Carbon dots(CDs)with aggregation-induced emission(AIE)have sparked significant interest in multidimensional anti-counterfeiting due to their exceptional fluorescence properties.However,the preparation of AIE CDs with ...Carbon dots(CDs)with aggregation-induced emission(AIE)have sparked significant interest in multidimensional anti-counterfeiting due to their exceptional fluorescence properties.However,the preparation of AIE CDs with multicolor solid-state fluorescence remains a formidable challenge due to its complicated construction.In the present work,a novel class of multicolor AIE CDs(M-CDs)were fabricated using selected precursor(salicylic acid,thiosalicylic acid,and 2,2'-dithiodibenzoic acid),with an eco-friendly,low-cost one-pot solvothermal method.In the dilute organic solution,M-CDs manifested blue emission,but upon aggregation in the presence of water,the red,yellow,green,and blue emissions were displayed due to the AIE effect.Structural analysis,coupled with theoretical calculations,revealed that the increase in the size of sp2 domains would lower the Eg and cause a red-shift emission wavelength.Significantly,the continuous emission of M-CDs from blue to red can be utilized as ink for multimode printing,enabling the creation of a variety of school badges and quick response codes.These findings hold promising implications for multi-information encryption applications.展开更多
The successful synthesis of the pentazolate anion(cyclo-N-5)has been a great breakthrough in the field of energetic materials.However,the detection methods for these energetic materials based on the pentazolate anion ...The successful synthesis of the pentazolate anion(cyclo-N-5)has been a great breakthrough in the field of energetic materials.However,the detection methods for these energetic materials based on the pentazolate anion are quite rare.Herein,two fluorescent probes for cyclo-N-5anion were designed.Sensor 1(TPE2N)was synthesized with a tetraphenylethylene functionalized by two cationic groups which can generate strong electrostatic interactions with pentazolate anion and result in specific fluorescent changes.Sensor 2 was designed based on sensor 1 and supramolecular cucurbit[7]uril(CB[7]).The unique structural features of CB[7]provide sites for the interaction between the cations and N-5anion in its cavity,which would generate a platform for the detection and enhance the recognition performance.Isothermal titration calorimetry(ITC)experiment and fluorescence titration experiment indicate the binding molar ratio between sensor 1 with CB[7]is 1:2.Both sensors display typical aggregation-induced emission(AIE)features and good water-solubility.The sensors demonstrate excellent sensitivity to pentazole hydrazine salt with high enhancement constant(sensor 1:1.34×10^(6);sensor 2:3.78×10^(6))and low limit of detection(LOD:sensor 1=4.33μM;sensor 2=1.54μM).The formation of an AIE-based supramolecular sensor effectively improves the sensitivity to N-5anion.In addition,the probes also have good selectivity of N-5anion salts.The research would shed some light on the design of novel fluorescent sensors to detect pentazolate-based molecules and provides an example of supramolecular chemistry combined with fluorescent probes.展开更多
Specific bioconjugation for native primary amines is highly valuable for both chemistry and biomedical research.Despite all the efforts,scientists lack a proper strategy to achieve high selectivity for primary amines,...Specific bioconjugation for native primary amines is highly valuable for both chemistry and biomedical research.Despite all the efforts,scientists lack a proper strategy to achieve high selectivity for primary amines,not to mention the requirement of fast response in real applications.Herein,we report a chromone-based aggregation-induced emission(AIE)fluorogen called CMVMN as a self-reporting bioconjugation reagent for selective primary amine identification,and its applications for monitoring bioprocesses of amination and protein labeling.CMVMN is AIE-active and capable of solid-state sensing.Thus,its electrospun films are manufactured for visualization of amine diffusion and leakage process.CMVMN also shows good biocompatibility and potential mitochondria-staining ability,which provides new insight for organelle-staining probe design.Combined with its facile synthesis and good reversibility,CMVMN would not only show wide potential applications in biology,but also offer new possibilities for molecular engineering.展开更多
Fluorescent hydrogels with fast and reversible responses have attracted extensive attention, and it remains a challenge to designmultistimuli-responsive fluorescent hydrogel through a facile and versatile method. Mean...Fluorescent hydrogels with fast and reversible responses have attracted extensive attention, and it remains a challenge to designmultistimuli-responsive fluorescent hydrogel through a facile and versatile method. Meanwhile, the segmental motion inhydrogels is of significance for the various functions of hydrogels such as chemical reactivity, self-healing, and mechanicalstrength, etc., however, it is difficult and complicated to in situ investigate the segmental motion under different conditions. In thiswork, a multistimuli-responsive fluorescent hydrogel was designed and fabricated by introducing a tetraphenylethylene (TPE)derivative as a nonaggregated crosslinker in the gel network. Since the intermolecular rotation of TPE at the crosslinking pointwas directly integrated with the dynamic conformational transition of the macromolecular network, the mobility of macromolecularsegments can be monitored by the fluorescence intensity of the hydrogel. The prepared hydrogel has promising fluorescenceresponses to temperature, pH, metal ions, and hydrogen bonding agents, and characterization of the fluorescence and the chainsegmental motion showed that the weaker the mobility of the network macromolecular chain is, the stronger the fluorescenceintensity is. Furthermore, due to the multistimuli-responsive fluorescence of the hydrogel, such fluorescent hydrogels can bedesigned as reversible patterning displays and biomimetic color/shape adjustable actuators, with various potential applications.展开更多
An ionic iridium（Ⅲ） complex[Ir（F2dpyb）（bzdpp）2Cl][OTf]with 1,3-difluoro-4,6-di（2-pyridinyl） benzene（F2dpybH） terdentate ligand and benzyldiphenylphosphine（bzdpp）ligand was synthesized and characterized.Th...An ionic iridium（Ⅲ） complex[Ir（F2dpyb）（bzdpp）2Cl][OTf]with 1,3-difluoro-4,6-di（2-pyridinyl） benzene（F2dpybH） terdentate ligand and benzyldiphenylphosphine（bzdpp）ligand was synthesized and characterized.The structure of iridium complex was verified by single-crystal X-ray crystallography.It crystallizes in monoclinic,space group P21/n with a =14.3654（7）,b = 23.0026（10）,c = 15.7964（7） A°,β = 97.6029（11）,V= 5173.9（4） A°3,Z = 4,F（000） =2552,Dc = 1.645 Mg/m^3,Mr = 1281.49 and μ = 0.071 mm^-1.The UV-vis absorption and phosphorescence of the complex were discussed.The complex was ＇aggregation induced emission（AIE）＇ active.It exhibited no emission in CH2Cl2 solution but strong blue-green emission in solid state under ultraviolet light excitation.The complex emitted a strong phosphorescence centered at493 nm when doped in PMMA.Its lifetime is 0.755 μs and quantum yield is approximately 0.134.展开更多
