An amphiphilic polymer bearing tetraphenylethene (TPE) moiety was synthesized by convenient reactions. The polymer exhibits unique aggregation-induced emission (AIE) characteristics and can self-assemble to size-tunab...An amphiphilic polymer bearing tetraphenylethene (TPE) moiety was synthesized by convenient reactions. The polymer exhibits unique aggregation-induced emission (AIE) characteristics and can self-assemble to size-tunable particles in DMF/water mixtures. The polymer nanoparticles can be used for cell imaging, which provides a potential stable fluorescent tool to monitor the distribution of drugs and bioconjugates in living cells.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
Tetraphenylethylene(TPE) and its derivatives, as the widely used aggregation-induced emission(AIE) fluorophores, have attracted rapidly growing interest in the fields of material science and biological technology due ...Tetraphenylethylene(TPE) and its derivatives, as the widely used aggregation-induced emission(AIE) fluorophores, have attracted rapidly growing interest in the fields of material science and biological technology due to their unique light-emitting mechanism—they are nearly non-emissive in dilute solution but emit brilliant fluorescence in the aggregate state because of the restriction of intramolecular motion. Coordination-driven self-assembly, which provides a highly effective method to put the individual chromophores together, is consistent with the AIE mechanism of TPE. During the past few years, some AIE-active metal-organic coordination complexes have been successfully constructed via coordination-driven self-assembly, and their AIE properties and applications have been investigated. In this review, we survey the recent progress on TPE-based metal-organic coordination complexes and their applications in fluorescence sensors, cell imaging, and light-emitting materials. We will introduce them from three different types of structures: metallacycles, metallacages, and metal-organic frameworks(MOFs).展开更多
The research in circularly polarized luminescence has attracted wide interest in recent years.Efforts on one side are directed toward the development of chiral materials with both high luminescence efficiency and diss...The research in circularly polarized luminescence has attracted wide interest in recent years.Efforts on one side are directed toward the development of chiral materials with both high luminescence efficiency and dissymmetry factors,and on the other side,are focused on the exploitations of these materials in optoelectronic applications.This review summarizes the recent frontiers(mostly within five years)in the research in circularly polarized luminescence,including the development of chiral emissive materials based on organic small molecules,compounds with aggregation-induced emissions,supramolecular assemblies,liquid crystals and liquids,polymers,metal-ligand coordination complexes and assemblies,metal clusters,inorganic nanomaterials,and photon upconversion systems.In addition,recent applications of related materials in organic light-emitting devices,circularly polarized light detectors,and organic lasers and displays are also discussed.展开更多
Laser ablation in liquids has emerged as a new branch of nanoscience for developing various nanomaterials with different shapes.However, how to design and control nanomaterial growth is still a challenge due to the un...Laser ablation in liquids has emerged as a new branch of nanoscience for developing various nanomaterials with different shapes.However, how to design and control nanomaterial growth is still a challenge due to the unique chemical-physical process chain correlated with nanomaterial nucleation and growth, including plasma phase(generation and rapid quenching), gas(bubble) phase,and liquid phase. In this review, through summarizing the literature about this topic and comparing with the well-established particle growth mechanisms of the conventional wet chemistry technique, our perspective on the possible nanoparticle growth mechanisms or routes is presented, aiming at shedding light on how laser-ablated particles grow in liquids. From the microscopic viewpoint, the nanoparticle growth contains six mechanisms, including LaMer-like growth, coalescence, Ostwald ripening, particle(oriented) attachment, adsorbate-induced growth and reaction-induced growth. For each microscopic growth mechanism, the vivid growth scenes of some representative nanomaterials recorded by TEM and SEM measurements are displayed. Afterwards,the scenes from the macroscopic viewpoint for the large submicro-and micro-scale nanospheres and anisotropic nanostructures formation and evolution from one nanostructure into another one are presented. The panorama of how diverse nanomaterials grow during and after laser ablation in liquids shown in this review is intended to offer a overview for researchers to search for the possible mechanisms correlated to their synthesized nanomaterials, and more expectation is desired to better design and tailor the morphology of the nanocrystals synthesized by LAL technique.展开更多
