Multilayer thin films of alternately adsorbed layers of polyelectrolytes PDDA and PS-119 were formed on both planar silica substrates and optical fibers through the ionic self-assembly technique. Intrinsic Fabry-Perot...Multilayer thin films of alternately adsorbed layers of polyelectrolytes PDDA and PS-119 were formed on both planar silica substrates and optical fibers through the ionic self-assembly technique. Intrinsic Fabry-Perot cavities were fabricated by stepwise assembling the polyelectrolytes onto the ends of optical fibers for the purposes of fiber optical device and sensor development. Ionically assembled polyelectrolyte multilayer thin films, in which. there are hydrophilic side groups with strong affinity towards water molecules, are a category of humidity-sensitive functional materials. The polyelectrolyte multilayer thin film Fabry-Perot cavity-type fiber optical humidity sensor can work over a wide range from about 0% RH to about 100% RH with a response time less than 1 s.展开更多
Peptide-based assemblies have gained increasing attention in different areas of nanotechnology,drug delivery and molecular biology.Among these,non-natural β-peptide scaffolds are particularly promising,as their progr...Peptide-based assemblies have gained increasing attention in different areas of nanotechnology,drug delivery and molecular biology.Among these,non-natural β-peptide scaffolds are particularly promising,as their programmable and diverse secondary structures,high metabolic stability and strong self-association propensity can be easily exploited to create variable constructs.We have recently demonstrated that heterochiral,acyclic β^(3)-peptides assembled into striped lamellar nanostructures that induced antibacterial activity.The process of this assembly formation could be exploited in diverse areas,however identifying oligomerisation stages,and more importantly,controlling the spontaneous process at different levels is still lacking.In this study,a set of analogues heterochiral hexameric β^(3)-peptide sequences was investigated to understand how systematic,small variations of the sequences,such as single point mutation or N-terminal chemical modification,can influence the resulting assemblies and allow the control of formed morphologies.TEM and cryo-EM combined with molecular dynamics simulation enabled the identification and differentiation of morphological stages throughout the entire multi-step process.Depending on the position of the sequence modifications,the self-assembled structures formed small oligomers,individual protofibrils,extended,flat lamellae,bundles and macroscopic clusters.These results outline how the self-assembly process of short heterochiral β-peptides can be qualitatively fine-tuned by sequence modifications,which contribute to understanding the general peptide assembly processes for their fibrillar morphologies.展开更多
Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.H...Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.Herein,we propose a self-assembly chemical strategy into the LCHEs induced by ordered nanostructure of zwitterionic co-solutes for highly efficient and ultrastable zinc(Zn)metal batteries.Through the systematic screening of six zwitterionic compounds,3-(decyldimethylammonio)propanesulfonate salt(C_(10))with the decyl chain and zwitterions was determined as an optimum to construct quasi-spherical aggregates with a periodic length of 3.77 nm,as confirmed by comprehensive synchronous small-angle X-ray scattering,Guinier,pair distance distribution function,Porod,and other spectroscopic characterizations and molecular dynamic simulation.In particularly,this self-assembled structure in electrolyte environments was attributed to increasing the proportion of both contact and aggregated ion pairs for the formation of LHCEs as well as to providing fast and selective Zn^(2+)conducting channels and uniform solid electrolyte interfaces for facilitated charge transfer kinetics.Moreover,the preferential adsorption of the self-assembled C_(10)on the Zn(002)surface modulated the electrical double layer to suppress hydrogen evolution and corrosion reactions.Consequently,the Zn‖Zn symmetric cells in Zn(OTf)_(2)/C_(10)electrolytes showed long-term plating/stripping behaviors over 2800 h at 1 mA cm^(-2)and 1 mAh cm^(-2)as well as over 1200 h even at 5 mA cm^(-2)and 5 mAh cm^(-2)with a very high depth of discharge of 42.7%.Furthermore,the ZnllVO_(2)/CNT full cells in Zn(OTf)_(2)/C_(10)electrolytes delivered a record-high capacity of 8.10 mAh cm^(-2)at an ultrahigh cathode mass loading of 50 mg cm^(-2)after 150 cycles.展开更多