Fluorescent light-up probes comprising a tetraphenylethene unit with aggregation-induced emission(AIE)characteristics and a water-soluble peptide have been designed and synthesized which provide cell membrane and nucl...Fluorescent light-up probes comprising a tetraphenylethene unit with aggregation-induced emission(AIE)characteristics and a water-soluble peptide have been designed and synthesized which provide cell membrane and nuclear permeability to live cells.This strategy has offered new opportunities for the development of probes with light-up ability and good signal-to-noise ratio.The selectivity or targeting specificity is determined by the peptide sequence,i.e.a nuclear localization signal that leads to nucleus imaging and a cell biomarker targeting peptide that offers specific light-up imaging of HT-29 cells.展开更多
Mechanistic studies promote scientific development from phenomena to theories.Aggregation-induced emission(AIE),as an unusual photophysical phenomenon,builds the bridge between molecular science and aggregate mesoscie...Mechanistic studies promote scientific development from phenomena to theories.Aggregation-induced emission(AIE),as an unusual photophysical phenomenon,builds the bridge between molecular science and aggregate mesoscience.With the twenty-year development of AIE,restriction of intramolecular motion(RIM)has been verified as the working mechanism of AIE effect.In this review,these mechanistic works about RIM are summarized from experimental and theoretical perspectives.Thereinto,the experimental studies are introduced from three parts:external rigidification,structural modification and structural characterization.In the theoretical part,calculations on the low-frequency motion of AIEgens have been performed to prove the RIM mechanism.By virtue of the theoretical calculations,some new mechanisms are proposed to supplement the RIM,such as restriction of access to conical intersection,suppression of Kasha transition,restriction of access to dark state,etc.It is foreseeable that the RIM mechanism will unify the photophysical theories for both molecules and aggregates,and inspire more progress in aggregate science.展开更多
New synthesis of multi-layer 3 D chiral molecules has been developed under novel conditions to give better outcomes.The aggregation-induced emission(AIE),UV irradiation/excitation,charge transfer(CT)and local excited(...New synthesis of multi-layer 3 D chiral molecules has been developed under novel conditions to give better outcomes.The aggregation-induced emission(AIE),UV irradiation/excitation,charge transfer(CT)and local excited(LE)ππ*transitions have been investigated on a representative individual enantiomer of pseudo C_2 asymmetry which was made possibly by differentiating moieties on phosphorous on N-phosphonyl ring of chiral sandwich framework.Meanwhile,a new tandem C–N/C–C coupling reaction was unexpectedly rendered providing a novel access to special benzo[a]carbazoles.展开更多
Aggregation-induced emission(AIE)is a photophysical phenomenon that a certain group of luminescent materials that become highly luminous when aggregated in a bad solvent or solid state.This year is the 20th anniversar...Aggregation-induced emission(AIE)is a photophysical phenomenon that a certain group of luminescent materials that become highly luminous when aggregated in a bad solvent or solid state.This year is the 20th anniversary since the AIE concept firstly proposed in 2001.Many advanced applications were gradually being explored,covering optics,electronics,energy,and bioscience and so on.At present,bibliometrics can enlighten the researchers with comprehensive sights of the achievements and trends of a specific field,which is critical for academic investigations.Herein,we presented a general bibliometric overview of AIE covering 20 years of evolution.With the assistance of Web of Science Core Collection database and several bibliometric software tools,the annual publication and citation,most influential countries/regions,most contributing authors,journals and institutions,second near-infrared(NIR-Ⅱ)related hotspots,as well as the forecast of frontiers were demonstrated and systematically analyzed.This study summarizes the current research status in AIE research field and provides a reference for future research directions.展开更多
Microorganisms and cancer have always been the fierce enemies of human beings,but the traditional methods of treating them still have many defects.Therefore,it is extremely important to develop rapid,effective and saf...Microorganisms and cancer have always been the fierce enemies of human beings,but the traditional methods of treating them still have many defects.Therefore,it is extremely important to develop rapid,effective and safe treatments.Photodynamic Therapy(PDT)has attracted much attention because of its advantages of non-invasive,non-drug tolerance,high selectivity and low toxicity.As a result,more and more scientists are committed to developing better photosensitizers to enhance the efficiency of PDT in the therapy of microorganisms as well as tumors.The discovery of aggregation-induced emission(AIE)phenomenon provides a novel research direction for the progress of photosensitizer and brings a broader prospect for PDT.This review focuses on the recent progress of photosensitizers(PSs)with AIE properties in PDT from two aspects of anti-microbial and anti-cancer.Among them,anti-microbial aspects were introduced from the perspectives of anti-bacterial,anti-fungal and anti-viral aspects,while anti-cancer aspects were first introduced from the perspective of different target sites of photosensitizers,and then based on the modification of their own structures.Finally,the current limitations,challenges and future development of AIE photosensitizer(AIE-PSs)are clarified in view of the existing strategies and obstacles,so as to promote the development of AIE-PSs in the future clinical applications.展开更多
