A novel wate r-soluble red-emissive AIE fluorescence probe for cysteine(Cys) in situ was prepared and the performance of selectivity and sensitivity has been carefully investigated in this study.The probe was establis...A novel wate r-soluble red-emissive AIE fluorescence probe for cysteine(Cys) in situ was prepared and the performance of selectivity and sensitivity has been carefully investigated in this study.The probe was established on the electrostatic interaction of sulfonate functionalized tetraphenylethene(TPE) and polycation generated by the reaction between a polymer bearing dinitrobenzenesulfonate groups and Cys.From the experimental results,it was easy to distinguish Cys from glutathione(GSH) and homocysteine(Hcy) with a detection limit of 73 nmol/L.The assay system also possessed strong antiinterference ability against multitudinous amino acids.The Stokes shift was 142 nm and the emission ranged from 550 nm to 850 nm.In addition,double responses in fluorescence and ultraviolet-visible spectra also make the red-emissive assay ideal for sensitive detection and quantification of Cys for most purposes,especially in-situ monitoring of Cys in aqueous medium.展开更多
Carbon dots(CDs)are prepared through a simple one-step hydrothermal treatment of o-phenylendiamine(OPD)and show yellow photoluminescent(PL)emission under the ultraviolet excitation,which can be further enhanced by Cu2...Carbon dots(CDs)are prepared through a simple one-step hydrothermal treatment of o-phenylendiamine(OPD)and show yellow photoluminescent(PL)emission under the ultraviolet excitation,which can be further enhanced by Cu2+ions owing to Cu2+ions induced aggregation of OPD-CDs through the coordination of Cu2+with amino groups on the surface of OPD-CDs.The aggregation induced emission enhancement(AIEE)property enables it feasible to develop a simple,sensitive and selective method to detect environmental and intracellular copper(Ⅱ)ions.The limit of detection as lowas 0.28μmol/L(3σ/k)and a dynamic range from 0.5μmol/L to 40μmol/L make it veryeasy to detect the copper content inwater samples,such as river closure reservoir.Furthermore,fluorescence imaging of intracellular Cu2+suggests that the AIEE features of OPD-CDs specific to Cu2+ions can be also applied in biological systems.展开更多
Four derivatives of 9,10-bis[2-（2-alkoxynaphthalen-1-yl）vinyl]anthracene（BNAs） were designed,successfully synthesized and characterized by spectrofluorometer, powder wide-angle X-ray diffraction（PXRD） and differ...Four derivatives of 9,10-bis[2-（2-alkoxynaphthalen-1-yl）vinyl]anthracene（BNAs） were designed,successfully synthesized and characterized by spectrofluorometer, powder wide-angle X-ray diffraction（PXRD） and differential scanning calorimetry experiments（DSC）, etc. It was found that these compounds exhibited aggregation-induced emission phenomenon. Moreover, these target compounds displayed reversible color change from yellow to orange upon pressing and annealing process. Interestingly, all of BNAs obviously presented red-shifted piezofluorochromic（PFC） properties and behaved mainly length dependence of alkoxy group, in which, BNA displayed the largest PFC spectral shift（DlPFC= 26 nm）. The PXRD profiles demonstrated the transformation from crystalline to amorphous state upon grinding, and the mechanism of PFC behaviors was proposed. Thus, changing the length of alkoxyl chain could be an alternative way to tune their PFC behaviors.展开更多
Macrocyclic hosts play a crucial role in supramolecular chemistry and the development of supramolecular functional materials.Their well-defined cavities and diverse host-vip interactions endow macrocycles with excel...Macrocyclic hosts play a crucial role in supramolecular chemistry and the development of supramolecular functional materials.Their well-defined cavities and diverse host-vip interactions endow macrocycles with excellent stimuli responsiveness,facilitating efficient assembly construction.However,the limited availability of functional groups in conventional macrocycles restricts their ability to meet the demand for fabricating materials with multiple functionalities.To address this limitation,several research groups have introduced tetraphenylethylene(TPE),a well-known building block renowned for its remarkable aggregation-induced emission(AIE)effect,into the macrocycle framework.Herein,this paper summarizes the combination strategies and synergistic approaches that achieve multi-functionality by integrating TPE and macrocyclic architectures.The emission characteristics of TPE-embedded macrocycles are elucidated,and it is anticipated that more AIE-type macrocycles with innovative backbones and broad applications will emerge.展开更多