Sustainability and scalability remain critical hurdles for the commercialization of organic solar cells(OSCs).However,addressing both poses challenge.Herein,we introduce a simple yet effective strategy utilizing 3,5-d...Sustainability and scalability remain critical hurdles for the commercialization of organic solar cells(OSCs).However,addressing both poses challenge.Herein,we introduce a simple yet effective strategy utilizing 3,5-dichloropyridine(PDCC)as a solid additive to fine-tune the self-assembly behavior of Y-series non-fullerene acceptors(NFAs)to tackle the upscaling limitations in green-solvent-processed OSCs.PDCC predominantly interacts with Y-series NFAs,facilitating molecular crystallization and thereby driving the self-assembly of Y-series NFAs during film-forming dynamics,leading to more uniform active layers with improved molecular packing and reduced charge recombination.As a result,PDCC-driven self-assembly strategy enables high-performance OSCs with a power conversion efficiency(PCE)of 20.47%.When translated to sustainable fabrication,this strategy significantly boosts the PCE of large-area green-solvent-processed OSC modules(19.3 cm^(2))from 13.87%to 15.79%,ranking it among the best-performing green-solvent-processed large-area OSC modules(>18 cm^(2)).Beyond its impact on PCE enhancement,PDCC serves as a multifunctional additive to improve long-term stability and exhibits strong universality across multiple material systems.This work establishes a promising approach for advancing sustainable and scalable OSCs,paving the way for their commercialization.展开更多
The rapid advancement of flexible electronics technology has placed higher demands on the structural design and performance regulation of elastic materials.Cellulosic elastomers,with their biodegradability,renewabilit...The rapid advancement of flexible electronics technology has placed higher demands on the structural design and performance regulation of elastic materials.Cellulosic elastomers,with their biodegradability,renewability,and tunability,emerge as ideal candidate materials.Entropy-driven self-as sembly promotes the spontaneous formation of ordered structures,serving as a crucial pathway for optimizing cellulose elastomer properties.However,the structure-property relationship between the self-assembled ordered structures of cellulose elastomers and their mechanical and electrical properties remains insufficiently explored.It hinders the expansion of their applications in electronic devices.This paper systematically reviews the structure-property regulation mechanisms of self-assembled cellulosic elastomers from an entropy-driven perspective.It elucidates the application principles and performance optimization strategies for mechanical energy harvesting and self-powered sensing,while also exploring the challenges and prospects for performance enhancement.This work provides a reference for the development of self-assembled cellulosic elastomers in the field of energy devices.展开更多
Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C_(3)N_(4))presents a promising and environmentally friendly approach.However,pristine g-...Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C_(3)N_(4))presents a promising and environmentally friendly approach.However,pristine g-C_(3)N_(4) suffers from limited visible-light absorption and low charge-carrier mobility.In this study,a phosphorus-doped tubular carbon nitride(5P-TCN)was synthesized via a precursor self-assembly method using phosphoric acid and melamine as raw materials,eliminating the need for organic solvents or templates.The 5P-TCN catalyst demonstrated enhanced visible-light absorption,improved charge transfer capability,and a 5.25-fold increase in specific surface area(31.092 m^(2)/g),which provided abundant active sites to efficiently drive the PMS-assisted photocatalytic reaction.The 5P-TCN/vis/PMS system exhibited exceptional degradation performance for organic pollutants across a broad pH range(3–9),achieving over 92%degradation of Rhodamine B(RhB)within 15 min.Notably,the system retained>98%RhB degradation efficiency after three consecutive operational cycles,demonstrating robust operational stability and reusability.Moreover,key parameters influencing,active radi-cals,degradation pathways,and potential mechanisms for RhB degradation were systematically investigated.This work proposes a green and cost-effective strategy for developing high-efficiency photocatalysts,while demon-strating the exceptional capability of a PMS-assisted photocatalytic system for rapid degradation of RhB.展开更多
Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments re...Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.展开更多
