Melamine sponge is a major concern for oil-water separation due to its lightweight,high porosity(>99%),cost-effectiveness,impressive mechanical properties,and chemical/thermal stability.However,its amphiphilic natu...Melamine sponge is a major concern for oil-water separation due to its lightweight,high porosity(>99%),cost-effectiveness,impressive mechanical properties,and chemical/thermal stability.However,its amphiphilic nature hinders selective oil absorption in water.Recent strategies to enhance hydrophobicity are reviewed,including synthetic methods and materials,with comprehensive explanations of the mechanisms driven by surface energy and roughness.Key performance indicators for MS in oil-water separation,including adsorption capacity,wettability,stability,emulsion separation,reversible wettability switching,flame retardancy,mechanical properties,and recyclability,are thoroughly discussed.In conclusion,this review provides insights into the future potential and direction of functional melamine sponges in oil-water separation.展开更多
Regulatory T(Treg)cells are pivotal for maintaining immune homeostasis and play essential roles in various diseases,such as autoimmune diseases,graft-versus-host disease(GVHD),tumors,and infectious diseases.Treg cells...Regulatory T(Treg)cells are pivotal for maintaining immune homeostasis and play essential roles in various diseases,such as autoimmune diseases,graft-versus-host disease(GVHD),tumors,and infectious diseases.Treg cells exert suppressive function via distinct mechanisms,including inhibitory cytokines,granzyme or perforin-mediated cytolysis,metabolic disruption,and suppression of dendritic cells.Forkhead Box P3(FOXP3),the characteristic transcription factor,is essential for Treg cell function and plasticity.Cumulative evidence has demonstrated that FOXP3 activity and Treg cell function are modulated by a variety of post-translational modifications(PTMs),including ubiquitination,acetylation,phosphorylation,methylation,glycosylation,poly(ADP-ribosyl)ation,and uncharacterized modifications.This review describes Treg cell suppressive mechanisms and summarizes the current evidence on PTM regulation of FOXP3 and Treg cell function.Understanding the regulatory role of PTMs in Treg cell plasticity and function will be helpful in designing therapeutic strategies for autoimmune diseases,GVHD,tumors,and infectious diseases.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
Fibrillization endows food proteins with anisotropic nanostructures,significantly enhancing their functional properties.The resultant food protein fibrils(FPFs)have garnered attention for their diverse applications ac...Fibrillization endows food proteins with anisotropic nanostructures,significantly enhancing their functional properties.The resultant food protein fibrils(FPFs)have garnered attention for their diverse applications across the food industry.However,the full potential of FPFs is hindered by inherent challenges,particularly their limited stability.This review critically examines the formation of FPFs in food processing,the new protein sources,and on the modification strategies of FPFs,thereby unlocking new avenues for FPF utilization in food processing.In particular,the strategies during and after fibrillization are highlighted.The first strategy is to modify the structure and function of protein fibrils by influencing fibrillization,such as through pretreatment,incubation conditions,nuclei induction,and ingredient interactions.The second strategy is to modify the mature FPFs by regulating their properties and interactions with other components.The review also discusses the potential applications and challenges of FPFs in food systems,such as food preservation,functional food design,and novel delivery carriers.展开更多
NiO_(x)as a hole transport material for inverted perovskite solar cells has received great attention owing to its high transparency,low fabrication temperature,and superior stability.However,the mismatched energy leve...NiO_(x)as a hole transport material for inverted perovskite solar cells has received great attention owing to its high transparency,low fabrication temperature,and superior stability.However,the mismatched energy levels and possible redox reactions at the NiO_(x)/perovskite interface severely limit the performance of NiO_(x) based inverted perovskite solar cells.Herein,we introduce a p-type self-assembled monolayer between NiO_(x)and perovskite layers to modify the interface and block the undesirable redox reaction between perovskite and NiO_(x)The selfassembled monolayer molecules all contain phosphoric acid function groups,which can be anchored onto the NiOr surface and passivate the surface defect.Moreover,the introduction of self-assembled monolayers can regulate the energy level structure of NiO_(x),reduce the interfacial band energy offset,and hence promote the hole transport from perovskite to NiO_(x)layer.Consequently,the device performance is significantly enhanced in terms of both power conversion efficiency and stability.展开更多
With the acceleration of advanced industrialization and urbanization,the environment is deteriorating rapidly,and non-renewable energy resources are depleted.The gradual advent of potential clean energy storage techno...With the acceleration of advanced industrialization and urbanization,the environment is deteriorating rapidly,and non-renewable energy resources are depleted.The gradual advent of potential clean energy storage technologies is particularly urgent.Electrochemical energy storage technologies have been widely used in multiple fields,especially supercapacitors and rechargeable batteries,as vital elements of storing renewable energy.In recent years,two-dimensional material MXene has shown great potential in energy and multiple application fields thanks to its excellent electrical properties,large specific surface area,and tunability.Based on the layered materials of MXene,researchers have successfully achieved the dual functions of energy storage and conversion by adjusting the surface terminals at the Fermi level.It is worth noting that compared with other two-dimensional materials,MXene has more active sites on the basal plane,showing excellent catalytic performance.In contrast,other two-dimensional materials have catalytic activity only at the edge sites.This article comprehensively overviews the synthesis process,structural characteristics,modification methods for MXene-based polymer materials,and their applications in electrochemical energy storage.It also briefly discusses the potential of MXene-polymer materials in electromagnetic shielding technology and sensors and looks forward to future research directions.展开更多
