Copolymers with super segregated structure of hydrophilic methoxy poly(ethylene glycol) (mPEG) and fluorophilic poly(1H,1H,2H,2H-perfluorodecyl acrylate) (PFA) were prepared. And just because of this super seg...Copolymers with super segregated structure of hydrophilic methoxy poly(ethylene glycol) (mPEG) and fluorophilic poly(1H,1H,2H,2H-perfluorodecyl acrylate) (PFA) were prepared. And just because of this super segregated structure which was resulted from the extremely strong incompatibility between the two blocks, several interesting self- assembly behaviors of the copolymers were displayed and studied under different conditions. Transmission electron microscope (TEM) showed that with the increase of PFA in the polymerization system, the incompatibility in this super segregated structure became stronger, and the self-assembly behavior changed from ball-like or rod-like to vesicles, and finally collapsed to sheet-like. The self-assembly behavior changed likewise when the initial concentration increased. And the interesting formation of these barrel-like and spindle-like vesicles was finally studied with different cooling speeds. It's finally found that with this super segregation structure, these new self-assembly morphology might be formed due to the extremely strong incompatibility between mPEG and PFA segments.展开更多
The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with th...The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.展开更多
N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A...N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A comparison of the two samples by measuring their photo physical properties using UV visible absorption and fluorescence emission spectra revealed that bay substitutions of bromine do not have significant effect on the perylene diimide( PDI) photo physical properties in solution. However,the solid state fluorescence properties were enhanced by brominating at bay areas. The solid fluorescence quantum yield of 1,7-Br-PDI-C12 was 2. 83%( Фf= 2. 83%) and 1,7-H-PDI-C12 was only 0. 02%( Фf= 0. 02%). This behavior was also reflected in the steady-state fluorescence spectra. This work shows that solid state photo physical properties of PDI could be improved without changing the other properties by simply using bromine substitution at bay areas. These types of materials are useful intermediate for further synthesis of PDI with tunnable optoelectronic properties.展开更多
The pH /temperature dually responsive microgels of interpenetrating polymer network( IPN) structure composed of poly( N-isopropylacrylamide)( PNIPAM) network and poly( acrylic acid)( PAA) network( PNIPAM /PAA IPN micr...The pH /temperature dually responsive microgels of interpenetrating polymer network( IPN) structure composed of poly( N-isopropylacrylamide)( PNIPAM) network and poly( acrylic acid)( PAA) network( PNIPAM /PAA IPN microgels) were synthesized by seed emulsion polymerization. The results obtained by dynamic laser light scattering( DLLS) show that the microgels have good pH /temperature dual sensitivities. The temperature sensitive component and the pH sensitive component inside the microgels have little interference with each other. The rheological properties of the concentrated PNIPAM /PAA IPN microgel dispersions as a function of temperature at pH 4. 0 or 7. 0 were investigated by viscometer,and the results displayed that only at pH 7. 0 the dispersions presented thermoreversible thickening behavior. Then the PNIPAM /PAA fibers were prepared by self-assembly of the PNIPAM /PAA IPN microgels in the ice-crystal templates formed by unidirectional liquid nitrogen freezing method. Field emission scanning electron microscopy( FESEM) images indicate that the PNIPAM /PAA fibers are rounded,randomly orientated and interweaved.展开更多
The self-assembly behavior of sphere-forming R_5C_(30)R_5 triblock copolymers within a planar slit is studied by performing dissipative particle dynamics simulations. A sequence of novel structures which are not obs...The self-assembly behavior of sphere-forming R_5C_(30)R_5 triblock copolymers within a planar slit is studied by performing dissipative particle dynamics simulations. A sequence of novel structures which are not observed in bulk are formed within slits, including wetting layers, island-like structure, parallel cylinders, perpendicular cylinders and crosscylindrical structures. Perpendicular cylinders are always formed before the increase in the layers of parallel cylinders. A phase diagram of the assembled structures with respective to the slit property and height is thus presented. The rod length is found to have a significant impact on the rod alignment, and a disordered-ordered transition of rod orientation occurs with an increase in the length of rod blocks. Some special structures, such as parallel half-cylinders and arrowhead-shaped morphology, are observed when the rod length increases to a certain extent. Our results show that the property and height of the slit and rod length all influence the self-assembly of rod-coil-rod triblock copolymers.展开更多