Herein,a reusable and portable surface-enhanced Raman spectroscopy(SERS)sandpaper was successfully synthesized for the sensitive detection of S-fenvalerate in foods.Commercial sandpapers were decorated with Ag@SiO2@Au...Herein,a reusable and portable surface-enhanced Raman spectroscopy(SERS)sandpaper was successfully synthesized for the sensitive detection of S-fenvalerate in foods.Commercial sandpapers were decorated with Ag@SiO2@Au nanoarrays via a liquid-liquid interface self-assembly method.The capacity of sandpaper to float directly on the cyclohexane-water interface allows nanoarrays to be formed directly on it,thereby minimizing stacking issues typically associated with nanoarray assemblies and significantly enhancing the sensitivity of S-fenvalerate detection.Moreover,the SERS sandpaper was reusable and portable due to its strong adhesion of the nanoarrays.Under optimized testing conditions,the developed SERS sandpaper method was capable of detecting S-fenvalerate,demonstrating a strong linear response within a concentration range of 10^(–7)–10^(3)μmol/L,with a limit of detection of 1.92×10^(−8)μmol/L.The analysis of spiked food samples containing S-fenvalerate using the developed SERS sandpaper afforded excellent recoveries(92.2%−109.7%).Additionally,the SERS sandpaper was successfully applied to quantify S-fenvalerate in real food samples,with results consistent with analyses conducted using gas chromatography.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
This work reports a SO2 derivative-detecting and colorful hyperbranched polymeric ionic liquid （HBPIL） vesicle through aqueous self-assembly. By a simple anion-exchange, we achieved the combination of functional sma...This work reports a SO2 derivative-detecting and colorful hyperbranched polymeric ionic liquid （HBPIL） vesicle through aqueous self-assembly. By a simple anion-exchange, we achieved the combination of functional small-molecule probe of acid fuchsin with HBPILs. The obtained HBPIL vesicle displayed ultraviolet absorption at 544 nm, and was used as a novel SO2 derivative sensor with high sensitivity and visualization. Due to the functional ion pairs enriching on the surface, the SO32 detection limit of the HBPILs vesicles was as low as 0.138 gmol/L, which was about 1.5 orders of magnitude lower than that of acid fuchsin.展开更多
Effective countermeasures against multidrug-resistant nosocomial pathogens,such as carbapenem-resistant Klebsiella pneumoniae and methicillin-resistant Staphylococcus aureus(MRSA),require the development of innovative...Effective countermeasures against multidrug-resistant nosocomial pathogens,such as carbapenem-resistant Klebsiella pneumoniae and methicillin-resistant Staphylococcus aureus(MRSA),require the development of innovative antimicrobial strategies.This study presents a structure-function approach to antimicrobial peptide(AMP)design through the strategic integration of a cationic backbone with a hydrophobic core.This dual-domain architecture enables robust hydrophobic and electrostatic interactions,promoting spontaneous self-assembly and efficient membrane engagement.The lead peptide,Tryptolycin(TRPY),formed stable,monodisperse nanoparticles and demonstrated broad-spectrum bactericidal activity,with minimum inhibitory concentrations≤1μmol/L against multiple strains of MRSA and K.pneumoniae,while exerting minimal cytotoxicity toward mammalian cells.TRPY achieved rapid bacterial elimination,eradicating 99.9%of both planktonic and persister populations within minutes.Mechanistic investigations revealed that TRPY induced membrane permeabilization,promoted reactive oxygen species(ROS)production,and inhibited biofilm formation.In murine infection models,TRPY effectively eradicated established infections,reducing bacterial burden across target organs by 3-to 5-fold without significant cytotoxicity at therapeutic concentrations.Collectively,these findings establish TRPY as a promising therapeutic agent for clinical translation in the treatment of refractory bacterial infections.展开更多
Mimicry of nature drives the development of bionic materials.Bionic superhydrophobic materials are a kind of high-efficiency materials to handle oil spills and water pollution.However,the stability of surface coatings...Mimicry of nature drives the development of bionic materials.Bionic superhydrophobic materials are a kind of high-efficiency materials to handle oil spills and water pollution.However,the stability of surface coatings of the superhydrophobic materials remains a challenge.Herein,a new category of self-assembly bionic superhydrophobic surface coating was prepared via one-step condensation/copolymerization of vinyltriethoxysilane(VTES)and divinylbenzene(DVB),which realized the close combination of covalent bonds between organic(e.g.DVB)and inorganic matter(e.g.VTES),and avoided the swelling of polydivinylbenzene(PDVB)in the process of collection of oil from water.This organic-inorganic hybrid polymer could self-assembly deposit on the surface of sponge even other substrates.For example,P(VTES-DVB)-Si0_(2)/MS obtained by assembling P(VTES-DVB)-Si0_(2)on the surface of Melamine Sponge(MS)exhibited superhydrophobicity with a Water Contact Angle(WCA)of 157.3,the optimal adsorption capacity of 77 g g 136 g g-1 for diverse oils,and an excellent separation efficiency of 99.3%.Besides,the excellent acid and alkali resistance of P(VTES-DVB)-Si0_(2)/MS suggested the potential value in practical oil-water separation.P(VTES-DVB)-Si0_(2)showed the outstanding hydrophobic performance by using as coating on different substrates.This work provided a new idea about the stable combination of organic and inorganic matter in the surface modification.