Aggregation-induced emission(AIE)is a phenomenon in which fluorescence is enhanced rather than quenched upon molecular assembly.AIE fluorogens(AIEgens)are flexible,conjugated systems that are limited in their dynamics...Aggregation-induced emission(AIE)is a phenomenon in which fluorescence is enhanced rather than quenched upon molecular assembly.AIE fluorogens(AIEgens)are flexible,conjugated systems that are limited in their dynamics when assembled,which improves their fluorescent properties.This intriguing feature has been incorporated in many different molecular assemblies and has been extended to nanoparticles composed of amphiphilic polymer building blocks.The integration of the fascinating AIE design principle with versatile polymer chemistry opens up new frontiers to approach and solve intrinsic obstacles of conventional fluorescent materials in nanoscience,including the aggregation-caused quenching effect.Furthermore,this integration has drawn significant attention from the nanomedicine community,due to the additional advantages of nanoparticles comprising AIEgenic molecules,such as emission brightness and fluorescence stability.In this regard,a range of AIEgenic amphiphilic polymers have been developed,displaying enhanced emission in the self-assembly/aggregated state.AIEgenic assemblies are regarded as attractive nanomaterials with inherent fluorescence,which display promising features in a biomedical context,for instance in biosensing,cell/tissue imaging and tracking,as well as(photo)therapeutics.In this review,we describe recent strategies for the design and synthesis of novel types of AIEgenic amphiphilic polymers via facile approaches including direct conjugation to natural/synthetic polymers,polymerization,post-polymerization and supramolecular host−guest interactions.Their self-assembly behavior and biomedical potential will be discussed.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
Reversible addition-fragmentation chain transfer(RAFT)-mediated polymerization-induced self-assembly(PISA)of star block copolymer and linear block copolymer using a binary mixture of a star-like macro-RAFT agent and a...Reversible addition-fragmentation chain transfer(RAFT)-mediated polymerization-induced self-assembly(PISA)of star block copolymer and linear block copolymer using a binary mixture of a star-like macro-RAFT agent and a linear macro-RAFT agent is reported.With this formulation,star block copolymer and diblock copolymer were formed simultaneously to generate colloidally stable star/linear block copolymer assemblies.Size exclusion chromatography(SEC)analysis confirmed the presence of two types of polymers in the final samples.The molar ratio of the star-like macro-RAFT agent and the linear macro-RAFT agent has a significant impact on the morphology of polymer assemblies.It was found that increasing the amount of star-like macro-RAFT agent facilitated the formation of higher-order morphologies.Additionally,effects of other reaction parameters including the length/number of the arm of the star-like macro-RAFT agent,degree of polymer(DP),monomer concentration on the morphology of star/linear block copolymer assemblies were also investigated.We expect that this work will offer new possibilities for the scalable preparation of polymer assemblies with unique structures and functions.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