ABCA tetrablock copolymers offer new opportunities for design of materials with novel structures. Using real-space self- consistent field theory and simulation, we systematically examined the self-assembly behavior of...ABCA tetrablock copolymers offer new opportunities for design of materials with novel structures. Using real-space self- consistent field theory and simulation, we systematically examined the self-assembly behavior of linear ABCA tetrablock copolymers in a 2D space. The simulation was carried out under conditions of symmetrical compositions and interactions. We focus on the influence of chain length ratio of block A and interactions between block A and other blocks B and C on the self-assembly behavior of the copolymer system. The simulation results show that most of the structures self-assembled by the ABCA tetrablock copolymers are centrosymmetric, such as diblock-like lameUa phase, two kinds of lameUae with beads at interface, two kinds of hierarchical lamella phase, hexagonal honeycomb-like phase, lamella phase with mixed BC and hexagonal spheres with mixed BC. Furthermore, we find that a novel noncentrosymmetric Janus spheres can be obtained when the interaction between blocks B and C is strong, whereas a noncentrosymmetric lamella phase was obtained at weak interaction between blocks B and C. Phase diagrams for the ABCA tetrablock copolymers with different interaction strength between blocks B and C are constructed by comparing free energies of candidate ordered structures. In addition, studies on the metastable behavior of the system reveal that enthalpy plays an important role in the metastable behavior of the ABCA tetrablock copolymer system. Our work can provide useful guide for structure control of such kind of tetrablock copolymers in experiments.展开更多
In this paper,supra-amphiphilic compounds containing disaccharides and azobenzene ends have been constructed via dynamic covalent bond.It was found that the slight structural difference of the disaccharides made signi...In this paper,supra-amphiphilic compounds containing disaccharides and azobenzene ends have been constructed via dynamic covalent bond.It was found that the slight structural difference of the disaccharides made significant difference in the self-assembled morphologies.Namely,three kinds of azodisaccharide supra-amphiphiles were found to assemble into different morphologies,with the only difference in chemical structure from the disaccharides.More importantly,the structural difference between the disaccharides,including lactoside,maltoside and cellobioside was trivial.Molecular simulation revealed the packing of molecules was due to the different contribution from hydrogen bonds.The above results clearly indicated the contribution of saccharide packing,especially the related hydrogen bonding,to the final morphology of the assembled structures.展开更多
Well-defined P4VP-b-PBLG diblock polymer composed of poly (4-vinylpyridine) (P4VP) and poly (γ-benzyl-L-glutamate) (PBLG) was synthesized by click reaction with alkyne- and azide-functionalized homopolymers. Besides,...Well-defined P4VP-b-PBLG diblock polymer composed of poly (4-vinylpyridine) (P4VP) and poly (γ-benzyl-L-glutamate) (PBLG) was synthesized by click reaction with alkyne- and azide-functionalized homopolymers. Besides, P4VP blocks were synthesized by copper-mediated atom transfer radical polymerization (ATRP) with a chlorine-containing alkyne bifunctional initiator, and the azido-terminated PBLG homopolymers were synthesized by ring-opening polymerization (ROP) of γ-benzyl-L-glutamate with an amine-containing azide initiator. In addition, the synthesized P4VP-b-PBLG with different block ratios has been characterized by proton nuclear magnetic resonance (1H NMR), Gel permeation chromatograph (GPC) and fourier transform infrated spectroscopy (FT-IR). Then, the self-assembly behaviors of P4VP-b-PBLG have been studied by changing parameters like dripping speed and block ratio. The morphologies of self-assembly of spherical, disk-like and ellipsoid-like shape particles have been observed and analyzed by scanning electron microscopy (SEM). These results have provided guidelines for the design of macromolecular self-assembly.展开更多
Cholesteryl trimeric phenylene vinylene (ChoI-TPV) has been synthesized and characterized. The self- assembly behaviors of ChoI-TPV in THF/H20 system at different water content (water content: 40% and 80%) and di...Cholesteryl trimeric phenylene vinylene (ChoI-TPV) has been synthesized and characterized. The self- assembly behaviors of ChoI-TPV in THF/H20 system at different water content (water content: 40% and 80%) and different solute concentration (solute concentration: 1.0 ×10^-5 mol/L and saturated concentration) were studied using UV-vis spectrophotometry, photoluminescence spectrophotometry, and circular dichroism spectroscopy. Based on an analysis of the UV-vis and photoluminescence spectra, Chol-TPV shows the typical H-type aggregation at saturated concentration in 80% aqueous THF. However, ChoI-TPV shows the non-typical H-type aggregation under other conditions. The circular dichroism signal suggests that the Chol-TPV exists in the right handed helical architectures with high water content at a concentration of 1.0 × 10^-5 mol/L, and a helix inversion was found at saturated concentration.展开更多