Organic dyes with conformational sensitivity can be used to probe weak interactions at the molecular level.Here,three molecules based on tetraphenyl-1,3-butadienes(TPBs)were synthesized and studied with respect to the...Organic dyes with conformational sensitivity can be used to probe weak interactions at the molecular level.Here,three molecules based on tetraphenyl-1,3-butadienes(TPBs)were synthesized and studied with respect to their synthesis,structural characterization and potential application.All TPBs showed aggregation-induced emission(AIE)characteristics and sensitive conformational properties,in which the emission wavelengths could be changed in different states.The TPBs single crystals revealed that the phenyl groups at the 4-position of the 1,3-butadienes contributed to their conformational sensitivity.Furthermore,the potential application for monitoring the interactions among polyelectrolyte complexes and metal ions was explored,and the results showed that TPBs could be used for sensitively probing some weak interactions by changing the emission wavelengths due to their conformation-sensitive properties.TPBs may become a new star in AIE research fields.展开更多
Organic conjugated materials combining high conductivity with strong solid-state emission are highly desired for organic electronic applications,yet still rather rare.Herein,a novel luminogen(TEN)comprised by linking ...Organic conjugated materials combining high conductivity with strong solid-state emission are highly desired for organic electronic applications,yet still rather rare.Herein,a novel luminogen(TEN)comprised by linking naphthalene diimides and triphenyl ethylene with vinyl bridges is reported.TEN exhibits aggregation-induced emission(AIE)behavior of a strong nearinfrared fluorescence over 700 nm and the efficiency above 60.5%in the solid state,while also shows promising application in vivo bio-imaging with good permeability and extremely low background.Single crystal of TEN reveals intra-and intermolecular C–H…O hydrogen bonds,contributing to an inclined molecular stacking along the a-axis of the cell,creating a 1 D charge carrier transporting channel under a shortπ-πinteraction distance of 3.42?,which might benefit the solid emission and charge transport ability simultaneously.Solution processed bottom contact,top gate organic field effect transistors based on TEN reveal a high ambipolar charge transport ability with the hole mobility up to 0.13 cm2 V-1 s-1 and electron mobility up to0.010 cm2 V-1 s-1.Further atomic force microscopy and X-ray diffraction analysis on TEN thin film confirm the existence of the1 Dπ-πstacking channel,suggesting the stacking geometry revealed in crystal crucial for facilitating high charge carrier mobility while preserving the strong solid emission at the same time.展开更多
Dual-functional materials with AIE behavior and mechanoresponsive behavior have attracted considerable attention due to their promising applications in mechano-sensors,optical storage,solid-state optoelectric devices ...Dual-functional materials with AIE behavior and mechanoresponsive behavior have attracted considerable attention due to their promising applications in mechano-sensors,optical storage,solid-state optoelectric devices and bioimage systems.AIEgens bearing tetraphenylethylene(TPE)core become elementary building blocks in many fluorescent functional materials.In this article,cyanoand isocyano-electronic withdrawing groups are incorporated with TPE skeleton to form tetracyanophenylethylene(TPE-CN)and tetraisocyanophenylethylene(TPE-NC).Their structures are confirmed by NMR,Mass Spectra and single crystal X-ray measurement.These two isomers reflect aggregation-induced emission(AIE)property in solution state and mechanochromic behavior in solid state.Interestingly,their luminescent intensities,quantum yields and fluorescent lifetime in solid state have an obvious increase upon grinding.The theoretical calculation of these two compounds clarify their difference in optical properties.The mechanochromic mechanism is also intensively explained by powder X-ray measurements.展开更多
Collecting both enantiomorphs with high optical purity and yield in a single crystallization process can be achieved by adding aggregated polymeric“tailor-made”additives,known as nano-splitters.Inefficient preparati...Collecting both enantiomorphs with high optical purity and yield in a single crystallization process can be achieved by adding aggregated polymeric“tailor-made”additives,known as nano-splitters.Inefficient preparation and large addition amount have hindered the practical application of such amazing nanoparticles.Herein,we report the first nano-splitters containing aggregation-induced emission luminogens prepared via polymerization-induced self-assembly of block copolymer,poly[(S)-2-(tert-butoxycarbonylamino)-6-(methacrylamido)hexanoic acid]-b-polystyrene,followed by the removal of tert-butoxycarbonyl groups.When added into the supersaturated solution of racemic amino acids(a.a.)with seeds,the fluorescent labeled nano-assemblies enantioselectivity dyed the crystals of S-a.a.and enabled the separation from colorless R-a.a.crystals in terms of fluorescent difference.Both enantiomers were obtained with high optical purity and yield(e.g.,R-asparagine monohydrate,>99 ee%;S-asparagine monohydrate,∼94 ee%;88%total yield).Owing to a low detection limit of fluorescence,the addition amount was reduced to 0.03 wt%without remarkably compromising the ee values of both enantiomorphs.Due to the low addition amount and efficient synthesis,the output–input ratio was increased greatly.展开更多
Light has been sought and explored by human since ancient times.As the most important form of light,fluorescence is significant to applications in bioimaging and optoelectronic devices.However,fluorescence quenching p...Light has been sought and explored by human since ancient times.As the most important form of light,fluorescence is significant to applications in bioimaging and optoelectronic devices.However,fluorescence quenching problem constitutes a serious bottleneck in materials creation.Inspired from the core–shell structure in nature,we report an effective strategy to overcome this long-standing problem by utilizing a molecular core–shell structure.With an emissive core and multifunctional shell fragments,these compounds show aggregation-induced delayed fluorescence(AIDF)properties by restricting singlet oxygen(^(1)O_(2))generation and suppressing the triplet–triplet annihilation(TTA).Protected by the functional shell,the aggregation-induced emission luminogens(AIEgens)exhibit strong emission with high photoluminescent quantum yield and exciton utilization.Furthermore,because the shell materials can form exciplex with electron-transport materials,the fully solution-processed organic light-emitting diodes(OLEDs)based on these core–shell materials show low turnon voltages,excellent device performance with current efficiency of 61.4 cd A–1 and power efficiency of 42.8 lm W–1,which is a record-breaking efficiency based on all-solution processed organic multilayer systems among the AIE-OLEDs so far.This simple visualization strategy based on molecular core–shell structure provides a promising platform for AIEgens used in the fully wet-processed optoelectronic field.展开更多
