectories,species evolution information,and reaction network analysis results for both heating and isothermal cracking processes,with a total data volume of approximately 141 GB(including 150000 atomic configuration frames).The data is stored in a hierarchical directory structure,supporting multi-scale oxidative pyrolysis mechanism studies and providing atomic-scale dynamic evidence for revealing carbon chain length effects and temperature sensitivity.
基金the National Natural Science Foundation of China (No. 82374301)the State Key Laboratory of Southwestern Chinese Medicine Resources (No. SKLTCM202410)+2 种基金the Key Project of Anhui Province Department of Education (No. 2023AH030070, 2024AH051040)Anhui Province Key Laboratory, China (KFKT202305, KFKT202507, 2024ZYFBAHKLA11, and 2024ZYFBAHKLA15)Greater Health Research Institute of Hefei Comprehensive National Science Center, China (2023CXMMTCM005)。
文摘Chemotherapeutic paclitaxel(PTX) formulations are widely used in clinical cancer treatment;however, they are also associated with concomitant programmed death-ligand(PD-L1) upregulation and an immunosuppressive microenvironment. Herein, we rationally designed carrier-free, reduction-sensitive PTX dimer self-assembling nanoprodrugs(di PC NPs), composed of a glutathione(GSH)-responsive PTX dimer prodrug(di PTX) and the PD-L1 downregulator celastrol(Cel) for combinational chemoimmunotherapy. Following intravenous administration, the di PC NPs exhibited prolonged blood circulation and preferential tumor accumulation by exploiting the enhanced permeability and retention effect. Subsequently, the elevated GSH levels in tumor cells cleaved the disulfide bonds,triggering the rapid release of PTX and Cel. The released PTX elicited potent cytotoxic effects and induced immunogenic cell death(ICD), whereas the released Cel synergistically enhanced ICD and downregulated PD-L1 expression in tumor cells. Together, these effects resulted in remarkable antitumor efficacy with exhibited a favorable safety profile within the therapeutic window in both Lewis lung carcinoma cells and B16F10 tumorbearing mice. Our findings highlight a promising strategy for highly efficient combination chemoimmunotherapy.
基金funded by the National Research,Development and Inno-vation Office,Hungary(TKP2021-EGA-31,2020-1.1.2-PIACI-KFI-2020-00021,KKP_22 Project no.144180 and FK_23 Project no.146081).Support from Hungarian Research Network(Eötvös Loránd Research Network)grant no.SA-87/2021 and KEP-5/2021 are also acknowledged.Project no.RRF-2.3.1-21-2022-00015+1 种基金supported by the European Union,Recovery and Resilience Facility.The János Bolyai Research Fellowship(A.W.)of the Hungarian Academy of Sciences is greatly acknowledged.The authors acknowledge CF CryoEM of CIISB,Instruct-CZ Centre,supported by Ministry of Education,Youth and Sports,Czech Republic(MEYS CR)(no.LM2023042)European Regional Development Fund-Project"UP CIISB"(n0.CZ.02.1.01/0.0/0.0/18_046/0015974).
文摘Peptide-based assemblies have gained increasing attention in different areas of nanotechnology,drug delivery and molecular biology.Among these,non-natural β-peptide scaffolds are particularly promising,as their programmable and diverse secondary structures,high metabolic stability and strong self-association propensity can be easily exploited to create variable constructs.We have recently demonstrated that heterochiral,acyclic β^(3)-peptides assembled into striped lamellar nanostructures that induced antibacterial activity.The process of this assembly formation could be exploited in diverse areas,however identifying oligomerisation stages,and more importantly,controlling the spontaneous process at different levels is still lacking.In this study,a set of analogues heterochiral hexameric β^(3)-peptide sequences was investigated to understand how systematic,small variations of the sequences,such as single point mutation or N-terminal chemical modification,can influence the resulting assemblies and allow the control of formed morphologies.TEM and cryo-EM combined with molecular dynamics simulation enabled the identification and differentiation of morphological stages throughout the entire multi-step process.Depending on the position of the sequence modifications,the self-assembled structures formed small oligomers,individual protofibrils,extended,flat lamellae,bundles and macroscopic clusters.These results outline how the self-assembly process of short heterochiral β-peptides can be qualitatively fine-tuned by sequence modifications,which contribute to understanding the general peptide assembly processes for their fibrillar morphologies.