Infections associated with titanium(Ti)-based implants present significant challenges in clinical treatments,especially when biofilms already form on the implant surface.Many antimicrobial agents,including antibiotics...Infections associated with titanium(Ti)-based implants present significant challenges in clinical treatments,especially when biofilms already form on the implant surface.Many antimicrobial agents,including antibiotics,metallic nanoparticles and antimicrobial peptides,have been extensively used to deal with Ti implant infections.However,these chemical approaches suffer from potential toxicity,antibiotic resistance and poor long-term antibacterial performance.Hence,physical antibacterial surfaces on Ti-based implants have attracted increasing attention.The antibacterial behavior of different surfaces on Ti-based biomaterials against various bacteria only by physical properties of the implants themselves(e.g.,nanotopography)or exogenous physical stimulus(e.g.,photocatalysis)was reviewed,as well as parameters influencing the physical antibacterial processes,such as size,shape and density of the surface nanotextures,and bacterial growth phases.Besides,mechanisms of different fabrication techniques for the physical antibacterial surfaces on Ti-based biomaterials were also summarized.展开更多
Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies.Among the proteogenic amino acids,lysine is extensively involved in posttra...Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies.Among the proteogenic amino acids,lysine is extensively involved in posttranslational modifications and the binding of ligands to target proteins,making its selective modification attractive.However,lysine’s high natural abundance and solvent accessibility,as well as its relatively low reactivity to cysteine,necessitate addressing chemoselectivity and regioselectivity for the Lys modification of native proteins.Although Lys chemoselective modification methods have been well developed,achieving site-selective modification of a specific Lys residue remains a great challenge.In this review,we discussed the challenges of Lys selective modification,presented recent examples of Lys chemoselective modification,and summarized the currently known methods and strategies for Lys site-selective modification.We also included an outlook on potential solutions for Lys site-selective labeling and its potential applications in chemical biology and drug development.展开更多
Nowadays,high-stable and ultrasensitive heavy metal detection is of utmost importance in water quality monitoring.Nanoparticle-enhanced laser-induced breakdown spectroscopy(NELIBS)shows high potential in hazardous met...Nowadays,high-stable and ultrasensitive heavy metal detection is of utmost importance in water quality monitoring.Nanoparticle-enhanced laser-induced breakdown spectroscopy(NELIBS)shows high potential in hazardous metal detection,however,encounters unstable and weak signals due to nonuniform distribution of analytes.Herein,we developed an interface self-assembly(ISA)method to create a uniformly distributed gold nanolayer at a liquid-liquid interface for positive heavy metal ions capture and NELIBS analysis.The electrostatically selfassembled Au nanoparticles(NPs)-analytes membrane was prepared at the oil-water interface by injecting ethanol into the mixture of cyclohexane and Au NPs-analytes water solution.Then,the interface self-assembled Au NPs-analytes membrane was transformed onto a laser-processed superhydrophilic Si slide for detection.Three heavy metals(cadmium(Cd),barium(Ba),and chromium(Cr))were analyzed to evaluate the stability and sensitivity of the ISA method for NELIBS.The results(Cd:RSD=3.6%,LoD=0.654 mg/L;Ba:RSD=3.4%,LoD=0.236 mg/L;Cr:RSD=7.7%,LoD=1.367 mg/L)demonstrated signal enhancement and high-stable and ultrasensitive detection.The actual sample detection(Cd:RE=7.71%,Ba:RE=6.78%)illustrated great reliability.The ISA method,creating a uniform distribution of NP-analytes at the interface,has promising prospects in NELIBS.展开更多
Diphenylalanine and its analogs cause many concerns owing to their perfect self-assembly properties in the fields of biology,medicine,and nanotechnology.Experimental research has shown that diphenylalanine-based analo...Diphenylalanine and its analogs cause many concerns owing to their perfect self-assembly properties in the fields of biology,medicine,and nanotechnology.Experimental research has shown that diphenylalanine-based analogs with ethylenediamine linkers(PA,P=phenylalanine,and A=analog)can self-assemble into spherical assemblies,which can serve as novel anticancer drug carriers.In this work,to understand the assembly pathways,drug loading behavior,and formation mechanism of PA aggregates at the molecular level,we carried out dissipative particle dynamics(DPD)simulations of PA molecule systems.Our simulation results demonstrate that PA molecules spontaneously assemble into nanospheres and can self-assemble into drug-loaded nanospheres upon addition of the cancer chemotherapeutic agent doxorubicin(DOX).We also found that the hydrophobic side chain beads of PA molecules exhibited a unique onion-like distribution inside the nanospheres,which was not observed in the experiment.The onion-like nanospheres were verified by calculating the radial distribution function(RDF)of the DPD beads.Furthermore,based on the analysis of the percentages of different interaction components in the total nonbonded energies,main chain-side chain interactions between PA molecules may be important in the formation of onion-like nanospheres,and the synergistic effects of main chain-side chain,main chain-drug,side chain-drug,and main chain-solvent interactions are significant in the formation of drug-loaded nanospheres.These findings provide new insights into the structure and self-assembly pathway of PA assemblies,which may be helpful for the design of efficient and effective drug delivery systems.展开更多
The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching(ACQ).In this study,an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence em...The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching(ACQ).In this study,an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence emission through protein coronas-controlled distance between gold nanoclusters(Au NCs).Interestingly,the gold ion complexes coated with proteins of low isoelectric point(pI)nucleate at the secondary structure of proteins with high p I through ionic exchange within cells,generating fluorescent Au NCs.It is worth noting that due to the steric hindrance formed by the protein coronas on the surface of Au NCs,the distance between Au NCs can be controlled,avoiding electron transfer caused by close proximity of Au NCs and inhibiting fluorescence ACQ.This strategy can achieve fluorescence imaging of clinical tissue samples without observable side effects.Therefore,this study proposes a distance-controllable self-assembled pitaya structure to provide a new approach for Au NCs with stable fluorescence.展开更多