The development of fluorescent nanocrystals based on organic small molecules is of great importance in bioimaging due to the merits of easy modification,high brightness and excellent photostability,however suffering f...The development of fluorescent nanocrystals based on organic small molecules is of great importance in bioimaging due to the merits of easy modification,high brightness and excellent photostability,however suffering from the emission-detrimental aggregation-caused quenching(ACQ)effect.Herein,we successfully designed and synthesized an AIE-active di(N,N-dimethylaniline)-dibenzofulvene(named as NFTPE),which exhibits the crystallization-induced emission enhancement(CIEE)effect.Interestingly,two types of yellow-and orange-emissive crystals for NFTPE were obtained,exhibiting aggregation microenvironment-dependent emission tuning in the solid state.Single-crystal analysis and density functional theory(DFT)calculations reveal that different aggregation microenvironments result in the distinct molecular conformation for various emission.Excitingly,the crystallization of NFTPE in an aqueous solution under the assistance of amphiphilic PEG polymer matrices could be monitored in situ by the fluorescence changes,facilitating the preparation of NFTPE nanocrystals(NFTPE-NCs)by adjusting the aggregation microenvironment.The obtained NFTPE-NCs exhibit the superior performance in cell imaging in respect to high brightness,photostability,and biocompatibility,thus demonstrating the potential in bioimaging applications.展开更多
Aggregation-induced emission(AIE)luminogens(AIEgens)with high brightness in aggregates exhibit great potentials in biological imaging,but these AIEgens are seldom applied in super-resolution biological imaging,especia...Aggregation-induced emission(AIE)luminogens(AIEgens)with high brightness in aggregates exhibit great potentials in biological imaging,but these AIEgens are seldom applied in super-resolution biological imaging,especially in the imaging by using the structural illumination microscope(SIM).Based on this consideration,we synthesized the donor-acceptor typed AIEgen of DTPA-BTN,which not only owns high brightness in the near-infrared(NIR)emission region from 600 nm to 1000 nm(photoluminescence quantum yield,PLQYs=11.35%),but also displays excellent photo-stability.In addition,AIE nanoparticles based on 4,7-ditriphenylamine-[1,2,5]-thiadiazolo[3,4-c]pyridine(DTPA-BTN)were also prepared with highly emissive features and excellent biocompatibility.Finally,the developed DTPA-BTN-based AIE nanoparticles were applied in the super-resolution cellular imaging via SIM,where much smaller full width at half-maximum values and high signal to noise ratios were obtained,indicating the superior imaging resolution.The results here imply that highly emissive AIEgens or AIE nanoparticles can be promising imaging agents for super-resolution imaging via SIM.展开更多
Aggregation-induced emission(AIE)has emerged as a new concept,giving highly efficient solid-state photoluminescence.Particularly,AIE luminogens(AIEgens)with deep blue emission(400–450 nm)have displayed salient advant...Aggregation-induced emission(AIE)has emerged as a new concept,giving highly efficient solid-state photoluminescence.Particularly,AIE luminogens(AIEgens)with deep blue emission(400–450 nm)have displayed salient advantages for non-doped organic light-emitting diodes(OLEDs).However,deep blue emitters with Commission Internationale de L’Eclairage(CIE)coordinates less than 0.08 are still rare.In this review,we outline the latest achievements in the molecular guidelines based on the AIE core of tetraphenylbenzene(TPB)for developing efficient deep blue AIEgens.We provide insights into the construction of deep blue emitters with high horizontal orientation by regulating the length of the linear molecule.We also discuss the luminescence mechanisms of these AIEgens-based OLEDs by using the magnetic field effects measurements.Finally,a summary of the challenges and perspectives of deep blue AIEgens for non-doped OLEDs is also presented.展开更多
The research of photo-responsive materials,with changed absorption and emission under light stimulus,has drawn more and more attention due to their wide applications.However,most of them suffered from the notorious ag...The research of photo-responsive materials,with changed absorption and emission under light stimulus,has drawn more and more attention due to their wide applications.However,most of them suffered from the notorious aggregation-caused quenching(ACQ)effect,which often led to the unconspicuous luminescent change in photo-responsive process.To solve this problem,the strategy of combining aggregation-induced emission(AIE)and photochromic properties was utilized,which largely enriched the phenomenon and application of photo-responsive materials.This short review summarized the recent progress of photo-responsive AIE materials with changed UV absorbance or PL phenomenon under UV-irradiation,including the types of molecular structures,internal mechanisms and the practical applications.Also,some outlooks were given on the further exploration of this field at the end of this paper.展开更多
The role of point-of-care(POC)diagnostics is important in public health.With the support of smartphones,POC diagnostic technologies can be greatly improved.This opportunity has arisen from not only the large number an...The role of point-of-care(POC)diagnostics is important in public health.With the support of smartphones,POC diagnostic technologies can be greatly improved.This opportunity has arisen from not only the large number and fast spread of cell-phones across the world but also their improved imaging/diagnostic functions.As a tool,the smartphone is regarded as part of a compact,portable,and low-cost system for real-time POC,even in areas with few resources.By combining near-infrared(NIR)imaging,measurement,and spectroscopy techniques,pathogens can be detected with high sensitivity.The whole process is rapid,accurate,and low-cost,and will set the future trend for POC diagnostics.In this review,the development of smartphone-based NIR fluorescent imaging technology was described,and the quality and potential of POC applications were discussed.展开更多
基金the National Natural Science Foundation of China(No.21807085)the Natural Science Foundation Research Project of Shaanxi Province(No.2023-JCYB-087)+2 种基金the Technology Innovation Leading Program of Shaanxi(No.2020QFY07-05)the Innovation Capability Support Program of Shaanxi(No.2022KJXX-88)the fund of Education Department of Shaanxi Province(Program No.Z20230071).