基金financially supported by the National Natural Science Foundation of China(Nos.51909023 and 51775077)the Natural Science Foundation of Liaoning Province(No.2021-MS-140)the Fundamental Research Funds for the Central Universities(No.3132025114)。
文摘Ultra-high molecular weight polyethylene(UHMWPE)is a key material for marine applications owing to its outstanding self-lubrication and corrosion resistance.However,its long-term performance is compromised by plastic deformation in seawater.In this study,we performed a comparative analysis of the UHMWPE dynamics under seawater and water conditions to investigate the plastic deformation of UHMWPE induced by seawater.The results show that the plastic deformation of UHMWPE is amplified in seawater relative to the water conditions.Under thin fluid conditions,frictional interfaces exhibit a higher interfacial friction force and interaction energy in seawater than in water.Compared to freely diffused water molecules,hydrated ions occupy larger interchain spaces within polyethylene.Furthermore,the diffusion of hydrated ions weakens the interchain interactions,promoting more severe polyethylene chain rearrangement and accelerating seawater-induced plastic deformation in UHMWPE during friction.Furthermore,the diffused seawater accelerated the disentangling of the polyethylene chains and enhanced the orderly orientation distribution of polyethylene.Compared to free water molecules,the water molecules of hydrated ions exhibit enhanced attraction to free-flowing water molecules,thereby accelerating seawater flow across submerged UHMWPE surfaces.This flow enhancement promotes surface polyethylene chain mobility in seawater.
基金financial support from the National Key R&D Program of China(2023YFA1407100)the National Natural Science Foundation of China(22373026)+1 种基金Guangdong Science and Technology Department(2021B0301030005,STKJ2023072,GDZX2304005,GDZX2504001,and 2021QN02X538)Ioan Bâldea gratefully acknowledges computational support by the state of Baden-Württemberg through bwHPC and the German Research Foundation through Grant Nos.INST 40/575-1,35/1597-1,and 35/1134-1(JUSTUS 2,bwUniCluster 2/3,and bwForCluster/MLS&WISO/HELIX 2).
文摘Control over charge transport in molecular–scale devices requires a deep understanding of how minute structural changes influence electronic properties.Here,we demonstrate dual transport regimes in tunnel junctions of n-alk-1-yne(CnA)molecules with gold electrodes driven by conformational bifurcation—the emergence of two nearly isoenergetic(planar and skewed)molecular conformers(dihedral anglesα=180°andα≈65°at the alkyne terminus in the gas phase).Although the energy differences are small,these subtle conformational differences manifest as distinct transport behaviors,uncovered through unsupervised machine learning,which identified two junction groups:“short”and“long”chains,with distinct attenuation factors(β_(short)≈1.0 vs.β_(long)≈0.74)and contact conductances(G_(c,short)≈200μS vs.G_(c,long)≈8μS).This dramatic impact of the dihedral angle exceeds the impact of the inter-ring twist angle in biphenyl-based junctions and rivals changes induced by switching from gold to platinum electrodes or from monothiol to dithiol anchors in oligoacene and oligophenylene junctions.X-ray photoelectron spectroscopy(XPS)confirmed this bifurcation,linking the“short”and“long”groups to planar and skewed conformers,with dihedrals remarkably agreeing with the gas-phase values.This work establishes conformational bifurcation as a promising route for designing programmable nanotransport properties through anchor-group control.
基金supported by the Hunan Science and Technology Innovation Plan(No.2024RC3015)the National Natural Science Foundation of China(No.22501053)+1 种基金National Key Research and Development Program(Nos.2022YFC3900902 and 2024YFC3907900)Major Science and Technology Projects of Yunnan Province(No.202302AB080016).
文摘The structural principles of traditional Chinese mortise-and-tenon joints have inspired breakthroughs in supramolecular engineering.Nevertheless,substantial challenges remain in constructing nanoscale supramolecular architectures with precisely controlled giant dimensions.Herein,we report a precision-guided synthetic strategy for constructing giant 2D and 3D supramolecular architectures with rhomboidal motifs,which was achieved through a dovetail joint strategy.Initial assembly of bis-mortise ligand L1 with dovetail tenon ligand L2 in the presence of Cd^(2+)ions yielded the fundamental bis-rhombic supramolecule R1.Subsequent structural elaboration of the dovetail tenon motif enabled the development of multitopic ligands L3 and L4,which facilitated the construction of expanded architectures of the giant bis-propeller supramolecule R2 and tris-propeller supramolecule R3.The synthesized supramolecules R1-R3 were fully characterized multidimensional NMR spectroscopy,electrospray ionization mass spectrometry(ESI-MS),traveling wave ion mobility mass spectrometry(TWIM-MS),transmission electron microscopy(TEM),and atomic force microscopy(AFM).This work develops an innovative dovetail-joint assembly strategy for constructing rigid giant supramolecular architectures,establishing a new paradigm for precision engineering of complex 3D molecular systems.