Here,we demonstrate the use of branched macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agents in RAFT dispersion polymerization,to access branched block copolymers as well as well-defined...Here,we demonstrate the use of branched macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agents in RAFT dispersion polymerization,to access branched block copolymers as well as well-defined branched block copolymer assemblies.Two types of branched macro-RAFT agents were first synthesized by using either a monofunctional chain transfer monomer or a difunctional chain transfer monomer in RAFT polymerization,and subsequently utilized in RAFT dispersion polymerization.It was found that only branched macro-RAFT agents synthesized from the difunctional chain transfer monomer could lead to colloidally stable assemblies with well-defined morphologies.Reaction conditions including monomer concentration,degree of polymerization (DP) of the core-forming block,and DP of the solvophilic segment on morphologies of branched block copolymer assemblies were investigated in detail.Size exclusion chromatography (SEC) analysis further confirmed the successful formation of branched block copolymers by using branched macro-RAFT agents.This work on the synthesis of branched block copolymer assemblies by RAFT dispersion polymerization offers new opportunities for the rational design of polymer assemblies with well-defined structures.展开更多
Herein,we describe the selective formation of a barrel-shaped or a ball-shaped fluorescent metallacage by controlling the shape and stoichiometry of the building blocks.Specifically,the tetraphenylethylene-based donor...Herein,we describe the selective formation of a barrel-shaped or a ball-shaped fluorescent metallacage by controlling the shape and stoichiometry of the building blocks.Specifically,the tetraphenylethylene-based donor and two acceptors with different numbers of Pt(Ⅱ)centers were combined via coordination-driven self-assembly.Owing to the differences in the shapes of the assemblies,the resultant ball-shaped metallacage displayed stronger and blue-shifted fluorescence compared to the barrel-shaped one in dilute solutions,while a reversal of fluorescence intensities was observed in the aggregation process.Overall,this work demonstrates that the photophysical properties of supramolecular coordination complexes can be affected by subtle geometrical factors,which can be controlled precisely at the molecular level.展开更多
Cationic amphiphile aggregates exhibit superior antibacterial activity than monomers.However,the antimicrobial mechanism of aggregates has not been well understood because it is difficult to distinguish and monitor ag...Cationic amphiphile aggregates exhibit superior antibacterial activity than monomers.However,the antimicrobial mechanism of aggregates has not been well understood because it is difficult to distinguish and monitor aggregate and monomer in antimicrobial process.Herein,three bola-type cationic amphiphiles with aggregation-induced emission property have been developed to show distinguishable fluorescence in their monomer and aggregate.The hydrophilicity of monomer and the stability of aggregate are finely tuned by tailoring the linkers between two quaternary ammonium end groups and tetraphenylethylene skeleton.The sensitive fluorescence switching of monomer and aggregate achieves the quantitative monitoring of dynamic interaction of three amphiphiles with bacteria.The aggregates with cationic charges first attach to bacterial surface,and the monomers subsequently dissociate from aggregates to penetrate bacterial membrane.Further,our results reveal the vital role of stability of aggregates during antimicrobial process,shedding light on the rational design of high-efficient antimicrobials.展开更多
Polymer-induced self-assembly of inorganic nanoparticles has emerged as a powerful strategy for fabrication of stimuliresponsive drug delivery nanosystems.Herein,we designed and synthesized a series of lipoic acid-cap...Polymer-induced self-assembly of inorganic nanoparticles has emerged as a powerful strategy for fabrication of stimuliresponsive drug delivery nanosystems.Herein,we designed and synthesized a series of lipoic acid-capped polysarcosine-bpolycaprolactone(PSar-b-PCL)block copolymers.The self-assembly of gold nanoparticles drove by these block copolymers was systematically investigated,and the preparation of near-infrared(NIR)light-responsive PSar-decorated gold nanovesicle(PSGV)was optimized.DOX as anticancer drug was efficiently encapsulated within the cavity of PSGV.The PSGV greatly prevented doxorubicin(DOX)from premature leakage.While upon 808 nm laser irradiation,most of loaded DOX was rapidly released,along with the recovery of DOX fluorescence.Impressively,the DOX-loaded PSGV(DOX-PSGV)exhibited much higher cell uptake efficiency when compared to DOX-loaded polyethylene glycol(PEG)-coated gold nanovesicle(DOX-PEGV).Thanks to the synergistic photothermal/chemo therapy,the DOX-PSGV had highly superior antitumor efficacy in established 4T1 tumor model.展开更多