Traditional fluorescent emitters cannot eff ectively utilize triplet excitons owing to the spin statistical limitation, thus their electrochemiluminescence(ECL) efficiency(Φ_(ECL)) is relatively low. Improving the ut...Traditional fluorescent emitters cannot eff ectively utilize triplet excitons owing to the spin statistical limitation, thus their electrochemiluminescence(ECL) efficiency(Φ_(ECL)) is relatively low. Improving the utilization efficiency of triplet excitons is of great significance for developing efficient luminescent materials. Here we designed a hot exciton molecule(NZ2TPA) containing highly efficient chromophore naphthothiadiazole as an electron acceptor and triphenylamine(TPA) with aggregation induced emission(AIE) property as the strong electron donor to synthesize an ECL nanoemitter-NZ2TPA nanoparticles(NT NPs). The hybridized local and charge-transfer(HLCT) excited state of NZ2TPA achieved a high exciton utilization through the reverse intersystem crossing from higher triplet states( h RISC). The combination of HLCT and AIE characteristics endowed NT NPs with superior ΦECLover other nanoemitters, which provided an excellent material for the design of highly sensitive ECL biosensors. Using alkaline phosphatase(ALP) as an analyte model, a “signal-on” ECL biosensing approach was constructed by combining the quenching of manganese dioxide nanosheets(MnO_(2)NSs) on ECL emission of NT NPs and the reduction of MnO_(2)by ascorbic acid produced from ALP-catalyzed dephosphorylation, which showed a detectable range of 0.004-400 U/L with a detection limit of 0.57 mU/L. The excellent performance demonstrated the immense potential of organic nanomaterials through combining HLCT and AIE properties to improve ΦECL.展开更多
The aggregation process plays a significant role in regulating the aggregate structures from molecules toward macroscopic photophysical properties.Pyrene(Py),as the simplest dimer candidate,serves as a suitable model ...The aggregation process plays a significant role in regulating the aggregate structures from molecules toward macroscopic photophysical properties.Pyrene(Py),as the simplest dimer candidate,serves as a suitable model for studying the aggregation.Herein,a series of Py-based aggregation-induced emission(AIE)materials have been investigated by clarifying the comprehensive roles of oxygen,substituents,molecular motion,and packing during aggregation,initially realizing the aim of controlling aggregate structures.With a largely planar and conjugated conformation,Py shows anomalous AIE characteristics due to the oxygen quenching at the molecular level but turn-on fluorescence in the aggregate state because of the oxygen isolation.Although introducing substituents induces molecular motion and similarly weakened luminescence in the molecular state,the impact of substituents on the aggregate-state photophysical properties enormously differs,exhibiting from weak blue,strong cyan,and strong green to weak yellow emissions,due to variable aggregate structures.Interestingly,the natural alicycle-substituted Py-dehydroabietylamine(Py-DAA)exhibits both mechanochromism and acidichromism,which can be synergistically applied in dynamic encryption-decryption.This work not only elucidates the unique AIE property of Py for the first time but also clarifies the bridging role of aggregation between single-molecular and aggregate states,achieving preliminary control over the aggregate structures.展开更多
Fluorescence(FL)active 8-aryl guanosine derivatives were prepared and applied for cation mediated self-assembly to form the H-bonded G_(8)-quadruplexes.The p-cyano(p-CN)and 8-anthracene(8-An)substituted guanosines wer...Fluorescence(FL)active 8-aryl guanosine derivatives were prepared and applied for cation mediated self-assembly to form the H-bonded G_(8)-quadruplexes.The p-cyano(p-CN)and 8-anthracene(8-An)substituted guanosines were identified to give the strongest fluorescence with the formation of G_(8)-octamers(G_(8))both in solution(NMR)and solid state(X-ray).This well-defined G_(8)-octamer system has provided the first direct evidence on the self-assembled G-quadruplex fluorescence emission with aggregation-induced emission(AIE),which could be applied as the foundation for FL molecular probe design toward G-quadruplex recognition.展开更多
