Dimethyl sulfoxide(DMSO)possessing strong solvency and high boiling point is a very important aprotic polar solvent in organic and polymer synthesis.Notably,it is also a useful synthon in organic chemistry.However,the...Dimethyl sulfoxide(DMSO)possessing strong solvency and high boiling point is a very important aprotic polar solvent in organic and polymer synthesis.Notably,it is also a useful synthon in organic chemistry.However,the direct incorporation of DMSO in polymer synthesis remains challenging.In this work,DMSO was successfully converted to nitrogen-containing heterocyclic polymers as a monomer via multicomponent polymerizations(MCPs)with dialdehydes and diamines in the presence of K_(2)S_(2)O_(8)/t-BuOK at 120℃in 6 h.A series of poly(phenylquinoline)s with high M_(w)values(up to 5.11×10^(4))were obtained in satisfactory yields(up to 82%),performing good solubility,good thermal and morphological stability as well as excellent film-forming ability.The thin films of poly(phenylquinoline)s exhibit high refractive index value in a wide wavelength range of 400–1700 nm.Thus,this work not only enriches the family of MCPs but also provides an efficient strategy for the conversion of DMSO into functional polymeric materials that are potentially applicable in diverse areas.展开更多
Multicomponent polymerizations(MCPs)are powerful tools to synthesize functional polymers with great structural diversity,low cost and high efficiency,which usually generate single polymer product.Herein,a robust one-p...Multicomponent polymerizations(MCPs)are powerful tools to synthesize functional polymers with great structural diversity,low cost and high efficiency,which usually generate single polymer product.Herein,a robust one-pot diamines,CS_(2)and monoisocyanide-participated catalyst-free polymerization was developed at room temperature to produce polythiourea and thioformamide simultaneously in equal equivalent,which was featured with cheap monomers,simple operation and mild condition,affording various polythioureas with high Mws of up to 4.75×10^(4)g/mol in high yields of up to 98%.Polythioureas with varied chain composition and sequence-controlled structure could be synthesized in 62 g-scale from copolymerization or multicomponent tandem polymerization,enabling facile tuning of thermal property,crystallinity,mechanical property,and fluorescence.The abundant irregular hydrogen bonds endowed the polythioureas excellent glassy state self-healing property at room temperature or below 0℃.This polymerization provided an efficient and economic approach to access functional polythioureas.展开更多
Owing to the outstanding photophysical properties,organic luminescent materials featuring aggregation-induced emission(AIE)characteristics have attracted wide attention in various fields.Numerous researches focused on...Owing to the outstanding photophysical properties,organic luminescent materials featuring aggregation-induced emission(AIE)characteristics have attracted wide attention in various fields.Numerous researches focused on low-mass AIE luminogens,and relatively less attention has been paid on AIE polymers and the related applications,in spite of the fact that AIE polymers exhibit excellent advantages of processability,multifunctional integration and synergistic effects.In this review,we briefly summarize and discuss the superiorities of AIE polymers in preparation,properties and bio-applications,and the considerable progress in these aspects are introduced as well.Finally,the structure-property relationship,challenges and opportunities are also discussed.Hopefully,this review will be a trigger for smart AIE polymer research and further broaden their applications.展开更多
Immunogenic cell death(ICD)has been demonstrated as a reliable approach to improve therapeutic effect in cancer treatment by triggering antitumor immunity.However,the trigger of ICD on the basis of chemotherapy and ph...Immunogenic cell death(ICD)has been demonstrated as a reliable approach to improve therapeutic effect in cancer treatment by triggering antitumor immunity.However,the trigger of ICD on the basis of chemotherapy and phototherapy meets the obstacles of serious side effect and poor penetration ability,which seriously impedes the therapeutic effect.The development of sonodynamic immunotherapy with the evoking of ICD presents high promise for cancer treatment with high efficacy.Herein,high performance aggregation-induced emission(AIE)sonosensitizer is constructed on the basis of the engineering structure modulation for sonodynamic-augmented immunotherapy.By regulating the intermolecular interaction and pull-push electronic effect,sonosensitizer bearing AIE feature and amplified sono-sensitizing effect is developed.In addition,in vitro observation demonstrated that thiolate-substituted segment incorporation endows the molecules with enhanced cellular uptake efficiency and improved tumor cell eradication ability.More importantly,the developed sonosensitizer could efficiently evoke ICD upon the trigger of ultrasound,which allows for the efficient tumor eradication both at cellular level and in solid tumor.The inhibition of primary tumor and further boost systemic immunity response with the complete elimination toward the distant tumor is achieved.The investigation highlights the promise of utilizing AIE sonosensitizers in sonodynamic immunotherapy to conquer the current limitation of immunotherapy in solid tumor treatment.展开更多
Fluorescent lateral flow immunoassay(LFIA)has emerged as a critical point-of-care(POC)diagnostic platform for in vitro diagnosis.However,the analytical sensitivity of conventional fluorescent LFIA is constrained by th...Fluorescent lateral flow immunoassay(LFIA)has emerged as a critical point-of-care(POC)diagnostic platform for in vitro diagnosis.However,the analytical sensitivity of conventional fluorescent LFIA is constrained by the suboptimal quantum yield(QY)and photostability of conventional fluorophores.Here,we developed a class of fluorescent nanoparticles by encapsulating butterfly-shaped aggregation-induced emission(AIE)luminogens with polystyrene microspheres,achieving a remarkable QYs of 91%—representing a 2.2-fold enhancement compared to previous AIEgens(42%QY).In addition,the broad emission spectrum characteristic of AIE fluorophores enables significant improvements in detection sensitivity and system stability of LFIAs through strategic optimization of optical filter configurations.Comparative performance evaluation revealed that the optimized 30 nm filter-AIE LFIAs platform presents outstanding performance relative to conventional,in which 85-folds and 43-folds improvements in detection limits for cardiac troponin I is achieved with excellent reproducibility(coefficient of variation<15%).Overall,the synergistic combination of high-manufacturing efficiency,high sensitivity,and good biocompatibility of the developed AIE-RNPs enables it as an efficiency and broadly applicable signal amplifier for LFIA applications,which is expected to extend the application of LFIA for trace and quantitative detection,paving the way for more reliable POC testing in clinical and resource-limited setting.展开更多
Molecular interactions are crucial in diverse fields of protein folding,material science,nanotechnology,and life origins.Although mounting experimental research controls luminescent behavior by adjusting molecular int...Molecular interactions are crucial in diverse fields of protein folding,material science,nanotechnology,and life origins.Although mounting experimental research controls luminescent behavior by adjusting molecular interactions in light-emitting materials,it remains elusive to correlate microscopic molecular interactions with macroscopic luminescent behavior directly.Here,we synthesized three red luminogens with subtle structural variation and investigated the influence of molecular interactions on their luminescent behavior in solution and aggregate states.Our results indicate that strongπ-πand D-A interactions in both dilute solution(between luminogen and solvent molecules)and aggregate(between luminogens)states cause the redshift in emission,while weak interactions(e.g.,Van der Waals,C–H…π,and C–H…F interactions)enhance the quantum yield.This work provides a thoughtful investigation into the complicated influence of various molecular interactions on luminescent behavior.展开更多