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 cooperative electrostatic attraction and π-π aromatic stacking interactions between tetrahedral tetrapyridinium TP and three tetraanionic tetraphenylethylene derivatives TPE-1～3 led to the formation of a new ki...The cooperative electrostatic attraction and π-π aromatic stacking interactions between tetrahedral tetrapyridinium TP and three tetraanionic tetraphenylethylene derivatives TPE-1～3 led to the formation of a new kind of supramolecular polymer networks in water, which have been confirmed by^1 H NMR,fluorescence, isothermal titration calorimetric(ITC) and dynamic light scattering(DLS) experiments. ITC studies show that the contributions of enthalpy and entropy were comparable, reflecting the importance of hydrophobicity in driving the intermolecular aromatic stacking. DLS experiments indicate that the linear supramolecular polymers formed by these tetratopic monomers further aggregated into networks of 10~2-nm size.展开更多
The development of heterogeneous acid catalysts with higher activity than homogeneous acid catalysts is critical and still challenging.In this study,acidic poly(ionic liquid)s with swelling ability(SAPILs)were designe...The development of heterogeneous acid catalysts with higher activity than homogeneous acid catalysts is critical and still challenging.In this study,acidic poly(ionic liquid)s with swelling ability(SAPILs)were designed and synthesized via the free radical copolymerization of ionic liquid monomers,sodium p-styrenesulfonate,and crosslinkers,followed by acidification.The 31P nuclear magnetic resonance chemical shifts of adsorbed trimethylphosphine oxide indicated that the synthesized SAPILs presented moderate and single acid strength.The thermogravimetric analysis results in the temperature range of 300–345°C revealed that the synthesized SAPILs were more stable than the commercial resin Amberlite IR-120(H)(245°C).Cryogenic scanning electron microscopy testing demonstrated that SAPILs presented unique three-dimensional(3D)honeycomb structure in water,which was ascribed to the swelling-induced self-assembly of the molecules.Moreover,we used SAPILs with micron-sized honeycomb structure in water as catalysts for the hydrolysis of cyclohexyl acetate to cyclohexanol,and determined that their catalytic activity was much higher than that of homogeneous acid catalysts.The equilibrium concentrations of all reaction components inside and outside the synthesized SAPILs were quantitatively analyzed using a series of simulated reaction mixtures.Depending on the reaction mixture,the concentration of cyclohexyl acetate inside SAPIL-1 was 7.5–23.3 times higher than that outside of it,which suggested the high enrichment ability of SAPILs for cyclohexyl acetate.The excellent catalytic performance of SAPILs was attributed to their 3D honeycomb structure in water and high enrichment ability for cyclohexyl acetate,which opened up new avenues for designing highly efficient heterogeneous acid catalysts that could eventually replace conventional homogeneous acid catalysts.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 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
基金This research was financially supported by the China Scholarship Council and the Natural Science Foundation of Hubei Province (Project 2000J002).
文摘Multilayer thin films of alternately adsorbed layers of polyelectrolytes PDDA and PS-119 were formed on both planar silica substrates and optical fibers through the ionic self-assembly technique. Intrinsic Fabry-Perot cavities were fabricated by stepwise assembling the polyelectrolytes onto the ends of optical fibers for the purposes of fiber optical device and sensor development. Ionically assembled polyelectrolyte multilayer thin films, in which. there are hydrophilic side groups with strong affinity towards water molecules, are a category of humidity-sensitive functional materials. The polyelectrolyte multilayer thin film Fabry-Perot cavity-type fiber optical humidity sensor can work over a wide range from about 0% RH to about 100% RH with a response time less than 1 s.