We employed the extended self-consistent field theory to investigate the supramolecular self-assembly behaviors of asymmetric diblock copolymer blends(AB/B’C)with hydrogen bonding interactions between shorter B and B...We employed the extended self-consistent field theory to investigate the supramolecular self-assembly behaviors of asymmetric diblock copolymer blends(AB/B’C)with hydrogen bonding interactions between shorter B and B’blocks.The hydrogen bonding interactions are described by Yukawa potentials,where the hydrogen bonding donors and acceptors were modelled as two blocks smeared with opposite screened charges.The hierarchical microstructures with parallelly packed lamellae-in-lamellae(Lam)and 4.8.8 Archimedean tilting pattern(4.8.8)were observed at lower and higher hydrogen bonding density(θ),respectively.The hierarchy of Lam and 4.8.8 were demonstrated by the one-and two-dimensional density profiles and the underlying order of the large-length-scale and small-length-scale microstructures were also clarified.It was found that the 4.8.8 is favorable to the stronger hydrogen bonding density or interactions.Asθincreases,the microphase transition from Lam to 4.8.8 occurs atθ=0.34,which is mainly attributed to the optimization of the electrostatic energy and conformational entropy with sacrificing the interfacial energy.This work can provide a new strategy to understand the supramolecular self-assembly as well as the mechanism behind the formation of complex hierarchical microstructures.展开更多
Emerging evidence has established artesunate(ART)as a potent anticancer candidate,yet its clinical utility remains constrained by rapid clearance and limited bioavailability.To overcome these limitations,we developed ...Emerging evidence has established artesunate(ART)as a potent anticancer candidate,yet its clinical utility remains constrained by rapid clearance and limited bioavailability.To overcome these limitations,we developed fatty chain-driven self-assembling nanoassemblies(NAs)as an innovative therapeutic platform.In contrast to conventional prodrug-based self-assembled nanoassemblies(PBSANs),our ART conjugates(ART-R)activate antitumor effects without requiring responsive modules,substantially streamlining drug design.In this study,we investigated the assembly behavior,stability,and antitumor efficacy of ART-R conjugates with varying side chain lengths:short(ART-C4),medium(ART-C8,ART-C12),and long(ART-C14,ART-C18).To prolong systemic circulation and achieve tumor-selective release,we engineered reduction-responsive sp-ART-R NAs via 2-Distearoyl-sn-glycero-3-phosphoethanolamine-disulfide bond-polyethylene glycol 2000(DSPE-SS-PEG_(2K))modification.Following comprehensive evaluation,sp-ART-C14 NAs with the optimal side chain length were selected,which exhibit the most suitable octanol-water partition coefficient(logP),good assembly capability,stability,cytotoxicity,as well as optimal pharmacokinetic behavior and tumor accumulation ability.In the 4T1 breast tumor model,sp-ART-C14 NAs also demonstrated excellent therapeutic efficacy.This study overcomes the limitations of traditional PBSANs,eliminates dependence on response modules,and provides a new drug delivery solution for ART.展开更多
The mono-modified β-cyclodextrin derivative,6-O-(4-aminobenzoyl)-β-cyclodextrin(1) ,was synthesized and characterized. We compared its self-assembling behavior with structurally related β-cyclodextrin derivative,6-...The mono-modified β-cyclodextrin derivative,6-O-(4-aminobenzoyl)-β-cyclodextrin(1) ,was synthesized and characterized. We compared its self-assembling behavior with structurally related β-cyclodextrin derivative,6-O-(4-hydroxybenzoyl)-βcyclodextrin(2) ,in aqueous solution and in the solid state using NMR spectroscopy and single crystal X-ray structure analysis. The two complexes displayed different self-assembling behaviors.Complex 1 formed a head-to-tail helical columnar superstructure in which the substituent group penetrated deeply into the hydrophobic cavity of the adjacent β-cyclodextrin from the second side and aligned along the screw axis,whereas 2 exhibited a channel superstructure with a tail-to-tail dimer as the repeating motif.Further NMR studies in aqueous solution supported the result of the solid state.The influence of substituent groups on the self-assembly behavior was examined in mono-modified β-cyclodextrins by means of substituting an amino group for a hydroxyl group,which indicates that the weak intermolecular interaction is a critical factor in determining the self-assembling behavior.展开更多
Graphene derivatives,such as graphene oxide(GO)and reduced graphene oxide(RGO),have been widely used as promising two-dimensional nanoscale building blocks due to their fascinating properties,cost-effective production...Graphene derivatives,such as graphene oxide(GO)and reduced graphene oxide(RGO),have been widely used as promising two-dimensional nanoscale building blocks due to their fascinating properties,cost-effective production,and good processability.Understanding the intrinsic self-assembling,colloidal,and rheological features of graphene derivatives is of critical importance to establish the formation-structure-property relationship of graphene-based materials.This article reviews recent progresses in our studies of these interesting properties of graphene derivatives for developing