The research on pharmacology usually focuses on the structure-activity relationships of drugs,such as antibiotics,to enhance their activity,but often ignores their optical properties.However,investigating the photophy...The research on pharmacology usually focuses on the structure-activity relationships of drugs,such as antibiotics,to enhance their activity,but often ignores their optical properties.However,investigating the photophysical properties of drugs is of great significance because they could be used to in situ visualize their positions and help us to understand their working metabolism.In this work,we identified a class of commercialized antibiotics,such as levofloxacin,norfloxacin,and moxifloxacin(MXF)hydrochloride,featuring the unique aggregation-induced emission(AIE)characteristics.By taking advantage of their AIE feature,antibiotic metabolism in cells could be in situ visualized,which clearly shows that the luminescent aggregates accumulate in the lysosomes.Moreover,after a structure-activity relationship study,we found an ideal site of MXF to be modified with a triphenylphosphonium and an antibiotic derivative MXF-P was prepared,which is able to specifically differentiate bacterial species after only 10 min of treatment.Moreover,MXF-P shows highly effective broad-spectrum antibacterial activity,excellent therapeutic effects and biosafety for S.aureus-infected wound recovery.Thus,this work not only discovers the multifunctionalities of the antibiotics but also provides a feasible strategy to make the commercialized drugs more powerful.展开更多
Ferroptosis is a form of regulated cell death characterized by iron-dependent accumulation of lipid peroxidation and lethal reactive oxygen species(ROS).To date,misregulated ferroptosis has been implicated in several ...Ferroptosis is a form of regulated cell death characterized by iron-dependent accumulation of lipid peroxidation and lethal reactive oxygen species(ROS).To date,misregulated ferroptosis has been implicated in several types of cancers,and ferroptosis inducers can be used to promote ferroptosis in tumor cells and play an anti-tumor role.However,the specificity and efficacy of ferroptosis inducers remain unsatisfactory.Here,a new mitochondria-targeted photosensitizer(PS)with aggregation-induced emission(AIE)characteristic named TCSVP was designed,which efficiently generates ROS in mitochondria after light exposure.TCSVP administration significantly sensitizes tumor cells to ferroptosis inducer(RSL3)-mediated cell death by specifically and light-dependently triggering a moderate ROS generation in vitro and in vivo.Mechanically,the expression levels of ferroptosis related proteins Acyl-CoA synthetase long-chain family member 4(FACL4/ACSL4)and cyclooxygenase-2(COX2)were increased in TCSVP/RSL3-treated cells after light exposure,coupled with decreased Glutathione peroxidase 4(GPX4)activity and excessive malondialdehyde(MDA)accumulation.This study declared that light-induced moderate ROS generation within mitochondria in cancer cells by AIE-PS can be used to enhance the specificity and efficacy of ferroptosis inducers,bringing a new synergistic strategy for tumor intervention.展开更多
The stimuli-responsive polymers with upper critical solution temperatures(UCST) are highly attractive for drug delivery applications. However, the phase transition process of UCST polymer is usually characterized by t...The stimuli-responsive polymers with upper critical solution temperatures(UCST) are highly attractive for drug delivery applications. However, the phase transition process of UCST polymer is usually characterized by turbidity measurement and electron microscopy, which are significantly restricted by low sensitivity and static observation. In contrary, the fluorescence technique has significant advantages in terms of high sensitivity, easy operation, and dynamic observation. However, the conventional fluorophores suffer from the drawbacks of aggregation-caused quenching(ACQ) after being encapsulated by UCST polymers, which are not suitable for direct visualization of the phase transition process. To tackle this challenge, we herein developed a series of UCST polymers based on polyacrylamides decorated with bile acid and aggregation-induced emission(AIE)-active tetraphenylethene(TPE) groups, which can be used for direct fluorescence monitoring of the phase transition process. Moreover, the AIE-active UCST polymers can serve as drug carriers, which can not only monitor the drug release process under thermal stimuli, but also verify the drug release by fluorescence recovery after thermal stimuli. It is expected that the AIE-active UCST polymers with self-monitoring ability are promising for biomedical applications.展开更多
A“turn-on”fluorescent sensing strategy was developed for ultrasensitive detection of heavy metal mercury ion(Hg2+)directly in water.It utilized an aqueous soluble aggregation-induced emission(AIE)-active probe,named...A“turn-on”fluorescent sensing strategy was developed for ultrasensitive detection of heavy metal mercury ion(Hg2+)directly in water.It utilized an aqueous soluble aggregation-induced emission(AIE)-active probe,named 1,1,2,2-tetrakis(4-(1Htetrazol-5-yl)phenyl)ethene(TPE-4TA),composing of a luminescent tetraphenylene core and multiple anionic tetrazolate spawns.The probe retained dark when molecularly dissolved in water.However,mercury ions can ligate with multiple tetrazolate groups to form infinite coordination polymer particles spontaneously,thus inducing a fluorogenic AIE response for in situ analysis.Moreover,by embedding this AIE sensing molecules in a hydrophilic polyvinyl alcohol substrate,the resulting hydrogel film allowed in situ detection of Hg^(2+)on a laser-induced fluorescence analysis setup in aqueous environment.This strategy worked effectively in common aqueous environments with pH from 4 to 7.5 and showed high sensitivity(limit of detection down to 0.38 ppb/1.9 nM),good selectivity and a wide linearity range for quantification.This work may lead to a reliable and promising platform for on-site environmental water analysis.展开更多
Observations of the micro world,especially the structures of organelles,have been attractive topics since the 17th century.As a powerful detection tool,the fluorescence technique has played a significant role in bioim...Observations of the micro world,especially the structures of organelles,have been attractive topics since the 17th century.As a powerful detection tool,the fluorescence technique has played a significant role in bioimaging to provide more details and enhance the signal-to-noise ratio compared to that of traditional optical microscopes.The boom of aggregate-induced emission luminogens(AIEgens)in the last two decades has revolutionized the design strategy of luminescent materials for biological applications.This Review summarizes the advantages and recent progress of AIEgens in imaging and tracking.Different imaging strategies of AIEgens including turn-on imaging,stimuli-response sensing,and longterm tracking are presented.NIR AIEgens used for in-depth bioimaging via different methods are also discussed.Finally,we propose several potential development directions for AIEgens in bioimaging.展开更多
