The abuse of plastic food packaging has brought about severe white pollution issues around the world.Developing green and sustainable biomass packaging is an effective way to solve this problem.Hence,a chitosan/sodium...The abuse of plastic food packaging has brought about severe white pollution issues around the world.Developing green and sustainable biomass packaging is an effective way to solve this problem.Hence,a chitosan/sodium alginate-based multilayer film is fabricated via a layer-by-layer(LBL)self-assembly method.With the help of superior interaction between the layers,the multilayer film possesses excellent mechanical properties(with a tensile strength of 50 MPa).Besides,the film displays outstanding water retention property(blocking moisture of 97.56%)and ultraviolet blocking property.Anthocyanin is introduced into the film to detect the food quality since it is one natural plant polyphenol that is sensitive to the pH changes ranging from 1 to 13 in food when spoilage occurs.It is noted that the film is also bacteriostatic which is desired for food packaging.This study describes a simple technique for the development of advanced multifunctional and fully biodegradable food packaging film and it is a sustainable alternative to plastic packaging.展开更多
Spherical polyelectrolyte brushes (SPBs) consisting of polystyrene (PS) core and poly(2-aminoethyl methacrylate hydrochloride) (PAEMH) shell were prepared by photo-emulsion polymerization. Au nanoparticles (A...Spherical polyelectrolyte brushes (SPBs) consisting of polystyrene (PS) core and poly(2-aminoethyl methacrylate hydrochloride) (PAEMH) shell were prepared by photo-emulsion polymerization. Au nanoparticles (Au-NPs) with controlled size and size distribution were synthesized in situ using SPBs as nanoreactors. Via layer-by-layer deposition technique on the surface of SPBs, nano-composite particles with Au/Ag-NPs bilayer and Au/Ag/Au-NPs trilayer were prepared. The structures of the as-prepared Au/Ag multilayer SPBs were characterized by UV-Vis spectroscopy, TEM, ICP-AES and DLS. The charge reversal of the nano-composite particles observed by zeta potential confirmed the success of layer-by-layer assembly. The Au/Ag-NPs bilayer nano-composite particles showed high catalytic efficiency with an apparent activation energy of about 41.2 kJ/mol in the reduction reaction of 4-nitrophenol to 4-aminophenol in the existence of sodium borohydride monitored. The catalytic activity ofAu/Ag-NPs multilayer SPBs close to that of Au-NPs SPBs and much higher than that of Ag-NPs SPBs reveals its potential applications in cost-effective catalysts with high-performance.展开更多
Orthopedic implants for the treatment of bone defects from various causes have been challenged by insufficient osseointegration,bacterial infection,oxidative stress,immune rejection,and insufficient individualized tre...Orthopedic implants for the treatment of bone defects from various causes have been challenged by insufficient osseointegration,bacterial infection,oxidative stress,immune rejection,and insufficient individualized treatment.These challenges not only impact treatment outcomes but also severely impact patients’daily lives.Layer-by-Layer(LbL)serves as a simple surface coating technique,in simple terms,to functionalize implants by sequentially adsorbing oppositely charged materials onto a substrate.In orthopaedics,LbL self-assembly technology solves some of the challenges by loading various drugs or biological agents on the implant surface and controlling their release precisely to the site of bone defects in a personalized way.This review will introduce the basic principle and the development of LbL in orthopaedics,review and analyze the chemical strategy of LbL in the preparation of bone implants to ensure the stability of the implant,and introduce the use of LbL bone implants in orthopaedics in recent years.The application of LbL includes the realization of programmed drug delivery and sustained release,thereby promoting osseointegration and the formation of new blood vessels,antibacterial,antioxidant,etc.This review focuses on the LbL technology,involving the technology selection for the preparation of bone implants,the chemical strategies of the stability guarantee of LbL implants,the pharmacological properties,loading and release mechanisms of loaded drugs,and the molecular mechanisms of osteogenesis and angiogenesis.The aim of this review is to provide an overview of current research advances,and a prospect in this field was also described.展开更多
A film with“brick-and-mortar”structure was prepared by layer-by-layer(LBL)technique using polyvinyl alcohol(PVA)and polymethyl methacrylate(PMMA)as the flexible material or“mortar”and mica as the rigid material or...A film with“brick-and-mortar”structure was prepared by layer-by-layer(LBL)technique using polyvinyl alcohol(PVA)and polymethyl methacrylate(PMMA)as the flexible material or“mortar”and mica as the rigid material or“brick”.The film deposited on a glass slide after self-assembly cycles had a thickness of 3μm thick and an uneven,wavy surface.The film exhibits enhanced mechanical properties,i e,the hardness and indentation modulus values could reach 6.14 and 68.41 GPa,respectively.The hardness and elastic toughness were found to be depended on three factors,i e,the ratio of PVA to mica,the number of self-assembly cycles,and the pretreatment method of the mica suspension.The self-assembly process was driven by formation of the hydrogen bonds between the silanol groups of mica and the hydroxyl groups of PVA and carbonyl groups of PMMA.展开更多
Magnesium alloy has been generally accepted as an important biodegradable material on cardiovascular stent development for a long time. However, its limited biocompatibility, especially delayed endothelialization proc...Magnesium alloy has been generally accepted as an important biodegradable material on cardiovascular stent development for a long time. However, its limited biocompatibility, especially delayed endothelialization process restricts its further application. In this contribution, we modified the Mg-Zn-Y-Nd alloy surface with citric acid and dopamine via a layer-by-layer self-assembly assay, aiming at improving the biocompatibility of the magnesium alloy. The citric acid/dopamine(CA/PDA) layer exhibited a remarkable suppression of platelet activation/aggregation and thrombosis under 15 dyn/cm2 blood flowing. Inhibition on vascular smooth muscle cells growth and macrophages attachment/activation were also observed on this layer. In particular, the CA/PDA layer presented a promoted property for the vascular endothelial cells growth and spreading compared with the bare magnesium alloy, suggesting the pro-endotelialized function. In conclusion, this research may support potential application on surface modification of magnesium alloy based cardiovascular stents for better biocompatibility.展开更多
Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practica...Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practical performance is limited by inhomogeneous agglomeration,increased binder requirements,and high tortuosity within the electrode.To overcome these problems and high tortuosity within the electrode,this study introduces a pomegranate-like carbon microcluster composed of primary HCSs(P-CMs)as a novel Li metal host.This unique nanostructure can be easily prepared using the spray-drying technique,enabling its mass production.Comprehensive analyses with various tools demonstrate that compared with HCS hosts,the P-CM host requires a smaller amount of binder to fabricate a sufficiently robust and even surface electrode.Furthermore,owing to reduced tortuosity,the well-designed P-CM electrode can provide continuous and shortened pathways for electron/ion transport,accelerating the Li-ion transfer kinetics and prohibiting preferential Li plating at the upper region of the electrode.Due to these characteristics,Li metal can be effectively encapsulated in the large inner voids of the primary HCSs constituting the P-CM,thereby enhancing the electrochemical performance of P-CM hosts in Li metal batteries.Specifically,the Coulombic efficiency of the P-CM host can be maintained at 97%over 100 cycles,with a high Li deposition areal capacity of 3 mAh·cm^(-2)and long cycle life(1000 h,1 mA·cm^(-2),and 1.0 mAh·cm^(-2)).Furthermore,a full cell incorporating a LiFePO4 cathode exhibits excellent cycle life.展开更多
Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,whic...Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,which can be used to construct self-assembled nanoparticles in aqueous solution driven by hydrophobic interaction.Dynamic light scattering experiments show that M1 and M2 can be driven hydrophobically to aggregate into extremely stable nanoparticles in water at the micromolar concentrations.Fluorescence titration and zeta potential experiments support that the nanoparticles formed by M1 and M2 are able to efficiently encapsulate short DNA(sDNA).Fluorescence imaging and flow cytometry studies reveal that their nano sizes enable intracellular delivery of the encapsulated sDNA into both normal and cancer cells,with delivery percentage reaching up to 94%,while in vitro experiments indicate that the two compounds have excellent biocompatibility and low cytotoxicity.展开更多
The increasing consciousness about the depletion of natural resources and the sustainability agenda are the major driving forces to try to reuse and recycle organic materials such as agri-food and industrial wastes.In...The increasing consciousness about the depletion of natural resources and the sustainability agenda are the major driving forces to try to reuse and recycle organic materials such as agri-food and industrial wastes.In this context,keratin fibers,as a waste from the tannery industry,represent a great opportunity for the development of green functional materials.In this paper,keratin fibers were surface functionalized using the Layer-by-Layer(LbL)deposition technique and then freeze-dried in order to obtain a lightweight,fire-resistant,and sustainable material.The LbL coating,made with chitosan and carboxymethylated cellulose nanofibers,is fundamental in enabling the formation of a self-sustained structure after freeze-drying.The prepared porous fiber networks(density 100 kg m^(-3))display a keratin fiber content greater than 95 wt%and can easily self-extinguish the flame during a flammability test in a vertical configuration.In addition,during forced combustion tests(50 kW m^(-2))the samples exhibited a reduction of 37% in heat release rate and a reduction of 75%in smoke production if compared with a commercial polyurethane foam.The results obtained represent an excellent opportunity for the development of fire-safe sustainable materials based on fiber wastes.展开更多
Nowadays,high-stable and ultrasensitive heavy metal detection is of utmost importance in water quality monitoring.Nanoparticle-enhanced laser-induced breakdown spectroscopy(NELIBS)shows high potential in hazardous met...Nowadays,high-stable and ultrasensitive heavy metal detection is of utmost importance in water quality monitoring.Nanoparticle-enhanced laser-induced breakdown spectroscopy(NELIBS)shows high potential in hazardous metal detection,however,encounters unstable and weak signals due to nonuniform distribution of analytes.Herein,we developed an interface self-assembly(ISA)method to create a uniformly distributed gold nanolayer at a liquid-liquid interface for positive heavy metal ions capture and NELIBS analysis.The electrostatically selfassembled Au nanoparticles(NPs)-analytes membrane was prepared at the oil-water interface by injecting ethanol into the mixture of cyclohexane and Au NPs-analytes water solution.Then,the interface self-assembled Au NPs-analytes membrane was transformed onto a laser-processed superhydrophilic Si slide for detection.Three heavy metals(cadmium(Cd),barium(Ba),and chromium(Cr))were analyzed to evaluate the stability and sensitivity of the ISA method for NELIBS.The results(Cd:RSD=3.6%,LoD=0.654 mg/L;Ba:RSD=3.4%,LoD=0.236 mg/L;Cr:RSD=7.7%,LoD=1.367 mg/L)demonstrated signal enhancement and high-stable and ultrasensitive detection.The actual sample detection(Cd:RE=7.71%,Ba:RE=6.78%)illustrated great reliability.The ISA method,creating a uniform distribution of NP-analytes at the interface,has promising prospects in NELIBS.展开更多
Diphenylalanine and its analogs cause many concerns owing to their perfect self-assembly properties in the fields of biology,medicine,and nanotechnology.Experimental research has shown that diphenylalanine-based analo...Diphenylalanine and its analogs cause many concerns owing to their perfect self-assembly properties in the fields of biology,medicine,and nanotechnology.Experimental research has shown that diphenylalanine-based analogs with ethylenediamine linkers(PA,P=phenylalanine,and A=analog)can self-assemble into spherical assemblies,which can serve as novel anticancer drug carriers.In this work,to understand the assembly pathways,drug loading behavior,and formation mechanism of PA aggregates at the molecular level,we carried out dissipative particle dynamics(DPD)simulations of PA molecule systems.Our simulation results demonstrate that PA molecules spontaneously assemble into nanospheres and can self-assemble into drug-loaded nanospheres upon addition of the cancer chemotherapeutic agent doxorubicin(DOX).We also found that the hydrophobic side chain beads of PA molecules exhibited a unique onion-like distribution inside the nanospheres,which was not observed in the experiment.The onion-like nanospheres were verified by calculating the radial distribution function(RDF)of the DPD beads.Furthermore,based on the analysis of the percentages of different interaction components in the total nonbonded energies,main chain-side chain interactions between PA molecules may be important in the formation of onion-like nanospheres,and the synergistic effects of main chain-side chain,main chain-drug,side chain-drug,and main chain-solvent interactions are significant in the formation of drug-loaded nanospheres.These findings provide new insights into the structure and self-assembly pathway of PA assemblies,which may be helpful for the design of efficient and effective drug delivery systems.展开更多