high performance supercapacitors.The content is organized to include characteristics of the dispersions of graphene derivatives,self-assembly of nanosheets from liquid medium,colloidal behavior,rheological properties of the dispersions,processing methods based on the properties,and performance of the fabricated supercapacitors.GO and RGO nanosheets are proved to form different types of assembled structures with unique morphologies,such as ultrathin layer-by-layer films,porous aggregates,and nanoscrolls.The unique rheological properties of GO dispersions and hydrogels,feasible for both the traditional wet-processing and newly-developed technology like three-dimensional printing,are highlighted for their potential in structural manipulation and scalable fabrication of graphene-based devices.The research devoted to up-grading the performance of supercapacitors is presented in some details,which could be applicable for fabricating other graphene-based energy storage devices.Some challenges and perspectives in our point of view are given in the last part of this feature article.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
The self-assembly behavior of mono(6-phenolic-6-deoxy)-β-cyclodextrin bothin solution and the solid state is comparatively studied by X-ray crystallography and ~1H NMRspectroscopy. The results obtained show that the ...The self-assembly behavior of mono(6-phenolic-6-deoxy)-β-cyclodextrin bothin solution and the solid state is comparatively studied by X-ray crystallography and ~1H NMRspectroscopy. The results obtained show that the phenolic groups in the crystal 1 can successivelypenetrate into the adjacent β-cyclodextrin cavities from the secondary side to form head-to-taillinear polymeric su-pramolecule with a 2-fold screw axis. The self-assembly behavior also can bedetermined in D_2O solution, giving a self-association constant of 240 mol^(-1)·L. Using thepresent and previous structures reported for the relevant β-cyclodextrin derivatives, i.e.,mono(6-anilino-6-deoxy)-β-cyclodextrin, mono(6-phenylselenyl-6-deoxy)-β-cyclodextrin, andmono(6-phenylthio-6-deoxy)-β-cyclodextrin, we further reveal the factors governing the formationsof supramolecular assemblies.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
Peptide self-assembles with bionic properties have been widely utilized for bioactive drugs and biomedical materials.Collagen mimetic peptide(CMP)gains more attention due to its unique advantages in biosecurity and fu...Peptide self-assembles with bionic properties have been widely utilized for bioactive drugs and biomedical materials.Collagen mimetic peptide(CMP)gains more attention due to its unique advantages in biosecurity and function.Unfortunately,the self-assembly mechanism of CMP,particularly the effect of intermolecular forces on its self-assembly behavior and morphology,is still unrecognized.Herein,the hydrophilic glycidol(GCD)and hydrophobic Y-glycidyl ether oxypropyl trimethoxysilane(GLH)were grafted onto the side chains of CMP through the ring-opening reaction(GCD/CMP,GLH/CMP).Subsequently,the effects of hydrophilic and hydrophobic interactions on the self-assembly behavior and morphology of CMP were further studied.The results substantiated that the GCD/CMP and GLH/CMP self-assembly followed“nucleation-growth”mechanism,and the supererogatory hydrophilic and hydrophobic groups prolonged the nucleation and growth time of CMP self-assembly.Noted that the hydrophilic interaction had stronger driving effects than hydrophobic interaction on the self-assembly of CMP.The GCD/CMP and GLH/CMP self-assembles exhibited fibrous 3D network and microsphere morphology,respectively.Furthermore,the GLH/CMP self-assembles had better resistance to degradation.Consequently,the microtopography and degradation properties of CMP self-assembles could be controlled by the hydrophilic and hydrophobic interactions between CMP,which would further provide a way for subsequent purposeful design of biomedical materials.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
基金financially supported by the National Natural Science Foundation of China(Nos.51173185 and 51303179)
文摘Copolymers with super segregated structure of hydrophilic methoxy poly(ethylene glycol) (mPEG) and fluorophilic poly(1H,1H,2H,2H-perfluorodecyl acrylate) (PFA) were prepared. And just because of this super segregated structure which was resulted from the extremely strong incompatibility between the two blocks, several interesting self- assembly behaviors of the copolymers were displayed and studied under different conditions. Transmission electron microscope (TEM) showed that with the increase of PFA in the polymerization system, the incompatibility in this super segregated structure became stronger, and the self-assembly behavior changed from ball-like or rod-like to vesicles, and finally collapsed to sheet-like. The self-assembly behavior changed likewise when the initial concentration increased. And the interesting formation of these barrel-like and spindle-like vesicles was finally studied with different cooling speeds. It's finally found that with this super segregation structure, these new self-assembly morphology might be formed due to the extremely strong incompatibility between mPEG and PFA segments.