The development of novel photosensitizers(PSs)with aggregation-induced emission(AIE)properties has emerged as a crucial advancement in the field of photodynamic therapy(PDT).However,the versatile applications of AIE P...The development of novel photosensitizers(PSs)with aggregation-induced emission(AIE)properties has emerged as a crucial advancement in the field of photodynamic therapy(PDT).However,the versatile applications of AIE PSs are limited by low encapsulation efficiency and inadequate target tissue permeability.Biomimetic technology stands out as a promising strategy to overcome these challenges,aiming to enhance AIE PSs tumor penetration efficacy,and their association with antitumor immune responses.In this review,recent advancements in biomimetic AIE PSs for PDT and immunotherapy are summarized.We start with introducing strategies involving biomimetic AIE PSs based on cell membranes and extracellular vesicles for the combined application of PDT and immunotherapy.We then discuss the preparation of biomimetic AIE PSs nanoparticles.Finally,we briefly outline the challenges and prospects associated with biomimetic AIE PSs.展开更多
AIEgens can serve as an effective platform for the construction of photosensitizer-based immunogenic cell death(ICD)inducers.To date,several mitochondria or endoplasmic reticulum(ER)-targeted aggregationinduced emissi...AIEgens can serve as an effective platform for the construction of photosensitizer-based immunogenic cell death(ICD)inducers.To date,several mitochondria or endoplasmic reticulum(ER)-targeted aggregationinduced emission(AIE)molecules have been developed and have evoked massive ICD in cells.However,due to the complex physicochemical environment in cells,these small AIE molecules cannot maintain a stable aggregate state,which not only affects the fluorescence intensity of the photosensitizer but also decreases the generation of reactive oxygen species(ROS),and thus reducing the effect of the photosensitizer to elicit ICD.AIEgen-based nanomicelles,which maintain a stable micellar structure,can prevent defects of AIE molecules in photodynamic therapy(PDT)applications.Therefore,in this study,a mitochondria-targeted AIE nanophotosensitizer was synthesized and used as a highly potent ICD inducer for vaccine preparation and tumor prevention.展开更多
Parathyroid hormone (PTH) is an important factor in maintaining blood calcium levels in the human body. Therefore, monitoring PTH levels is essential for assessing the various diseases progression and managing overall...Parathyroid hormone (PTH) is an important factor in maintaining blood calcium levels in the human body. Therefore, monitoring PTH levels is essential for assessing the various diseases progression and managing overall health. In this study, a fluorescence and optical sensor based on an aggregation-induced emissive liquid crystal photopolymer (AIE-LC-Poly) film was established for the qualitative and quantitative detection of PTH. The specific interaction between PTH and anti-PTH on the substrate surface was utilized, and variations in orientation and aggregation state of the fluorescent LCs were evaluated by both optic and fluorescent means. The detection limit for PTH using optical image was above 10 µg/mL, while fluorescence detection achieved a much lower limit of 1 ng/mL. Additionally, the photopolymer further amplified the detection signals by strengthening the AIE effect of the fluorescent LCs in initiate state, and enhancing the disturbance of LCs ordered orientation upon PTH addition. Ultimately, the detection limits for PTH were reduced to 0.01 µg/mL for optical detection and 50 pg/mL for fluorescence detection. The quantitative and sensitive AIE-LC-Poly biosensing technology presented here sets the stage to develop LC-based sensor for biomedical applications without labeling.展开更多