Comprehensive Summary,Hyperbranched polysiloxanes have attracted increasing interest due to their unique fluorescence properties.However,the relatively short emission wavelength and low fluorescence lifetime are still...Comprehensive Summary,Hyperbranched polysiloxanes have attracted increasing interest due to their unique fluorescence properties.However,the relatively short emission wavelength and low fluorescence lifetime are still the main obstacles to their broader application.In this study,we first synthesized aβ-diketone contained hyperbranched polysiloxane with excitation-dependent multicolor emission.Further through the coordination of HBPSi-NMDEA with Eu^(3+)ion,a hybrid luminescent material was prepared.It exhibited not only aggregation-induced red emission at 613 nm,but also a long fluorescence lifetime of 681.45μs.Particularly,it showed highly sensitive reversible fluorescence response to temperature variation,thus displaying the potential to be used in fluorescence temperature detection.展开更多
What is the most favorite and original chemistry developed in your research group?Ring-opening polymerization-induced self-assembly of N-carboxyanhydrides(NCA-PISA),and fusion-induced particle assembly(FIPA).How do yo...What is the most favorite and original chemistry developed in your research group?Ring-opening polymerization-induced self-assembly of N-carboxyanhydrides(NCA-PISA),and fusion-induced particle assembly(FIPA).How do you get into this specific field?Could you please share some experiences with our readers?NCA-PISA was developed to solve the biodegradability problem of nanoparticles by traditional PISA,while FIPA was inspired by nature.展开更多
Two kinds of mesoporous carbon solid acids(LDMCE-SO3H and LDMCS-SO3H)were successfully prepared using masson pine alkali lignin as carbon source by evaporation-induced self-assembly(EISA)and salt-induced selfassembly(...Two kinds of mesoporous carbon solid acids(LDMCE-SO3H and LDMCS-SO3H)were successfully prepared using masson pine alkali lignin as carbon source by evaporation-induced self-assembly(EISA)and salt-induced selfassembly(SISA)followed by sulfonation,respectively.In terms of preparation process,SISA(self-assembly in water and preparation time of 2 days)is greener and simpler than EISA(self-assembly in ethanol and preparation time of 7 days).The prepared LDMCE-SO3H and LDMCS-SO3H exhibit obvious differences in structural characteristics such as pore channel structure,specific surface area,mesopore volume and the density of-SO3H groups.Furthermore,the catalytic performances of LDMCE-SO3H and LDMCS-SO3H were investigated in the hydrolysis of microcrystalline cellulose in water,and the glucose yields of 48.99%and 54.42%were obtained under the corresponding optimal reaction conditions.More importantly,the glucose yields still reached 28.85%and 30.35%after five runs,and restored to 39.02%and 45.98%through catalysts regeneration,respectively,demonstrating that LDMCE-SO3H and LDMCS-SO3H have excellent recyclability and regenerability.展开更多
Supramolecular chirality and molecular self-assembly are important and interesting phenomena in living and non-living systems.In this work,supramolecular chirality of achiral pseudoisocyanine(PIC) J-aggregates was suc...Supramolecular chirality and molecular self-assembly are important and interesting phenomena in living and non-living systems.In this work,supramolecular chirality of achiral pseudoisocyanine(PIC) J-aggregates was successfully induced by D-,L-phenylalanine(Phe) and other amino acids in NaCl solution.The chiral J-aggregates showed a characteristic,induced circular dichroism(ICD) in the visible region of J-band chromophore which depends on the absolute configuration,concentration and side groups of α-amino acids,as well as temperature.The atomic force microscopy images indicated that the J-aggregates exist in large bundles of entangled nanofibers,and the observed ICD might result from the macroscopic helical arrangement of the assemblies.展开更多
基金supported by the National Natural Science Foundation of China (20974028, 20974098, and 21174120)the National Basic Research Program of China (2009CB623605)+1 种基金the Research Grants Council of Hong Kong (603509, HKUST2/CRF/10, 604711, and N_HKUST620/11)B.Z.T. thanks the support from the Cao Guangbiao Foundation of Zhejiang University
文摘An amphiphilic polymer bearing tetraphenylethene (TPE) moiety was synthesized by convenient reactions. The polymer exhibits unique aggregation-induced emission (AIE) characteristics and can self-assemble to size-tunable particles in DMF/water mixtures. The polymer nanoparticles can be used for cell imaging, which provides a potential stable fluorescent tool to monitor the distribution of drugs and bioconjugates in living cells.