基金supported by the National Natural Science Foundation of China(22078211)the China Postdoctoral Science Foundation(2022M721115).
文摘The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.
基金Shanghai Natural Science Foundation,China(No.13ZR1400700)The Program for Innovative Research Team in University,China(No.IRT1221)
文摘N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A comparison of the two samples by measuring their photo physical properties using UV visible absorption and fluorescence emission spectra revealed that bay substitutions of bromine do not have significant effect on the perylene diimide( PDI) photo physical properties in solution. However,the solid state fluorescence properties were enhanced by brominating at bay areas. The solid fluorescence quantum yield of 1,7-Br-PDI-C12 was 2. 83%( Фf= 2. 83%) and 1,7-H-PDI-C12 was only 0. 02%( Фf= 0. 02%). This behavior was also reflected in the steady-state fluorescence spectra. This work shows that solid state photo physical properties of PDI could be improved without changing the other properties by simply using bromine substitution at bay areas. These types of materials are useful intermediate for further synthesis of PDI with tunnable optoelectronic properties.
基金National Natural Science Foundations of China(Nos.51073033,51373030)the Fundamental Research Funds for the Central Universities,China(No.2232014D3-43)
文摘The pH /temperature dually responsive microgels of interpenetrating polymer network( IPN) structure composed of poly( N-isopropylacrylamide)( PNIPAM) network and poly( acrylic acid)( PAA) network( PNIPAM /PAA IPN microgels) were synthesized by seed emulsion polymerization. The results obtained by dynamic laser light scattering( DLLS) show that the microgels have good pH /temperature dual sensitivities. The temperature sensitive component and the pH sensitive component inside the microgels have little interference with each other. The rheological properties of the concentrated PNIPAM /PAA IPN microgel dispersions as a function of temperature at pH 4. 0 or 7. 0 were investigated by viscometer,and the results displayed that only at pH 7. 0 the dispersions presented thermoreversible thickening behavior. Then the PNIPAM /PAA fibers were prepared by self-assembly of the PNIPAM /PAA IPN microgels in the ice-crystal templates formed by unidirectional liquid nitrogen freezing method. Field emission scanning electron microscopy( FESEM) images indicate that the PNIPAM /PAA fibers are rounded,randomly orientated and interweaved.
基金financially supported by the National Natural Science Foundation of China(No.21574117)
文摘The self-assembly behavior of sphere-forming R_5C_(30)R_5 triblock copolymers within a planar slit is studied by performing dissipative particle dynamics simulations. A sequence of novel structures which are not observed in bulk are formed within slits, including wetting layers, island-like structure, parallel cylinders, perpendicular cylinders and crosscylindrical structures. Perpendicular cylinders are always formed before the increase in the layers of parallel cylinders. A phase diagram of the assembled structures with respective to the slit property and height is thus presented. The rod length is found to have a significant impact on the rod alignment, and a disordered-ordered transition of rod orientation occurs with an increase in the length of rod blocks. Some special structures, such as parallel half-cylinders and arrowhead-shaped morphology, are observed when the rod length increases to a certain extent. Our results show that the property and height of the slit and rod length all influence the self-assembly of rod-coil-rod triblock copolymers.