Comprehensive Summary Currently,solid-state fluorescent carbonized polymer dots(CPDs)have attracted attention increasingly due to their applications for optoelectronic display.However,designing CPDs possessing solid-s...Comprehensive Summary Currently,solid-state fluorescent carbonized polymer dots(CPDs)have attracted attention increasingly due to their applications for optoelectronic display.However,designing CPDs possessing solid-state fluorescence and clarifying the fluorescence mechanism remain challenging.Herein,we initially synthesized a novel type of polythiophene derivatives CPDs,poly-4,4’-(thiophene-3,4-diyl)dibenzoic acid carbonized polymer dots(PDBA-CPDs)with solid-state fluorescence.Subsequently,the structural and optical characterization revealed that the solid-state fluorescence originated from the aggregation induced emission of the CPDs.In brief,in aggregation state,the remaining polymer structure groups on the surface of the CPDs overlapped and weakened the non-radiative transition,enhancing solid-state fluorescence emission.Thirdly,three polythiophene-derived CPDs were designed to further demonstrate the aggregation induced solid-state fluorescence mechanism.Finally,owing to their unique properties of solid-state fluorescence,the white LEDs(light emitting diodes)were fabricated with high color rendering index(CRI)of 82.7 and CIE coordinates of(0.37,0.39)using commercial 460 nm chip.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
Theranostic systems by integrating the tumor imaging and tumor therapeutic capabilities into one platform have attracted numerous attentions from worldwide researchers.Despite the great developments,their clinical app...Theranostic systems by integrating the tumor imaging and tumor therapeutic capabilities into one platform have attracted numerous attentions from worldwide researchers.Despite the great developments,their clinical application is still in the nascent stage,owing to the unsatisfied imaging quality and limited therapeutic efficacy.Fortunately,the emerging of aggregation-induced emission(AIE)molecules with unique fluorescence property offers an opportunity to solve the imaging problem.Besides,further utilizing the tumor microenvironments and external triggers to design the stimuli-responsive imaging-guided therapy could enhance the therapeutic efficacy and reduce the side effects.In this review,the advancements in stimuli-responsive theranostic systems with AIE characteristics are summarized.Theranostic systems are first classified according to their treatment modes,and then subdivided based on various stimuli,including pH,redox,enzyme,and light.In each section,the design strategies and application examples are introduced.At last,the current state of the art,limitations,as well as prospects are also discussed.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
A new chiral bromobinaphthol-pyrene compound was developed to achieve a green circularly polarized luminescence(CPL)from its excimer with a dissymmetry factor(|glum|)value of 4.3×10^-3 and a high quantum yieldΦF...A new chiral bromobinaphthol-pyrene compound was developed to achieve a green circularly polarized luminescence(CPL)from its excimer with a dissymmetry factor(|glum|)value of 4.3×10^-3 and a high quantum yieldΦF,solid up to 55.9%,while no CPL signals could be observed for the blue luminescence from unimolecule.Meanwhile,reversal CPL signals can be observed from both concentrated solution and solid.展开更多
Since the discovery of aggregation induced emission(AIE)phenomenon,various stimuli-responsive materials have been rapidly developed,but there are still great challenges in the application of ink printing due to the ba...Since the discovery of aggregation induced emission(AIE)phenomenon,various stimuli-responsive materials have been rapidly developed,but there are still great challenges in the application of ink printing due to the bad water solubility.In this research,a new cationic amphiphilic TPE-functionalized pyridine salt(TPE-OTs)was designed,which shows good water solubility and hydrochromic properties.The optical properties of the compound have been studied,which is equipped with the typical AIEE characteristics and TICT effect.The compound can self-assemble to form aggregates with a particle size of about 30 nm in water.What is more,the compound is responsive to the environmental humidity,whose fluorescent color changes from green to yellow as the humidity gradually increased.Based on this characteristic,we applied it to the fluorescent anti-counterfeiting ink,realizing the protection and encryption of information.展开更多