The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching(ACQ).In this study,an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence em...The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching(ACQ).In this study,an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence emission through protein coronas-controlled distance between gold nanoclusters(Au NCs).Interestingly,the gold ion complexes coated with proteins of low isoelectric point(pI)nucleate at the secondary structure of proteins with high p I through ionic exchange within cells,generating fluorescent Au NCs.It is worth noting that due to the steric hindrance formed by the protein coronas on the surface of Au NCs,the distance between Au NCs can be controlled,avoiding electron transfer caused by close proximity of Au NCs and inhibiting fluorescence ACQ.This strategy can achieve fluorescence imaging of clinical tissue samples without observable side effects.Therefore,this study proposes a distance-controllable self-assembled pitaya structure to provide a new approach for Au NCs with stable fluorescence.展开更多
The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements.In this pape r,the extractant(N,N-methyl py ridineethyl-N',N'-dicyclohexyl-3-oxadiglycola...The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements.In this pape r,the extractant(N,N-methyl py ridineethyl-N',N'-dicyclohexyl-3-oxadiglycolamide,MPyEDChDGA) with a new structure was synthesized,and the pyridine group was successfully grafted onto the 3-oxadiglycolamide structure.Using MPyEDChDGA for efficient enrichment of rare earth ions,the self-assembled solids were recovered by simple filtration without further backextraction and final precipitation,achieving a one-step strategy for the recovery of rare earth ions.Several important parameters affecting the self-assembly extraction,including pH,diluent,temperature,and extractant concentration,were systematically evaluated using La(NO_(3))_(3),Tb(NO_(3))_(3),and Lu(NO_(3))_(3) as representatives.The self-assembled solids were investigated in detail by X-ray diffraction(XRD),scanning electron microscopy(SEM),1H nuclear magnetic resonance(1H NMR),Fourier transform infrared spectroscopy(FT-IR),Raman,and X-ray photoelectron spectroscopy(XPS) analyses.The stoichiometry of the extraction species was characterized using the Job's method and electrospray ionization mass spectrometry(ESI-MS).In addition,MPyEDChDGA was applied to the recovery of Sm in SmCoCu simulated liquid,and the results show that MPyEDChDGA has good selectivity of Sm from transition metals(Co,Cu).The separation factor of Sm/Co can reach 6281±117,which provides a new approach to recovering Sm from SmCoCu scrap magnets.This study presents an efficient and convenient new strategy for the recovery and separation of rare earth elements.展开更多
Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AAB...Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AABCs presents challenges,which greatly limits the exploration of their self-assembly behaviors.In this work,we employed dissipative particle dynamics(DPD)simulations to investigate the self-assembly behaviors of AABCs in selective solution.By varying the copolymer concentration and structure,we conducted the self-assembly phase diagrams of AABCs,revealing complex morphologies such as channelized micelles with one or more solvophilic channels.Moreover,the number,surface area,and one-dimensional density distribution of the channelized micelles were calculated to demonstrate the internal structure and morphological transformation during the self-assembly process.Our findings indicate that the morphology of the internal solvophilic channels is greatly influenced by the copolymer structure,concentration,and interaction parameters between the different side chains.The simulation results are consistent with available experimental observations,which can offer theoretical insights into the self-assembly of AABCs.展开更多
The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable.Here,we...The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable.Here,we report a fluorinated N-heterocyclic carbene(NHC)–based pillarplex with a tunable quaternary structure,employed as an efficient building block for constructing hierarchical superstructures.Initially,multiple noncovalent interactions in the NHC-based pillarplex,particularly those between the fluorinated pillarplex and PF_(6)-anions,induce the formation of a supramolecular gel at high concentrations.Additionally,this hierarchical self-assembled structure can be regulated by adjusting anion types,facilitating the controlled transformation from a supramolecular gel into a supramolecular channel upon the introduction of four monocarboxylic acids as anions.The study provides insight into the construction and controlled regulation of superstructures based on NHC-based pillarplexes.展开更多
Polymerization-induced self-assembly(PISA)has become one of the most versatile approaches for scalable preparation of linear block copolymer nanoparticles with various morphologies.However,the controlled introduction ...Polymerization-induced self-assembly(PISA)has become one of the most versatile approaches for scalable preparation of linear block copolymer nanoparticles with various morphologies.However,the controlled introduction of branching into the core-forming block and the effect on the morphologies of block copolymer nanoparticles under PISA conditions have rarely been explored.Herein,a series of multifunctional macromolecular chain transfer agents(macro-CTAs)were first synthesized by a two-step green light-activated photoiniferter polymerization using two types of chain transfer monomers(CTMs).These macro-CTAs were then used to mediate reversible addition-fragmentation chain transfer(RAFT)dispersion polymerization of styrene(St)to prepare block copolymers with different core-forming block structures and the assemblies.The effect of the core-forming block structure on the morphology of block copolymer nanoparticles was investigated in detail.Transmission electron microscopy(TEM)analysis indicated that the brush-like core-forming block structure facilitated the formation of higher-order morphologies,while the branched core-forming block structure favored the formation of lower-order morphologies.Moreover,it was found that using macroCTAs with a shorter length also promoted the formation of higher-order morphologies.Finally,structures of block copolymers and the assemblies were further controlled by changing the structure of macro-CTA or using a binary mixture of two different macro-CTAs.We expect that this work not only sheds light on the synthesis of block copolymer nanoparticles but also provide important mechanistic insights into PISA of nonlinear block copolymers.展开更多