基金funded by the National Research,Development and Inno-vation Office,Hungary(TKP2021-EGA-31,2020-1.1.2-PIACI-KFI-2020-00021,KKP_22 Project no.144180 and FK_23 Project no.146081).Support from Hungarian Research Network(Eötvös Loránd Research Network)grant no.SA-87/2021 and KEP-5/2021 are also acknowledged.Project no.RRF-2.3.1-21-2022-00015+1 种基金supported by the European Union,Recovery and Resilience Facility.The János Bolyai Research Fellowship(A.W.)of the Hungarian Academy of Sciences is greatly acknowledged.The authors acknowledge CF CryoEM of CIISB,Instruct-CZ Centre,supported by Ministry of Education,Youth and Sports,Czech Republic(MEYS CR)(no.LM2023042)European Regional Development Fund-Project"UP CIISB"(n0.CZ.02.1.01/0.0/0.0/18_046/0015974).
文摘Peptide-based assemblies have gained increasing attention in different areas of nanotechnology,drug delivery and molecular biology.Among these,non-natural β-peptide scaffolds are particularly promising,as their programmable and diverse secondary structures,high metabolic stability and strong self-association propensity can be easily exploited to create variable constructs.We have recently demonstrated that heterochiral,acyclic β^(3)-peptides assembled into striped lamellar nanostructures that induced antibacterial activity.The process of this assembly formation could be exploited in diverse areas,however identifying oligomerisation stages,and more importantly,controlling the spontaneous process at different levels is still lacking.In this study,a set of analogues heterochiral hexameric β^(3)-peptide sequences was investigated to understand how systematic,small variations of the sequences,such as single point mutation or N-terminal chemical modification,can influence the resulting assemblies and allow the control of formed morphologies.TEM and cryo-EM combined with molecular dynamics simulation enabled the identification and differentiation of morphological stages throughout the entire multi-step process.Depending on the position of the sequence modifications,the self-assembled structures formed small oligomers,individual protofibrils,extended,flat lamellae,bundles and macroscopic clusters.These results outline how the self-assembly process of short heterochiral β-peptides can be qualitatively fine-tuned by sequence modifications,which contribute to understanding the general peptide assembly processes for their fibrillar morphologies.
基金financially supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.NRF-2020R1A3B2079803 and No.RS-2024-00453815),Republic of Korea。
文摘Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.Herein,we propose a self-assembly chemical strategy into the LCHEs induced by ordered nanostructure of zwitterionic co-solutes for highly efficient and ultrastable zinc(Zn)metal batteries.Through the systematic screening of six zwitterionic compounds,3-(decyldimethylammonio)propanesulfonate salt(C_(10))with the decyl chain and zwitterions was determined as an optimum to construct quasi-spherical aggregates with a periodic length of 3.77 nm,as confirmed by comprehensive synchronous small-angle X-ray scattering,Guinier,pair distance distribution function,Porod,and other spectroscopic characterizations and molecular dynamic simulation.In particularly,this self-assembled structure in electrolyte environments was attributed to increasing the proportion of both contact and aggregated ion pairs for the formation of LHCEs as well as to providing fast and selective Zn^(2+)conducting channels and uniform solid electrolyte interfaces for facilitated charge transfer kinetics.Moreover,the preferential adsorption of the self-assembled C_(10)on the Zn(002)surface modulated the electrical double layer to suppress hydrogen evolution and corrosion reactions.Consequently,the Zn‖Zn symmetric cells in Zn(OTf)_(2)/C_(10)electrolytes showed long-term plating/stripping behaviors over 2800 h at 1 mA cm^(-2)and 1 mAh cm^(-2)as well as over 1200 h even at 5 mA cm^(-2)and 5 mAh cm^(-2)with a very high depth of discharge of 42.7%.Furthermore,the ZnllVO_(2)/CNT full cells in Zn(OTf)_(2)/C_(10)electrolytes delivered a record-high capacity of 8.10 mAh cm^(-2)at an ultrahigh cathode mass loading of 50 mg cm^(-2)after 150 cycles.
