Core-shell colloidal particles with a polymer layer have broad applications in different areas.Herein,we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembl...Core-shell colloidal particles with a polymer layer have broad applications in different areas.Herein,we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembly and photoinduced seeded reversible addition-fragmentation chain transfer(RAFT)polymerization to prepare a diverse set of core-shell colloidal particles with a well-defined polymer layer.Chemical compositions,structures,and thicknesses of polymer layers could be conveniently regulated by using different types of monomers and feed[monomer]/[chain transfer agent]ratios during seeded RAFT polymerization.展开更多
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
Polymerization-induced self-assembly(PISA)is an emerging method for the preparation of block copolymer nano-objects at high concentrations.However,most PISA formulations have oxygen inhibition problems and inert atmos...Polymerization-induced self-assembly(PISA)is an emerging method for the preparation of block copolymer nano-objects at high concentrations.However,most PISA formulations have oxygen inhibition problems and inert atmospheres(e.g.argon,nitrogen)are usually required.Moreover,the large-scale preparation of block copolymer nano-objects at room temperature is challenging.Herein,we report an enzyme-assisted photoinitiated polymerization-induced self-assembly(photo-PISA)in continuous flow reactors with oxygen toleranee.The addition of glucose oxidase(GOx)and glucose into the reaction mixture can consume oxygen efficiently and constantly,allow the flow photo-PISA to be performed under open-air conditions.Polymerization kinetics indicated that only a small amount of GOx(0.5 μmol/L)was needed to achieve the oxygen tolerance.Block copolymer nano-objects with different morphologies can be prepared by varying reaction conditions including the degree of polymerization(DP)of core-forming block,monomer concentration,reaction temperature,and solvent composition.We expect this study will provide a facile platform for the large-scale production of block copolymer nano-objects with different morphologies at room temperature.展开更多
Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast...Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl(n BHMA) and tert-butyl(t BHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of n BHMA and t BHMA employing poly(ethylene glycol) macromolecular chain transfer agents(macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for t BHMA, which has a higher water solubility than that of n BHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.展开更多
Polymerization-induced self-assembly(PISA)combines synthesis and self-assembly of artificial polymers in one-pot,which brings us one step closer to emulating biosynthesis.However,the reported PISA formulations primari...Polymerization-induced self-assembly(PISA)combines synthesis and self-assembly of artificial polymers in one-pot,which brings us one step closer to emulating biosynthesis.However,the reported PISA formulations primarily focus on developing nano-objects with new chemical compositions and rarely on structural regulation of polymers with specific components.Herein,sequence structure controllable polymerization-induced self-assembly(SCPISA)is reported by using 7-(2-methacryloyloxyethoxy)-4-methylcoumarin(CMA)as a monomer.During the copolymerization of 2-hydroxyethyl methacrylate(HEMA)and CMA,controlled incorporation of CMA units into the polymer chains can be realized by programmable light/heat changes.SCPISA-based P(HEMA-co-CMA)copolymers with the same composition but different sequence structures generate a range of assemblies.Moreover,the morphologies of the resultant nano-objects can also be controlled by regulating the feed molar ratio of CMA and HEMA,which is similar to the conventional PISA,but the synthesis procedure is obviously simplified in SCPISA.The versatility of the methodology is further demonstrated by the fabrication of different functional nano-objects with sequence structure-dependent morphologies in SCPISA systems with different functional monomers.展开更多
Polymerization-induced self-assembly(PISA)enables the simultaneous growth and self-assembly of block copolymers in one pot and therefore has developed into a high-efficiency platform for the preparation of polymer ass...Polymerization-induced self-assembly(PISA)enables the simultaneous growth and self-assembly of block copolymers in one pot and therefore has developed into a high-efficiency platform for the preparation of polymer assemblies with high concentration and excellent reproducibility.During the past decade,the driving force of PISA has extended from hydrophobic interactions to other supramolecular interactions,which has greatly innovated the design of PISA,enlarged the monomer/solvent toolkit,and endowed the polymer assemblies with intrinsic dynamicity and responsiveness.To unravel the important role of driving forces in the formation of polymeric assemblies,this review summarized the recent development of PISA from the perspective of driving forces.Motivated by this goal,here we give a brief overview of the basic principles of PISA and systematically discuss the various driving forces in the PISA system,including hydrophobic interactions,hydrogen bonding,electrostatic interactions,andπ-πinteractions.Furthermore,PISA systems that are driven and regulated by crystallization or liquid crystalline ordering were also highlighted.展开更多