基金financially supported by the National Natural Science Foundation of China(No.21474107)
文摘ABCA tetrablock copolymers offer new opportunities for design of materials with novel structures. Using real-space self- consistent field theory and simulation, we systematically examined the self-assembly behavior of linear ABCA tetrablock copolymers in a 2D space. The simulation was carried out under conditions of symmetrical compositions and interactions. We focus on the influence of chain length ratio of block A and interactions between block A and other blocks B and C on the self-assembly behavior of the copolymer system. The simulation results show that most of the structures self-assembled by the ABCA tetrablock copolymers are centrosymmetric, such as diblock-like lameUa phase, two kinds of lameUae with beads at interface, two kinds of hierarchical lamella phase, hexagonal honeycomb-like phase, lamella phase with mixed BC and hexagonal spheres with mixed BC. Furthermore, we find that a novel noncentrosymmetric Janus spheres can be obtained when the interaction between blocks B and C is strong, whereas a noncentrosymmetric lamella phase was obtained at weak interaction between blocks B and C. Phase diagrams for the ABCA tetrablock copolymers with different interaction strength between blocks B and C are constructed by comparing free energies of candidate ordered structures. In addition, studies on the metastable behavior of the system reveal that enthalpy plays an important role in the metastable behavior of the ABCA tetrablock copolymer system. Our work can provide useful guide for structure control of such kind of tetrablock copolymers in experiments.
基金the National Natural Science Foundation of China(NSFC,Nos.52125303,51721002,91956127 and 21975047)for financial supportthe National Natural Science Foundation of China(NSFC,Nos.21674114 and 91956127)for financial support+1 种基金supported by the Shanghai Municipal Science and Technology Major Project(No.2018SHZDZX01)ZJ Lab。
文摘In this paper,supra-amphiphilic compounds containing disaccharides and azobenzene ends have been constructed via dynamic covalent bond.It was found that the slight structural difference of the disaccharides made significant difference in the self-assembled morphologies.Namely,three kinds of azodisaccharide supra-amphiphiles were found to assemble into different morphologies,with the only difference in chemical structure from the disaccharides.More importantly,the structural difference between the disaccharides,including lactoside,maltoside and cellobioside was trivial.Molecular simulation revealed the packing of molecules was due to the different contribution from hydrogen bonds.The above results clearly indicated the contribution of saccharide packing,especially the related hydrogen bonding,to the final morphology of the assembled structures.
文摘Well-defined P4VP-b-PBLG diblock polymer composed of poly (4-vinylpyridine) (P4VP) and poly (γ-benzyl-L-glutamate) (PBLG) was synthesized by click reaction with alkyne- and azide-functionalized homopolymers. Besides, P4VP blocks were synthesized by copper-mediated atom transfer radical polymerization (ATRP) with a chlorine-containing alkyne bifunctional initiator, and the azido-terminated PBLG homopolymers were synthesized by ring-opening polymerization (ROP) of γ-benzyl-L-glutamate with an amine-containing azide initiator. In addition, the synthesized P4VP-b-PBLG with different block ratios has been characterized by proton nuclear magnetic resonance (1H NMR), Gel permeation chromatograph (GPC) and fourier transform infrated spectroscopy (FT-IR). Then, the self-assembly behaviors of P4VP-b-PBLG have been studied by changing parameters like dripping speed and block ratio. The morphologies of self-assembly of spherical, disk-like and ellipsoid-like shape particles have been observed and analyzed by scanning electron microscopy (SEM). These results have provided guidelines for the design of macromolecular self-assembly.
基金supported by the National Science Foundation of China(No.51173155)the Hebei Province Science Foundation of China(No.F2011203160)
文摘Cholesteryl trimeric phenylene vinylene (ChoI-TPV) has been synthesized and characterized. The self- assembly behaviors of ChoI-TPV in THF/H20 system at different water content (water content: 40% and 80%) and different solute concentration (solute concentration: 1.0 ×10^-5 mol/L and saturated concentration) were studied using UV-vis spectrophotometry, photoluminescence spectrophotometry, and circular dichroism spectroscopy. Based on an analysis of the UV-vis and photoluminescence spectra, Chol-TPV shows the typical H-type aggregation at saturated concentration in 80% aqueous THF. However, ChoI-TPV shows the non-typical H-type aggregation under other conditions. The circular dichroism signal suggests that the Chol-TPV exists in the right handed helical architectures with high water content at a concentration of 1.0 × 10^-5 mol/L, and a helix inversion was found at saturated concentration.