Organic light-emitting diodes(OLEDs)based on purely organic room-temperature phosphorescence(RTP)materials often encounter issues of relatively low efficiency and spectral instability.To overcome these limitations,thr...Organic light-emitting diodes(OLEDs)based on purely organic room-temperature phosphorescence(RTP)materials often encounter issues of relatively low efficiency and spectral instability.To overcome these limitations,three(arylthio)benzene derivatives(4S,5S,and 6S)with gradually increased RTP component are designed and compared.Theoretical calculation and photophysical investigation reveal that the fully substituted arylthio effect could enhance the aggregation-induced phosphorescence,enlarge the spin orbital coupling,and reduce the energy gap between S_(1)and T_(1)as much as possible.As a result,6S can exhibit single spectra in films with a high phosphorescence efficiency of up to 76.7%,and its doped RTP-OLED furnishes a high maximum external quantum efficiency(EQE)of 15.3%and ultra-stable spectra with the brightness raised from 30 to 2000 cd m^(−2).Furthermore,serving 6S as the sensitizer,the RTP-sensitized-fluorescent OLEDs based on fluorescence dopant TBRb and multiple resonance type dopant BN3 both show near three times improvement in electroluminescence performance,with EQE values of 11.3%and 25.6%,respectively.These results demonstrate the feasibility of fully substituted arylthio effect in designing RTP materials and could advance the development of high-performance RTP OLEDs.展开更多
Hydrogels loaded with microRNA(miRNA)have shown promise in bone-defect repair.Here,we present the first report of miRNA-loaded hydrogels containing bioactivities to treat steroid-induced osteonecrosis of the femoral h...Hydrogels loaded with microRNA(miRNA)have shown promise in bone-defect repair.Here,we present the first report of miRNA-loaded hydrogels containing bioactivities to treat steroid-induced osteonecrosis of the femoral head(SONFH),based on the mechanism of competing endogenous RNAs.Transcriptome sequencing of human bone marrow mesenchymal stem cells(HBMSCs)extracted from the proximal femoral bone marrow and subsequent functional assays revealed that the circSRPK1/miR-320a axis promotes HBMSCs osteogenic differentiation.By incorporating antagomir-320a(a miR-320a inhibitor)encapsulated in liposomes into injectable hyaluronic acid(HA)hydrogels,we constructed an injectable hydrogel,HA@antagomir-320a.This hydrogel demonstrated exceptional osteogenic properties,targeting multiple osteogenic pathways via CDH2 and Osterix and exhibited excellent in vitro biocompatibility.In vivo,it substantially enhanced bone formation in the osteonecrotic area of the femoral head.This injectable HA@antagomir-320a hydrogel,which exhibited exceptional biocompatibility and osteogenic properties in vivo and in vitro,offers a promising and minimally invasive solution for the treatment of SONFH.展开更多
Polythiocarbonates with similar structures to polycarbonates,have emerged as a group of promising sulfur-containing polymers with a range of practical applications,taking advantages of their excellent optical properti...Polythiocarbonates with similar structures to polycarbonates,have emerged as a group of promising sulfur-containing polymers with a range of practical applications,taking advantages of their excellent optical properties,good thermal stability and filmforming ability,and so on.However,the synthesis of polythiocarbonates generally suffered from mixed isomeric structures of repeating units,and hazardous sulfur-containing reagents.In this work,an efficient multicomponent reaction of elemental sulfur,difluoromethylene phosphobetaine(PDFA),and aryl silyl ethers was designed with the assistance of organic base 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene(MTBD)to produce 12 kinds of O,O'-monothiocarbonate compounds in up to 93%yields,taking advantages of the unique chemical property of difluorocarbene,and the deprotection of silyl group by F-generated from PDFA.Most importantly,the MTBD-assisted multicomponent polymerization of bis(aryl silyl ether)s,elemental sulfur,and PDFA was developed,affording 12 kinds of poly(O,O'-monothiocarbonate)s with well-defined structures,high Mws of up to 16900 g/mol and high yields(up to 99%).These poly(O,O'-monothiocarbonate)s possessed good film-forming properties and thermal stability,high light refractive indices and transmittance.The facile synthesis of these polymonothiocarbonates might pave the way for the development of promising sulfur-containing polymer materials.展开更多
The development of near-infrared(NIR)photosensitizers with aggregation-induced emission(AIE)properties;switchable luminescence colors;and satisfactory photodynamic therapy(PDT)effects on the treatment of fungal infect...The development of near-infrared(NIR)photosensitizers with aggregation-induced emission(AIE)properties;switchable luminescence colors;and satisfactory photodynamic therapy(PDT)effects on the treatment of fungal infection is of great importance but very challenging.Herein;two ionic organic luminogens are constructed by employing diphenylamine;diphenylacrylonitrile/1;2-diphenylethene;and methylated quinoline cation as building blocks.It is found that the resulting compounds TCQF and TQF show apparent AIE properties and produce intense fluorescence with high photoluminescence quantum yields of up to 31.2%in the solid state.In the meantime;their emission colors can be switched between red and NIR and in the NIR region by mechanical force and solvent vapor;respectively;thereby enabling remarkable and reversible mechanochromism with emission variations of up to 104 nm.More excitingly;TCQF and TQF can efficiently generate ROS under the illumination of white light and show excellent antimicrobial activities and satisfactory PDT capabilities.Inspired by the unique anti-fungus properties;TCQF is employed as a biocompatible NIR photosensitizer for treating wound infection with C.albicans;and apparent PDT effects are achieved.This work provides a new direction for the development of multifunctional NIR materials with AIE properties.展开更多
The development of an advanced phototheranostic platform that combines imaging and therapy in a single agent is an appealing yet challenging task.In this study,we successfully constructed three novel fluorescent probe...The development of an advanced phototheranostic platform that combines imaging and therapy in a single agent is an appealing yet challenging task.In this study,we successfully constructed three novel fluorescent probes by leveraging pharmaceutical chemistry and the design philosophy of theπ-bridge effect.Through a systematic comparative analysis of their fluorescence properties,water solubility,molecular conformation,and electrostatic potential,we revealed the fundamental principles governing the optical behavior and biological selectivity of these probes.Notably,the probe TPh IQ-CNTh demonstrated extended fluorescence in the near-infrared region,a significant aggregation-induced emission(AIE)effect,and the ability to distinguish tumor cells from normal cells.Moreover,it efficiently generated reactive oxygen species(ROS)and specifically labeled lipid droplets,enabling the precise staining and killing of cancer cells.This study presents a practical strategy for designing precise tumor treatments that integrate efficient imaging-guided photodynamic therapy(PDT)by harnessing the unique properties of AIE materials.展开更多