Main observation and conclusion Polymerization-induced self-assembly(PISA)is an effective method to prepare block copolymer(BCP)particles with various morphologies.However,BCPs with inverse bicontinuous phase structur...Main observation and conclusion Polymerization-induced self-assembly(PISA)is an effective method to prepare block copolymer(BCP)particles with various morphologies.However,BCPs with inverse bicontinuous phase structure have been rarely prepared via PISA.Herein,we report the preparation of particles.展开更多
A chemical reaction that drives a physical polymer selfassembly process,namely,polymerization-induced self-assembly(PISA),combines block copolymer synthesis and nanoparticle formation efficiently at high polymer conce...A chemical reaction that drives a physical polymer selfassembly process,namely,polymerization-induced self-assembly(PISA),combines block copolymer synthesis and nanoparticle formation efficiently at high polymer concentrations.Various nanoparticlemorphologies such as spheres,worms,and vesicles can be prepared readily in polar and nonpolarmedia.PISA has been well developed in combination with reversible addition-fragmentation chain transfer(RAFT)polymerization.Notably,developments with other polymerization methods are also achieved.In this report,first,we discuss the general principles of RAFT-PISA and the nanoparticles generated from this method.Specifically,new insights into polymer nucleation and subsequent morphological evolution are highlighted.Subsequently,PISA formulations that use other polymerization methods[atom transfer radical polymerization(ATRP),nitroxide-mediated polymerization(NMP),ring-opening metathesis polymerization(ROMP),and ring-opening polymerization(ROP)of N-carboxyanhydrides(NCAs)]are summarized in detail.Finally,more exotic PISA formulations are emphasized:these are based on organotelluriummediated living radical polymerization(TERP),living anionic polymerization(LAP),addition-fragmentation chain transfer(AFCT)polymerization,reversible complexation-mediated polymerization(RCMP),and cobalt-mediated radical polymerization(CMRP),or utilize a comonomer that undergoes radical ringopening polymerization(rROP).This reviewis concluded with a perspective on the status and potential of PISA.展开更多
Polymerization-induced chiral self-assembly(PICSA)is an efficient strategy that not only allows the construction of the supramolecular chiral assemblies in a controlled manner but also can regulate the morphology in s...Polymerization-induced chiral self-assembly(PICSA)is an efficient strategy that not only allows the construction of the supramolecular chiral assemblies in a controlled manner but also can regulate the morphology in situ.Herein,a series of azobenzene-containing block copolymer(Azo-BCP)assemblies with tunable morphologies and supramolecular chirality were obtained through the PICSA strategy.The supramolecular chirality of Azo-BCP assemblies could be regulated by carbon dioxide(CO_(2))stimulus,and completely recovered by bubbling with Ar.A reversible morphology transformation and chiroptical switching process could also be achieved by the alternative 365 nm UV light irradiation and heatingcooling treatment.Moreover,the supramolecular chirality is thermo-responsive and a reversible chiral-achiral switching was successfully realized,which can be reversibly repeated for at least five times.This work provides a feasible strategy for constructing triple stimuli-responsive supramolecular chiral nano-objects in situ.展开更多
pH-and reductive-responsive prodrug nanoparticles are constructed via a highly efficient strategy, polymerization-induced selfassembly(PISA). First, reversible addition-fragmentation chain transfer(RAFT) polymerizatio...pH-and reductive-responsive prodrug nanoparticles are constructed via a highly efficient strategy, polymerization-induced selfassembly(PISA). First, reversible addition-fragmentation chain transfer(RAFT) polymerization of 2-(diisopropylamino) ethyl methacrylate(DIPEMA) and camptothecin prodrug monomer(CPTM) using biocompatible poly(N-(2-hydroxypropyl) methacrylamide)(PHPMA-CPDB) as the macro RAFT agent is carried out, forming prodrug diblock copolymer PHPMA-P(DIPEMA-co-CPTM). Then, simultaneous fulfillment of polymerization, self-assembly, and drug encapsulation are achieved via RAFT dispersion polymerization of benzyl methacrylate(Bz MA) using the PHPMA-P(DIPEMA-co-CPTM) as the macro RAFT agent. The prodrug nanoparticles have three layers, the biocompatible shell(PHPMA), the drug-conjugated middle layer(P(DIPEMA-co-CPTM)) and the PBz MA core, and relatively high concentration(250 mg/g). The prodrug nanoparticles can respond to two stimuli(reductive and acidic conditions). Due to reductive microenvironment of cytosol, the cleavage of the conjugated camptothecin(CPT) within the prodrug nanoparticles could be effectively triggered. p H-Induced hydrophobic/hydrophilic transition of the PDIPEMA chains results in faster diffusion of GSH into the CPTM units, thus accelerated release of CPT is observed in mild acidic and reductive conditions. Cell viability assays show that the prodrug nanoparticles exhibit well performance of intracellular drug delivery and good anticancer activity.展开更多