文摘Carbon dots(CDs)with aggregation-induced emission(AIE)have sparked significant interest in multidimensional anti-counterfeiting due to their exceptional fluorescence properties.However,the preparation of AIE CDs with multicolor solid-state fluorescence remains a formidable challenge due to its complicated construction.In the present work,a novel class of multicolor AIE CDs(M-CDs)were fabricated using selected precursor(salicylic acid,thiosalicylic acid,and 2,2'-dithiodibenzoic acid),with an eco-friendly,low-cost one-pot solvothermal method.In the dilute organic solution,M-CDs manifested blue emission,but upon aggregation in the presence of water,the red,yellow,green,and blue emissions were displayed due to the AIE effect.Structural analysis,coupled with theoretical calculations,revealed that the increase in the size of sp2 domains would lower the Eg and cause a red-shift emission wavelength.Significantly,the continuous emission of M-CDs from blue to red can be utilized as ink for multimode printing,enabling the creation of a variety of school badges and quick response codes.These findings hold promising implications for multi-information encryption applications.
基金supported by the National Natural Science Foundation of China(Grant Nos.22175093 and 22007047)the Natural Science Foundation of Jiangsu Province(Grant No.BK20200474)the China Postdoctoral Science Foundation(Grant No.2022M721615)。
文摘The successful synthesis of the pentazolate anion(cyclo-N-5)has been a great breakthrough in the field of energetic materials.However,the detection methods for these energetic materials based on the pentazolate anion are quite rare.Herein,two fluorescent probes for cyclo-N-5anion were designed.Sensor 1(TPE2N)was synthesized with a tetraphenylethylene functionalized by two cationic groups which can generate strong electrostatic interactions with pentazolate anion and result in specific fluorescent changes.Sensor 2 was designed based on sensor 1 and supramolecular cucurbit[7]uril(CB[7]).The unique structural features of CB[7]provide sites for the interaction between the cations and N-5anion in its cavity,which would generate a platform for the detection and enhance the recognition performance.Isothermal titration calorimetry(ITC)experiment and fluorescence titration experiment indicate the binding molar ratio between sensor 1 with CB[7]is 1:2.Both sensors display typical aggregation-induced emission(AIE)features and good water-solubility.The sensors demonstrate excellent sensitivity to pentazole hydrazine salt with high enhancement constant(sensor 1:1.34×10^(6);sensor 2:3.78×10^(6))and low limit of detection(LOD:sensor 1=4.33μM;sensor 2=1.54μM).The formation of an AIE-based supramolecular sensor effectively improves the sensitivity to N-5anion.In addition,the probes also have good selectivity of N-5anion salts.The research would shed some light on the design of novel fluorescent sensors to detect pentazolate-based molecules and provides an example of supramolecular chemistry combined with fluorescent probes.
基金National Natural Science Foundation of China,Grant/Award Number:21788102Research Grants Council of Hong Kong,Grant/Award Numbers:16307020,16306620,16305518,N_HKUST609/19,C6009-17G,C6014-20w+1 种基金Innovation and Technology Commission,Grant/Award Numbers:ITC-CNERC14SC01,ITCPD/17-9Natural Science Foundation of Guangdong Province,Grant/Award Number:201913121205002。
文摘Specific bioconjugation for native primary amines is highly valuable for both chemistry and biomedical research.Despite all the efforts,scientists lack a proper strategy to achieve high selectivity for primary amines,not to mention the requirement of fast response in real applications.Herein,we report a chromone-based aggregation-induced emission(AIE)fluorogen called CMVMN as a self-reporting bioconjugation reagent for selective primary amine identification,and its applications for monitoring bioprocesses of amination and protein labeling.CMVMN is AIE-active and capable of solid-state sensing.Thus,its electrospun films are manufactured for visualization of amine diffusion and leakage process.CMVMN also shows good biocompatibility and potential mitochondria-staining ability,which provides new insight for organelle-staining probe design.Combined with its facile synthesis and good reversibility,CMVMN would not only show wide potential applications in biology,but also offer new possibilities for molecular engineering.
基金the National Natural Science Foundation of China(No.51903250).
文摘Fluorescent hydrogels with fast and reversible responses have attracted extensive attention, and it remains a challenge to designmultistimuli-responsive fluorescent hydrogel through a facile and versatile method. Meanwhile, the segmental motion inhydrogels is of significance for the various functions of hydrogels such as chemical reactivity, self-healing, and mechanicalstrength, etc., however, it is difficult and complicated to in situ investigate the segmental motion under different conditions. In thiswork, a multistimuli-responsive fluorescent hydrogel was designed and fabricated by introducing a tetraphenylethylene (TPE)derivative as a nonaggregated crosslinker in the gel network. Since the intermolecular rotation of TPE at the crosslinking pointwas directly integrated with the dynamic conformational transition of the macromolecular network, the mobility of macromolecularsegments can be monitored by the fluorescence intensity of the hydrogel. The prepared hydrogel has promising fluorescenceresponses to temperature, pH, metal ions, and hydrogen bonding agents, and characterization of the fluorescence and the chainsegmental motion showed that the weaker the mobility of the network macromolecular chain is, the stronger the fluorescenceintensity is. Furthermore, due to the multistimuli-responsive fluorescence of the hydrogel, such fluorescent hydrogels can bedesigned as reversible patterning displays and biomimetic color/shape adjustable actuators, with various potential applications.
基金Supported by the National Natural Science Foundation of China(21572001)the Natural Science Foundation from Bureau of Education of Anhui Province(KJ2013A063)the Anhui Province Undergraduate Innovation and Entrepreneurship Training Program(201510360119)
文摘An ionic iridium（Ⅲ） complex[Ir（F2dpyb）（bzdpp）2Cl][OTf]with 1,3-difluoro-4,6-di（2-pyridinyl） benzene（F2dpybH） terdentate ligand and benzyldiphenylphosphine（bzdpp）ligand was synthesized and characterized.The structure of iridium complex was verified by single-crystal X-ray crystallography.It crystallizes in monoclinic,space group P21/n with a =14.3654（7）,b = 23.0026（10）,c = 15.7964（7） A°,β = 97.6029（11）,V= 5173.9（4） A°3,Z = 4,F（000） =2552,Dc = 1.645 Mg/m^3,Mr = 1281.49 and μ = 0.071 mm^-1.The UV-vis absorption and phosphorescence of the complex were discussed.The complex was ＇aggregation induced emission（AIE）＇ active.It exhibited no emission in CH2Cl2 solution but strong blue-green emission in solid state under ultraviolet light excitation.The complex emitted a strong phosphorescence centered at493 nm when doped in PMMA.Its lifetime is 0.755 μs and quantum yield is approximately 0.134.