The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements.In this pape r,the extractant(N,N-methyl py ridineethyl-N',N'-dicyclohexyl-3-oxadiglycola...The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements.In this pape r,the extractant(N,N-methyl py ridineethyl-N',N'-dicyclohexyl-3-oxadiglycolamide,MPyEDChDGA) with a new structure was synthesized,and the pyridine group was successfully grafted onto the 3-oxadiglycolamide structure.Using MPyEDChDGA for efficient enrichment of rare earth ions,the self-assembled solids were recovered by simple filtration without further backextraction and final precipitation,achieving a one-step strategy for the recovery of rare earth ions.Several important parameters affecting the self-assembly extraction,including pH,diluent,temperature,and extractant concentration,were systematically evaluated using La(NO_(3))_(3),Tb(NO_(3))_(3),and Lu(NO_(3))_(3) as representatives.The self-assembled solids were investigated in detail by X-ray diffraction(XRD),scanning electron microscopy(SEM),1H nuclear magnetic resonance(1H NMR),Fourier transform infrared spectroscopy(FT-IR),Raman,and X-ray photoelectron spectroscopy(XPS) analyses.The stoichiometry of the extraction species was characterized using the Job's method and electrospray ionization mass spectrometry(ESI-MS).In addition,MPyEDChDGA was applied to the recovery of Sm in SmCoCu simulated liquid,and the results show that MPyEDChDGA has good selectivity of Sm from transition metals(Co,Cu).The separation factor of Sm/Co can reach 6281±117,which provides a new approach to recovering Sm from SmCoCu scrap magnets.This study presents an efficient and convenient new strategy for the recovery and separation of rare earth elements.展开更多
An imbalanced dataset often challenges machine learning, particularly classification methods. Underrepresented minority classes can result in biased and inaccurate models. The Synthetic Minority Over-Sampling Techniqu...An imbalanced dataset often challenges machine learning, particularly classification methods. Underrepresented minority classes can result in biased and inaccurate models. The Synthetic Minority Over-Sampling Technique (SMOTE) was developed to address the problem of imbalanced data. Over time, several weaknesses of the SMOTE method have been identified in generating synthetic minority class data, such as overlapping, noise, and small disjuncts. However, these studies generally focus on only one of SMOTE’s weaknesses: noise or overlapping. Therefore, this study addresses both issues simultaneously by tackling noise and overlapping in SMOTE-generated data. This study proposes a combined approach of filtering, clustering, and distance modification to reduce noise and overlapping produced by SMOTE. Filtering removes minority class data (noise) located in majority class regions, with the k-nn method applied for filtering. The use of Noise Reduction (NR), which removes data that is considered noise before applying SMOTE, has a positive impact in overcoming data imbalance. Clustering establishes decision boundaries by partitioning data into clusters, allowing SMOTE with modified distance metrics to generate minority class data within each cluster. This SMOTE clustering and distance modification approach aims to minimize overlap in synthetic minority data that could introduce noise. The proposed method is called “NR-Clustering SMOTE,” which has several stages in balancing data: (1) filtering by removing minority classes close to majority classes (data noise) using the k-nn method;(2) clustering data using K-means aims to establish decision boundaries by partitioning data into several clusters;(3) applying SMOTE oversampling with Manhattan distance within each cluster. Test results indicate that the proposed NR-Clustering SMOTE method achieves the best performance across all evaluation metrics for classification methods such as Random Forest, SVM, and Naїve Bayes, compared to the original data and traditional SMOTE. The proposed method (NR-Clustering SMOTE) improves accuracy by 15.34% on the Pima dataset and 20.96% on the Haberman dataset compared to SMOTE-LOF. Compared to Radius-SMOTE, this method increases accuracy by 3.16% on the Pima dataset and 13.24% on the Haberman dataset. Meanwhile, compared to RN-SMOTE, the accuracy improvement reaches 15.56% on the Pima dataset and 19.84% on the Haberman dataset. This research result implies that the proposed method experiences consistent performance improvement compared to traditional SMOTE and its latest variants, such as SMOTE-LOF, Radius-SMOTE, and RN-SMOTE, in solving imbalanced health data with class binaries.展开更多
Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AAB...Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AABCs presents challenges,which greatly limits the exploration of their self-assembly behaviors.In this work,we employed dissipative particle dynamics(DPD)simulations to investigate the self-assembly behaviors of AABCs in selective solution.By varying the copolymer concentration and structure,we conducted the self-assembly phase diagrams of AABCs,revealing complex morphologies such as channelized micelles with one or more solvophilic channels.Moreover,the number,surface area,and one-dimensional density distribution of the channelized micelles were calculated to demonstrate the internal structure and morphological transformation during the self-assembly process.Our findings indicate that the morphology of the internal solvophilic channels is greatly influenced by the copolymer structure,concentration,and interaction parameters between the different side chains.The simulation results are consistent with available experimental observations,which can offer theoretical insights into the self-assembly of AABCs.展开更多
The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable.Here,we...The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable.Here,we report a fluorinated N-heterocyclic carbene(NHC)–based pillarplex with a tunable quaternary structure,employed as an efficient building block for constructing hierarchical superstructures.Initially,multiple noncovalent interactions in the NHC-based pillarplex,particularly those between the fluorinated pillarplex and PF_(6)-anions,induce the formation of a supramolecular gel at high concentrations.Additionally,this hierarchical self-assembled structure can be regulated by adjusting anion types,facilitating the controlled transformation from a supramolecular gel into a supramolecular channel upon the introduction of four monocarboxylic acids as anions.The study provides insight into the construction and controlled regulation of superstructures based on NHC-based pillarplexes.展开更多
Paraphenylenediamine(PPDA)-grafted maleic anhydride(MAH)-modified graphene oxide(PGO)was synthesized through a dual modification process.Initially,MAH was employed to modify graphene oxide(GO)to enhance its reactive s...Paraphenylenediamine(PPDA)-grafted maleic anhydride(MAH)-modified graphene oxide(PGO)was synthesized through a dual modification process.Initially,MAH was employed to modify graphene oxide(GO)to enhance its reactive sites.Subsequently,PPDA was utilized for further modification of MAH-modified GO(MGO).Through a comprehensive analysis,the successful grafting of MAH and PPDA onto GO was confirmed.It was concurrently established that the optimal ratio of PPDA to MGO is 1:1.This approach yielded PGO characterized by outstanding dispersibility and barrier properties in epoxy resin(EP)coaings for Q235 steel.The corrosion resistance of EP coatings containing varying amounts of PGO was assessed using electrochemical workstation and salt spray testing.After immersing in a 3.5 wt.%NaCl solution for 300 h,the composite coating containing 0.1 wt.%PGO exhibited superior performance in terms of low-frequency impedance modulus,measuring at 1.1×10^(8)Ωcm^(2).The lowest corrosion current density was 2.32×10^(–10)A cm^(−2),and the self-corrosion voltage was−0.301 V.Additionally,polarization testing indicated that this coating also displayed the lowest corrosion rate,specifically 1.383×10^(–7)mm/a.展开更多
Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy,mainly comprise drug modules,response modules and modification modules.However,existing studies usually compare the differe...Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy,mainly comprise drug modules,response modules and modification modules.However,existing studies usually compare the differences between single types of modification modules,neglecting the impact of steric-hindrance effect caused by chemical structure.Herein,single-tailed modification module with low-steric-hindrance effect and two-tailed modification module with high-steric-hindrance effect were selected to construct paclitaxel prodrugs(P-LA_(C18)and P-BAC18),and the in-depth insights of the sterichindrance effect on prodrug nanoassemblies were explored.Notably,the size stability of the two-tailed prodrugs was enhanced due to improved intermolecular interactions and steric hindrance.Single-tailed prodrug nanoassemblies were more susceptible to attack by redox agents,showing faster drug release and stronger antitumor efficacy,but with poorer safety.In contrast,two-tailed prodrug nanoassemblies exhibited significant advantages in terms of pharmacokinetics,tumor accumulation and safety due to the good size stability,thus ensuring equivalent antitumor efficacy at tolerance dose.These findings highlighted the critical role of steric-hindrance effect of the modification module in regulating the structureactivity relationship of prodrug nanoassemblies and proposed new perspectives into the precise design of self-assembled prodrugs for high-performance cancer therapeutics.展开更多
Lithium-sulfur batteries(LSBs)have undoubtedly become one of the most promising battery systems due to their high energy density and the cost-effectiveness of sulfur cathodes.However,challenges,such as the shuttle eff...Lithium-sulfur batteries(LSBs)have undoubtedly become one of the most promising battery systems due to their high energy density and the cost-effectiveness of sulfur cathodes.However,challenges,such as the shuttle effect from soluble long-chain lithium polysulfides(LiPSs)and the low conductivity of active materials,hinder their commercialization.Under this circumstance,molybdenum sulfide(MoS_(2))has attracted widespread attention due to its unique physicochemical properties,particularly its capability to mitigate the shuttle effect in LSBs through electrostatic or chemical bonds.Nonetheless,the industrial application of MoS_(2)in LSBs is limited by the inertness of its basal surface and inadequate electron transfer properties.This review mainly introduces various modification strategies of MoS_(2)materials in LSBs and their effects on electrochemical and catalytic performance.Unlike previous reviews and related papers,detailed discussions were conducted on the specific mechanisms of each modification strategy,including(1)shape manipulation,(2)support engineering,(3)heterostructure engineering,(4)defect engineering,(5)interlayer engineering,(6)phase engineering,(7)strain engineering,(8)hybridization.Comprehensive conclusions and outlook on the development of MoS_(2)as an abundant electrocatalyst for LSBs are also discussed in the end.展开更多
Polymerization-induced self-assembly(PISA)has become one of the most versatile approaches for scalable preparation of linear block copolymer nanoparticles with various morphologies.However,the controlled introduction ...Polymerization-induced self-assembly(PISA)has become one of the most versatile approaches for scalable preparation of linear block copolymer nanoparticles with various morphologies.However,the controlled introduction of branching into the core-forming block and the effect on the morphologies of block copolymer nanoparticles under PISA conditions have rarely been explored.Herein,a series of multifunctional macromolecular chain transfer agents(macro-CTAs)were first synthesized by a two-step green light-activated photoiniferter polymerization using two types of chain transfer monomers(CTMs).These macro-CTAs were then used to mediate reversible addition-fragmentation chain transfer(RAFT)dispersion polymerization of styrene(St)to prepare block copolymers with different core-forming block structures and the assemblies.The effect of the core-forming block structure on the morphology of block copolymer nanoparticles was investigated in detail.Transmission electron microscopy(TEM)analysis indicated that the brush-like core-forming block structure facilitated the formation of higher-order morphologies,while the branched core-forming block structure favored the formation of lower-order morphologies.Moreover,it was found that using macroCTAs with a shorter length also promoted the formation of higher-order morphologies.Finally,structures of block copolymers and the assemblies were further controlled by changing the structure of macro-CTA or using a binary mixture of two different macro-CTAs.We expect that this work not only sheds light on the synthesis of block copolymer nanoparticles but also provide important mechanistic insights into PISA of nonlinear block copolymers.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52372093 and 52102145)the Key R&D Program of Shaanxi Province(Nos.2023GXLH-045 and 2022SF-168)+4 种基金the Xi’an Programs for Science and Technology Plan(Nos.2020KJRC0090 and 21XJZZ0045)the Opening Project of Shanxi Key Laboratory of Advanced Manufacturing Technology(No.XJZZ202001)the Xi’an Municipal Bureau of Science and Technology(No.21XJZZ0054)the Open Foundation of Key Laboratory of Auxiliary Chemistry and Technology for Chemical Industry,Ministry of Education,Shaanxi University of Science and Technology(No.KFKT2021-01)the Shaanxi Collaborative Innovation Center of Industrial Auxiliary Chemistry and Technology,Shaanxi University of Science and Technology(No.KFKT2021-01).
文摘Melamine sponge is a major concern for oil-water separation due to its lightweight,high porosity(>99%),cost-effectiveness,impressive mechanical properties,and chemical/thermal stability.However,its amphiphilic nature hinders selective oil absorption in water.Recent strategies to enhance hydrophobicity are reviewed,including synthetic methods and materials,with comprehensive explanations of the mechanisms driven by surface energy and roughness.Key performance indicators for MS in oil-water separation,including adsorption capacity,wettability,stability,emulsion separation,reversible wettability switching,flame retardancy,mechanical properties,and recyclability,are thoroughly discussed.In conclusion,this review provides insights into the future potential and direction of functional melamine sponges in oil-water separation.
基金supported by grants from the National Key R&D Program of China(2022YFC2403000 and 2021YFC2400500)the National Natural Science Foundation of China(32200728 and 32170925)+3 种基金the Clinical Research Project of Shenzhen Medical Academy of Research and Translation(C2301008)Shenzhen Science and Technology Program(JCYJ20220531100406014,JCYJ2022081800807016,RCBS20221008093336088,KQTD20210811090115019)Guangdong Basic and Applied Basic Research Foundation(2021A1515110375)the Innovative Research Team of High-level Local Universities in Shanghai(SHSMU-ZDCX20210601).