Collecting both enantiomorphs with high optical purity and yield in a single crystallization process can be achieved by adding aggregated polymeric“tailor-made”additives,known as nano-splitters.Inefficient preparati...Collecting both enantiomorphs with high optical purity and yield in a single crystallization process can be achieved by adding aggregated polymeric“tailor-made”additives,known as nano-splitters.Inefficient preparation and large addition amount have hindered the practical application of such amazing nanoparticles.Herein,we report the first nano-splitters containing aggregation-induced emission luminogens prepared via polymerization-induced self-assembly of block copolymer,poly[(S)-2-(tert-butoxycarbonylamino)-6-(methacrylamido)hexanoic acid]-b-polystyrene,followed by the removal of tert-butoxycarbonyl groups.When added into the supersaturated solution of racemic amino acids(a.a.)with seeds,the fluorescent labeled nano-assemblies enantioselectivity dyed the crystals of S-a.a.and enabled the separation from colorless R-a.a.crystals in terms of fluorescent difference.Both enantiomers were obtained with high optical purity and yield(e.g.,R-asparagine monohydrate,>99 ee%;S-asparagine monohydrate,∼94 ee%;88%total yield).Owing to a low detection limit of fluorescence,the addition amount was reduced to 0.03 wt%without remarkably compromising the ee values of both enantiomorphs.Due to the low addition amount and efficient synthesis,the output–input ratio was increased greatly.展开更多
Comprehensive Summary The size and size distribution of polymeric nanoparticles have great impact on their physicochemical and biological properties.Polymerization-induced self-assembly(PISA)has been demonstrated to b...Comprehensive Summary The size and size distribution of polymeric nanoparticles have great impact on their physicochemical and biological properties.Polymerization-induced self-assembly(PISA)has been demonstrated to be an efficient method to fabricate various polymeric nanoparticles,among which polymeric vesicles have attracted great interest due to their unique hollow structure.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
Nowadays,high-stable and ultrasensitive heavy metal detection is of utmost importance in water quality monitoring.Nanoparticle-enhanced laser-induced breakdown spectroscopy(NELIBS)shows high potential in hazardous met...Nowadays,high-stable and ultrasensitive heavy metal detection is of utmost importance in water quality monitoring.Nanoparticle-enhanced laser-induced breakdown spectroscopy(NELIBS)shows high potential in hazardous metal detection,however,encounters unstable and weak signals due to nonuniform distribution of analytes.Herein,we developed an interface self-assembly(ISA)method to create a uniformly distributed gold nanolayer at a liquid-liquid interface for positive heavy metal ions capture and NELIBS analysis.The electrostatically selfassembled Au nanoparticles(NPs)-analytes membrane was prepared at the oil-water interface by injecting ethanol into the mixture of cyclohexane and Au NPs-analytes water solution.Then,the interface self-assembled Au NPs-analytes membrane was transformed onto a laser-processed superhydrophilic Si slide for detection.Three heavy metals(cadmium(Cd),barium(Ba),and chromium(Cr))were analyzed to evaluate the stability and sensitivity of the ISA method for NELIBS.The results(Cd:RSD=3.6%,LoD=0.654 mg/L;Ba:RSD=3.4%,LoD=0.236 mg/L;Cr:RSD=7.7%,LoD=1.367 mg/L)demonstrated signal enhancement and high-stable and ultrasensitive detection.The actual sample detection(Cd:RE=7.71%,Ba:RE=6.78%)illustrated great reliability.The ISA method,creating a uniform distribution of NP-analytes at the interface,has promising prospects in NELIBS.展开更多
Diphenylalanine and its analogs cause many concerns owing to their perfect self-assembly properties in the fields of biology,medicine,and nanotechnology.Experimental research has shown that diphenylalanine-based analo...Diphenylalanine and its analogs cause many concerns owing to their perfect self-assembly properties in the fields of biology,medicine,and nanotechnology.Experimental research has shown that diphenylalanine-based analogs with ethylenediamine linkers(PA,P=phenylalanine,and A=analog)can self-assemble into spherical assemblies,which can serve as novel anticancer drug carriers.In this work,to understand the assembly pathways,drug loading behavior,and formation mechanism of PA aggregates at the molecular level,we carried out dissipative particle dynamics(DPD)simulations of PA molecule systems.Our simulation results demonstrate that PA molecules spontaneously assemble into nanospheres and can self-assemble into drug-loaded nanospheres upon addition of the cancer chemotherapeutic agent doxorubicin(DOX).We also found that the hydrophobic side chain beads of PA molecules exhibited a unique onion-like distribution inside the nanospheres,which was not observed in the experiment.The onion-like nanospheres were verified by calculating the radial distribution function(RDF)of the DPD beads.Furthermore,based on the analysis of the percentages of different interaction components in the total nonbonded energies,main chain-side chain interactions between PA molecules may be important in the formation of onion-like nanospheres,and the synergistic effects of main chain-side chain,main chain-drug,side chain-drug,and main chain-solvent interactions are significant in the formation of drug-loaded nanospheres.These findings provide new insights into the structure and self-assembly pathway of PA assemblies,which may be helpful for the design of efficient and effective drug delivery systems.展开更多