Antiferromagnetic(AFM)spintronics have sparked extensive research interest in the field of information storage due to the considerable advantages offered by antiferromagnets,including non-volatile data storage,higher ...Antiferromagnetic(AFM)spintronics have sparked extensive research interest in the field of information storage due to the considerable advantages offered by antiferromagnets,including non-volatile data storage,higher storage density,and accelerating data processing.However,the manipulation and detection of internal AFM order in antiferromagnets hinders their applications in spintronic devices.Here,we proposed a design idea for an AFM material that is self-assembled from one-dimensional(1D)ferromagnetic(FM)chains.To validate this idea,we screened a two-dimensional(2D)selfassembled CrBr_(2)antiferromagnet of an AFM semiconductor from a large amount of data.This 2D CrBr_(2)antiferromagnet is composed of 1D FM CrBr_(2)chains that are arranged in a staggered and parallel configuration.In this type of antiferromagnet,the write-data operation of information is achieved in 1D FM chains,followed by a self-assembly process driving the assembly of 1D FM chains into an antiferromagnet.These constituent 1D FM chains become decoupled by external perturbations,such as heat,pressure,strain,etc.,thereby realizing the read-data operation of information.We anticipate that this antiferromagnet,composed of 1D FM chains,can be realized not only in the 1D to 2D system,but also is expected to expand to 2D to three-dimensional(3D)system,and even 1D to 3D system.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
The hydration state of amphiphilic block copolymers during the self-assembly transition is closely related to the structure and properties of copolymers. In this study, the temperature-induced self-assembly of copolym...The hydration state of amphiphilic block copolymers during the self-assembly transition is closely related to the structure and properties of copolymers. In this study, the temperature-induced self-assembly of copolymer poly(N,N-dimethylacrylamide)-poly(diacetone acrylamide)(PDMAA_(30)-PDAAM_(60))_(2)in aqueous solution was monitored by near-infrared spectroscopy with water as a probe. The wavelet packet transform was employed to improve the spectral resolution. The spectral information of hydrated water surrounding the hydrophilic PDMAA and hydrophobic PDAAM blocks was then extracted, revealing the significant roles of water in morphological transition of the copolymer from spherical to worm-like micelles. Specifically, water molecules interacting with N atoms and C=O groups of the hydrophilic block gradually decrease during the morphological transition, while hydrogen-bond structures NH–CO of the hydrophobic block gradually break, bringing more water molecules into contact with the hydrophobic block. This work provides a foundation for exploring the role of water molecules during the self-assembly transition of complex block copolymers.展开更多
Core-shell colloidal particles with a polymer layer have broad applications in different areas.Herein,we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembl...Core-shell colloidal particles with a polymer layer have broad applications in different areas.Herein,we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembly and photoinduced seeded reversible addition-fragmentation chain transfer(RAFT)polymerization to prepare a diverse set of core-shell colloidal particles with a well-defined polymer layer.Chemical compositions,structures,and thicknesses of polymer layers could be conveniently regulated by using different types of monomers and feed[monomer]/[chain transfer agent]ratios during seeded RAFT polymerization.展开更多
Developing novel building blocks with predictable side-chain orientations and minimal intramolecular interactions is essential for peptide-based self-assembling materials.Traditional structures likeα-helices andβ-sh...Developing novel building blocks with predictable side-chain orientations and minimal intramolecular interactions is essential for peptide-based self-assembling materials.Traditional structures likeα-helices andβ-sheets rely on such interactions for stability,limiting control over exposed interacting moieties.Here,we reported a novel,frame-like peptide scaffold that maintains exceptional stability without intramolecular interactions.This structure exposes its backbone and orients side chains for hierarchical self-assembly into micron-scale cubes.By introducing mutations at specific sites,we controlled packing orientations,offering new options for tunable self-assembly.Our scaffold provides a versatile platform for designing advanced peptide materials,with applications in nanotechnology and biomaterials.展开更多
基金National Undergraduate Training Program for Innovation and Entrepreneurship of China (Grant No.202210288027).
文摘The abuse of plastic food packaging has brought about severe white pollution issues around the world.Developing green and sustainable biomass packaging is an effective way to solve this problem.Hence,a chitosan/sodium alginate-based multilayer film is fabricated via a layer-by-layer(LBL)self-assembly method.With the help of superior interaction between the layers,the multilayer film possesses excellent mechanical properties(with a tensile strength of 50 MPa).Besides,the film displays outstanding water retention property(blocking moisture of 97.56%)and ultraviolet blocking property.Anthocyanin is introduced into the film to detect the food quality since it is one natural plant polyphenol that is sensitive to the pH changes ranging from 1 to 13 in food when spoilage occurs.It is noted that the film is also bacteriostatic which is desired for food packaging.This study describes a simple technique for the development of advanced multifunctional and fully biodegradable food packaging film and it is a sustainable alternative to plastic packaging.