文摘Regulatory T(Treg)cells are pivotal for maintaining immune homeostasis and play essential roles in various diseases,such as autoimmune diseases,graft-versus-host disease(GVHD),tumors,and infectious diseases.Treg cells exert suppressive function via distinct mechanisms,including inhibitory cytokines,granzyme or perforin-mediated cytolysis,metabolic disruption,and suppression of dendritic cells.Forkhead Box P3(FOXP3),the characteristic transcription factor,is essential for Treg cell function and plasticity.Cumulative evidence has demonstrated that FOXP3 activity and Treg cell function are modulated by a variety of post-translational modifications(PTMs),including ubiquitination,acetylation,phosphorylation,methylation,glycosylation,poly(ADP-ribosyl)ation,and uncharacterized modifications.This review describes Treg cell suppressive mechanisms and summarizes the current evidence on PTM regulation of FOXP3 and Treg cell function.Understanding the regulatory role of PTMs in Treg cell plasticity and function will be helpful in designing therapeutic strategies for autoimmune diseases,GVHD,tumors,and infectious diseases.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.2020R1C1C1003375)。
文摘Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practical performance is limited by inhomogeneous agglomeration,increased binder requirements,and high tortuosity within the electrode.To overcome these problems and high tortuosity within the electrode,this study introduces a pomegranate-like carbon microcluster composed of primary HCSs(P-CMs)as a novel Li metal host.This unique nanostructure can be easily prepared using the spray-drying technique,enabling its mass production.Comprehensive analyses with various tools demonstrate that compared with HCS hosts,the P-CM host requires a smaller amount of binder to fabricate a sufficiently robust and even surface electrode.Furthermore,owing to reduced tortuosity,the well-designed P-CM electrode can provide continuous and shortened pathways for electron/ion transport,accelerating the Li-ion transfer kinetics and prohibiting preferential Li plating at the upper region of the electrode.Due to these characteristics,Li metal can be effectively encapsulated in the large inner voids of the primary HCSs constituting the P-CM,thereby enhancing the electrochemical performance of P-CM hosts in Li metal batteries.Specifically,the Coulombic efficiency of the P-CM host can be maintained at 97%over 100 cycles,with a high Li deposition areal capacity of 3 mAh·cm^(-2)and long cycle life(1000 h,1 mA·cm^(-2),and 1.0 mAh·cm^(-2)).Furthermore,a full cell incorporating a LiFePO4 cathode exhibits excellent cycle life.
文摘Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,which can be used to construct self-assembled nanoparticles in aqueous solution driven by hydrophobic interaction.Dynamic light scattering experiments show that M1 and M2 can be driven hydrophobically to aggregate into extremely stable nanoparticles in water at the micromolar concentrations.Fluorescence titration and zeta potential experiments support that the nanoparticles formed by M1 and M2 are able to efficiently encapsulate short DNA(sDNA).Fluorescence imaging and flow cytometry studies reveal that their nano sizes enable intracellular delivery of the encapsulated sDNA into both normal and cancer cells,with delivery percentage reaching up to 94%,while in vitro experiments indicate that the two compounds have excellent biocompatibility and low cytotoxicity.
基金supported by the Natural Science Foundation of Jiangxi Province(20232BAB205075,20224ACB205014).
文摘Fibrillization endows food proteins with anisotropic nanostructures,significantly enhancing their functional properties.The resultant food protein fibrils(FPFs)have garnered attention for their diverse applications across the food industry.However,the full potential of FPFs is hindered by inherent challenges,particularly their limited stability.This review critically examines the formation of FPFs in food processing,the new protein sources,and on the modification strategies of FPFs,thereby unlocking new avenues for FPF utilization in food processing.In particular,the strategies during and after fibrillization are highlighted.The first strategy is to modify the structure and function of protein fibrils by influencing fibrillization,such as through pretreatment,incubation conditions,nuclei induction,and ingredient interactions.The second strategy is to modify the mature FPFs by regulating their properties and interactions with other components.The review also discusses the potential applications and challenges of FPFs in food systems,such as food preservation,functional food design,and novel delivery carriers.
文摘NiO_(x)as a hole transport material for inverted perovskite solar cells has received great attention owing to its high transparency,low fabrication temperature,and superior stability.However,the mismatched energy levels and possible redox reactions at the NiO_(x)/perovskite interface severely limit the performance of NiO_(x) based inverted perovskite solar cells.Herein,we introduce a p-type self-assembled monolayer between NiO_(x)and perovskite layers to modify the interface and block the undesirable redox reaction between perovskite and NiO_(x)The selfassembled monolayer molecules all contain phosphoric acid function groups,which can be anchored onto the NiOr surface and passivate the surface defect.Moreover,the introduction of self-assembled monolayers can regulate the energy level structure of NiO_(x),reduce the interfacial band energy offset,and hence promote the hole transport from perovskite to NiO_(x)layer.Consequently,the device performance is significantly enhanced in terms of both power conversion efficiency and stability.
基金supported by the Natural Science Basic Research Plan in the Shaanxi Province of China(No.2023-JC-ZD-25)Shaanxi Province(Qin ChuangYuan)“Scientist+Engineer”Team Building(No.2022KXJ-040)+1 种基金Shaanxi Provincial Department of Education Key Scientific Research Project(No.22JY024)Science and Technology Guidance Project Plan of China National Textile and Apparel Council(No.2022038,2023018).
文摘With the acceleration of advanced industrialization and urbanization,the environment is deteriorating rapidly,and non-renewable energy resources are depleted.The gradual advent of potential clean energy storage technologies is particularly urgent.Electrochemical energy storage technologies have been widely used in multiple fields,especially supercapacitors and rechargeable batteries,as vital elements of storing renewable energy.In recent years,two-dimensional material MXene has shown great potential in energy and multiple application fields thanks to its excellent electrical properties,large specific surface area,and tunability.Based on the layered materials of MXene,researchers have successfully achieved the dual functions of energy storage and conversion by adjusting the surface terminals at the Fermi level.It is worth noting that compared with other two-dimensional materials,MXene has more active sites on the basal plane,showing excellent catalytic performance.In contrast,other two-dimensional materials have catalytic activity only at the edge sites.This article comprehensively overviews the synthesis process,structural characteristics,modification methods for MXene-based polymer materials,and their applications in electrochemical energy storage.It also briefly discusses the potential of MXene-polymer materials in electromagnetic shielding technology and sensors and looks forward to future research directions.
基金National Natural Science Foundation of China(52171114)。
文摘Infections associated with titanium(Ti)-based implants present significant challenges in clinical treatments,especially when biofilms already form on the implant surface.Many antimicrobial agents,including antibiotics,metallic nanoparticles and antimicrobial peptides,have been extensively used to deal with Ti implant infections.However,these chemical approaches suffer from potential toxicity,antibiotic resistance and poor long-term antibacterial performance.Hence,physical antibacterial surfaces on Ti-based implants have attracted increasing attention.The antibacterial behavior of different surfaces on Ti-based biomaterials against various bacteria only by physical properties of the implants themselves(e.g.,nanotopography)or exogenous physical stimulus(e.g.,photocatalysis)was reviewed,as well as parameters influencing the physical antibacterial processes,such as size,shape and density of the surface nanotextures,and bacterial growth phases.Besides,mechanisms of different fabrication techniques for the physical antibacterial surfaces on Ti-based biomaterials were also summarized.