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financially supported by STCSM (No. 16XD 1401000)Program for Changjiang Scholars and Innovative Research Team in University
文摘Tetraphenylethylene(TPE) and its derivatives, as the widely used aggregation-induced emission(AIE) fluorophores, have attracted rapidly growing interest in the fields of material science and biological technology due to their unique light-emitting mechanism—they are nearly non-emissive in dilute solution but emit brilliant fluorescence in the aggregate state because of the restriction of intramolecular motion. Coordination-driven self-assembly, which provides a highly effective method to put the individual chromophores together, is consistent with the AIE mechanism of TPE. During the past few years, some AIE-active metal-organic coordination complexes have been successfully constructed via coordination-driven self-assembly, and their AIE properties and applications have been investigated. In this review, we survey the recent progress on TPE-based metal-organic coordination complexes and their applications in fluorescence sensors, cell imaging, and light-emitting materials. We will introduce them from three different types of structures: metallacycles, metallacages, and metal-organic frameworks(MOFs).
基金financially supported by the National Natural Science Foundation of China(21925112,22090021,21890734,21975118,51973011,52003022,91956119,92061201,21825106,91856115,21874058,21771114,91956130)the Research Grants Council of Hong Kong(C6014-20W)the Innovation and Technology Commission(ITC-CNERC14SC01)。
文摘The research in circularly polarized luminescence has attracted wide interest in recent years.Efforts on one side are directed toward the development of chiral materials with both high luminescence efficiency and dissymmetry factors,and on the other side,are focused on the exploitations of these materials in optoelectronic applications.This review summarizes the recent frontiers(mostly within five years)in the research in circularly polarized luminescence,including the development of chiral emissive materials based on organic small molecules,compounds with aggregation-induced emissions,supramolecular assemblies,liquid crystals and liquids,polymers,metal-ligand coordination complexes and assemblies,metal clusters,inorganic nanomaterials,and photon upconversion systems.In addition,recent applications of related materials in organic light-emitting devices,circularly polarized light detectors,and organic lasers and displays are also discussed.
基金supported by the National Key Basic Research Program of China (Grant No. 2014CB931704)the National Natural Science Foundation of China (Grant No. 11304315, 51401206, 11404338, 51371166, 51571186, and 11504375)the Chinese Academy of Sciences/State Administration of Foreign Experts Affairs (CAS/SAFEA) International Partnership Program for Creative Research Teams
文摘Laser ablation in liquids has emerged as a new branch of nanoscience for developing various nanomaterials with different shapes.However, how to design and control nanomaterial growth is still a challenge due to the unique chemical-physical process chain correlated with nanomaterial nucleation and growth, including plasma phase(generation and rapid quenching), gas(bubble) phase,and liquid phase. In this review, through summarizing the literature about this topic and comparing with the well-established particle growth mechanisms of the conventional wet chemistry technique, our perspective on the possible nanoparticle growth mechanisms or routes is presented, aiming at shedding light on how laser-ablated particles grow in liquids. From the microscopic viewpoint, the nanoparticle growth contains six mechanisms, including LaMer-like growth, coalescence, Ostwald ripening, particle(oriented) attachment, adsorbate-induced growth and reaction-induced growth. For each microscopic growth mechanism, the vivid growth scenes of some representative nanomaterials recorded by TEM and SEM measurements are displayed. Afterwards,the scenes from the macroscopic viewpoint for the large submicro-and micro-scale nanospheres and anisotropic nanostructures formation and evolution from one nanostructure into another one are presented. The panorama of how diverse nanomaterials grow during and after laser ablation in liquids shown in this review is intended to offer a overview for researchers to search for the possible mechanisms correlated to their synthesized nanomaterials, and more expectation is desired to better design and tailor the morphology of the nanocrystals synthesized by LAL technique.