基金the research grant from the Youth Fund of the National Natural Science Foundation of China(62305340)the financial support from the Hong Kong Research Grant Council via STEM Postdoctoral Fellowship(Project no.9446002)+6 种基金the Alexander von Humboldt Foundation and the support during his stay in Christoph J.Brabec’s group at Friedrich-Alexander-Universität Erlangen-Nürnberg and Helmholtz-Institute Erlangen-Nürnberg(HI ERN)the research grant from KAUST global fellowship postdocfinancial support from the Innovation and Technology Commission(Grant no.MHP/104/21)Shenzhen Science and Technology Innovation Commission(JCYJ20210324125612035,R-IND12303,and R-IND12304)the National Key Research and Development Program of China(no.2021YFA1500900)the National Natural Science Foundation of China(no.52071174)the support from the Hong Kong Jockey Club under the research work Hong Kong JC STEM Lab for Circular Bio-economy(Project No.2023-0078)。
文摘Sustainability and scalability remain critical hurdles for the commercialization of organic solar cells(OSCs).However,addressing both poses challenge.Herein,we introduce a simple yet effective strategy utilizing 3,5-dichloropyridine(PDCC)as a solid additive to fine-tune the self-assembly behavior of Y-series non-fullerene acceptors(NFAs)to tackle the upscaling limitations in green-solvent-processed OSCs.PDCC predominantly interacts with Y-series NFAs,facilitating molecular crystallization and thereby driving the self-assembly of Y-series NFAs during film-forming dynamics,leading to more uniform active layers with improved molecular packing and reduced charge recombination.As a result,PDCC-driven self-assembly strategy enables high-performance OSCs with a power conversion efficiency(PCE)of 20.47%.When translated to sustainable fabrication,this strategy significantly boosts the PCE of large-area green-solvent-processed OSC modules(19.3 cm^(2))from 13.87%to 15.79%,ranking it among the best-performing green-solvent-processed large-area OSC modules(>18 cm^(2)).Beyond its impact on PCE enhancement,PDCC serves as a multifunctional additive to improve long-term stability and exhibits strong universality across multiple material systems.This work establishes a promising approach for advancing sustainable and scalable OSCs,paving the way for their commercialization.
基金supported by the National Natural Science Foundation of China(32571991)Guangxi Natural Science Foundation of China(2023GXNSFGA026001&2025GXNSFAA069870)the Foundation of State Key Laboratory of Biobased Material and Green Papermaking.(No.GZKF202323)。
文摘The rapid advancement of flexible electronics technology has placed higher demands on the structural design and performance regulation of elastic materials.Cellulosic elastomers,with their biodegradability,renewability,and tunability,emerge as ideal candidate materials.Entropy-driven self-as sembly promotes the spontaneous formation of ordered structures,serving as a crucial pathway for optimizing cellulose elastomer properties.However,the structure-property relationship between the self-assembled ordered structures of cellulose elastomers and their mechanical and electrical properties remains insufficiently explored.It hinders the expansion of their applications in electronic devices.This paper systematically reviews the structure-property regulation mechanisms of self-assembled cellulosic elastomers from an entropy-driven perspective.It elucidates the application principles and performance optimization strategies for mechanical energy harvesting and self-powered sensing,while also exploring the challenges and prospects for performance enhancement.This work provides a reference for the development of self-assembled cellulosic elastomers in the field of energy devices.
文摘Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C_(3)N_(4))presents a promising and environmentally friendly approach.However,pristine g-C_(3)N_(4) suffers from limited visible-light absorption and low charge-carrier mobility.In this study,a phosphorus-doped tubular carbon nitride(5P-TCN)was synthesized via a precursor self-assembly method using phosphoric acid and melamine as raw materials,eliminating the need for organic solvents or templates.The 5P-TCN catalyst demonstrated enhanced visible-light absorption,improved charge transfer capability,and a 5.25-fold increase in specific surface area(31.092 m^(2)/g),which provided abundant active sites to efficiently drive the PMS-assisted photocatalytic reaction.The 5P-TCN/vis/PMS system exhibited exceptional degradation performance for organic pollutants across a broad pH range(3–9),achieving over 92%degradation of Rhodamine B(RhB)within 15 min.Notably,the system retained>98%RhB degradation efficiency after three consecutive operational cycles,demonstrating robust operational stability and reusability.Moreover,key parameters influencing,active radi-cals,degradation pathways,and potential mechanisms for RhB degradation were systematically investigated.This work proposes a green and cost-effective strategy for developing high-efficiency photocatalysts,while demon-strating the exceptional capability of a PMS-assisted photocatalytic system for rapid degradation of RhB.