基金the National Natural Science Foundation of China(Nos.82373722,22077144)Hunan Provincial Natural Science Foundation of China(No.2023JJ30527)+2 种基金Guangdong Basic and Applied Basic Research Foundation(No.2023B1515040006)Guangdong Provincial Key Laboratory of Construction Foundation(No.2023B1212060022)Key Research and Development Program of Guangdong Province(No.2020B1111110003).
文摘Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies.Among the proteogenic amino acids,lysine is extensively involved in posttranslational modifications and the binding of ligands to target proteins,making its selective modification attractive.However,lysine’s high natural abundance and solvent accessibility,as well as its relatively low reactivity to cysteine,necessitate addressing chemoselectivity and regioselectivity for the Lys modification of native proteins.Although Lys chemoselective modification methods have been well developed,achieving site-selective modification of a specific Lys residue remains a great challenge.In this review,we discussed the challenges of Lys selective modification,presented recent examples of Lys chemoselective modification,and summarized the currently known methods and strategies for Lys site-selective modification.We also included an outlook on potential solutions for Lys site-selective labeling and its potential applications in chemical biology and drug development.
基金supported by the National Natural Science Foundation of China(No.62075069 and 52303092)the Water Conservancy Technology project of Hunan Province,China(XSKJ2021000-32)+1 种基金the City University of Hong Kong(#7005507)the Open Project of Yunnan Precious Metals Laboratory Co.,Ltd(grant number YPML-2023050278).
文摘Nowadays,high-stable and ultrasensitive heavy metal detection is of utmost importance in water quality monitoring.Nanoparticle-enhanced laser-induced breakdown spectroscopy(NELIBS)shows high potential in hazardous metal detection,however,encounters unstable and weak signals due to nonuniform distribution of analytes.Herein,we developed an interface self-assembly(ISA)method to create a uniformly distributed gold nanolayer at a liquid-liquid interface for positive heavy metal ions capture and NELIBS analysis.The electrostatically selfassembled Au nanoparticles(NPs)-analytes membrane was prepared at the oil-water interface by injecting ethanol into the mixture of cyclohexane and Au NPs-analytes water solution.Then,the interface self-assembled Au NPs-analytes membrane was transformed onto a laser-processed superhydrophilic Si slide for detection.Three heavy metals(cadmium(Cd),barium(Ba),and chromium(Cr))were analyzed to evaluate the stability and sensitivity of the ISA method for NELIBS.The results(Cd:RSD=3.6%,LoD=0.654 mg/L;Ba:RSD=3.4%,LoD=0.236 mg/L;Cr:RSD=7.7%,LoD=1.367 mg/L)demonstrated signal enhancement and high-stable and ultrasensitive detection.The actual sample detection(Cd:RE=7.71%,Ba:RE=6.78%)illustrated great reliability.The ISA method,creating a uniform distribution of NP-analytes at the interface,has promising prospects in NELIBS.
基金financially supported by the National Natural Science Foundation of China(Nos.20904047 and 12074151)the Natural Science Foundation of Zhejiang Province(Nos.LY17A040001 and LY19F03004)。
文摘Diphenylalanine and its analogs cause many concerns owing to their perfect self-assembly properties in the fields of biology,medicine,and nanotechnology.Experimental research has shown that diphenylalanine-based analogs with ethylenediamine linkers(PA,P=phenylalanine,and A=analog)can self-assemble into spherical assemblies,which can serve as novel anticancer drug carriers.In this work,to understand the assembly pathways,drug loading behavior,and formation mechanism of PA aggregates at the molecular level,we carried out dissipative particle dynamics(DPD)simulations of PA molecule systems.Our simulation results demonstrate that PA molecules spontaneously assemble into nanospheres and can self-assemble into drug-loaded nanospheres upon addition of the cancer chemotherapeutic agent doxorubicin(DOX).We also found that the hydrophobic side chain beads of PA molecules exhibited a unique onion-like distribution inside the nanospheres,which was not observed in the experiment.The onion-like nanospheres were verified by calculating the radial distribution function(RDF)of the DPD beads.Furthermore,based on the analysis of the percentages of different interaction components in the total nonbonded energies,main chain-side chain interactions between PA molecules may be important in the formation of onion-like nanospheres,and the synergistic effects of main chain-side chain,main chain-drug,side chain-drug,and main chain-solvent interactions are significant in the formation of drug-loaded nanospheres.These findings provide new insights into the structure and self-assembly pathway of PA assemblies,which may be helpful for the design of efficient and effective drug delivery systems.
基金supported by the National Natural Science Foundation of China(Nos.82061148012,82027806,21974019)SEU Innovation Capability Enhancement Plan for Doctoral Students(No.CXJH_SEU 24138)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX24_0469)。
文摘The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching(ACQ).In this study,an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence emission through protein coronas-controlled distance between gold nanoclusters(Au NCs).Interestingly,the gold ion complexes coated with proteins of low isoelectric point(pI)nucleate at the secondary structure of proteins with high p I through ionic exchange within cells,generating fluorescent Au NCs.It is worth noting that due to the steric hindrance formed by the protein coronas on the surface of Au NCs,the distance between Au NCs can be controlled,avoiding electron transfer caused by close proximity of Au NCs and inhibiting fluorescence ACQ.This strategy can achieve fluorescence imaging of clinical tissue samples without observable side effects.Therefore,this study proposes a distance-controllable self-assembled pitaya structure to provide a new approach for Au NCs with stable fluorescence.