The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching(ACQ).In this study,an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence em...The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching(ACQ).In this study,an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence emission through protein coronas-controlled distance between gold nanoclusters(Au NCs).Interestingly,the gold ion complexes coated with proteins of low isoelectric point(pI)nucleate at the secondary structure of proteins with high p I through ionic exchange within cells,generating fluorescent Au NCs.It is worth noting that due to the steric hindrance formed by the protein coronas on the surface of Au NCs,the distance between Au NCs can be controlled,avoiding electron transfer caused by close proximity of Au NCs and inhibiting fluorescence ACQ.This strategy can achieve fluorescence imaging of clinical tissue samples without observable side effects.Therefore,this study proposes a distance-controllable self-assembled pitaya structure to provide a new approach for Au NCs with stable fluorescence.展开更多
The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements.In this pape r,the extractant(N,N-methyl py ridineethyl-N',N'-dicyclohexyl-3-oxadiglycola...The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements.In this pape r,the extractant(N,N-methyl py ridineethyl-N',N'-dicyclohexyl-3-oxadiglycolamide,MPyEDChDGA) with a new structure was synthesized,and the pyridine group was successfully grafted onto the 3-oxadiglycolamide structure.Using MPyEDChDGA for efficient enrichment of rare earth ions,the self-assembled solids were recovered by simple filtration without further backextraction and final precipitation,achieving a one-step strategy for the recovery of rare earth ions.Several important parameters affecting the self-assembly extraction,including pH,diluent,temperature,and extractant concentration,were systematically evaluated using La(NO_(3))_(3),Tb(NO_(3))_(3),and Lu(NO_(3))_(3) as representatives.The self-assembled solids were investigated in detail by X-ray diffraction(XRD),scanning electron microscopy(SEM),1H nuclear magnetic resonance(1H NMR),Fourier transform infrared spectroscopy(FT-IR),Raman,and X-ray photoelectron spectroscopy(XPS) analyses.The stoichiometry of the extraction species was characterized using the Job's method and electrospray ionization mass spectrometry(ESI-MS).In addition,MPyEDChDGA was applied to the recovery of Sm in SmCoCu simulated liquid,and the results show that MPyEDChDGA has good selectivity of Sm from transition metals(Co,Cu).The separation factor of Sm/Co can reach 6281±117,which provides a new approach to recovering Sm from SmCoCu scrap magnets.This study presents an efficient and convenient new strategy for the recovery and separation of rare earth elements.展开更多
Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AAB...Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AABCs presents challenges,which greatly limits the exploration of their self-assembly behaviors.In this work,we employed dissipative particle dynamics(DPD)simulations to investigate the self-assembly behaviors of AABCs in selective solution.By varying the copolymer concentration and structure,we conducted the self-assembly phase diagrams of AABCs,revealing complex morphologies such as channelized micelles with one or more solvophilic channels.Moreover,the number,surface area,and one-dimensional density distribution of the channelized micelles were calculated to demonstrate the internal structure and morphological transformation during the self-assembly process.Our findings indicate that the morphology of the internal solvophilic channels is greatly influenced by the copolymer structure,concentration,and interaction parameters between the different side chains.The simulation results are consistent with available experimental observations,which can offer theoretical insights into the self-assembly of AABCs.展开更多
The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable.Here,we...The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable.Here,we report a fluorinated N-heterocyclic carbene(NHC)–based pillarplex with a tunable quaternary structure,employed as an efficient building block for constructing hierarchical superstructures.Initially,multiple noncovalent interactions in the NHC-based pillarplex,particularly those between the fluorinated pillarplex and PF_(6)-anions,induce the formation of a supramolecular gel at high concentrations.Additionally,this hierarchical self-assembled structure can be regulated by adjusting anion types,facilitating the controlled transformation from a supramolecular gel into a supramolecular channel upon the introduction of four monocarboxylic acids as anions.The study provides insight into the construction and controlled regulation of superstructures based on NHC-based pillarplexes.展开更多
基金support from the Science and Technology Program of Guangzhou(No.2024A04J2821)the National Natural Science Foundation of China(Nos.52222301,22171055)the Guangdong Natural Science Foundation for Distinguished Young Scholar(No.2022B1515020078)。
文摘Core-shell colloidal particles with a polymer layer have broad applications in different areas.Herein,we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembly and photoinduced seeded reversible addition-fragmentation chain transfer(RAFT)polymerization to prepare a diverse set of core-shell colloidal particles with a well-defined polymer layer.Chemical compositions,structures,and thicknesses of polymer layers could be conveniently regulated by using different types of monomers and feed[monomer]/[chain transfer agent]ratios during seeded RAFT polymerization.