基金financially supported by the Natural Science Foundation of Shanghai(No.21ZR1402800)the Fundamental Research Funds for the Central Universities(No.2232020D-11)+1 种基金the China Postdoctoral Science Foundation(No.2021M690597)the Open Project Program of Fujian Provincial Key Laboratory of Textiles Inspection Technology(Fujian Fiber Inspection Center)(Nos.2020-MXJ-04)。
文摘We employed the extended self-consistent field theory to investigate the supramolecular self-assembly behaviors of asymmetric diblock copolymer blends(AB/B’C)with hydrogen bonding interactions between shorter B and B’blocks.The hydrogen bonding interactions are described by Yukawa potentials,where the hydrogen bonding donors and acceptors were modelled as two blocks smeared with opposite screened charges.The hierarchical microstructures with parallelly packed lamellae-in-lamellae(Lam)and 4.8.8 Archimedean tilting pattern(4.8.8)were observed at lower and higher hydrogen bonding density(θ),respectively.The hierarchy of Lam and 4.8.8 were demonstrated by the one-and two-dimensional density profiles and the underlying order of the large-length-scale and small-length-scale microstructures were also clarified.It was found that the 4.8.8 is favorable to the stronger hydrogen bonding density or interactions.Asθincreases,the microphase transition from Lam to 4.8.8 occurs atθ=0.34,which is mainly attributed to the optimization of the electrostatic energy and conformational entropy with sacrificing the interfacial energy.This work can provide a new strategy to understand the supramolecular self-assembly as well as the mechanism behind the formation of complex hierarchical microstructures.
基金supported by the Liaoning Revitalization Talents Program(No.XLYC2403107)the Excellent Youth Science Foundation of Liaoning Province(No.2024JH3/10200046)+1 种基金the National Natural Science Foundation of China(No.82204317)the Basic Scientific Research Project of Liaoning Provincial Department of Education(No.LJ212410163015).
文摘Emerging evidence has established artesunate(ART)as a potent anticancer candidate,yet its clinical utility remains constrained by rapid clearance and limited bioavailability.To overcome these limitations,we developed fatty chain-driven self-assembling nanoassemblies(NAs)as an innovative therapeutic platform.In contrast to conventional prodrug-based self-assembled nanoassemblies(PBSANs),our ART conjugates(ART-R)activate antitumor effects without requiring responsive modules,substantially streamlining drug design.In this study,we investigated the assembly behavior,stability,and antitumor efficacy of ART-R conjugates with varying side chain lengths:short(ART-C4),medium(ART-C8,ART-C12),and long(ART-C14,ART-C18).To prolong systemic circulation and achieve tumor-selective release,we engineered reduction-responsive sp-ART-R NAs via 2-Distearoyl-sn-glycero-3-phosphoethanolamine-disulfide bond-polyethylene glycol 2000(DSPE-SS-PEG_(2K))modification.Following comprehensive evaluation,sp-ART-C14 NAs with the optimal side chain length were selected,which exhibit the most suitable octanol-water partition coefficient(logP),good assembly capability,stability,cytotoxicity,as well as optimal pharmacokinetic behavior and tumor accumulation ability.In the 4T1 breast tumor model,sp-ART-C14 NAs also demonstrated excellent therapeutic efficacy.This study overcomes the limitations of traditional PBSANs,eliminates dependence on response modules,and provides a new drug delivery solution for ART.
基金supported by the National Natural Science Foundation of China(20704031)Tianjin Natural Science Fund(09JCYBJC06300)Science Fund of Tianjin Education Committee(20060515)
文摘The mono-modified β-cyclodextrin derivative,6-O-(4-aminobenzoyl)-β-cyclodextrin(1) ,was synthesized and characterized. We compared its self-assembling behavior with structurally related β-cyclodextrin derivative,6-O-(4-hydroxybenzoyl)-βcyclodextrin(2) ,in aqueous solution and in the solid state using NMR spectroscopy and single crystal X-ray structure analysis. The two complexes displayed different self-assembling behaviors.Complex 1 formed a head-to-tail helical columnar superstructure in which the substituent group penetrated deeply into the hydrophobic cavity of the adjacent β-cyclodextrin from the second side and aligned along the screw axis,whereas 2 exhibited a channel superstructure with a tail-to-tail dimer as the repeating motif.Further NMR studies in aqueous solution supported the result of the solid state.The influence of substituent groups on the self-assembly behavior was examined in mono-modified β-cyclodextrins by means of substituting an amino group for a hydroxyl group,which indicates that the weak intermolecular interaction is a critical factor in determining the self-assembling behavior.