Ultralong organic room-temperature phosphorescence(RTP)materials have attracted tremendous attention recently due to their diverse applications.Several ultralong organic RTP materials mimicking the host-vip architec...Ultralong organic room-temperature phosphorescence(RTP)materials have attracted tremendous attention recently due to their diverse applications.Several ultralong organic RTP materials mimicking the host-vip architecture of inorganic systems have been exploited successfully.However,complicated synthesis and high expenditure are still inevitable in these studies.Herein,we develop a series of novel host-vip organic phosphorescence systems,in which all luminophores are electron-rich,commercially available and halogen-atom-free.The maximum phosphorescence efficiency and the longest lifetime could reach 23.6%and 362 ms,respectively.Experimental results and theoretical calculation indicate that the host molecules not only play a vital role in providing a rigid environment to suppress non-radiative decay of the vip,but also show a synergistic effect to the vip through Förster resonance energy transfer(FRET).The commercial availability,facile preparation and unique properties also make these new host-vip materials an excellent candidate for the anti-counterfeiting application.This work will inspire researchers to develop new RTP systems with different wavelengths from commercially available luminophores.展开更多
Hyperbranched polymers with unique topological structures,large number of branching sites and terminal groups have attracted much attention,and are expected to possess advanced functionalities compared with their line...Hyperbranched polymers with unique topological structures,large number of branching sites and terminal groups have attracted much attention,and are expected to possess advanced functionalities compared with their linear polymer counterparts.The devel-opment of hyperbranched polymers is hence highly desired but challenging,especially for sulfur-containing polymers which are at-tractive metal absorbents,optical materials,dielectric materials,and self-healing materials.In this work,six hyperbranched polythi-oamides with various topological structures,well-defined repeating units,satisfying yields(up to 99%),and high molecular weights(up to 101400 g/mol)were successfully designed and synthesized from the catalyst-free multicomponent polymerization of ele-mental sulfur,aromatic alkynes and aliphatic amines,through different monomer combination strategies based on the designed three-or four-functional alkyne and amine monomers.The hyperbranched polythioamides possess unique luminescence property,and strong affinity toward Hg^(2+),which can be utilized in the fluorescence detection of Hg^(2+),as well as mercury removal from aque-ous solutions with high efficiency of 99.99%and low mercury residue of 0.1 ppb.Hyperbranched polythioamides with unique struc-tures may be developed to a group of fascinating materials and find their potential applications as metal absorbents and optoelec-tronic materials.展开更多
Conjugation,as an essential chemical term used to describe electron delocalization,can be roughly grouped into two categories,through-bond conjugation(TBC)and through-space conjugation(TSC).A hybrid conjugation system...Conjugation,as an essential chemical term used to describe electron delocalization,can be roughly grouped into two categories,through-bond conjugation(TBC)and through-space conjugation(TSC).A hybrid conjugation system integrating both TBC and TSC is rarely studied and utilized,for lack of a well-established model and difficulty of structure modification and property tuning,despite its theoretical significance and potential applications.Herein,various foldamers with a tetraphenylethene(TPE)core are employed as hybrid conjugation models to investigate structure–property correlation by introducing heterocycles of furan/thiophene into theπ-stacking TSC component.For comparison,two kinds of TPE-cored foldamers with different stacking models,a benzene–heterocycle stacking model and a benzene–benzene stacking model,are designed.Combining experimental measurements and theoretical calculations,the impact of benzene–heterocycle interaction on the hybrid conjugation natures and photophysical properties has been studied systematically.The results reveal that the benzene–heterocycle stacking model can fabricate a hybrid conjugation nature with an improved TSC component to make a more dominant contribution to the electronic transition natures than the benzene–benzene stacking model,leading to the distinguishing photophysical behavior.This work provides valuable guidance for the design of new functional materials with hybrid conjugation systems.展开更多
Main observation and conclusion Fluorescent intelligent materials have attracted wide attention because of their great potential applications.One major hurdle for the development and application of fluorescent intelli...Main observation and conclusion Fluorescent intelligent materials have attracted wide attention because of their great potential applications.One major hurdle for the development and application of fluorescent intelligent materials is the aggregation-caused quenching effect in the solid state.Herein,tetraphenylethylene-based trithiocarbonate polymers with satisfactory molecular weights(Mw up to 24900)were synthesized through a one-pot polymerization route under mild conditions.The polymers were non-emissive due to the quenching effect of the trithiocarbonate group.However,upon UV irradiation,the polymers degraded and strong emission from the tetraphenylethylene unit was observed.Such a unique property endows them with great potential applications,such as photopatterning,anti-counterfeit labels,and UV detection.展开更多
基金supported by the Scientific Research Start-up Fund Project of Anhui Polytechnic University for Introducing Talents(No.2022YQQ081)Natural Science Research Project of the Anhui Educational Committee(No.2024AH050133)the National Natural Science Foundation of China(No.22101088)。
文摘Dimethyl sulfoxide(DMSO)possessing strong solvency and high boiling point is a very important aprotic polar solvent in organic and polymer synthesis.Notably,it is also a useful synthon in organic chemistry.However,the direct incorporation of DMSO in polymer synthesis remains challenging.In this work,DMSO was successfully converted to nitrogen-containing heterocyclic polymers as a monomer via multicomponent polymerizations(MCPs)with dialdehydes and diamines in the presence of K_(2)S_(2)O_(8)/t-BuOK at 120℃in 6 h.A series of poly(phenylquinoline)s with high M_(w)values(up to 5.11×10^(4))were obtained in satisfactory yields(up to 82%),performing good solubility,good thermal and morphological stability as well as excellent film-forming ability.The thin films of poly(phenylquinoline)s exhibit high refractive index value in a wide wavelength range of 400–1700 nm.Thus,this work not only enriches the family of MCPs but also provides an efficient strategy for the conversion of DMSO into functional polymeric materials that are potentially applicable in diverse areas.
基金supported by the National Natural Science Foundation of China(Nos.52173005,21788102 and 21822102)the Ministry of Science and Technology of China(No.2021YFA1501600)+1 种基金the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(No.2019B030301003)the Fundamental Research Funds for the Central Universities.
文摘Multicomponent polymerizations(MCPs)are powerful tools to synthesize functional polymers with great structural diversity,low cost and high efficiency,which usually generate single polymer product.Herein,a robust one-pot diamines,CS_(2)and monoisocyanide-participated catalyst-free polymerization was developed at room temperature to produce polythiourea and thioformamide simultaneously in equal equivalent,which was featured with cheap monomers,simple operation and mild condition,affording various polythioureas with high Mws of up to 4.75×10^(4)g/mol in high yields of up to 98%.Polythioureas with varied chain composition and sequence-controlled structure could be synthesized in 62 g-scale from copolymerization or multicomponent tandem polymerization,enabling facile tuning of thermal property,crystallinity,mechanical property,and fluorescence.The abundant irregular hydrogen bonds endowed the polythioureas excellent glassy state self-healing property at room temperature or below 0℃.This polymerization provided an efficient and economic approach to access functional polythioureas.