基金financially supported by the National Natural Science Foundation of China(Nos.22171055 and 52222301)the Guangdong Natural Science Foundation for Distinguished Young Scholar(No.2022B1515020078)the Science and Technology Program of Guangzhou(No.2024A04J2821)。
文摘Polymerization-induced self-assembly(PISA)has become one of the most versatile approaches for scalable preparation of linear block copolymer nanoparticles with various morphologies.However,the controlled introduction of branching into the core-forming block and the effect on the morphologies of block copolymer nanoparticles under PISA conditions have rarely been explored.Herein,a series of multifunctional macromolecular chain transfer agents(macro-CTAs)were first synthesized by a two-step green light-activated photoiniferter polymerization using two types of chain transfer monomers(CTMs).These macro-CTAs were then used to mediate reversible addition-fragmentation chain transfer(RAFT)dispersion polymerization of styrene(St)to prepare block copolymers with different core-forming block structures and the assemblies.The effect of the core-forming block structure on the morphology of block copolymer nanoparticles was investigated in detail.Transmission electron microscopy(TEM)analysis indicated that the brush-like core-forming block structure facilitated the formation of higher-order morphologies,while the branched core-forming block structure favored the formation of lower-order morphologies.Moreover,it was found that using macroCTAs with a shorter length also promoted the formation of higher-order morphologies.Finally,structures of block copolymers and the assemblies were further controlled by changing the structure of macro-CTA or using a binary mixture of two different macro-CTAs.We expect that this work not only sheds light on the synthesis of block copolymer nanoparticles but also provide important mechanistic insights into PISA of nonlinear block copolymers.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21971047 and 21504017)Innovation Project of Education Department in Guangdong(No.2018KTSCX053)+1 种基金Y.C.acknowledges the support from Guangdong Special Support Program(No.2017TX04N371)J.T.acknowledges the support from Pearl River Young Scholar of Guangdong.
文摘Polymerization-induced self-assembly(PISA)is an emerging method for the preparation of block copolymer nano-objects at high concentrations.However,most PISA formulations have oxygen inhibition problems and inert atmospheres(e.g.argon,nitrogen)are usually required.Moreover,the large-scale preparation of block copolymer nano-objects at room temperature is challenging.Herein,we report an enzyme-assisted photoinitiated polymerization-induced self-assembly(photo-PISA)in continuous flow reactors with oxygen toleranee.The addition of glucose oxidase(GOx)and glucose into the reaction mixture can consume oxygen efficiently and constantly,allow the flow photo-PISA to be performed under open-air conditions.Polymerization kinetics indicated that only a small amount of GOx(0.5 μmol/L)was needed to achieve the oxygen tolerance.Block copolymer nano-objects with different morphologies can be prepared by varying reaction conditions including the degree of polymerization(DP)of core-forming block,monomer concentration,reaction temperature,and solvent composition.We expect this study will provide a facile platform for the large-scale production of block copolymer nano-objects with different morphologies at room temperature.
基金financially supported by the National Natural Science Foundation of China (No. 21674059)
文摘Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl(n BHMA) and tert-butyl(t BHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of n BHMA and t BHMA employing poly(ethylene glycol) macromolecular chain transfer agents(macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for t BHMA, which has a higher water solubility than that of n BHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.
基金supported by the National Natural Science Foundation of China(22171255,22131010,52021002)。
文摘Polymerization-induced self-assembly(PISA)combines synthesis and self-assembly of artificial polymers in one-pot,which brings us one step closer to emulating biosynthesis.However,the reported PISA formulations primarily focus on developing nano-objects with new chemical compositions and rarely on structural regulation of polymers with specific components.Herein,sequence structure controllable polymerization-induced self-assembly(SCPISA)is reported by using 7-(2-methacryloyloxyethoxy)-4-methylcoumarin(CMA)as a monomer.During the copolymerization of 2-hydroxyethyl methacrylate(HEMA)and CMA,controlled incorporation of CMA units into the polymer chains can be realized by programmable light/heat changes.SCPISA-based P(HEMA-co-CMA)copolymers with the same composition but different sequence structures generate a range of assemblies.Moreover,the morphologies of the resultant nano-objects can also be controlled by regulating the feed molar ratio of CMA and HEMA,which is similar to the conventional PISA,but the synthesis procedure is obviously simplified in SCPISA.The versatility of the methodology is further demonstrated by the fabrication of different functional nano-objects with sequence structure-dependent morphologies in SCPISA systems with different functional monomers.
基金National Natural Science Foundation of China,Grant/Award Number:21905171。
文摘Polymerization-induced self-assembly(PISA)enables the simultaneous growth and self-assembly of block copolymers in one pot and therefore has developed into a high-efficiency platform for the preparation of polymer assemblies with high concentration and excellent reproducibility.During the past decade,the driving force of PISA has extended from hydrophobic interactions to other supramolecular interactions,which has greatly innovated the design of PISA,enlarged the monomer/solvent toolkit,and endowed the polymer assemblies with intrinsic dynamicity and responsiveness.To unravel the important role of driving forces in the formation of polymeric assemblies,this review summarized the recent development of PISA from the perspective of driving forces.Motivated by this goal,here we give a brief overview of the basic principles of PISA and systematically discuss the various driving forces in the PISA system,including hydrophobic interactions,hydrogen bonding,electrostatic interactions,andπ-πinteractions.Furthermore,PISA systems that are driven and regulated by crystallization or liquid crystalline ordering were also highlighted.