基金the National Natural Science Foundation of China(No.21921003 for Z.T.L.and 22201293 for S.B.Y.)Shanghai Sailing Program(No.22YF1458300 for S.B.Y.)for financial support。
文摘Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
基金financially supported by the Key R&D Program of Shandong Province,China(2023CXGC010712).
文摘Herein,a reusable and portable surface-enhanced Raman spectroscopy(SERS)sandpaper was successfully synthesized for the sensitive detection of S-fenvalerate in foods.Commercial sandpapers were decorated with Ag@SiO2@Au nanoarrays via a liquid-liquid interface self-assembly method.The capacity of sandpaper to float directly on the cyclohexane-water interface allows nanoarrays to be formed directly on it,thereby minimizing stacking issues typically associated with nanoarray assemblies and significantly enhancing the sensitivity of S-fenvalerate detection.Moreover,the SERS sandpaper was reusable and portable due to its strong adhesion of the nanoarrays.Under optimized testing conditions,the developed SERS sandpaper method was capable of detecting S-fenvalerate,demonstrating a strong linear response within a concentration range of 10^(–7)–10^(3)μmol/L,with a limit of detection of 1.92×10^(−8)μmol/L.The analysis of spiked food samples containing S-fenvalerate using the developed SERS sandpaper afforded excellent recoveries(92.2%−109.7%).Additionally,the SERS sandpaper was successfully applied to quantify S-fenvalerate in real food samples,with results consistent with analyses conducted using gas chromatography.
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supported by the National Basic Research Program(No.2013CB834506)the National Science Fund for Distinguished Young Scholars(No.21225420)+1 种基金the National Natural Science Foundation of China(Nos.91127047,21474062 and 21404070)Program of Shanghai Subject Chief Scientist(No.15XD1502400)
文摘This work reports a SO2 derivative-detecting and colorful hyperbranched polymeric ionic liquid （HBPIL） vesicle through aqueous self-assembly. By a simple anion-exchange, we achieved the combination of functional small-molecule probe of acid fuchsin with HBPILs. The obtained HBPIL vesicle displayed ultraviolet absorption at 544 nm, and was used as a novel SO2 derivative sensor with high sensitivity and visualization. Due to the functional ion pairs enriching on the surface, the SO32 detection limit of the HBPILs vesicles was as low as 0.138 gmol/L, which was about 1.5 orders of magnitude lower than that of acid fuchsin.
基金supported by the National Key Research and Development Program of China(2022YFC2105003,2022YFC2602500)National Natural Science Foundation of China(92469103,32400769,32300404)+6 种基金Chinese Academy of Sciences(YSBR-111,SAJC202402)Yunnan Provincial Science and Technology Department(202305AH340007,202301AT070343,202502AA310005)Yunnan Characteristic Plant Extraction Laboratory(2025YKZY002)Kunming Science and Technology Bureau(2022SCP007)New Cornerstone Investigator Program from Shenzhen New Cornerstone Science Foundation(NCI202238)Tianfu Jincheng Laboratory Foundation(TFJC2023010007)Chinese Academy of Sciences and World Academy of Sciences(CAS-TWAS)President’s Fellowship Program(2019A8010415001)。
文摘Effective countermeasures against multidrug-resistant nosocomial pathogens,such as carbapenem-resistant Klebsiella pneumoniae and methicillin-resistant Staphylococcus aureus(MRSA),require the development of innovative antimicrobial strategies.This study presents a structure-function approach to antimicrobial peptide(AMP)design through the strategic integration of a cationic backbone with a hydrophobic core.This dual-domain architecture enables robust hydrophobic and electrostatic interactions,promoting spontaneous self-assembly and efficient membrane engagement.The lead peptide,Tryptolycin(TRPY),formed stable,monodisperse nanoparticles and demonstrated broad-spectrum bactericidal activity,with minimum inhibitory concentrations≤1μmol/L against multiple strains of MRSA and K.pneumoniae,while exerting minimal cytotoxicity toward mammalian cells.TRPY achieved rapid bacterial elimination,eradicating 99.9%of both planktonic and persister populations within minutes.Mechanistic investigations revealed that TRPY induced membrane permeabilization,promoted reactive oxygen species(ROS)production,and inhibited biofilm formation.In murine infection models,TRPY effectively eradicated established infections,reducing bacterial burden across target organs by 3-to 5-fold without significant cytotoxicity at therapeutic concentrations.Collectively,these findings establish TRPY as a promising therapeutic agent for clinical translation in the treatment of refractory bacterial infections.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22008092,21822807 and 51803080)Postgraduate Research&Practice Innovation Program of Jiangsu Prov ince(KYCX19_1592)Science and Technology Planning Social Development Project of Zhenjiang City(SH2020003).