基金Natural Science Foundation of Guangdong Province,Grant/Award Number:2019B030301003National Natural Science Foundation of China,Grant/Award Number:21788102Innovation and Technology Commission of Hong Kong,Grant/Award Number:ITC-CNERC14S01。
文摘Owing to the outstanding photophysical properties,organic luminescent materials featuring aggregation-induced emission(AIE)characteristics have attracted wide attention in various fields.Numerous researches focused on low-mass AIE luminogens,and relatively less attention has been paid on AIE polymers and the related applications,in spite of the fact that AIE polymers exhibit excellent advantages of processability,multifunctional integration and synergistic effects.In this review,we briefly summarize and discuss the superiorities of AIE polymers in preparation,properties and bio-applications,and the considerable progress in these aspects are introduced as well.Finally,the structure-property relationship,challenges and opportunities are also discussed.Hopefully,this review will be a trigger for smart AIE polymer research and further broaden their applications.
基金financially supported by the Hunan Provincial Natural Science Foundation(Grants 2024RC3206,2022JJ40375,2021JJ304060,LINC00475,and 2023JJ40552)the Scientific Research Fund of Hunan Provincial Education Department(Grants 22A0287 and 22B0404)the Open Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates,Guangzhou 510640,China(South China University of Technology)(Grant 2023B1212060003).
文摘Immunogenic cell death(ICD)has been demonstrated as a reliable approach to improve therapeutic effect in cancer treatment by triggering antitumor immunity.However,the trigger of ICD on the basis of chemotherapy and phototherapy meets the obstacles of serious side effect and poor penetration ability,which seriously impedes the therapeutic effect.The development of sonodynamic immunotherapy with the evoking of ICD presents high promise for cancer treatment with high efficacy.Herein,high performance aggregation-induced emission(AIE)sonosensitizer is constructed on the basis of the engineering structure modulation for sonodynamic-augmented immunotherapy.By regulating the intermolecular interaction and pull-push electronic effect,sonosensitizer bearing AIE feature and amplified sono-sensitizing effect is developed.In addition,in vitro observation demonstrated that thiolate-substituted segment incorporation endows the molecules with enhanced cellular uptake efficiency and improved tumor cell eradication ability.More importantly,the developed sonosensitizer could efficiently evoke ICD upon the trigger of ultrasound,which allows for the efficient tumor eradication both at cellular level and in solid tumor.The inhibition of primary tumor and further boost systemic immunity response with the complete elimination toward the distant tumor is achieved.The investigation highlights the promise of utilizing AIE sonosensitizers in sonodynamic immunotherapy to conquer the current limitation of immunotherapy in solid tumor treatment.
基金support from the National Natural Science Foundation of China(52473173)Natural Science Foundation of Guangdong Province(2022B1515020084)+4 种基金Guangdong Basic and Applied Basic Research Foundation(2023B1515040003)Key Project of Yunnan Provincial Department of Science and Technology(202303AC100021)Independent Research Project of State Key Lab of Luminescent Materials and Devices(SCUT)(Skllmd-2024-10)Science and Technology Program of Guangzhou(2023A04J0988)Key-Area Research and Development Program of Guangdong Province(2024B0101040001).
文摘Fluorescent lateral flow immunoassay(LFIA)has emerged as a critical point-of-care(POC)diagnostic platform for in vitro diagnosis.However,the analytical sensitivity of conventional fluorescent LFIA is constrained by the suboptimal quantum yield(QY)and photostability of conventional fluorophores.Here,we developed a class of fluorescent nanoparticles by encapsulating butterfly-shaped aggregation-induced emission(AIE)luminogens with polystyrene microspheres,achieving a remarkable QYs of 91%—representing a 2.2-fold enhancement compared to previous AIEgens(42%QY).In addition,the broad emission spectrum characteristic of AIE fluorophores enables significant improvements in detection sensitivity and system stability of LFIAs through strategic optimization of optical filter configurations.Comparative performance evaluation revealed that the optimized 30 nm filter-AIE LFIAs platform presents outstanding performance relative to conventional,in which 85-folds and 43-folds improvements in detection limits for cardiac troponin I is achieved with excellent reproducibility(coefficient of variation<15%).Overall,the synergistic combination of high-manufacturing efficiency,high sensitivity,and good biocompatibility of the developed AIE-RNPs enables it as an efficiency and broadly applicable signal amplifier for LFIA applications,which is expected to extend the application of LFIA for trace and quantitative detection,paving the way for more reliable POC testing in clinical and resource-limited setting.
基金supported by the National Natural Science Foundation of China(21788102,52003228)the Innovation and Technology Commission(ITC-CNERC14SC01)+1 种基金the Research Grants Council of Hong Kong(16307020,C6009-17G,C6014-20W,and N-HKUST609/19)the Natural Science Foundation of Guangdong Province(2019B121205012)。
文摘Molecular interactions are crucial in diverse fields of protein folding,material science,nanotechnology,and life origins.Although mounting experimental research controls luminescent behavior by adjusting molecular interactions in light-emitting materials,it remains elusive to correlate microscopic molecular interactions with macroscopic luminescent behavior directly.Here,we synthesized three red luminogens with subtle structural variation and investigated the influence of molecular interactions on their luminescent behavior in solution and aggregate states.Our results indicate that strongπ-πand D-A interactions in both dilute solution(between luminogen and solvent molecules)and aggregate(between luminogens)states cause the redshift in emission,while weak interactions(e.g.,Van der Waals,C–H…π,and C–H…F interactions)enhance the quantum yield.This work provides a thoughtful investigation into the complicated influence of various molecular interactions on luminescent behavior.
基金Animal experiment protocols were reviewed and approved by South China Agricultural University and complied with all relevant ethical regulations.(Approval number:2021c075).
文摘The research on pharmacology usually focuses on the structure-activity relationships of drugs,such as antibiotics,to enhance their activity,but often ignores their optical properties.However,investigating the photophysical properties of drugs is of great significance because they could be used to in situ visualize their positions and help us to understand their working metabolism.In this work,we identified a class of commercialized antibiotics,such as levofloxacin,norfloxacin,and moxifloxacin(MXF)hydrochloride,featuring the unique aggregation-induced emission(AIE)characteristics.By taking advantage of their AIE feature,antibiotic metabolism in cells could be in situ visualized,which clearly shows that the luminescent aggregates accumulate in the lysosomes.Moreover,after a structure-activity relationship study,we found an ideal site of MXF to be modified with a triphenylphosphonium and an antibiotic derivative MXF-P was prepared,which is able to specifically differentiate bacterial species after only 10 min of treatment.Moreover,MXF-P shows highly effective broad-spectrum antibacterial activity,excellent therapeutic effects and biosafety for S.aureus-infected wound recovery.Thus,this work not only discovers the multifunctionalities of the antibiotics but also provides a feasible strategy to make the commercialized drugs more powerful.