基金Financial support from the National Natural Science Founda-ton of China(No.21674059)the Fundamental Research Funds far the Central Universities is thanked.
文摘Main observation and conclusion Polymerization-induced self-assembly(PISA)is an effective method to prepare block copolymer(BCP)particles with various morphologies.However,BCPs with inverse bicontinuous phase structure have been rarely prepared via PISA.Herein,we report the preparation of particles.
基金This work was funded by the National Natural Science Foundation(NSFC)of China(grant no.21925505 and 21674081)the China Postdoctoral Science Foundation(grant no.2020M671197).
文摘A chemical reaction that drives a physical polymer selfassembly process,namely,polymerization-induced self-assembly(PISA),combines block copolymer synthesis and nanoparticle formation efficiently at high polymer concentrations.Various nanoparticlemorphologies such as spheres,worms,and vesicles can be prepared readily in polar and nonpolarmedia.PISA has been well developed in combination with reversible addition-fragmentation chain transfer(RAFT)polymerization.Notably,developments with other polymerization methods are also achieved.In this report,first,we discuss the general principles of RAFT-PISA and the nanoparticles generated from this method.Specifically,new insights into polymer nucleation and subsequent morphological evolution are highlighted.Subsequently,PISA formulations that use other polymerization methods[atom transfer radical polymerization(ATRP),nitroxide-mediated polymerization(NMP),ring-opening metathesis polymerization(ROMP),and ring-opening polymerization(ROP)of N-carboxyanhydrides(NCAs)]are summarized in detail.Finally,more exotic PISA formulations are emphasized:these are based on organotelluriummediated living radical polymerization(TERP),living anionic polymerization(LAP),addition-fragmentation chain transfer(AFCT)polymerization,reversible complexation-mediated polymerization(RCMP),and cobalt-mediated radical polymerization(CMRP),or utilize a comonomer that undergoes radical ringopening polymerization(rROP).This reviewis concluded with a perspective on the status and potential of PISA.
基金financial support from the National Natural Science Foundation of China(Nos.92056111 and 21971180)Nature Science Key Basic Research of Jiangsu Province for Higher Education(No.19KJA360006)+1 种基金Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX202655)the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions supported this work。
文摘Polymerization-induced chiral self-assembly(PICSA)is an efficient strategy that not only allows the construction of the supramolecular chiral assemblies in a controlled manner but also can regulate the morphology in situ.Herein,a series of azobenzene-containing block copolymer(Azo-BCP)assemblies with tunable morphologies and supramolecular chirality were obtained through the PICSA strategy.The supramolecular chirality of Azo-BCP assemblies could be regulated by carbon dioxide(CO_(2))stimulus,and completely recovered by bubbling with Ar.A reversible morphology transformation and chiroptical switching process could also be achieved by the alternative 365 nm UV light irradiation and heatingcooling treatment.Moreover,the supramolecular chirality is thermo-responsive and a reversible chiral-achiral switching was successfully realized,which can be reversibly repeated for at least five times.This work provides a feasible strategy for constructing triple stimuli-responsive supramolecular chiral nano-objects in situ.
基金supported by the National Key R&D Program of China (2017YFA0205601)the National Natural Science Foundation of China (51625305, 21704095, 21774113, 21525420)
文摘pH-and reductive-responsive prodrug nanoparticles are constructed via a highly efficient strategy, polymerization-induced selfassembly(PISA). First, reversible addition-fragmentation chain transfer(RAFT) polymerization of 2-(diisopropylamino) ethyl methacrylate(DIPEMA) and camptothecin prodrug monomer(CPTM) using biocompatible poly(N-(2-hydroxypropyl) methacrylamide)(PHPMA-CPDB) as the macro RAFT agent is carried out, forming prodrug diblock copolymer PHPMA-P(DIPEMA-co-CPTM). Then, simultaneous fulfillment of polymerization, self-assembly, and drug encapsulation are achieved via RAFT dispersion polymerization of benzyl methacrylate(Bz MA) using the PHPMA-P(DIPEMA-co-CPTM) as the macro RAFT agent. The prodrug nanoparticles have three layers, the biocompatible shell(PHPMA), the drug-conjugated middle layer(P(DIPEMA-co-CPTM)) and the PBz MA core, and relatively high concentration(250 mg/g). The prodrug nanoparticles can respond to two stimuli(reductive and acidic conditions). Due to reductive microenvironment of cytosol, the cleavage of the conjugated camptothecin(CPT) within the prodrug nanoparticles could be effectively triggered. p H-Induced hydrophobic/hydrophilic transition of the PDIPEMA chains results in faster diffusion of GSH into the CPTM units, thus accelerated release of CPT is observed in mild acidic and reductive conditions. Cell viability assays show that the prodrug nanoparticles exhibit well performance of intracellular drug delivery and good anticancer activity.