基金the Singapore National Research Foundation(R279-000-444-281)the Singapore-MIT Alliance for Research and Technology(R279-000-378-592)the Economic Development Board(Singapore-Peking-Oxford Research Enterprise,COY-15EWI-RCFSA/N197-1)
文摘Fluorescent light-up probes comprising a tetraphenylethene unit with aggregation-induced emission(AIE)characteristics and a water-soluble peptide have been designed and synthesized which provide cell membrane and nuclear permeability to live cells.This strategy has offered new opportunities for the development of probes with light-up ability and good signal-to-noise ratio.The selectivity or targeting specificity is determined by the peptide sequence,i.e.a nuclear localization signal that leads to nucleus imaging and a cell biomarker targeting peptide that offers specific light-up imaging of HT-29 cells.
基金This work is supported by the National Natural Science Foundation of China(No.21788102)the Research Grants of Council of Hong Kong,China(Nos.16304819,16305618,N_HKUST609/19,C6009-17G)the Innovation of Technology Commission of Hong Kong,China(No.ITC-CNERC14SC01).
文摘Mechanistic studies promote scientific development from phenomena to theories.Aggregation-induced emission(AIE),as an unusual photophysical phenomenon,builds the bridge between molecular science and aggregate mesoscience.With the twenty-year development of AIE,restriction of intramolecular motion(RIM)has been verified as the working mechanism of AIE effect.In this review,these mechanistic works about RIM are summarized from experimental and theoretical perspectives.Thereinto,the experimental studies are introduced from three parts:external rigidification,structural modification and structural characterization.In the theoretical part,calculations on the low-frequency motion of AIEgens have been performed to prove the RIM mechanism.By virtue of the theoretical calculations,some new mechanisms are proposed to supplement the RIM,such as restriction of access to conical intersection,suppression of Kasha transition,restriction of access to dark state,etc.It is foreseeable that the RIM mechanism will unify the photophysical theories for both molecules and aggregates,and inspire more progress in aggregate science.
基金supported by the National Natural Science Foundation of China(91956110,21672100)Robert A.Welch Foundation(D-1361,USA)+1 种基金financial support from Beijing National Laboratory for Molecular Sciences(BNLMS201910)support from the School of Pharmaceutical Science and Technology(SPST),Tianjin University,Tianjin,China。
文摘New synthesis of multi-layer 3 D chiral molecules has been developed under novel conditions to give better outcomes.The aggregation-induced emission(AIE),UV irradiation/excitation,charge transfer(CT)and local excited(LE)ππ*transitions have been investigated on a representative individual enantiomer of pseudo C_2 asymmetry which was made possibly by differentiating moieties on phosphorous on N-phosphonyl ring of chiral sandwich framework.Meanwhile,a new tandem C–N/C–C coupling reaction was unexpectedly rendered providing a novel access to special benzo[a]carbazoles.
基金National Key Research and Development Project,Grant/Award Number:2017YFC0110802Zhejiang province Key Research and Development Project,Grant/Award Number:2020C01059+3 种基金National Natural Science Foundation of China,Grant/Award Numbers:81874059,82102105,61975172,61735016Zhejiang Engineering Research Center of Cognitive Healthcare,Grant/Award Number:2017E10011National Key Scientific Instrument and Equipment Development Project,Grant/Award Number:81827804Fundamental Research Funds for the Central Universities,Grant/Award Number:2020-KYY-511108-0007。
文摘Aggregation-induced emission(AIE)is a photophysical phenomenon that a certain group of luminescent materials that become highly luminous when aggregated in a bad solvent or solid state.This year is the 20th anniversary since the AIE concept firstly proposed in 2001.Many advanced applications were gradually being explored,covering optics,electronics,energy,and bioscience and so on.At present,bibliometrics can enlighten the researchers with comprehensive sights of the achievements and trends of a specific field,which is critical for academic investigations.Herein,we presented a general bibliometric overview of AIE covering 20 years of evolution.With the assistance of Web of Science Core Collection database and several bibliometric software tools,the annual publication and citation,most influential countries/regions,most contributing authors,journals and institutions,second near-infrared(NIR-Ⅱ)related hotspots,as well as the forecast of frontiers were demonstrated and systematically analyzed.This study summarizes the current research status in AIE research field and provides a reference for future research directions.
基金support of the National Science and Technology Infrastructure Grant(NSTI-CR14-21)to Chao Shen.
文摘Microorganisms and cancer have always been the fierce enemies of human beings,but the traditional methods of treating them still have many defects.Therefore,it is extremely important to develop rapid,effective and safe treatments.Photodynamic Therapy(PDT)has attracted much attention because of its advantages of non-invasive,non-drug tolerance,high selectivity and low toxicity.As a result,more and more scientists are committed to developing better photosensitizers to enhance the efficiency of PDT in the therapy of microorganisms as well as tumors.The discovery of aggregation-induced emission(AIE)phenomenon provides a novel research direction for the progress of photosensitizer and brings a broader prospect for PDT.This review focuses on the recent progress of photosensitizers(PSs)with AIE properties in PDT from two aspects of anti-microbial and anti-cancer.Among them,anti-microbial aspects were introduced from the perspectives of anti-bacterial,anti-fungal and anti-viral aspects,while anti-cancer aspects were first introduced from the perspective of different target sites of photosensitizers,and then based on the modification of their own structures.Finally,the current limitations,challenges and future development of AIE photosensitizer(AIE-PSs)are clarified in view of the existing strategies and obstacles,so as to promote the development of AIE-PSs in the future clinical applications.
基金supported by the National Natural Science Foundation of China (51673024, 21875019, 21490574, 51803009)Beijing Institute of Technology Research Fund Program for Young Scholars
文摘Organic dyes with conformational sensitivity can be used to probe weak interactions at the molecular level.Here,three molecules based on tetraphenyl-1,3-butadienes(TPBs)were synthesized and studied with respect to their synthesis,structural characterization and potential application.All TPBs showed aggregation-induced emission(AIE)characteristics and sensitive conformational properties,in which the emission wavelengths could be changed in different states.The TPBs single crystals revealed that the phenyl groups at the 4-position of the 1,3-butadienes contributed to their conformational sensitivity.Furthermore,the potential application for monitoring the interactions among polyelectrolyte complexes and metal ions was explored,and the results showed that TPBs could be used for sensitively probing some weak interactions by changing the emission wavelengths due to their conformation-sensitive properties.TPBs may become a new star in AIE research fields.