基金Project supported by the Natural Science Foundation of Shandong Province (ZR2022QB067)。
文摘The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements.In this pape r,the extractant(N,N-methyl py ridineethyl-N',N'-dicyclohexyl-3-oxadiglycolamide,MPyEDChDGA) with a new structure was synthesized,and the pyridine group was successfully grafted onto the 3-oxadiglycolamide structure.Using MPyEDChDGA for efficient enrichment of rare earth ions,the self-assembled solids were recovered by simple filtration without further backextraction and final precipitation,achieving a one-step strategy for the recovery of rare earth ions.Several important parameters affecting the self-assembly extraction,including pH,diluent,temperature,and extractant concentration,were systematically evaluated using La(NO_(3))_(3),Tb(NO_(3))_(3),and Lu(NO_(3))_(3) as representatives.The self-assembled solids were investigated in detail by X-ray diffraction(XRD),scanning electron microscopy(SEM),1H nuclear magnetic resonance(1H NMR),Fourier transform infrared spectroscopy(FT-IR),Raman,and X-ray photoelectron spectroscopy(XPS) analyses.The stoichiometry of the extraction species was characterized using the Job's method and electrospray ionization mass spectrometry(ESI-MS).In addition,MPyEDChDGA was applied to the recovery of Sm in SmCoCu simulated liquid,and the results show that MPyEDChDGA has good selectivity of Sm from transition metals(Co,Cu).The separation factor of Sm/Co can reach 6281±117,which provides a new approach to recovering Sm from SmCoCu scrap magnets.This study presents an efficient and convenient new strategy for the recovery and separation of rare earth elements.
基金funded by Universitas Negeri Malang,contract number 4.4.841/UN32.14.1/LT/2024.
文摘An imbalanced dataset often challenges machine learning, particularly classification methods. Underrepresented minority classes can result in biased and inaccurate models. The Synthetic Minority Over-Sampling Technique (SMOTE) was developed to address the problem of imbalanced data. Over time, several weaknesses of the SMOTE method have been identified in generating synthetic minority class data, such as overlapping, noise, and small disjuncts. However, these studies generally focus on only one of SMOTE’s weaknesses: noise or overlapping. Therefore, this study addresses both issues simultaneously by tackling noise and overlapping in SMOTE-generated data. This study proposes a combined approach of filtering, clustering, and distance modification to reduce noise and overlapping produced by SMOTE. Filtering removes minority class data (noise) located in majority class regions, with the k-nn method applied for filtering. The use of Noise Reduction (NR), which removes data that is considered noise before applying SMOTE, has a positive impact in overcoming data imbalance. Clustering establishes decision boundaries by partitioning data into clusters, allowing SMOTE with modified distance metrics to generate minority class data within each cluster. This SMOTE clustering and distance modification approach aims to minimize overlap in synthetic minority data that could introduce noise. The proposed method is called “NR-Clustering SMOTE,” which has several stages in balancing data: (1) filtering by removing minority classes close to majority classes (data noise) using the k-nn method;(2) clustering data using K-means aims to establish decision boundaries by partitioning data into several clusters;(3) applying SMOTE oversampling with Manhattan distance within each cluster. Test results indicate that the proposed NR-Clustering SMOTE method achieves the best performance across all evaluation metrics for classification methods such as Random Forest, SVM, and Naїve Bayes, compared to the original data and traditional SMOTE. The proposed method (NR-Clustering SMOTE) improves accuracy by 15.34% on the Pima dataset and 20.96% on the Haberman dataset compared to SMOTE-LOF. Compared to Radius-SMOTE, this method increases accuracy by 3.16% on the Pima dataset and 13.24% on the Haberman dataset. Meanwhile, compared to RN-SMOTE, the accuracy improvement reaches 15.56% on the Pima dataset and 19.84% on the Haberman dataset. This research result implies that the proposed method experiences consistent performance improvement compared to traditional SMOTE and its latest variants, such as SMOTE-LOF, Radius-SMOTE, and RN-SMOTE, in solving imbalanced health data with class binaries.
基金supported by the National Science Foundation for Distinguished Young Scholars(No.52325308)the National Natural Science Foundation of China(Nos.52273008 and 52073092)+1 种基金Shanghai Scientific and Technological Innovation Projects(No.22ZR1479300)Shanghai Rising-Star Program(No.23QA1402500).
文摘Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AABCs presents challenges,which greatly limits the exploration of their self-assembly behaviors.In this work,we employed dissipative particle dynamics(DPD)simulations to investigate the self-assembly behaviors of AABCs in selective solution.By varying the copolymer concentration and structure,we conducted the self-assembly phase diagrams of AABCs,revealing complex morphologies such as channelized micelles with one or more solvophilic channels.Moreover,the number,surface area,and one-dimensional density distribution of the channelized micelles were calculated to demonstrate the internal structure and morphological transformation during the self-assembly process.Our findings indicate that the morphology of the internal solvophilic channels is greatly influenced by the copolymer structure,concentration,and interaction parameters between the different side chains.The simulation results are consistent with available experimental observations,which can offer theoretical insights into the self-assembly of AABCs.
基金financial support from the National Natural Science Fund for Distinguished Young Scholars of China(No.22025107)Shaanxi Fundamental Science Research Project for Chemistry&Biology(No.22JHZ003)+2 种基金the Key International Scientific and Technological Cooperation and Exchange Project of Shaanxi Province(No.2023-GHZD-15)the National Youth Top-notch Talent Support Program of Chinathe FM&EM International Joint Laboratory of Northwest University。
文摘The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable.Here,we report a fluorinated N-heterocyclic carbene(NHC)–based pillarplex with a tunable quaternary structure,employed as an efficient building block for constructing hierarchical superstructures.Initially,multiple noncovalent interactions in the NHC-based pillarplex,particularly those between the fluorinated pillarplex and PF_(6)-anions,induce the formation of a supramolecular gel at high concentrations.Additionally,this hierarchical self-assembled structure can be regulated by adjusting anion types,facilitating the controlled transformation from a supramolecular gel into a supramolecular channel upon the introduction of four monocarboxylic acids as anions.The study provides insight into the construction and controlled regulation of superstructures based on NHC-based pillarplexes.
基金supports for this work are the Inner Mongolia Major Science and Technology Project(No.2020ZD0024)Natural Science Foundation of Inner Mongolia(No.2024LHMS05046)+5 种基金Local Science and Technology Development Project of the Central Government(Nos.2021ZY0006 and 2022ZY0011)2023 Inner Mongolia Autonomous Region Doctoral Research Innovation Project(No.B20231023Z)Inner Mongolia Autonomous Region key Research and Technological Achievements Transformation Plan Project(No.2023YFHH0063)Autonomous Region higher education Carbon peak carbon neutral research project(No.STZX202206)Basic Scientific Research Expenses Program of Universities directly under Inner Mongolia Autonomous Region(No.JY20220043)Graphite and Graphene New Materials Discipline Team of Inner Mongolia University of Technology(No.PY202066).