Supramolecular chemistry has received considerable attention in host-vip recognition.The structureresponse relationship of host-vip recognition system is a meaningful issue.Herein,a series of tripodal nitrogen mus...Supramolecular chemistry has received considerable attention in host-vip recognition.The structureresponse relationship of host-vip recognition system is a meaningful issue.Herein,a series of tripodal nitrogen mustard derivatives(TMs)have been developed in this paper.By rationally design the intramolecular alkyl chain lengths of host,the host-vip binding model have been successfully tuned,which underwent a transformation fromπ-πto multiple hydrogen bonds.This process enhances the host-vip binding force and recognition efficiency.展开更多
Chiral metal nanoclusters(MNCs)are competitive candidates for fabricating circularly polarized light-emitting diodes(CPLEDs),but the device performance is greatly limited by the poor emission of MNCs in solid thin fil...Chiral metal nanoclusters(MNCs)are competitive candidates for fabricating circularly polarized light-emitting diodes(CPLEDs),but the device performance is greatly limited by the poor emission of MNCs in solid thin films.Herein,host molecule enhanced aggregation induced emission(AIE)of MNCs is demonstrated for fabricating highly efficient CPLEDs.Namely,on the basis of the AIE effect of atomically precise enantiomeric(R/S)-4-phenylthiazolidine-2-thione capped silver(R/S-Ag_(6)(PTLT)_(6))NCs in solid thin films,1,3-bis(carbazol-9-yl)benzene(mCP)is introduced as a host molecule to control the orientation and packing arrangements of R/S-Ag_(6)(PTLT)_(6) NCs throughπ–πinteractions with the R/S-Ag_(6)(PTLT)_(6) NCs and further enhance the AIE.The as-fabricated Ag_(6)(PTLT)_(6) NC/mCP hybrid solid thin film shows a high photoluminescence quantum yield of 71.0%close to that of Ag_(6)(PTLT)_(6) NC single crystal.As the hybrid films are employed as the active emission layers of CPLEDs,mCP also suppresses the triplettriplet annihilation and balances the charge transport.Thus,the CPLEDs exhibit a maximum brightness of 3,906 cd/m^(2),peak external quantum efficiency of 10.0%,electroluminescence dissymmetry factors of−5.3×10^(−3)and 4.7×10^(−3).展开更多
Influence of intramolecular π-π interaction on the luminescent properties of thermally activated delayed fluorescence（TADF） molecule（3, 5-bis（3,6-di-tert-butyl-9 H-carbazol-9-yl）-phenyl）（pyridin-4-yl） methan...Influence of intramolecular π-π interaction on the luminescent properties of thermally activated delayed fluorescence（TADF） molecule（3, 5-bis（3,6-di-tert-butyl-9 H-carbazol-9-yl）-phenyl）（pyridin-4-yl） methanone（DTCBPY） is theoretically studied by using the density functional theory（DFT） and time-dependent density functional theory（TD-DFT）.Four conformations（named as A, B, C, and D） of the DTCBPY can be found by relax scanning, and the configuration C corresponds to the luminescent molecule detected experimentally. Besides, we calculate the proportion of each conformation by Boltzmann distribution, high configuration ratios（44% and 52%） can be found for C and D. Moreover, C and D are found to exist with an intramolecular π-π interaction between one donor and the acceptor; the intramolecular interaction brings a smaller Huang-Rhys factor and reduced reorganization energy. Our work presents a rational explanation for the experimental results and demonstrates the importance of the intramolecular π-π interaction to the photophysical properties of TADF molecules.展开更多
Since the discovery of the triphenylmethyl(trityl)cation 120 years ago,a variety of aromatic cations having various colors and luminescence properties have been rigorously studied.Many,differently substituted trityl c...Since the discovery of the triphenylmethyl(trityl)cation 120 years ago,a variety of aromatic cations having various colors and luminescence properties have been rigorously studied.Many,differently substituted trityl cations have been synthesized,and their optical properties have been elucidated.However,the optical properties of the parent,non-substituted and highly reactive trityl cation,which was observed to be very weakly luminescent,have not been subjected to detailed investigation.In the effort described herein,we explored the optical nature of non-substituted trityl hexafluorophosphate(PF_(6))in the crystalline state.Trityl PF_(6) was found to exist as two crystal polymorphs including a yellow(Y)and an orange(O)form.Moreover,we observed that these crystalline forms display crystalline-state emission with different colors.The results of X-ray crystallographic analysis showed that the two polymorphs have totally different molecular packing arrangements.Furthermore,an investigation of their optical properties revealed that the O-crystal undergoes a distinct color change to yellow upon cooling as a consequence of a change in the nature of the charge transfer interaction between the cation and PF6 anion,and that both the Y-and O-crystal exhibit phosphorescence.展开更多