基金supported by the National Natural Science Foundation of China(81790633,61922047,81830054,81902412,81903184,81988101,91859205,21788102,51620105009)the Innovation Program of Shanghai Municipal Education Commission(2019-01-07-0007-E00065,21XD1404600)+4 种基金the Research Grants Council of Hong Kong(16306620,N_HKUST609/19 and C6014-20W)the Innovation and Technology Commission(ITC-CNERC14SC01,ITCPD/17-9,MHP/047/19 and ITS/301/18FX)the support of Shanghai Key Laboratory of Hepato-biliary Tumor BiologyMilitary Key Laboratory on Signal Transductionsupported by the Innovation Program of Shanghai Municipal Education Commission。
文摘Ferroptosis is a form of regulated cell death characterized by iron-dependent accumulation of lipid peroxidation and lethal reactive oxygen species(ROS).To date,misregulated ferroptosis has been implicated in several types of cancers,and ferroptosis inducers can be used to promote ferroptosis in tumor cells and play an anti-tumor role.However,the specificity and efficacy of ferroptosis inducers remain unsatisfactory.Here,a new mitochondria-targeted photosensitizer(PS)with aggregation-induced emission(AIE)characteristic named TCSVP was designed,which efficiently generates ROS in mitochondria after light exposure.TCSVP administration significantly sensitizes tumor cells to ferroptosis inducer(RSL3)-mediated cell death by specifically and light-dependently triggering a moderate ROS generation in vitro and in vivo.Mechanically,the expression levels of ferroptosis related proteins Acyl-CoA synthetase long-chain family member 4(FACL4/ACSL4)and cyclooxygenase-2(COX2)were increased in TCSVP/RSL3-treated cells after light exposure,coupled with decreased Glutathione peroxidase 4(GPX4)activity and excessive malondialdehyde(MDA)accumulation.This study declared that light-induced moderate ROS generation within mitochondria in cancer cells by AIE-PS can be used to enhance the specificity and efficacy of ferroptosis inducers,bringing a new synergistic strategy for tumor intervention.
基金supported by the National Natural Science Foundation of China(21704026,21788102,51620105009,21877040,U1801252,21602063,22075087)the Natural Science Foundation of Guangdong Province,China(2019A1515011129)+4 种基金the Science and Technology Program of Guangzhou(201804020060,202007020002,201704030069,202002030229)Pearl River S&T Nova Program of Guangzhou(201806010152)Fundamental Research Funds for the Central Universities(2018JQ01)Foundation for Xinghua Scholar of South China University of TechnologyNational Key R&D Program of China(2017YFC1103400,2017YFC1105004,2018YFC0311103)。
文摘The stimuli-responsive polymers with upper critical solution temperatures(UCST) are highly attractive for drug delivery applications. However, the phase transition process of UCST polymer is usually characterized by turbidity measurement and electron microscopy, which are significantly restricted by low sensitivity and static observation. In contrary, the fluorescence technique has significant advantages in terms of high sensitivity, easy operation, and dynamic observation. However, the conventional fluorophores suffer from the drawbacks of aggregation-caused quenching(ACQ) after being encapsulated by UCST polymers, which are not suitable for direct visualization of the phase transition process. To tackle this challenge, we herein developed a series of UCST polymers based on polyacrylamides decorated with bile acid and aggregation-induced emission(AIE)-active tetraphenylethene(TPE) groups, which can be used for direct fluorescence monitoring of the phase transition process. Moreover, the AIE-active UCST polymers can serve as drug carriers, which can not only monitor the drug release process under thermal stimuli, but also verify the drug release by fluorescence recovery after thermal stimuli. It is expected that the AIE-active UCST polymers with self-monitoring ability are promising for biomedical applications.
基金Hunan Provincial Grant for Innovative Province Construction,Grant/Award Number:2019RS2023Science and Technology Innovation Program of Hunan Province,Grant/Award Number:2020RC5033+4 种基金Shenzhen Science and Technology Program,Grant/Award Number:RCJC20200714114434015National Natural Science Foundation of China,Grant/Award Numbers:51922039,T2122011Natural science foundation of Hunan Province,Grant/Award Number:2020JJ3003Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2020A1515110786National Key Research and Development Program of China,Grant/Award Number:2020YFC1807302。
文摘A“turn-on”fluorescent sensing strategy was developed for ultrasensitive detection of heavy metal mercury ion(Hg2+)directly in water.It utilized an aqueous soluble aggregation-induced emission(AIE)-active probe,named 1,1,2,2-tetrakis(4-(1Htetrazol-5-yl)phenyl)ethene(TPE-4TA),composing of a luminescent tetraphenylene core and multiple anionic tetrazolate spawns.The probe retained dark when molecularly dissolved in water.However,mercury ions can ligate with multiple tetrazolate groups to form infinite coordination polymer particles spontaneously,thus inducing a fluorogenic AIE response for in situ analysis.Moreover,by embedding this AIE sensing molecules in a hydrophilic polyvinyl alcohol substrate,the resulting hydrogel film allowed in situ detection of Hg^(2+)on a laser-induced fluorescence analysis setup in aqueous environment.This strategy worked effectively in common aqueous environments with pH from 4 to 7.5 and showed high sensitivity(limit of detection down to 0.38 ppb/1.9 nM),good selectivity and a wide linearity range for quantification.This work may lead to a reliable and promising platform for on-site environmental water analysis.
基金supported by the National Natural Science Foundation of China(52003228,52273197,and 21788102)Shenzhen Key Laboratory of Functional Aggregate Materials(ZDSYS20211021111400001),the Science,Technology and Innovation Commission of Shenzhen Municipality(JCYJ20220818103007014,JCYJ2021324134613038,JCYJ20220530143805012,KQTD20210811090142053,JSGG20220606141800001,GJHZ20210705141810031)+3 种基金the China Postdoctoral Science Foundation(2022M713022)the Open Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(2021-kllma-08)Guangzhou 510640,China(South China University of Technology)Guangdong Basic and Applied Basic Research Foundation(2023A1515011342).