基金National Natural Science Foundation of China,Grant/Award Numbers:51833001,21674002,21905003China Postdoctoral Science Foundation,Grant/Award Numbers:2019M660002,2020T130011。
文摘Collecting both enantiomorphs with high optical purity and yield in a single crystallization process can be achieved by adding aggregated polymeric“tailor-made”additives,known as nano-splitters.Inefficient preparation and large addition amount have hindered the practical application of such amazing nanoparticles.Herein,we report the first nano-splitters containing aggregation-induced emission luminogens prepared via polymerization-induced self-assembly of block copolymer,poly[(S)-2-(tert-butoxycarbonylamino)-6-(methacrylamido)hexanoic acid]-b-polystyrene,followed by the removal of tert-butoxycarbonyl groups.When added into the supersaturated solution of racemic amino acids(a.a.)with seeds,the fluorescent labeled nano-assemblies enantioselectivity dyed the crystals of S-a.a.and enabled the separation from colorless R-a.a.crystals in terms of fluorescent difference.Both enantiomers were obtained with high optical purity and yield(e.g.,R-asparagine monohydrate,>99 ee%;S-asparagine monohydrate,∼94 ee%;88%total yield).Owing to a low detection limit of fluorescence,the addition amount was reduced to 0.03 wt%without remarkably compromising the ee values of both enantiomorphs.Due to the low addition amount and efficient synthesis,the output–input ratio was increased greatly.
基金the financial support of the National Natural Science Foundation of China(Nos.22171255,21774113,and 52021002)。
文摘Comprehensive Summary The size and size distribution of polymeric nanoparticles have great impact on their physicochemical and biological properties.Polymerization-induced self-assembly(PISA)has been demonstrated to be an efficient method to fabricate various polymeric nanoparticles,among which polymeric vesicles have attracted great interest due to their unique hollow structure.
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 National Natural Science Foundation of China(No.62075069 and 52303092)the Water Conservancy Technology project of Hunan Province,China(XSKJ2021000-32)+1 种基金the City University of Hong Kong(#7005507)the Open Project of Yunnan Precious Metals Laboratory Co.,Ltd(grant number YPML-2023050278).
文摘Nowadays,high-stable and ultrasensitive heavy metal detection is of utmost importance in water quality monitoring.Nanoparticle-enhanced laser-induced breakdown spectroscopy(NELIBS)shows high potential in hazardous metal detection,however,encounters unstable and weak signals due to nonuniform distribution of analytes.Herein,we developed an interface self-assembly(ISA)method to create a uniformly distributed gold nanolayer at a liquid-liquid interface for positive heavy metal ions capture and NELIBS analysis.The electrostatically selfassembled Au nanoparticles(NPs)-analytes membrane was prepared at the oil-water interface by injecting ethanol into the mixture of cyclohexane and Au NPs-analytes water solution.Then,the interface self-assembled Au NPs-analytes membrane was transformed onto a laser-processed superhydrophilic Si slide for detection.Three heavy metals(cadmium(Cd),barium(Ba),and chromium(Cr))were analyzed to evaluate the stability and sensitivity of the ISA method for NELIBS.The results(Cd:RSD=3.6%,LoD=0.654 mg/L;Ba:RSD=3.4%,LoD=0.236 mg/L;Cr:RSD=7.7%,LoD=1.367 mg/L)demonstrated signal enhancement and high-stable and ultrasensitive detection.The actual sample detection(Cd:RE=7.71%,Ba:RE=6.78%)illustrated great reliability.The ISA method,creating a uniform distribution of NP-analytes at the interface,has promising prospects in NELIBS.
基金financially supported by the National Natural Science Foundation of China(Nos.20904047 and 12074151)the Natural Science Foundation of Zhejiang Province(Nos.LY17A040001 and LY19F03004)。
文摘Diphenylalanine and its analogs cause many concerns owing to their perfect self-assembly properties in the fields of biology,medicine,and nanotechnology.Experimental research has shown that diphenylalanine-based analogs with ethylenediamine linkers(PA,P=phenylalanine,and A=analog)can self-assemble into spherical assemblies,which can serve as novel anticancer drug carriers.In this work,to understand the assembly pathways,drug loading behavior,and formation mechanism of PA aggregates at the molecular level,we carried out dissipative particle dynamics(DPD)simulations of PA molecule systems.Our simulation results demonstrate that PA molecules spontaneously assemble into nanospheres and can self-assemble into drug-loaded nanospheres upon addition of the cancer chemotherapeutic agent doxorubicin(DOX).We also found that the hydrophobic side chain beads of PA molecules exhibited a unique onion-like distribution inside the nanospheres,which was not observed in the experiment.The onion-like nanospheres were verified by calculating the radial distribution function(RDF)of the DPD beads.Furthermore,based on the analysis of the percentages of different interaction components in the total nonbonded energies,main chain-side chain interactions between PA molecules may be important in the formation of onion-like nanospheres,and the synergistic effects of main chain-side chain,main chain-drug,side chain-drug,and main chain-solvent interactions are significant in the formation of drug-loaded nanospheres.These findings provide new insights into the structure and self-assembly pathway of PA assemblies,which may be helpful for the design of efficient and effective drug delivery systems.