基金supported by the National Basic Research Program of China(973 Program,No.2012CB933402).
文摘Graphene derivatives,such as graphene oxide(GO)and reduced graphene oxide(RGO),have been widely used as promising two-dimensional nanoscale building blocks due to their fascinating properties,cost-effective production,and good processability.Understanding the intrinsic self-assembling,colloidal,and rheological features of graphene derivatives is of critical importance to establish the formation-structure-property relationship of graphene-based materials.This article reviews recent progresses in our studies of these interesting properties of graphene derivatives for developing high performance supercapacitors.The content is organized to include characteristics of the dispersions of graphene derivatives,self-assembly of nanosheets from liquid medium,colloidal behavior,rheological properties of the dispersions,processing methods based on the properties,and performance of the fabricated supercapacitors.GO and RGO nanosheets are proved to form different types of assembled structures with unique morphologies,such as ultrathin layer-by-layer films,porous aggregates,and nanoscrolls.The unique rheological properties of GO dispersions and hydrogels,feasible for both the traditional wet-processing and newly-developed technology like three-dimensional printing,are highlighted for their potential in structural manipulation and scalable fabrication of graphene-based devices.The research devoted to up-grading the performance of supercapacitors is presented in some details,which could be applicable for fabricating other graphene-based energy storage devices.Some challenges and perspectives in our point of view are given in the last part of this feature article.
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.
基金This work was supported by the National Natural Science Foundation of China (Grant Nos.90306009, 20272028, and 20421202) the Tianjin Natural Science Foundation (Grant No. 043604411).
文摘The self-assembly behavior of mono(6-phenolic-6-deoxy)-β-cyclodextrin bothin solution and the solid state is comparatively studied by X-ray crystallography and ~1H NMRspectroscopy. The results obtained show that the phenolic groups in the crystal 1 can successivelypenetrate into the adjacent β-cyclodextrin cavities from the secondary side to form head-to-taillinear polymeric su-pramolecule with a 2-fold screw axis. The self-assembly behavior also can bedetermined in D_2O solution, giving a self-association constant of 240 mol^(-1)·L. Using thepresent and previous structures reported for the relevant β-cyclodextrin derivatives, i.e.,mono(6-anilino-6-deoxy)-β-cyclodextrin, mono(6-phenylselenyl-6-deoxy)-β-cyclodextrin, andmono(6-phenylthio-6-deoxy)-β-cyclodextrin, we further reveal the factors governing the formationsof supramolecular assemblies.
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This work was financially supported by the National Natural Science Foundation of China(21808133)Scientific Research Foundation for Young Scholars of Shaanxi University of Science&Technology(contract grant number 2017BT-32)+1 种基金Xianyang Science and Technology Project(Y20190138)Shaanxi Province Key R&D Program(2018ZDXM-SF-091).
文摘Peptide self-assembles with bionic properties have been widely utilized for bioactive drugs and biomedical materials.Collagen mimetic peptide(CMP)gains more attention due to its unique advantages in biosecurity and function.Unfortunately,the self-assembly mechanism of CMP,particularly the effect of intermolecular forces on its self-assembly behavior and morphology,is still unrecognized.Herein,the hydrophilic glycidol(GCD)and hydrophobic Y-glycidyl ether oxypropyl trimethoxysilane(GLH)were grafted onto the side chains of CMP through the ring-opening reaction(GCD/CMP,GLH/CMP).Subsequently,the effects of hydrophilic and hydrophobic interactions on the self-assembly behavior and morphology of CMP were further studied.The results substantiated that the GCD/CMP and GLH/CMP self-assembly followed“nucleation-growth”mechanism,and the supererogatory hydrophilic and hydrophobic groups prolonged the nucleation and growth time of CMP self-assembly.Noted that the hydrophilic interaction had stronger driving effects than hydrophobic interaction on the self-assembly of CMP.The GCD/CMP and GLH/CMP self-assembles exhibited fibrous 3D network and microsphere morphology,respectively.Furthermore,the GLH/CMP self-assembles had better resistance to degradation.Consequently,the microtopography and degradation properties of CMP self-assembles could be controlled by the hydrophilic and hydrophobic interactions between CMP,which would further provide a way for subsequent purposeful design of biomedical materials.
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.