文摘Observations of the micro world,especially the structures of organelles,have been attractive topics since the 17th century.As a powerful detection tool,the fluorescence technique has played a significant role in bioimaging to provide more details and enhance the signal-to-noise ratio compared to that of traditional optical microscopes.The boom of aggregate-induced emission luminogens(AIEgens)in the last two decades has revolutionized the design strategy of luminescent materials for biological applications.This Review summarizes the advantages and recent progress of AIEgens in imaging and tracking.Different imaging strategies of AIEgens including turn-on imaging,stimuli-response sensing,and longterm tracking are presented.NIR AIEgens used for in-depth bioimaging via different methods are also discussed.Finally,we propose several potential development directions for AIEgens in bioimaging.
基金supported by the National Natural Science Foundation of China(52473173)Natural Science Foundation of Guangdong Province(2022B1515020084)+5 种基金Guangdong Basic and Applied Basic Research Foundation(2023B1515040003)Key Project of Yunnan Provincial Department of Science and Technology(202303AC100021)Independent Research Project of State Key Lab of Luminescent Materials and Devices(SCUT)(Skllmd-2024-10)Key-Area Research and Development Program of Guangdong Province(2024B0101040001)Science and Technology Program of Guangzhou(2023A04J0988)the Innovation and Technology Commission(ITC-CNERC14SC01).
文摘Organic light-emitting diodes(OLEDs)based on purely organic room-temperature phosphorescence(RTP)materials often encounter issues of relatively low efficiency and spectral instability.To overcome these limitations,three(arylthio)benzene derivatives(4S,5S,and 6S)with gradually increased RTP component are designed and compared.Theoretical calculation and photophysical investigation reveal that the fully substituted arylthio effect could enhance the aggregation-induced phosphorescence,enlarge the spin orbital coupling,and reduce the energy gap between S_(1)and T_(1)as much as possible.As a result,6S can exhibit single spectra in films with a high phosphorescence efficiency of up to 76.7%,and its doped RTP-OLED furnishes a high maximum external quantum efficiency(EQE)of 15.3%and ultra-stable spectra with the brightness raised from 30 to 2000 cd m^(−2).Furthermore,serving 6S as the sensitizer,the RTP-sensitized-fluorescent OLEDs based on fluorescence dopant TBRb and multiple resonance type dopant BN3 both show near three times improvement in electroluminescence performance,with EQE values of 11.3%and 25.6%,respectively.These results demonstrate the feasibility of fully substituted arylthio effect in designing RTP materials and could advance the development of high-performance RTP OLEDs.
基金supported by the Beijing Natural Science Foundation(L232006,J230001)National High-Level Hospital Clinical Research Funding(2022-PUMCH-C-036)+2 种基金Chinese Academy of Medical Sciences Innovation Fund for Medical Sciences(CIFMS)(2022-I2M-C&T-B-031)Tsinghua University-Peking Union Medical College Hospital Initiative Scientific Research Program(2019ZLH206)National Natural Science Foundation of China(81871740,81871786,81630064,82302708,52335004,and 52275199).
文摘Hydrogels loaded with microRNA(miRNA)have shown promise in bone-defect repair.Here,we present the first report of miRNA-loaded hydrogels containing bioactivities to treat steroid-induced osteonecrosis of the femoral head(SONFH),based on the mechanism of competing endogenous RNAs.Transcriptome sequencing of human bone marrow mesenchymal stem cells(HBMSCs)extracted from the proximal femoral bone marrow and subsequent functional assays revealed that the circSRPK1/miR-320a axis promotes HBMSCs osteogenic differentiation.By incorporating antagomir-320a(a miR-320a inhibitor)encapsulated in liposomes into injectable hyaluronic acid(HA)hydrogels,we constructed an injectable hydrogel,HA@antagomir-320a.This hydrogel demonstrated exceptional osteogenic properties,targeting multiple osteogenic pathways via CDH2 and Osterix and exhibited excellent in vitro biocompatibility.In vivo,it substantially enhanced bone formation in the osteonecrotic area of the femoral head.This injectable HA@antagomir-320a hydrogel,which exhibited exceptional biocompatibility and osteogenic properties in vivo and in vitro,offers a promising and minimally invasive solution for the treatment of SONFH.
基金partially supported by the National Natural Science Foundation of China(22325102 and 52173005)the Ministry of Science and Technology of China(2021YFA1501600)+2 种基金the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(2019B030301003)the Guangdong Basic and Applied Basic Research Foundation(2023B1515040003)the Fundamental Research Funds for the Central Universities(2022ZYGXZR107)。
文摘Polythiocarbonates with similar structures to polycarbonates,have emerged as a group of promising sulfur-containing polymers with a range of practical applications,taking advantages of their excellent optical properties,good thermal stability and filmforming ability,and so on.However,the synthesis of polythiocarbonates generally suffered from mixed isomeric structures of repeating units,and hazardous sulfur-containing reagents.In this work,an efficient multicomponent reaction of elemental sulfur,difluoromethylene phosphobetaine(PDFA),and aryl silyl ethers was designed with the assistance of organic base 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene(MTBD)to produce 12 kinds of O,O'-monothiocarbonate compounds in up to 93%yields,taking advantages of the unique chemical property of difluorocarbene,and the deprotection of silyl group by F-generated from PDFA.Most importantly,the MTBD-assisted multicomponent polymerization of bis(aryl silyl ether)s,elemental sulfur,and PDFA was developed,affording 12 kinds of poly(O,O'-monothiocarbonate)s with well-defined structures,high Mws of up to 16900 g/mol and high yields(up to 99%).These poly(O,O'-monothiocarbonate)s possessed good film-forming properties and thermal stability,high light refractive indices and transmittance.The facile synthesis of these polymonothiocarbonates might pave the way for the development of promising sulfur-containing polymer materials.
基金supported by the Natural Science Foundation of Guangdong Province of China(2023A1515010915,2024A1515010047)the Guangdong Provincial Key R&D Program-Nanotechnology Special Project(2023B0101200007).
文摘The development of near-infrared(NIR)photosensitizers with aggregation-induced emission(AIE)properties;switchable luminescence colors;and satisfactory photodynamic therapy(PDT)effects on the treatment of fungal infection is of great importance but very challenging.Herein;two ionic organic luminogens are constructed by employing diphenylamine;diphenylacrylonitrile/1;2-diphenylethene;and methylated quinoline cation as building blocks.It is found that the resulting compounds TCQF and TQF show apparent AIE properties and produce intense fluorescence with high photoluminescence quantum yields of up to 31.2%in the solid state.In the meantime;their emission colors can be switched between red and NIR and in the NIR region by mechanical force and solvent vapor;respectively;thereby enabling remarkable and reversible mechanochromism with emission variations of up to 104 nm.More excitingly;TCQF and TQF can efficiently generate ROS under the illumination of white light and show excellent antimicrobial activities and satisfactory PDT capabilities.Inspired by the unique anti-fungus properties;TCQF is employed as a biocompatible NIR photosensitizer for treating wound infection with C.albicans;and apparent PDT effects are achieved.This work provides a new direction for the development of multifunctional NIR materials with AIE properties.