文摘Paraphenylenediamine(PPDA)-grafted maleic anhydride(MAH)-modified graphene oxide(PGO)was synthesized through a dual modification process.Initially,MAH was employed to modify graphene oxide(GO)to enhance its reactive sites.Subsequently,PPDA was utilized for further modification of MAH-modified GO(MGO).Through a comprehensive analysis,the successful grafting of MAH and PPDA onto GO was confirmed.It was concurrently established that the optimal ratio of PPDA to MGO is 1:1.This approach yielded PGO characterized by outstanding dispersibility and barrier properties in epoxy resin(EP)coaings for Q235 steel.The corrosion resistance of EP coatings containing varying amounts of PGO was assessed using electrochemical workstation and salt spray testing.After immersing in a 3.5 wt.%NaCl solution for 300 h,the composite coating containing 0.1 wt.%PGO exhibited superior performance in terms of low-frequency impedance modulus,measuring at 1.1×10^(8)Ωcm^(2).The lowest corrosion current density was 2.32×10^(–10)A cm^(−2),and the self-corrosion voltage was−0.301 V.Additionally,polarization testing indicated that this coating also displayed the lowest corrosion rate,specifically 1.383×10^(–7)mm/a.
基金supported by the National Natural Science Foundation of China,(Nos.82272151,82204318)Liaoning Revitalization Talents Program(No.XLYC2203083)+2 种基金Shenyang Young and Middle-aged Science and Technology Innovation Talent Support Program(No.RC220389)Postdoctoral Fellowship Program of CPSF(No.GZC20231732)China Postdoctoral Science Foundation(Nos.2023TQ0222,2023MD744229).
文摘Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy,mainly comprise drug modules,response modules and modification modules.However,existing studies usually compare the differences between single types of modification modules,neglecting the impact of steric-hindrance effect caused by chemical structure.Herein,single-tailed modification module with low-steric-hindrance effect and two-tailed modification module with high-steric-hindrance effect were selected to construct paclitaxel prodrugs(P-LA_(C18)and P-BAC18),and the in-depth insights of the sterichindrance effect on prodrug nanoassemblies were explored.Notably,the size stability of the two-tailed prodrugs was enhanced due to improved intermolecular interactions and steric hindrance.Single-tailed prodrug nanoassemblies were more susceptible to attack by redox agents,showing faster drug release and stronger antitumor efficacy,but with poorer safety.In contrast,two-tailed prodrug nanoassemblies exhibited significant advantages in terms of pharmacokinetics,tumor accumulation and safety due to the good size stability,thus ensuring equivalent antitumor efficacy at tolerance dose.These findings highlighted the critical role of steric-hindrance effect of the modification module in regulating the structureactivity relationship of prodrug nanoassemblies and proposed new perspectives into the precise design of self-assembled prodrugs for high-performance cancer therapeutics.
基金supported by the Macao Science and Technology Development Fund(FDCT)for funding of the Macao Centre for Research and Development in Advanced Materials(2022-2024)(Nos.0026/2022/AMJ,0098/2020/A2 and 006/2022/ALC)the Natural Science Foundation of Guangdong Province(No.2023A1515010765)+2 种基金Science and Technology Planning Project of Shenzhen of China(Shenzhen-Hong Kong-Macao Category C)(No.SGDX20220530111004028)the Science and Technology Planning Project of Guangdong Province of China(No.2023A0505030001)the School-level Research Projects of Yancheng Institute of Technology(No.xjr2023023).
文摘Lithium-sulfur batteries(LSBs)have undoubtedly become one of the most promising battery systems due to their high energy density and the cost-effectiveness of sulfur cathodes.However,challenges,such as the shuttle effect from soluble long-chain lithium polysulfides(LiPSs)and the low conductivity of active materials,hinder their commercialization.Under this circumstance,molybdenum sulfide(MoS_(2))has attracted widespread attention due to its unique physicochemical properties,particularly its capability to mitigate the shuttle effect in LSBs through electrostatic or chemical bonds.Nonetheless,the industrial application of MoS_(2)in LSBs is limited by the inertness of its basal surface and inadequate electron transfer properties.This review mainly introduces various modification strategies of MoS_(2)materials in LSBs and their effects on electrochemical and catalytic performance.Unlike previous reviews and related papers,detailed discussions were conducted on the specific mechanisms of each modification strategy,including(1)shape manipulation,(2)support engineering,(3)heterostructure engineering,(4)defect engineering,(5)interlayer engineering,(6)phase engineering,(7)strain engineering,(8)hybridization.Comprehensive conclusions and outlook on the development of MoS_(2)as an abundant electrocatalyst for LSBs are also discussed in the end.
基金financially supported by the National Natural Science Foundation of China(Nos.22171055 and 52222301)the Guangdong Natural Science Foundation for Distinguished Young Scholar(No.2022B1515020078)the Science and Technology Program of Guangzhou(No.2024A04J2821)。
文摘Polymerization-induced self-assembly(PISA)has become one of the most versatile approaches for scalable preparation of linear block copolymer nanoparticles with various morphologies.However,the controlled introduction of branching into the core-forming block and the effect on the morphologies of block copolymer nanoparticles under PISA conditions have rarely been explored.Herein,a series of multifunctional macromolecular chain transfer agents(macro-CTAs)were first synthesized by a two-step green light-activated photoiniferter polymerization using two types of chain transfer monomers(CTMs).These macro-CTAs were then used to mediate reversible addition-fragmentation chain transfer(RAFT)dispersion polymerization of styrene(St)to prepare block copolymers with different core-forming block structures and the assemblies.The effect of the core-forming block structure on the morphology of block copolymer nanoparticles was investigated in detail.Transmission electron microscopy(TEM)analysis indicated that the brush-like core-forming block structure facilitated the formation of higher-order morphologies,while the branched core-forming block structure favored the formation of lower-order morphologies.Moreover,it was found that using macroCTAs with a shorter length also promoted the formation of higher-order morphologies.Finally,structures of block copolymers and the assemblies were further controlled by changing the structure of macro-CTA or using a binary mixture of two different macro-CTAs.We expect that this work not only sheds light on the synthesis of block copolymer nanoparticles but also provide important mechanistic insights into PISA of nonlinear block copolymers.