基金ERC Advanced Grant Artisym,Grant/Award Number:694120Dutch Ministry of Education,Culture and Science,Grant/Award Number:024.001.035+4 种基金NWO-NSFC Advanced Materials,Grant/Award Number:792.001.015European Union’s Horizon 2020Marie Sklodowska-Curie Innovative Training Networks Nanomed,Grant/Award Number:676137H2020 Marie Sklodowska-Curie Actions,Grant/Award Numbers:Innovative Training Networks Nanomed,(No.,676137)H2020 European Research Council,Grant/Award Number:ERC Advanced Grant Artisym 694120。
文摘Aggregation-induced emission(AIE)is a phenomenon in which fluorescence is enhanced rather than quenched upon molecular assembly.AIE fluorogens(AIEgens)are flexible,conjugated systems that are limited in their dynamics when assembled,which improves their fluorescent properties.This intriguing feature has been incorporated in many different molecular assemblies and has been extended to nanoparticles composed of amphiphilic polymer building blocks.The integration of the fascinating AIE design principle with versatile polymer chemistry opens up new frontiers to approach and solve intrinsic obstacles of conventional fluorescent materials in nanoscience,including the aggregation-caused quenching effect.Furthermore,this integration has drawn significant attention from the nanomedicine community,due to the additional advantages of nanoparticles comprising AIEgenic molecules,such as emission brightness and fluorescence stability.In this regard,a range of AIEgenic amphiphilic polymers have been developed,displaying enhanced emission in the self-assembly/aggregated state.AIEgenic assemblies are regarded as attractive nanomaterials with inherent fluorescence,which display promising features in a biomedical context,for instance in biosensing,cell/tissue imaging and tracking,as well as(photo)therapeutics.In this review,we describe recent strategies for the design and synthesis of novel types of AIEgenic amphiphilic polymers via facile approaches including direct conjugation to natural/synthetic polymers,polymerization,post-polymerization and supramolecular host−guest interactions.Their self-assembly behavior and biomedical potential will be discussed.
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the National Natural Science Foundation of China(Grant 22171055,52222301,and 21971047)the Guangdong Natural Science Foundation for Distinguished Young Scholar(Grant 2022B1515020078)the Science and Technology Program of Guangzhou(Grant SL2023A04J00142).
文摘Reversible addition-fragmentation chain transfer(RAFT)-mediated polymerization-induced self-assembly(PISA)of star block copolymer and linear block copolymer using a binary mixture of a star-like macro-RAFT agent and a linear macro-RAFT agent is reported.With this formulation,star block copolymer and diblock copolymer were formed simultaneously to generate colloidally stable star/linear block copolymer assemblies.Size exclusion chromatography(SEC)analysis confirmed the presence of two types of polymers in the final samples.The molar ratio of the star-like macro-RAFT agent and the linear macro-RAFT agent has a significant impact on the morphology of polymer assemblies.It was found that increasing the amount of star-like macro-RAFT agent facilitated the formation of higher-order morphologies.Additionally,effects of other reaction parameters including the length/number of the arm of the star-like macro-RAFT agent,degree of polymer(DP),monomer concentration on the morphology of star/linear block copolymer assemblies were also investigated.We expect that this work will offer new possibilities for the scalable preparation of polymer assemblies with unique structures and functions.
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support from the National Natural Science Foundation of China(Grant 52222301,21971047,and 22171055)the Guangdong Natural Science Foundation for Distinguished Young Scholar(Grant 2022B1515020078)the Science and Technology Program of Guangzhou(Grant 202102020631).
文摘Here,we demonstrate the use of branched macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agents in RAFT dispersion polymerization,to access branched block copolymers as well as well-defined branched block copolymer assemblies.Two types of branched macro-RAFT agents were first synthesized by using either a monofunctional chain transfer monomer or a difunctional chain transfer monomer in RAFT polymerization,and subsequently utilized in RAFT dispersion polymerization.It was found that only branched macro-RAFT agents synthesized from the difunctional chain transfer monomer could lead to colloidally stable assemblies with well-defined morphologies.Reaction conditions including monomer concentration,degree of polymerization (DP) of the core-forming block,and DP of the solvophilic segment on morphologies of branched block copolymer assemblies were investigated in detail.Size exclusion chromatography (SEC) analysis further confirmed the successful formation of branched block copolymers by using branched macro-RAFT agents.This work on the synthesis of branched block copolymer assemblies by RAFT dispersion polymerization offers new opportunities for the rational design of polymer assemblies with well-defined structures.