基金the China Scholarship Councilthe National Natural Science Foundation of China(21702016,21905015)+1 种基金the Chongqing Science and Technology Commission(cstc2018jcyj AX0091)the Fundamental Research Funds for the Central Universities(2019CDQYHG023)。
文摘Organic conjugated materials combining high conductivity with strong solid-state emission are highly desired for organic electronic applications,yet still rather rare.Herein,a novel luminogen(TEN)comprised by linking naphthalene diimides and triphenyl ethylene with vinyl bridges is reported.TEN exhibits aggregation-induced emission(AIE)behavior of a strong nearinfrared fluorescence over 700 nm and the efficiency above 60.5%in the solid state,while also shows promising application in vivo bio-imaging with good permeability and extremely low background.Single crystal of TEN reveals intra-and intermolecular C–H…O hydrogen bonds,contributing to an inclined molecular stacking along the a-axis of the cell,creating a 1 D charge carrier transporting channel under a shortπ-πinteraction distance of 3.42?,which might benefit the solid emission and charge transport ability simultaneously.Solution processed bottom contact,top gate organic field effect transistors based on TEN reveal a high ambipolar charge transport ability with the hole mobility up to 0.13 cm2 V-1 s-1 and electron mobility up to0.010 cm2 V-1 s-1.Further atomic force microscopy and X-ray diffraction analysis on TEN thin film confirm the existence of the1 Dπ-πstacking channel,suggesting the stacking geometry revealed in crystal crucial for facilitating high charge carrier mobility while preserving the strong solid emission at the same time.
基金supported by the National Natural Science Foundation of China(21905127,22065023,21861026,22075123)Natural Science Foundation of Jiangxi Province(20212BAB203029)。
文摘Dual-functional materials with AIE behavior and mechanoresponsive behavior have attracted considerable attention due to their promising applications in mechano-sensors,optical storage,solid-state optoelectric devices and bioimage systems.AIEgens bearing tetraphenylethylene(TPE)core become elementary building blocks in many fluorescent functional materials.In this article,cyanoand isocyano-electronic withdrawing groups are incorporated with TPE skeleton to form tetracyanophenylethylene(TPE-CN)and tetraisocyanophenylethylene(TPE-NC).Their structures are confirmed by NMR,Mass Spectra and single crystal X-ray measurement.These two isomers reflect aggregation-induced emission(AIE)property in solution state and mechanochromic behavior in solid state.Interestingly,their luminescent intensities,quantum yields and fluorescent lifetime in solid state have an obvious increase upon grinding.The theoretical calculation of these two compounds clarify their difference in optical properties.The mechanochromic mechanism is also intensively explained by powder X-ray measurements.
基金National Natural Science Foundation of China,Grant/Award Numbers:51833001,21674002,21905003China Postdoctoral Science Foundation,Grant/Award Numbers:2019M660002,2020T130011。
文摘Collecting both enantiomorphs with high optical purity and yield in a single crystallization process can be achieved by adding aggregated polymeric“tailor-made”additives,known as nano-splitters.Inefficient preparation and large addition amount have hindered the practical application of such amazing nanoparticles.Herein,we report the first nano-splitters containing aggregation-induced emission luminogens prepared via polymerization-induced self-assembly of block copolymer,poly[(S)-2-(tert-butoxycarbonylamino)-6-(methacrylamido)hexanoic acid]-b-polystyrene,followed by the removal of tert-butoxycarbonyl groups.When added into the supersaturated solution of racemic amino acids(a.a.)with seeds,the fluorescent labeled nano-assemblies enantioselectivity dyed the crystals of S-a.a.and enabled the separation from colorless R-a.a.crystals in terms of fluorescent difference.Both enantiomers were obtained with high optical purity and yield(e.g.,R-asparagine monohydrate,>99 ee%;S-asparagine monohydrate,∼94 ee%;88%total yield).Owing to a low detection limit of fluorescence,the addition amount was reduced to 0.03 wt%without remarkably compromising the ee values of both enantiomorphs.Due to the low addition amount and efficient synthesis,the output–input ratio was increased greatly.
基金National Natural Science Foundation of China,Grant/Award Numbers:21875036,22135004Open Fund of theKeyLab of Organic Optoelec-tronics&Molecular EngineeringInnovation and Technology Commission,Grant/Award Number:ITC-CNERC14SC01。
文摘Light has been sought and explored by human since ancient times.As the most important form of light,fluorescence is significant to applications in bioimaging and optoelectronic devices.However,fluorescence quenching problem constitutes a serious bottleneck in materials creation.Inspired from the core–shell structure in nature,we report an effective strategy to overcome this long-standing problem by utilizing a molecular core–shell structure.With an emissive core and multifunctional shell fragments,these compounds show aggregation-induced delayed fluorescence(AIDF)properties by restricting singlet oxygen(^(1)O_(2))generation and suppressing the triplet–triplet annihilation(TTA).Protected by the functional shell,the aggregation-induced emission luminogens(AIEgens)exhibit strong emission with high photoluminescent quantum yield and exciton utilization.Furthermore,because the shell materials can form exciplex with electron-transport materials,the fully solution-processed organic light-emitting diodes(OLEDs)based on these core–shell materials show low turnon voltages,excellent device performance with current efficiency of 61.4 cd A–1 and power efficiency of 42.8 lm W–1,which is a record-breaking efficiency based on all-solution processed organic multilayer systems among the AIE-OLEDs so far.This simple visualization strategy based on molecular core–shell structure provides a promising platform for AIEgens used in the fully wet-processed optoelectronic field.