基金supported by the grants from National Key R&D Program of China(No.2022YFA1104800)Shenzhen Science and Technology Program(No.JCYJ20210324124214038)+4 种基金National Natural Science Foundation of China(Nos.52072418,82300016)Natural Science Foundation of Guangdong Province(No.2023A1515140072)Shenzhen Key Laboratory of Neural Cell Reprogramming and Drug Research,Social Development Science and Technology Key Project of Dongguan(No.20231800940512)the National Medical Research Council(NMRC,No.23-0740-A0001)the Ministry of Education(MOE,No.T2EP10222-0002)of Singapore.
文摘Lysine-targeting reversible covalent inhibitors,particularly salicylaldehyde-based compounds such as the Food and Drug Administration(FDA)-approved drug Voxelotor,exhibit significant therapeutic potential but are limited by challenges including instability and off-target effects.To overcome these limitations in kinase inhibitor A5,we devised a pH-responsive prodrug strategy by masking its reactive aldehyde group with an acid-labile hydrazone linkage and enhancing intracellular delivery through conjugation with FK506.The optimized prodrug demonstrated robust antitumor efficacy in K562 tumor-bearing mice.Furthermore,the incorporation of the photosensitizer chlorin e6(Ce6)led to the formation of self-assembled nanoparticles(AKNP),which not only improved physiological stability and prolonged tumor retention but also enabled light-triggered release of A5 in conjunction with photodynamic therapy(PDT).Our study thus presents a promising prodrug self-assembly strategy that combines the on-demand release of a novel lysine-targeting,reversible covalent kinase inhibitor with PDT in clinical cancer therapy.
基金financially supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.NRF-2020R1A3B2079803 and No.RS-2024-00453815),Republic of Korea。
文摘Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.Herein,we propose a self-assembly chemical strategy into the LCHEs induced by ordered nanostructure of zwitterionic co-solutes for highly efficient and ultrastable zinc(Zn)metal batteries.Through the systematic screening of six zwitterionic compounds,3-(decyldimethylammonio)propanesulfonate salt(C_(10))with the decyl chain and zwitterions was determined as an optimum to construct quasi-spherical aggregates with a periodic length of 3.77 nm,as confirmed by comprehensive synchronous small-angle X-ray scattering,Guinier,pair distance distribution function,Porod,and other spectroscopic characterizations and molecular dynamic simulation.In particularly,this self-assembled structure in electrolyte environments was attributed to increasing the proportion of both contact and aggregated ion pairs for the formation of LHCEs as well as to providing fast and selective Zn^(2+)conducting channels and uniform solid electrolyte interfaces for facilitated charge transfer kinetics.Moreover,the preferential adsorption of the self-assembled C_(10)on the Zn(002)surface modulated the electrical double layer to suppress hydrogen evolution and corrosion reactions.Consequently,the Zn‖Zn symmetric cells in Zn(OTf)_(2)/C_(10)electrolytes showed long-term plating/stripping behaviors over 2800 h at 1 mA cm^(-2)and 1 mAh cm^(-2)as well as over 1200 h even at 5 mA cm^(-2)and 5 mAh cm^(-2)with a very high depth of discharge of 42.7%.Furthermore,the ZnllVO_(2)/CNT full cells in Zn(OTf)_(2)/C_(10)electrolytes delivered a record-high capacity of 8.10 mAh cm^(-2)at an ultrahigh cathode mass loading of 50 mg cm^(-2)after 150 cycles.
基金the research grant from the Youth Fund of the National Natural Science Foundation of China(62305340)the financial support from the Hong Kong Research Grant Council via STEM Postdoctoral Fellowship(Project no.9446002)+6 种基金the Alexander von Humboldt Foundation and the support during his stay in Christoph J.Brabec’s group at Friedrich-Alexander-Universität Erlangen-Nürnberg and Helmholtz-Institute Erlangen-Nürnberg(HI ERN)the research grant from KAUST global fellowship postdocfinancial support from the Innovation and Technology Commission(Grant no.MHP/104/21)Shenzhen Science and Technology Innovation Commission(JCYJ20210324125612035,R-IND12303,and R-IND12304)the National Key Research and Development Program of China(no.2021YFA1500900)the National Natural Science Foundation of China(no.52071174)the support from the Hong Kong Jockey Club under the research work Hong Kong JC STEM Lab for Circular Bio-economy(Project No.2023-0078)。
文摘Sustainability and scalability remain critical hurdles for the commercialization of organic solar cells(OSCs).However,addressing both poses challenge.Herein,we introduce a simple yet effective strategy utilizing 3,5-dichloropyridine(PDCC)as a solid additive to fine-tune the self-assembly behavior of Y-series non-fullerene acceptors(NFAs)to tackle the upscaling limitations in green-solvent-processed OSCs.PDCC predominantly interacts with Y-series NFAs,facilitating molecular crystallization and thereby driving the self-assembly of Y-series NFAs during film-forming dynamics,leading to more uniform active layers with improved molecular packing and reduced charge recombination.As a result,PDCC-driven self-assembly strategy enables high-performance OSCs with a power conversion efficiency(PCE)of 20.47%.When translated to sustainable fabrication,this strategy significantly boosts the PCE of large-area green-solvent-processed OSC modules(19.3 cm^(2))from 13.87%to 15.79%,ranking it among the best-performing green-solvent-processed large-area OSC modules(>18 cm^(2)).Beyond its impact on PCE enhancement,PDCC serves as a multifunctional additive to improve long-term stability and exhibits strong universality across multiple material systems.This work establishes a promising approach for advancing sustainable and scalable OSCs,paving the way for their commercialization.
