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
Fluorescent vesicles have recently attracted increasing attention because of their potential applications in bioimaging,diagnostics, and theranostics, for example, in vivo study of the delivery and the distribution of...Fluorescent vesicles have recently attracted increasing attention because of their potential applications in bioimaging,diagnostics, and theranostics, for example, in vivo study of the delivery and the distribution of active substances. However, fluorescent vesicles containing conventional organic dyes often suffer from the problem of aggregation-caused quenching(ACQ) of fluorescence.Fluorescent vesicles working with aggregation-induced emission(AIE) offer an extraordinary tool to tackle the ACQ issue, showing advantages such as high emission efficiency, superior photophysical stability, low background interference, and high sensitivity. AIE fluorescent vesicles represent a new type of fluorescent and functional nanomaterials. In this review, we summarize the recent advances in the development of AIE fluorescent vesicles. The review is organized according to the chemical structures and architectures of the amphiphilic molecules that constitute the AIE vesicles, i.e., small-molecule amphiphiles, amphiphilic polymers, and amphiphilic supramolecules and supramacromolecules. The studies on the applications of these AIE vesicles as stimuli-responsive vesicles,fluorescence-guided drug release carriers, cell imaging tools, and fluorescent materials based on fluorescence resonance energy transfer(FRET) are also discussed.展开更多
Compared with spherical micelles,rod/worm-like micelles not only have extended blood circulation duration,but also exhibit favorable cellular uptake behavior,which is promising for next-generation nanomedicine and bio...Compared with spherical micelles,rod/worm-like micelles not only have extended blood circulation duration,but also exhibit favorable cellular uptake behavior,which is promising for next-generation nanomedicine and biomaterials.However,the controllable fabrication of narrowly dispersed nanorods in aqueous media is still challenging.Herein,the methodology of thermal annealing was developed for the fabrication of helical nanorods as well as a series of nanorods with different lengths.The thermal annealing process generally consisted of adding a percentage of organic solvent(10%(V/V)or 20%(V/V))to the digital micellar aqueous dispersion,followed by heating at 90℃for 1 h,then cooling naturally to room temperature,and dialyzing against water to remove the organic solvent.Right-handed helical nanorods were afforded by the treatment of 45 nm digital micelles in the presence of 10%(V/V)dioxane,while left-handed helical nanorods were obtained in the presence of 20%(V/V)dioxane.Meanwhile,the controlled growth of rod-like digital micelles was achieved after thermal annealing in the presence of different types of organic solvents,and the length of the annealed nanorods was correlated with the types of organic solvent.Furthermore,no matter the size of initial digital micelles,they all exhibited similar trend of rod growth in the presence of a certain amount of organic solvent,allowing for controllable formulation of narrowly dispersed nanorods.In addition,supramolecular self-assembly by amphiphilic dendritic oligourethane readily fabricated diverse uniform nanorods in aqueous media.Overall,this work provided an attractive methodology to fabricate uniform digital nanorods.展开更多
Nanoprobes that offer both fluorescence imaging(FI)and magnetic resonance imaging(MRI)can provide supplementary information and hold synergistic advantages.However,synthesis of such dual-modality imaging probes that s...Nanoprobes that offer both fluorescence imaging(FI)and magnetic resonance imaging(MRI)can provide supplementary information and hold synergistic advantages.However,synthesis of such dual-modality imaging probes that simultaneously exhibit tunability of functional groups,high stability,great biocompatibility and desired dual-modality imaging results remains challenging.In this study,we used an amphiphilic block polymer from(ethylene glycol)methyl ether methacrylate(OEGMA)and N-(2-hydroxypropyl)methacrylamide(HPMA)derivatives as a carrier to conjugate a MR contrast agent,Gd-DOTA,and a two-photon fluorophore with an aggregation-induced emission(AIE)effect,TPBP,to construct a MR/two-photon fluorescence dual-modality contrast agent,Gd-DOTA-TPBP.Incorporation of gadolinium in the hydrophilic chain segment of the OEGMA-based carrier resulted in a high r_(1)value for Gd-DOTA-TPBP,revealing a great MR imaging resolution.The contrast agent specifically accumulated in the tumor region,allowing a long enhancement duration for vascular and tumor contrast-enhanced MR imaging.Meanwhile,coupling TPBP with AIE properties to the hydrophobic chain segment of the carrier not only improved its water solubility and reduced its cytotoxicity,but also significantly enhanced its imaging performance in an aqueous phase.Gd-DOTA-TPBP was also demonstrated to act as an excellent fluorescence probe for two-photon-excited bioimaging with higher resolution and greater sensitivity than MRI.Since high-resolution,complementary MRI/FI dual-modal images were acquired at both cellular and tissue levels in tumor-bearing mice after application of Gd-DOTA-TPBP,it has great potential in the early phase of disease diagnosis.展开更多
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financially supported by the French National Research Agency (No. ANR-16-CE29-0028)the National Natural Science Foundation of China (Nos. 21604001 and 21528402)
文摘Fluorescent vesicles have recently attracted increasing attention because of their potential applications in bioimaging,diagnostics, and theranostics, for example, in vivo study of the delivery and the distribution of active substances. However, fluorescent vesicles containing conventional organic dyes often suffer from the problem of aggregation-caused quenching(ACQ) of fluorescence.Fluorescent vesicles working with aggregation-induced emission(AIE) offer an extraordinary tool to tackle the ACQ issue, showing advantages such as high emission efficiency, superior photophysical stability, low background interference, and high sensitivity. AIE fluorescent vesicles represent a new type of fluorescent and functional nanomaterials. In this review, we summarize the recent advances in the development of AIE fluorescent vesicles. The review is organized according to the chemical structures and architectures of the amphiphilic molecules that constitute the AIE vesicles, i.e., small-molecule amphiphiles, amphiphilic polymers, and amphiphilic supramolecules and supramacromolecules. The studies on the applications of these AIE vesicles as stimuli-responsive vesicles,fluorescence-guided drug release carriers, cell imaging tools, and fluorescent materials based on fluorescence resonance energy transfer(FRET) are also discussed.