基金financially supported by Interdisciplinary Program of Shanghai Jiao Tong University(No.YG2019QNA16)Shanghai Sailing Program(No.20YF1422600)+1 种基金Natural Science Foundation of Shanghai(No.22dz1207603)National Natural Science Foundation of China(Nos.32101092 and 21901161).
文摘Herein,we describe the selective formation of a barrel-shaped or a ball-shaped fluorescent metallacage by controlling the shape and stoichiometry of the building blocks.Specifically,the tetraphenylethylene-based donor and two acceptors with different numbers of Pt(Ⅱ)centers were combined via coordination-driven self-assembly.Owing to the differences in the shapes of the assemblies,the resultant ball-shaped metallacage displayed stronger and blue-shifted fluorescence compared to the barrel-shaped one in dilute solutions,while a reversal of fluorescence intensities was observed in the aggregation process.Overall,this work demonstrates that the photophysical properties of supramolecular coordination complexes can be affected by subtle geometrical factors,which can be controlled precisely at the molecular level.
基金National Natural Science Foundation of China,Grant/Award Number:22002137Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20200920+1 种基金Beijing Natural Science Foundation,Grant/Award Number:2212013Shenzhen Key Laboratory of Functional Aggregate Materials,Grant/Award Number:ZDSYS20211021111400001。
文摘Cationic amphiphile aggregates exhibit superior antibacterial activity than monomers.However,the antimicrobial mechanism of aggregates has not been well understood because it is difficult to distinguish and monitor aggregate and monomer in antimicrobial process.Herein,three bola-type cationic amphiphiles with aggregation-induced emission property have been developed to show distinguishable fluorescence in their monomer and aggregate.The hydrophilicity of monomer and the stability of aggregate are finely tuned by tailoring the linkers between two quaternary ammonium end groups and tetraphenylethylene skeleton.The sensitive fluorescence switching of monomer and aggregate achieves the quantitative monitoring of dynamic interaction of three amphiphiles with bacteria.The aggregates with cationic charges first attach to bacterial surface,and the monomers subsequently dissociate from aggregates to penetrate bacterial membrane.Further,our results reveal the vital role of stability of aggregates during antimicrobial process,shedding light on the rational design of high-efficient antimicrobials.
基金supported by the financial support from the Natural Science Foundation of Jiangsu Province(No.BK20200709)the Natural Science Foundation of the Jiangsu Higher Education Institutes(No.20KJB430031)the startup fund from Nanjing Tech University.
文摘Polymer-induced self-assembly of inorganic nanoparticles has emerged as a powerful strategy for fabrication of stimuliresponsive drug delivery nanosystems.Herein,we designed and synthesized a series of lipoic acid-capped polysarcosine-bpolycaprolactone(PSar-b-PCL)block copolymers.The self-assembly of gold nanoparticles drove by these block copolymers was systematically investigated,and the preparation of near-infrared(NIR)light-responsive PSar-decorated gold nanovesicle(PSGV)was optimized.DOX as anticancer drug was efficiently encapsulated within the cavity of PSGV.The PSGV greatly prevented doxorubicin(DOX)from premature leakage.While upon 808 nm laser irradiation,most of loaded DOX was rapidly released,along with the recovery of DOX fluorescence.Impressively,the DOX-loaded PSGV(DOX-PSGV)exhibited much higher cell uptake efficiency when compared to DOX-loaded polyethylene glycol(PEG)-coated gold nanovesicle(DOX-PEGV).Thanks to the synergistic photothermal/chemo therapy,the DOX-PSGV had highly superior antitumor efficacy in established 4T1 tumor model.
基金supported by the National Natural Science Foundation of China(22175143)Guangdong Basic and Applied Basic Research Foundation(2019A1515110527)Science Center for Gas Turbine Project(P2022-DB-V-001-001).