基金financially supported by the National Natural Science Foundation of China(No.51273063 and 51003028)the Fundamental Research Funds for the Central Universities+1 种基金the Higher School Specialized Research Fund for the Doctoral Program(No.20110074110003)111 Project Grant(No.B08021)
文摘Spherical polyelectrolyte brushes (SPBs) consisting of polystyrene (PS) core and poly(2-aminoethyl methacrylate hydrochloride) (PAEMH) shell were prepared by photo-emulsion polymerization. Au nanoparticles (Au-NPs) with controlled size and size distribution were synthesized in situ using SPBs as nanoreactors. Via layer-by-layer deposition technique on the surface of SPBs, nano-composite particles with Au/Ag-NPs bilayer and Au/Ag/Au-NPs trilayer were prepared. The structures of the as-prepared Au/Ag multilayer SPBs were characterized by UV-Vis spectroscopy, TEM, ICP-AES and DLS. The charge reversal of the nano-composite particles observed by zeta potential confirmed the success of layer-by-layer assembly. The Au/Ag-NPs bilayer nano-composite particles showed high catalytic efficiency with an apparent activation energy of about 41.2 kJ/mol in the reduction reaction of 4-nitrophenol to 4-aminophenol in the existence of sodium borohydride monitored. The catalytic activity ofAu/Ag-NPs multilayer SPBs close to that of Au-NPs SPBs and much higher than that of Ag-NPs SPBs reveals its potential applications in cost-effective catalysts with high-performance.
文摘Orthopedic implants for the treatment of bone defects from various causes have been challenged by insufficient osseointegration,bacterial infection,oxidative stress,immune rejection,and insufficient individualized treatment.These challenges not only impact treatment outcomes but also severely impact patients’daily lives.Layer-by-Layer(LbL)serves as a simple surface coating technique,in simple terms,to functionalize implants by sequentially adsorbing oppositely charged materials onto a substrate.In orthopaedics,LbL self-assembly technology solves some of the challenges by loading various drugs or biological agents on the implant surface and controlling their release precisely to the site of bone defects in a personalized way.This review will introduce the basic principle and the development of LbL in orthopaedics,review and analyze the chemical strategy of LbL in the preparation of bone implants to ensure the stability of the implant,and introduce the use of LbL bone implants in orthopaedics in recent years.The application of LbL includes the realization of programmed drug delivery and sustained release,thereby promoting osseointegration and the formation of new blood vessels,antibacterial,antioxidant,etc.This review focuses on the LbL technology,involving the technology selection for the preparation of bone implants,the chemical strategies of the stability guarantee of LbL implants,the pharmacological properties,loading and release mechanisms of loaded drugs,and the molecular mechanisms of osteogenesis and angiogenesis.The aim of this review is to provide an overview of current research advances,and a prospect in this field was also described.
基金Funded by the Wuhan Science and Technology Bureau(No.2020020601012279)。
文摘A film with“brick-and-mortar”structure was prepared by layer-by-layer(LBL)technique using polyvinyl alcohol(PVA)and polymethyl methacrylate(PMMA)as the flexible material or“mortar”and mica as the rigid material or“brick”.The film deposited on a glass slide after self-assembly cycles had a thickness of 3μm thick and an uneven,wavy surface.The film exhibits enhanced mechanical properties,i e,the hardness and indentation modulus values could reach 6.14 and 68.41 GPa,respectively.The hardness and elastic toughness were found to be depended on three factors,i e,the ratio of PVA to mica,the number of self-assembly cycles,and the pretreatment method of the mica suspension.The self-assembly process was driven by formation of the hydrogen bonds between the silanol groups of mica and the hydroxyl groups of PVA and carbonyl groups of PMMA.
基金supported by the National Key Research and Development Program of China(Grant Nos.2016YFC1102403&2017YFGX090043-04)Fostering Talents of National Natural Science Foundation of China and Henan Province(Grant No.U1504310)National Center for International Research of Micro-nano Molding Technology&Key Laboratory for Micro Molding Technology of Henan Province(Grant No.MMT2017-01)
文摘Magnesium alloy has been generally accepted as an important biodegradable material on cardiovascular stent development for a long time. However, its limited biocompatibility, especially delayed endothelialization process restricts its further application. In this contribution, we modified the Mg-Zn-Y-Nd alloy surface with citric acid and dopamine via a layer-by-layer self-assembly assay, aiming at improving the biocompatibility of the magnesium alloy. The citric acid/dopamine(CA/PDA) layer exhibited a remarkable suppression of platelet activation/aggregation and thrombosis under 15 dyn/cm2 blood flowing. Inhibition on vascular smooth muscle cells growth and macrophages attachment/activation were also observed on this layer. In particular, the CA/PDA layer presented a promoted property for the vascular endothelial cells growth and spreading compared with the bare magnesium alloy, suggesting the pro-endotelialized function. In conclusion, this research may support potential application on surface modification of magnesium alloy based cardiovascular stents for better biocompatibility.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.2020R1C1C1003375)。
文摘Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practical performance is limited by inhomogeneous agglomeration,increased binder requirements,and high tortuosity within the electrode.To overcome these problems and high tortuosity within the electrode,this study introduces a pomegranate-like carbon microcluster composed of primary HCSs(P-CMs)as a novel Li metal host.This unique nanostructure can be easily prepared using the spray-drying technique,enabling its mass production.Comprehensive analyses with various tools demonstrate that compared with HCS hosts,the P-CM host requires a smaller amount of binder to fabricate a sufficiently robust and even surface electrode.Furthermore,owing to reduced tortuosity,the well-designed P-CM electrode can provide continuous and shortened pathways for electron/ion transport,accelerating the Li-ion transfer kinetics and prohibiting preferential Li plating at the upper region of the electrode.Due to these characteristics,Li metal can be effectively encapsulated in the large inner voids of the primary HCSs constituting the P-CM,thereby enhancing the electrochemical performance of P-CM hosts in Li metal batteries.Specifically,the Coulombic efficiency of the P-CM host can be maintained at 97%over 100 cycles,with a high Li deposition areal capacity of 3 mAh·cm^(-2)and long cycle life(1000 h,1 mA·cm^(-2),and 1.0 mAh·cm^(-2)).Furthermore,a full cell incorporating a LiFePO4 cathode exhibits excellent cycle life.