基金supported by the National Natural Science Foundation of China(32571991)Guangxi Natural Science Foundation of China(2023GXNSFGA026001&2025GXNSFAA069870)the Foundation of State Key Laboratory of Biobased Material and Green Papermaking.(No.GZKF202323)。
文摘The rapid advancement of flexible electronics technology has placed higher demands on the structural design and performance regulation of elastic materials.Cellulosic elastomers,with their biodegradability,renewability,and tunability,emerge as ideal candidate materials.Entropy-driven self-as sembly promotes the spontaneous formation of ordered structures,serving as a crucial pathway for optimizing cellulose elastomer properties.However,the structure-property relationship between the self-assembled ordered structures of cellulose elastomers and their mechanical and electrical properties remains insufficiently explored.It hinders the expansion of their applications in electronic devices.This paper systematically reviews the structure-property regulation mechanisms of self-assembled cellulosic elastomers from an entropy-driven perspective.It elucidates the application principles and performance optimization strategies for mechanical energy harvesting and self-powered sensing,while also exploring the challenges and prospects for performance enhancement.This work provides a reference for the development of self-assembled cellulosic elastomers in the field of energy devices.
基金supported by grants by National Natural Science Foundation of China(No.82571024,No.81400489)Zhejiang Provincial Natural Science Foundation of China(LZ23H140001,LTGY23H200006,LGC22H200012)+3 种基金Zhejiang Qianjiang Talent Program(21040040-E)the Fundamental Research Funds of Zhejiang Sci-Tech University(2021Q031)Zhejiang Jiaxing Science Technology Foundation(2023AZ31004,2023AY11045,2023AY31012,2020AY10001)Zhejiang Drug&Health Foundation(2022507032,2023KY340)。
文摘The transforming growth factor-β(TGF-β)and bone morphogenetic protein(BMP)signaling pathways are pivotal regulators of cellular processes,playing indispensable roles in embryogenesis,postnatal development,and tissue homeostasis.These pathways are particularly critical within the skeletal system,as they coordinate osteogenesis,chondrogenesis,and bone remodeling through intricate molecular mechanisms.TGF-β/BMP signaling is primarily transduced via canonical Smad-dependent pathways(e.g.,ligands,receptors,and intracellular Smads)and the non-canonical Smad-independent(e.g.,p38 mitogen-activated protein kinase,MAPK)cascade.Both pathways converge on master transcriptional regulators,including Runx2 and Osterix,and their precise coordination is indispensable for skeletal development,maintenance,and repair.The dysregulation of TGF-β/BMP signaling contributes to a spectrum of skeletal dysplasia and bone pathologies.Advances in molecular genetics,particularly gene-targeting strategies and transgenic mouse models,have deepened our understanding of the spatiotemporal control of TGF-β/BMP signaling in bone and cartilage development.Moreover,emerging research underscores extensive crosstalk between TGF-β/BMP and other critical pathways,such as Wnt/β-catenin,mitogen-activated protein kinase(MAPK),parathyroid hormone(PTH)/PTH-related protein(PTHrP),fibroblast growth factors(FGF),Hedgehog,Notch,insulin-like growth factors(IGF)/insulin-like growth factors receptor(IGFR),Mammalian target of rapamycin(mTOR),and autophagy,forming an integrated regulatory network that ensures skeletal integrity.Our review synthesizes the current knowledge on the molecular components,regulatory mechanisms,and functional integration of TGF-β/BMP signaling in skeletal biology,with an emphasis on its roles in development,regeneration,and disease.By elucidating the molecular underpinnings of TGF-β/BMP pathways and their contextual interactions,we aim to highlight translational opportunities and novel therapeutic strategies for treating skeletal disorders.