基金supported by the National Natural Science Foundation of China (52473173)Natural Science Foundation of Guangdong Province (2022B1515020084)+3 种基金Guangdong Basic and Applied Basic Research Foundation (2023B1515040003)Key Project of Yunnan Provincial Department of Science and Technology (202303AC100021)Independent Research Project of State Key Lab of Luminescent Materials and Devices (SCUT) (Skllmd-2024-10)Key-Area Research and Development Program of Guangdong Province (2024B0101040001)。
文摘The development of an advanced phototheranostic platform that combines imaging and therapy in a single agent is an appealing yet challenging task.In this study,we successfully constructed three novel fluorescent probes by leveraging pharmaceutical chemistry and the design philosophy of theπ-bridge effect.Through a systematic comparative analysis of their fluorescence properties,water solubility,molecular conformation,and electrostatic potential,we revealed the fundamental principles governing the optical behavior and biological selectivity of these probes.Notably,the probe TPh IQ-CNTh demonstrated extended fluorescence in the near-infrared region,a significant aggregation-induced emission(AIE)effect,and the ability to distinguish tumor cells from normal cells.Moreover,it efficiently generated reactive oxygen species(ROS)and specifically labeled lipid droplets,enabling the precise staining and killing of cancer cells.This study presents a practical strategy for designing precise tumor treatments that integrate efficient imaging-guided photodynamic therapy(PDT)by harnessing the unique properties of AIE materials.
基金This work was supported by the National Natural Science Foundation of China(21788102 and 21525417)the Natural Science Foundation of Guangdong Province(2019B030301003 and 2016A030312002)the Innovation and Technology Commission of Hong Kong(ITC-CNERC14S01).
文摘Ultralong organic room-temperature phosphorescence(RTP)materials have attracted tremendous attention recently due to their diverse applications.Several ultralong organic RTP materials mimicking the host-vip architecture of inorganic systems have been exploited successfully.However,complicated synthesis and high expenditure are still inevitable in these studies.Herein,we develop a series of novel host-vip organic phosphorescence systems,in which all luminophores are electron-rich,commercially available and halogen-atom-free.The maximum phosphorescence efficiency and the longest lifetime could reach 23.6%and 362 ms,respectively.Experimental results and theoretical calculation indicate that the host molecules not only play a vital role in providing a rigid environment to suppress non-radiative decay of the vip,but also show a synergistic effect to the vip through Förster resonance energy transfer(FRET).The commercial availability,facile preparation and unique properties also make these new host-vip materials an excellent candidate for the anti-counterfeiting application.This work will inspire researchers to develop new RTP systems with different wavelengths from commercially available luminophores.
基金supported by the National Natural Science Foundation of China(21822102,21788102,52173005,and 21774034)the Natural Science Foundation of Guangdong Province(2016A030306045)+1 种基金Guangdong Special Support Program(2017TQ04C901)the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(2019B030301003)。
文摘Hyperbranched polymers with unique topological structures,large number of branching sites and terminal groups have attracted much attention,and are expected to possess advanced functionalities compared with their linear polymer counterparts.The devel-opment of hyperbranched polymers is hence highly desired but challenging,especially for sulfur-containing polymers which are at-tractive metal absorbents,optical materials,dielectric materials,and self-healing materials.In this work,six hyperbranched polythi-oamides with various topological structures,well-defined repeating units,satisfying yields(up to 99%),and high molecular weights(up to 101400 g/mol)were successfully designed and synthesized from the catalyst-free multicomponent polymerization of ele-mental sulfur,aromatic alkynes and aliphatic amines,through different monomer combination strategies based on the designed three-or four-functional alkyne and amine monomers.The hyperbranched polythioamides possess unique luminescence property,and strong affinity toward Hg^(2+),which can be utilized in the fluorescence detection of Hg^(2+),as well as mercury removal from aque-ous solutions with high efficiency of 99.99%and low mercury residue of 0.1 ppb.Hyperbranched polythioamides with unique struc-tures may be developed to a group of fascinating materials and find their potential applications as metal absorbents and optoelec-tronic materials.
基金This research was made possible as a result of a generous grant from the National Natural Science Foundation of China(nos.21788102 and 21673082)the Natural Science Foundation of Guangdong Province(no.2019B030301003)the Fundamental Research Funds for the Central Universities.
文摘Conjugation,as an essential chemical term used to describe electron delocalization,can be roughly grouped into two categories,through-bond conjugation(TBC)and through-space conjugation(TSC).A hybrid conjugation system integrating both TBC and TSC is rarely studied and utilized,for lack of a well-established model and difficulty of structure modification and property tuning,despite its theoretical significance and potential applications.Herein,various foldamers with a tetraphenylethene(TPE)core are employed as hybrid conjugation models to investigate structure–property correlation by introducing heterocycles of furan/thiophene into theπ-stacking TSC component.For comparison,two kinds of TPE-cored foldamers with different stacking models,a benzene–heterocycle stacking model and a benzene–benzene stacking model,are designed.Combining experimental measurements and theoretical calculations,the impact of benzene–heterocycle interaction on the hybrid conjugation natures and photophysical properties has been studied systematically.The results reveal that the benzene–heterocycle stacking model can fabricate a hybrid conjugation nature with an improved TSC component to make a more dominant contribution to the electronic transition natures than the benzene–benzene stacking model,leading to the distinguishing photophysical behavior.This work provides valuable guidance for the design of new functional materials with hybrid conjugation systems.
基金support from the National Natural Science Foundation of China(No.21788102)the Research Grants Council of Hong Kong(Nos.16305618,16304819 and C6014-2000)+2 种基金the Innovation and Technology Commission(No.ITC-CNERC14SC01)the Science and Technology Plan of Shenzhen(Nos.JCYJ20160229205601482 and JCY20170818113602462)the National Science Foundation of Guangdong Province(No,2019B121205002).
文摘Main observation and conclusion Fluorescent intelligent materials have attracted wide attention because of their great potential applications.One major hurdle for the development and application of fluorescent intelligent materials is the aggregation-caused quenching effect in the solid state.Herein,tetraphenylethylene-based trithiocarbonate polymers with satisfactory molecular weights(Mw up to 24900)were synthesized through a one-pot polymerization route under mild conditions.The polymers were non-emissive due to the quenching effect of the trithiocarbonate group.However,upon UV irradiation,the polymers degraded and strong emission from the tetraphenylethylene unit was observed.Such a unique property endows them with great potential applications,such as photopatterning,anti-counterfeit labels,and UV detection.