文摘Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,which can be used to construct self-assembled nanoparticles in aqueous solution driven by hydrophobic interaction.Dynamic light scattering experiments show that M1 and M2 can be driven hydrophobically to aggregate into extremely stable nanoparticles in water at the micromolar concentrations.Fluorescence titration and zeta potential experiments support that the nanoparticles formed by M1 and M2 are able to efficiently encapsulate short DNA(sDNA).Fluorescence imaging and flow cytometry studies reveal that their nano sizes enable intracellular delivery of the encapsulated sDNA into both normal and cancer cells,with delivery percentage reaching up to 94%,while in vitro experiments indicate that the two compounds have excellent biocompatibility and low cytotoxicity.
基金supported by the Italian Ministry of University(MIUR)call PRIN 2017 with the project“PANACEA:A technology Platform for the sustainable recovery and advanced use of NAnostructured CEllulose from Agro-food residues”(grant No.2017LEPH3M).
文摘The increasing consciousness about the depletion of natural resources and the sustainability agenda are the major driving forces to try to reuse and recycle organic materials such as agri-food and industrial wastes.In this context,keratin fibers,as a waste from the tannery industry,represent a great opportunity for the development of green functional materials.In this paper,keratin fibers were surface functionalized using the Layer-by-Layer(LbL)deposition technique and then freeze-dried in order to obtain a lightweight,fire-resistant,and sustainable material.The LbL coating,made with chitosan and carboxymethylated cellulose nanofibers,is fundamental in enabling the formation of a self-sustained structure after freeze-drying.The prepared porous fiber networks(density 100 kg m^(-3))display a keratin fiber content greater than 95 wt%and can easily self-extinguish the flame during a flammability test in a vertical configuration.In addition,during forced combustion tests(50 kW m^(-2))the samples exhibited a reduction of 37% in heat release rate and a reduction of 75%in smoke production if compared with a commercial polyurethane foam.The results obtained represent an excellent opportunity for the development of fire-safe sustainable materials based on fiber wastes.
基金supported by the National Natural Science Foundation of China(No.62075069 and 52303092)the Water Conservancy Technology project of Hunan Province,China(XSKJ2021000-32)+1 种基金the City University of Hong Kong(#7005507)the Open Project of Yunnan Precious Metals Laboratory Co.,Ltd(grant number YPML-2023050278).
文摘Nowadays,high-stable and ultrasensitive heavy metal detection is of utmost importance in water quality monitoring.Nanoparticle-enhanced laser-induced breakdown spectroscopy(NELIBS)shows high potential in hazardous metal detection,however,encounters unstable and weak signals due to nonuniform distribution of analytes.Herein,we developed an interface self-assembly(ISA)method to create a uniformly distributed gold nanolayer at a liquid-liquid interface for positive heavy metal ions capture and NELIBS analysis.The electrostatically selfassembled Au nanoparticles(NPs)-analytes membrane was prepared at the oil-water interface by injecting ethanol into the mixture of cyclohexane and Au NPs-analytes water solution.Then,the interface self-assembled Au NPs-analytes membrane was transformed onto a laser-processed superhydrophilic Si slide for detection.Three heavy metals(cadmium(Cd),barium(Ba),and chromium(Cr))were analyzed to evaluate the stability and sensitivity of the ISA method for NELIBS.The results(Cd:RSD=3.6%,LoD=0.654 mg/L;Ba:RSD=3.4%,LoD=0.236 mg/L;Cr:RSD=7.7%,LoD=1.367 mg/L)demonstrated signal enhancement and high-stable and ultrasensitive detection.The actual sample detection(Cd:RE=7.71%,Ba:RE=6.78%)illustrated great reliability.The ISA method,creating a uniform distribution of NP-analytes at the interface,has promising prospects in NELIBS.
基金financially supported by the National Natural Science Foundation of China(Nos.20904047 and 12074151)the Natural Science Foundation of Zhejiang Province(Nos.LY17A040001 and LY19F03004)。
文摘Diphenylalanine and its analogs cause many concerns owing to their perfect self-assembly properties in the fields of biology,medicine,and nanotechnology.Experimental research has shown that diphenylalanine-based analogs with ethylenediamine linkers(PA,P=phenylalanine,and A=analog)can self-assemble into spherical assemblies,which can serve as novel anticancer drug carriers.In this work,to understand the assembly pathways,drug loading behavior,and formation mechanism of PA aggregates at the molecular level,we carried out dissipative particle dynamics(DPD)simulations of PA molecule systems.Our simulation results demonstrate that PA molecules spontaneously assemble into nanospheres and can self-assemble into drug-loaded nanospheres upon addition of the cancer chemotherapeutic agent doxorubicin(DOX).We also found that the hydrophobic side chain beads of PA molecules exhibited a unique onion-like distribution inside the nanospheres,which was not observed in the experiment.The onion-like nanospheres were verified by calculating the radial distribution function(RDF)of the DPD beads.Furthermore,based on the analysis of the percentages of different interaction components in the total nonbonded energies,main chain-side chain interactions between PA molecules may be important in the formation of onion-like nanospheres,and the synergistic effects of main chain-side chain,main chain-drug,side chain-drug,and main chain-solvent interactions are significant in the formation of drug-loaded nanospheres.These findings provide new insights into the structure and self-assembly pathway of PA assemblies,which may be helpful for the design of efficient and effective drug delivery systems.