文摘Mimicry of nature drives the development of bionic materials.Bionic superhydrophobic materials are a kind of high-efficiency materials to handle oil spills and water pollution.However,the stability of surface coatings of the superhydrophobic materials remains a challenge.Herein,a new category of self-assembly bionic superhydrophobic surface coating was prepared via one-step condensation/copolymerization of vinyltriethoxysilane(VTES)and divinylbenzene(DVB),which realized the close combination of covalent bonds between organic(e.g.DVB)and inorganic matter(e.g.VTES),and avoided the swelling of polydivinylbenzene(PDVB)in the process of collection of oil from water.This organic-inorganic hybrid polymer could self-assembly deposit on the surface of sponge even other substrates.For example,P(VTES-DVB)-Si0_(2)/MS obtained by assembling P(VTES-DVB)-Si0_(2)on the surface of Melamine Sponge(MS)exhibited superhydrophobicity with a Water Contact Angle(WCA)of 157.3,the optimal adsorption capacity of 77 g g 136 g g-1 for diverse oils,and an excellent separation efficiency of 99.3%.Besides,the excellent acid and alkali resistance of P(VTES-DVB)-Si0_(2)/MS suggested the potential value in practical oil-water separation.P(VTES-DVB)-Si0_(2)showed the outstanding hydrophobic performance by using as coating on different substrates.This work provided a new idea about the stable combination of organic and inorganic matter in the surface modification.
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National Natural Science Foundation of China (Nos. 21432004 and 21472023) for financial support
文摘The cooperative electrostatic attraction and π-π aromatic stacking interactions between tetrahedral tetrapyridinium TP and three tetraanionic tetraphenylethylene derivatives TPE-1～3 led to the formation of a new kind of supramolecular polymer networks in water, which have been confirmed by^1 H NMR,fluorescence, isothermal titration calorimetric(ITC) and dynamic light scattering(DLS) experiments. ITC studies show that the contributions of enthalpy and entropy were comparable, reflecting the importance of hydrophobicity in driving the intermolecular aromatic stacking. DLS experiments indicate that the linear supramolecular polymers formed by these tetratopic monomers further aggregated into networks of 10~2-nm size.
文摘The development of heterogeneous acid catalysts with higher activity than homogeneous acid catalysts is critical and still challenging.In this study,acidic poly(ionic liquid)s with swelling ability(SAPILs)were designed and synthesized via the free radical copolymerization of ionic liquid monomers,sodium p-styrenesulfonate,and crosslinkers,followed by acidification.The 31P nuclear magnetic resonance chemical shifts of adsorbed trimethylphosphine oxide indicated that the synthesized SAPILs presented moderate and single acid strength.The thermogravimetric analysis results in the temperature range of 300–345°C revealed that the synthesized SAPILs were more stable than the commercial resin Amberlite IR-120(H)(245°C).Cryogenic scanning electron microscopy testing demonstrated that SAPILs presented unique three-dimensional(3D)honeycomb structure in water,which was ascribed to the swelling-induced self-assembly of the molecules.Moreover,we used SAPILs with micron-sized honeycomb structure in water as catalysts for the hydrolysis of cyclohexyl acetate to cyclohexanol,and determined that their catalytic activity was much higher than that of homogeneous acid catalysts.The equilibrium concentrations of all reaction components inside and outside the synthesized SAPILs were quantitatively analyzed using a series of simulated reaction mixtures.Depending on the reaction mixture,the concentration of cyclohexyl acetate inside SAPIL-1 was 7.5–23.3 times higher than that outside of it,which suggested the high enrichment ability of SAPILs for cyclohexyl acetate.The excellent catalytic performance of SAPILs was attributed to their 3D honeycomb structure in water and high enrichment ability for cyclohexyl acetate,which opened up new avenues for designing highly efficient heterogeneous acid catalysts that could eventually replace conventional homogeneous acid catalysts.
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.