基金This work was partially supported by the National Natural Science Foundation of China(Nos.21702016,21905015 and 52003023)the Fund of the Beijing National Laboratory for Molecular Sciences,China(No.BNLMS201813).B.Z.Tang acknowledges the financial support from the National Natural Science Foundation of China(No.21788102)+1 种基金the Research Grants Council of Hong Kong(Nos.N_HKUT609/19,16305518,and C6009-17G)the Innovation and Technology Commission(No.ITC-CNERC14SC01).
文摘The development of fluorescent nanocrystals based on organic small molecules is of great importance in bioimaging due to the merits of easy modification,high brightness and excellent photostability,however suffering from the emission-detrimental aggregation-caused quenching(ACQ)effect.Herein,we successfully designed and synthesized an AIE-active di(N,N-dimethylaniline)-dibenzofulvene(named as NFTPE),which exhibits the crystallization-induced emission enhancement(CIEE)effect.Interestingly,two types of yellow-and orange-emissive crystals for NFTPE were obtained,exhibiting aggregation microenvironment-dependent emission tuning in the solid state.Single-crystal analysis and density functional theory(DFT)calculations reveal that different aggregation microenvironments result in the distinct molecular conformation for various emission.Excitingly,the crystallization of NFTPE in an aqueous solution under the assistance of amphiphilic PEG polymer matrices could be monitored in situ by the fluorescence changes,facilitating the preparation of NFTPE nanocrystals(NFTPE-NCs)by adjusting the aggregation microenvironment.The obtained NFTPE-NCs exhibit the superior performance in cell imaging in respect to high brightness,photostability,and biocompatibility,thus demonstrating the potential in bioimaging applications.
基金This work was supported by the National Natural Science Foundation of China(Nos.21975197,21674085,51603165)the Young Talent Fund of University Association for Science and Technology in Shaanxi Province,China(No.20180601)+3 种基金the Natural Science Basic Research Plan in Shaanxi Province of China(No.2019JM-040)the Key Laboratory Construction Program of Xi’an Municipal Bureau of Science and Technology,China(No.201805056ZD7CG40)the Innovation Capability Support Program of Shaanxi Province,China(Nos.2018PT-28,2019PT-05)school of Materials Science and Engineering,Jiangsu Engineering Laboratory of Light-Electricity-Heart Energy-coverting Materials and Applications,China(No.GDRGCS2019001).
文摘Aggregation-induced emission(AIE)luminogens(AIEgens)with high brightness in aggregates exhibit great potentials in biological imaging,but these AIEgens are seldom applied in super-resolution biological imaging,especially in the imaging by using the structural illumination microscope(SIM).Based on this consideration,we synthesized the donor-acceptor typed AIEgen of DTPA-BTN,which not only owns high brightness in the near-infrared(NIR)emission region from 600 nm to 1000 nm(photoluminescence quantum yield,PLQYs=11.35%),but also displays excellent photo-stability.In addition,AIE nanoparticles based on 4,7-ditriphenylamine-[1,2,5]-thiadiazolo[3,4-c]pyridine(DTPA-BTN)were also prepared with highly emissive features and excellent biocompatibility.Finally,the developed DTPA-BTN-based AIE nanoparticles were applied in the super-resolution cellular imaging via SIM,where much smaller full width at half-maximum values and high signal to noise ratios were obtained,indicating the superior imaging resolution.The results here imply that highly emissive AIEgens or AIE nanoparticles can be promising imaging agents for super-resolution imaging via SIM.
基金This work is supported by the National Natural Science Foundation of China(Nos.21788102,21525417)the Natural Science Foundation of Guangdong Province,China(Nos.2019B030301003,2016A030312002)the Innovation and Technology Commission of Hong Kong,China(No.ITC-CNERC14S01).
文摘Aggregation-induced emission(AIE)has emerged as a new concept,giving highly efficient solid-state photoluminescence.Particularly,AIE luminogens(AIEgens)with deep blue emission(400–450 nm)have displayed salient advantages for non-doped organic light-emitting diodes(OLEDs).However,deep blue emitters with Commission Internationale de L’Eclairage(CIE)coordinates less than 0.08 are still rare.In this review,we outline the latest achievements in the molecular guidelines based on the AIE core of tetraphenylbenzene(TPB)for developing efficient deep blue AIEgens.We provide insights into the construction of deep blue emitters with high horizontal orientation by regulating the length of the linear molecule.We also discuss the luminescence mechanisms of these AIEgens-based OLEDs by using the magnetic field effects measurements.Finally,a summary of the challenges and perspectives of deep blue AIEgens for non-doped OLEDs is also presented.
基金This work was supported by the National Natural Science Foundation of China(No.21905197)the Starting Grants of Tianjin University and Tianjin Government,China.
文摘The research of photo-responsive materials,with changed absorption and emission under light stimulus,has drawn more and more attention due to their wide applications.However,most of them suffered from the notorious aggregation-caused quenching(ACQ)effect,which often led to the unconspicuous luminescent change in photo-responsive process.To solve this problem,the strategy of combining aggregation-induced emission(AIE)and photochromic properties was utilized,which largely enriched the phenomenon and application of photo-responsive materials.This short review summarized the recent progress of photo-responsive AIE materials with changed UV absorbance or PL phenomenon under UV-irradiation,including the types of molecular structures,internal mechanisms and the practical applications.Also,some outlooks were given on the further exploration of this field at the end of this paper.
基金supported by the National Natural Science Foundation of China(No.81773352)the China Scholarship Council(No.201703170071)。
文摘The role of point-of-care(POC)diagnostics is important in public health.With the support of smartphones,POC diagnostic technologies can be greatly improved.This opportunity has arisen from not only the large number and fast spread of cell-phones across the world but also their improved imaging/diagnostic functions.As a tool,the smartphone is regarded as part of a compact,portable,and low-cost system for real-time POC,even in areas with few resources.By combining near-infrared(NIR)imaging,measurement,and spectroscopy techniques,pathogens can be detected with high sensitivity.The whole process is rapid,accurate,and low-cost,and will set the future trend for POC diagnostics.In this review,the development of smartphone-based NIR fluorescent imaging technology was described,and the quality and potential of POC applications were discussed.