基金supported by the National Natural Science Foundation of China(Nos.82061148012,82027806,21974019)SEU Innovation Capability Enhancement Plan for Doctoral Students(No.CXJH_SEU 24138)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX24_0469)。
文摘The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching(ACQ).In this study,an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence emission through protein coronas-controlled distance between gold nanoclusters(Au NCs).Interestingly,the gold ion complexes coated with proteins of low isoelectric point(pI)nucleate at the secondary structure of proteins with high p I through ionic exchange within cells,generating fluorescent Au NCs.It is worth noting that due to the steric hindrance formed by the protein coronas on the surface of Au NCs,the distance between Au NCs can be controlled,avoiding electron transfer caused by close proximity of Au NCs and inhibiting fluorescence ACQ.This strategy can achieve fluorescence imaging of clinical tissue samples without observable side effects.Therefore,this study proposes a distance-controllable self-assembled pitaya structure to provide a new approach for Au NCs with stable fluorescence.
基金Project supported by the Natural Science Foundation of Shandong Province (ZR2022QB067)。
文摘The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements.In this pape r,the extractant(N,N-methyl py ridineethyl-N',N'-dicyclohexyl-3-oxadiglycolamide,MPyEDChDGA) with a new structure was synthesized,and the pyridine group was successfully grafted onto the 3-oxadiglycolamide structure.Using MPyEDChDGA for efficient enrichment of rare earth ions,the self-assembled solids were recovered by simple filtration without further backextraction and final precipitation,achieving a one-step strategy for the recovery of rare earth ions.Several important parameters affecting the self-assembly extraction,including pH,diluent,temperature,and extractant concentration,were systematically evaluated using La(NO_(3))_(3),Tb(NO_(3))_(3),and Lu(NO_(3))_(3) as representatives.The self-assembled solids were investigated in detail by X-ray diffraction(XRD),scanning electron microscopy(SEM),1H nuclear magnetic resonance(1H NMR),Fourier transform infrared spectroscopy(FT-IR),Raman,and X-ray photoelectron spectroscopy(XPS) analyses.The stoichiometry of the extraction species was characterized using the Job's method and electrospray ionization mass spectrometry(ESI-MS).In addition,MPyEDChDGA was applied to the recovery of Sm in SmCoCu simulated liquid,and the results show that MPyEDChDGA has good selectivity of Sm from transition metals(Co,Cu).The separation factor of Sm/Co can reach 6281±117,which provides a new approach to recovering Sm from SmCoCu scrap magnets.This study presents an efficient and convenient new strategy for the recovery and separation of rare earth elements.
基金supported by the National Science Foundation for Distinguished Young Scholars(No.52325308)the National Natural Science Foundation of China(Nos.52273008 and 52073092)+1 种基金Shanghai Scientific and Technological Innovation Projects(No.22ZR1479300)Shanghai Rising-Star Program(No.23QA1402500).
文摘Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AABCs presents challenges,which greatly limits the exploration of their self-assembly behaviors.In this work,we employed dissipative particle dynamics(DPD)simulations to investigate the self-assembly behaviors of AABCs in selective solution.By varying the copolymer concentration and structure,we conducted the self-assembly phase diagrams of AABCs,revealing complex morphologies such as channelized micelles with one or more solvophilic channels.Moreover,the number,surface area,and one-dimensional density distribution of the channelized micelles were calculated to demonstrate the internal structure and morphological transformation during the self-assembly process.Our findings indicate that the morphology of the internal solvophilic channels is greatly influenced by the copolymer structure,concentration,and interaction parameters between the different side chains.The simulation results are consistent with available experimental observations,which can offer theoretical insights into the self-assembly of AABCs.
基金financial support from the National Natural Science Fund for Distinguished Young Scholars of China(No.22025107)Shaanxi Fundamental Science Research Project for Chemistry&Biology(No.22JHZ003)+2 种基金the Key International Scientific and Technological Cooperation and Exchange Project of Shaanxi Province(No.2023-GHZD-15)the National Youth Top-notch Talent Support Program of Chinathe FM&EM International Joint Laboratory of Northwest University。
文摘The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable.Here,we report a fluorinated N-heterocyclic carbene(NHC)–based pillarplex with a tunable quaternary structure,employed as an efficient building block for constructing hierarchical superstructures.Initially,multiple noncovalent interactions in the NHC-based pillarplex,particularly those between the fluorinated pillarplex and PF_(6)-anions,induce the formation of a supramolecular gel at high concentrations.Additionally,this hierarchical self-assembled structure can be regulated by adjusting anion types,facilitating the controlled transformation from a supramolecular gel into a supramolecular channel upon the introduction of four monocarboxylic acids as anions.The study provides insight into the construction and controlled regulation of superstructures based on NHC-based pillarplexes.