基金supported by the National Natural Science Foundation of China(Nos.82061148012,82027806,21974019)SEU Innovation Capability Enhancement Plan for Doctoral Students(No.CXJH_SEU 24138)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX24_0469)。
文摘The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching(ACQ).In this study,an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence emission through protein coronas-controlled distance between gold nanoclusters(Au NCs).Interestingly,the gold ion complexes coated with proteins of low isoelectric point(pI)nucleate at the secondary structure of proteins with high p I through ionic exchange within cells,generating fluorescent Au NCs.It is worth noting that due to the steric hindrance formed by the protein coronas on the surface of Au NCs,the distance between Au NCs can be controlled,avoiding electron transfer caused by close proximity of Au NCs and inhibiting fluorescence ACQ.This strategy can achieve fluorescence imaging of clinical tissue samples without observable side effects.Therefore,this study proposes a distance-controllable self-assembled pitaya structure to provide a new approach for Au NCs with stable fluorescence.
基金Project supported by the Natural Science Foundation of Shandong Province (ZR2022QB067)。
文摘The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements.In this pape r,the extractant(N,N-methyl py ridineethyl-N',N'-dicyclohexyl-3-oxadiglycolamide,MPyEDChDGA) with a new structure was synthesized,and the pyridine group was successfully grafted onto the 3-oxadiglycolamide structure.Using MPyEDChDGA for efficient enrichment of rare earth ions,the self-assembled solids were recovered by simple filtration without further backextraction and final precipitation,achieving a one-step strategy for the recovery of rare earth ions.Several important parameters affecting the self-assembly extraction,including pH,diluent,temperature,and extractant concentration,were systematically evaluated using La(NO_(3))_(3),Tb(NO_(3))_(3),and Lu(NO_(3))_(3) as representatives.The self-assembled solids were investigated in detail by X-ray diffraction(XRD),scanning electron microscopy(SEM),1H nuclear magnetic resonance(1H NMR),Fourier transform infrared spectroscopy(FT-IR),Raman,and X-ray photoelectron spectroscopy(XPS) analyses.The stoichiometry of the extraction species was characterized using the Job's method and electrospray ionization mass spectrometry(ESI-MS).In addition,MPyEDChDGA was applied to the recovery of Sm in SmCoCu simulated liquid,and the results show that MPyEDChDGA has good selectivity of Sm from transition metals(Co,Cu).The separation factor of Sm/Co can reach 6281±117,which provides a new approach to recovering Sm from SmCoCu scrap magnets.This study presents an efficient and convenient new strategy for the recovery and separation of rare earth elements.
基金supported by the National Science Foundation for Distinguished Young Scholars(No.52325308)the National Natural Science Foundation of China(Nos.52273008 and 52073092)+1 种基金Shanghai Scientific and Technological Innovation Projects(No.22ZR1479300)Shanghai Rising-Star Program(No.23QA1402500).
文摘Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AABCs presents challenges,which greatly limits the exploration of their self-assembly behaviors.In this work,we employed dissipative particle dynamics(DPD)simulations to investigate the self-assembly behaviors of AABCs in selective solution.By varying the copolymer concentration and structure,we conducted the self-assembly phase diagrams of AABCs,revealing complex morphologies such as channelized micelles with one or more solvophilic channels.Moreover,the number,surface area,and one-dimensional density distribution of the channelized micelles were calculated to demonstrate the internal structure and morphological transformation during the self-assembly process.Our findings indicate that the morphology of the internal solvophilic channels is greatly influenced by the copolymer structure,concentration,and interaction parameters between the different side chains.The simulation results are consistent with available experimental observations,which can offer theoretical insights into the self-assembly of AABCs.
基金financial support from the National Natural Science Fund for Distinguished Young Scholars of China(No.22025107)Shaanxi Fundamental Science Research Project for Chemistry&Biology(No.22JHZ003)+2 种基金the Key International Scientific and Technological Cooperation and Exchange Project of Shaanxi Province(No.2023-GHZD-15)the National Youth Top-notch Talent Support Program of Chinathe FM&EM International Joint Laboratory of Northwest University。
文摘The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable.Here,we report a fluorinated N-heterocyclic carbene(NHC)–based pillarplex with a tunable quaternary structure,employed as an efficient building block for constructing hierarchical superstructures.Initially,multiple noncovalent interactions in the NHC-based pillarplex,particularly those between the fluorinated pillarplex and PF_(6)-anions,induce the formation of a supramolecular gel at high concentrations.Additionally,this hierarchical self-assembled structure can be regulated by adjusting anion types,facilitating the controlled transformation from a supramolecular gel into a supramolecular channel upon the introduction of four monocarboxylic acids as anions.The study provides insight into the construction and controlled regulation of superstructures based on NHC-based pillarplexes.