文摘Comprehensive Summary,Hyperbranched polysiloxanes have attracted increasing interest due to their unique fluorescence properties.However,the relatively short emission wavelength and low fluorescence lifetime are still the main obstacles to their broader application.In this study,we first synthesized aβ-diketone contained hyperbranched polysiloxane with excitation-dependent multicolor emission.Further through the coordination of HBPSi-NMDEA with Eu^(3+)ion,a hybrid luminescent material was prepared.It exhibited not only aggregation-induced red emission at 613 nm,but also a long fluorescence lifetime of 681.45μs.Particularly,it showed highly sensitive reversible fluorescence response to temperature variation,thus displaying the potential to be used in fluorescence temperature detection.
基金This work was supported by the National Natural Science Foundation of China(Nos.21925505,52003195,and 22101207)Shanghai International Scientific Collaboration Fund(No.21520710100)+1 种基金the China Postdoctoral Science Foundation(Nos.2019M661614 and 2020M671197)J.D.is a recipient of the National Science Fund for Distinguished Young Scholars.
文摘What is the most favorite and original chemistry developed in your research group?Ring-opening polymerization-induced self-assembly of N-carboxyanhydrides(NCA-PISA),and fusion-induced particle assembly(FIPA).How do you get into this specific field?Could you please share some experiences with our readers?NCA-PISA was developed to solve the biodegradability problem of nanoparticles by traditional PISA,while FIPA was inspired by nature.
基金financial support from the National Natural Science Foundation of China(grant No.21706085)Subsidized Project for Postgraduates’Innovative Fund in Scientific Research of Huaqiao Universitythe Foundation of Key Laboratory of Pulp and Paper Science and Technology of Ministry of Education/Shandong Province of China(grant No.KF201804)。
文摘Two kinds of mesoporous carbon solid acids(LDMCE-SO3H and LDMCS-SO3H)were successfully prepared using masson pine alkali lignin as carbon source by evaporation-induced self-assembly(EISA)and salt-induced selfassembly(SISA)followed by sulfonation,respectively.In terms of preparation process,SISA(self-assembly in water and preparation time of 2 days)is greener and simpler than EISA(self-assembly in ethanol and preparation time of 7 days).The prepared LDMCE-SO3H and LDMCS-SO3H exhibit obvious differences in structural characteristics such as pore channel structure,specific surface area,mesopore volume and the density of-SO3H groups.Furthermore,the catalytic performances of LDMCE-SO3H and LDMCS-SO3H were investigated in the hydrolysis of microcrystalline cellulose in water,and the glucose yields of 48.99%and 54.42%were obtained under the corresponding optimal reaction conditions.More importantly,the glucose yields still reached 28.85%and 30.35%after five runs,and restored to 39.02%and 45.98%through catalysts regeneration,respectively,demonstrating that LDMCE-SO3H and LDMCS-SO3H have excellent recyclability and regenerability.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 20571085, 20604033 & 20877099)the Fund of the State Key Laboratory of Natural and Biomimetic Drugs (Grant No. 20080208)+1 种基金Graduate University of Chinese Academy of Sciences (Grant No. 2007-2009)Jiangsu Provincial Key Laboratory of Organic Chemistry Foundation and Natural Science Foundation of Jiangsu Province (Grant No. BK2007047)
文摘Supramolecular chirality and molecular self-assembly are important and interesting phenomena in living and non-living systems.In this work,supramolecular chirality of achiral pseudoisocyanine(PIC) J-aggregates was successfully induced by D-,L-phenylalanine(Phe) and other amino acids in NaCl solution.The chiral J-aggregates showed a characteristic,induced circular dichroism(ICD) in the visible region of J-band chromophore which depends on the absolute configuration,concentration and side groups of α-amino acids,as well as temperature.The atomic force microscopy images indicated that the J-aggregates exist in large bundles of entangled nanofibers,and the observed ICD might result from the macroscopic helical arrangement of the assemblies.