基金financially supported by the National Key R&D Program of China(No.2020YFA0710700)the National Natural Science Foundation of China(Nos.52021002,52233009,U19A2094,52073270 and 51973071)。
文摘Compared with spherical micelles,rod/worm-like micelles not only have extended blood circulation duration,but also exhibit favorable cellular uptake behavior,which is promising for next-generation nanomedicine and biomaterials.However,the controllable fabrication of narrowly dispersed nanorods in aqueous media is still challenging.Herein,the methodology of thermal annealing was developed for the fabrication of helical nanorods as well as a series of nanorods with different lengths.The thermal annealing process generally consisted of adding a percentage of organic solvent(10%(V/V)or 20%(V/V))to the digital micellar aqueous dispersion,followed by heating at 90℃for 1 h,then cooling naturally to room temperature,and dialyzing against water to remove the organic solvent.Right-handed helical nanorods were afforded by the treatment of 45 nm digital micelles in the presence of 10%(V/V)dioxane,while left-handed helical nanorods were obtained in the presence of 20%(V/V)dioxane.Meanwhile,the controlled growth of rod-like digital micelles was achieved after thermal annealing in the presence of different types of organic solvents,and the length of the annealed nanorods was correlated with the types of organic solvent.Furthermore,no matter the size of initial digital micelles,they all exhibited similar trend of rod growth in the presence of a certain amount of organic solvent,allowing for controllable formulation of narrowly dispersed nanorods.In addition,supramolecular self-assembly by amphiphilic dendritic oligourethane readily fabricated diverse uniform nanorods in aqueous media.Overall,this work provided an attractive methodology to fabricate uniform digital nanorods.
基金supported by National Natural Science Foundation of China(52073193,51873120,81621003,51903173)1⋅3⋅5 Project for Disciplines of Excellence,West China Hospital,Sichuan University(ZYJC21013)+1 种基金Science and Technology Program of Sichuan province(2020YJ0231)China Postdoctoral Science Foundation(2021M692255).
文摘Nanoprobes that offer both fluorescence imaging(FI)and magnetic resonance imaging(MRI)can provide supplementary information and hold synergistic advantages.However,synthesis of such dual-modality imaging probes that simultaneously exhibit tunability of functional groups,high stability,great biocompatibility and desired dual-modality imaging results remains challenging.In this study,we used an amphiphilic block polymer from(ethylene glycol)methyl ether methacrylate(OEGMA)and N-(2-hydroxypropyl)methacrylamide(HPMA)derivatives as a carrier to conjugate a MR contrast agent,Gd-DOTA,and a two-photon fluorophore with an aggregation-induced emission(AIE)effect,TPBP,to construct a MR/two-photon fluorescence dual-modality contrast agent,Gd-DOTA-TPBP.Incorporation of gadolinium in the hydrophilic chain segment of the OEGMA-based carrier resulted in a high r_(1)value for Gd-DOTA-TPBP,revealing a great MR imaging resolution.The contrast agent specifically accumulated in the tumor region,allowing a long enhancement duration for vascular and tumor contrast-enhanced MR imaging.Meanwhile,coupling TPBP with AIE properties to the hydrophobic chain segment of the carrier not only improved its water solubility and reduced its cytotoxicity,but also significantly enhanced its imaging performance in an aqueous phase.Gd-DOTA-TPBP was also demonstrated to act as an excellent fluorescence probe for two-photon-excited bioimaging with higher resolution and greater sensitivity than MRI.Since high-resolution,complementary MRI/FI dual-modal images were acquired at both cellular and tissue levels in tumor-bearing mice after application of Gd-DOTA-TPBP,it has great potential in the early phase of disease diagnosis.