基金financially supported by the National Natural Science Foundation of China(Nos.22171055 and 52222301)the Guangdong Natural Science Foundation for Distinguished Young Scholar(No.2022B1515020078)the Science and Technology Program of Guangzhou(No.2024A04J2821)。
文摘Polymerization-induced self-assembly(PISA)has become one of the most versatile approaches for scalable preparation of linear block copolymer nanoparticles with various morphologies.However,the controlled introduction of branching into the core-forming block and the effect on the morphologies of block copolymer nanoparticles under PISA conditions have rarely been explored.Herein,a series of multifunctional macromolecular chain transfer agents(macro-CTAs)were first synthesized by a two-step green light-activated photoiniferter polymerization using two types of chain transfer monomers(CTMs).These macro-CTAs were then used to mediate reversible addition-fragmentation chain transfer(RAFT)dispersion polymerization of styrene(St)to prepare block copolymers with different core-forming block structures and the assemblies.The effect of the core-forming block structure on the morphology of block copolymer nanoparticles was investigated in detail.Transmission electron microscopy(TEM)analysis indicated that the brush-like core-forming block structure facilitated the formation of higher-order morphologies,while the branched core-forming block structure favored the formation of lower-order morphologies.Moreover,it was found that using macroCTAs with a shorter length also promoted the formation of higher-order morphologies.Finally,structures of block copolymers and the assemblies were further controlled by changing the structure of macro-CTA or using a binary mixture of two different macro-CTAs.We expect that this work not only sheds light on the synthesis of block copolymer nanoparticles but also provide important mechanistic insights into PISA of nonlinear block copolymers.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12435001,12304006,and 12404265)the Natural Science Foundation of Shanghai,China(Grant No.23JC1401400)+1 种基金the Fundamental Research Funds for the Central Universities of East China University,the Natural Science Foundation of WIUCAS(Grant No.WIUCASQD2023004)the Natural Science Foundation of Wenzhou(Grant No.L2023005)。
文摘Antiferromagnetic(AFM)spintronics have sparked extensive research interest in the field of information storage due to the considerable advantages offered by antiferromagnets,including non-volatile data storage,higher storage density,and accelerating data processing.However,the manipulation and detection of internal AFM order in antiferromagnets hinders their applications in spintronic devices.Here,we proposed a design idea for an AFM material that is self-assembled from one-dimensional(1D)ferromagnetic(FM)chains.To validate this idea,we screened a two-dimensional(2D)selfassembled CrBr_(2)antiferromagnet of an AFM semiconductor from a large amount of data.This 2D CrBr_(2)antiferromagnet is composed of 1D FM CrBr_(2)chains that are arranged in a staggered and parallel configuration.In this type of antiferromagnet,the write-data operation of information is achieved in 1D FM chains,followed by a self-assembly process driving the assembly of 1D FM chains into an antiferromagnet.These constituent 1D FM chains become decoupled by external perturbations,such as heat,pressure,strain,etc.,thereby realizing the read-data operation of information.We anticipate that this antiferromagnet,composed of 1D FM chains,can be realized not only in the 1D to 2D system,but also is expected to expand to 2D to three-dimensional(3D)system,and even 1D to 3D system.
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supported by the National Natural Science Foundation of China (Nos. 22174075 and 22374082)the Haihe Laboratory of Sustainable Chemical Transformations。
文摘The hydration state of amphiphilic block copolymers during the self-assembly transition is closely related to the structure and properties of copolymers. In this study, the temperature-induced self-assembly of copolymer poly(N,N-dimethylacrylamide)-poly(diacetone acrylamide)(PDMAA_(30)-PDAAM_(60))_(2)in aqueous solution was monitored by near-infrared spectroscopy with water as a probe. The wavelet packet transform was employed to improve the spectral resolution. The spectral information of hydrated water surrounding the hydrophilic PDMAA and hydrophobic PDAAM blocks was then extracted, revealing the significant roles of water in morphological transition of the copolymer from spherical to worm-like micelles. Specifically, water molecules interacting with N atoms and C=O groups of the hydrophilic block gradually decrease during the morphological transition, while hydrogen-bond structures NH–CO of the hydrophobic block gradually break, bringing more water molecules into contact with the hydrophobic block. This work provides a foundation for exploring the role of water molecules during the self-assembly transition of complex block copolymers.
基金support from the Science and Technology Program of Guangzhou(No.2024A04J2821)the National Natural Science Foundation of China(Nos.52222301,22171055)the Guangdong Natural Science Foundation for Distinguished Young Scholar(No.2022B1515020078)。
文摘Core-shell colloidal particles with a polymer layer have broad applications in different areas.Herein,we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembly and photoinduced seeded reversible addition-fragmentation chain transfer(RAFT)polymerization to prepare a diverse set of core-shell colloidal particles with a well-defined polymer layer.Chemical compositions,structures,and thicknesses of polymer layers could be conveniently regulated by using different types of monomers and feed[monomer]/[chain transfer agent]ratios during seeded RAFT polymerization.
基金supported by the National Basic Research Program of China 973 Program(Nos.2021YFA0910803,2021YFC2103900)the National Natural Science Foundation of China(No.21977011)+4 种基金the Natural Science Foundation of Guangdong Province(Nos.2022A1515010996 and 2020A1515011544)the Shenzhen Science and Technology Innovation Committee(Nos.RCJC20200714114433053,JCYJ20180507181527112 and JCYJ20200109140406047)the Shenzhen-Hong Kong Institute of Brain Science-Shenzhen Fundamental Research Institutions(No.2019SHIBS0004)the Shenzhen Fundamental Research Program(No.GXWD20201231165807007–20200827170132001)Tian Fu Jin Cheng Laboratory(Advanced Medical Center)Group Racing Project(No.TFJC2023010008)。
文摘Developing novel building blocks with predictable side-chain orientations and minimal intramolecular interactions is essential for peptide-based self-assembling materials.Traditional structures likeα-helices andβ-sheets rely on such interactions for stability,limiting control over exposed interacting moieties.Here,we reported a novel,frame-like peptide scaffold that maintains exceptional stability without intramolecular interactions.This structure exposes its backbone and orients side chains for hierarchical self-assembly into micron-scale cubes.By introducing mutations at specific sites,we controlled packing orientations,offering new options for tunable self-assembly.Our scaffold provides a versatile platform for designing advanced peptide materials,with applications in nanotechnology and biomaterials.