基金financial support from the National Key Research and Development Program of China (No. 2017YFA0701303)the National Natural Science Foundation of China (Nos.51873097 and 21674058)。
文摘A novel wate r-soluble red-emissive AIE fluorescence probe for cysteine(Cys) in situ was prepared and the performance of selectivity and sensitivity has been carefully investigated in this study.The probe was established on the electrostatic interaction of sulfonate functionalized tetraphenylethene(TPE) and polycation generated by the reaction between a polymer bearing dinitrobenzenesulfonate groups and Cys.From the experimental results,it was easy to distinguish Cys from glutathione(GSH) and homocysteine(Hcy) with a detection limit of 73 nmol/L.The assay system also possessed strong antiinterference ability against multitudinous amino acids.The Stokes shift was 142 nm and the emission ranged from 550 nm to 850 nm.In addition,double responses in fluorescence and ultraviolet-visible spectra also make the red-emissive assay ideal for sensitive detection and quantification of Cys for most purposes,especially in-situ monitoring of Cys in aqueous medium.
基金financially supported by the National Natural Science Foundation of China(NSFC,No.21535006)
文摘Carbon dots(CDs)are prepared through a simple one-step hydrothermal treatment of o-phenylendiamine(OPD)and show yellow photoluminescent(PL)emission under the ultraviolet excitation,which can be further enhanced by Cu2+ions owing to Cu2+ions induced aggregation of OPD-CDs through the coordination of Cu2+with amino groups on the surface of OPD-CDs.The aggregation induced emission enhancement(AIEE)property enables it feasible to develop a simple,sensitive and selective method to detect environmental and intracellular copper(Ⅱ)ions.The limit of detection as lowas 0.28μmol/L(3σ/k)and a dynamic range from 0.5μmol/L to 40μmol/L make it veryeasy to detect the copper content inwater samples,such as river closure reservoir.Furthermore,fluorescence imaging of intracellular Cu2+suggests that the AIEE features of OPD-CDs specific to Cu2+ions can be also applied in biological systems.
基金financial support from the National Natural Science Foundation of China(No.21576194)
文摘Four derivatives of 9,10-bis[2-（2-alkoxynaphthalen-1-yl）vinyl]anthracene（BNAs） were designed,successfully synthesized and characterized by spectrofluorometer, powder wide-angle X-ray diffraction（PXRD） and differential scanning calorimetry experiments（DSC）, etc. It was found that these compounds exhibited aggregation-induced emission phenomenon. Moreover, these target compounds displayed reversible color change from yellow to orange upon pressing and annealing process. Interestingly, all of BNAs obviously presented red-shifted piezofluorochromic（PFC） properties and behaved mainly length dependence of alkoxy group, in which, BNA displayed the largest PFC spectral shift（DlPFC= 26 nm）. The PXRD profiles demonstrated the transformation from crystalline to amorphous state upon grinding, and the mechanism of PFC behaviors was proposed. Thus, changing the length of alkoxyl chain could be an alternative way to tune their PFC behaviors.
基金the National Natural Science Foundation of China(No.22271154)the Science Fund for Distinguished Young Scholars of Jiangsu Province(No.BK20240078).
文摘Macrocyclic hosts play a crucial role in supramolecular chemistry and the development of supramolecular functional materials.Their well-defined cavities and diverse host-vip interactions endow macrocycles with excellent stimuli responsiveness,facilitating efficient assembly construction.However,the limited availability of functional groups in conventional macrocycles restricts their ability to meet the demand for fabricating materials with multiple functionalities.To address this limitation,several research groups have introduced tetraphenylethylene(TPE),a well-known building block renowned for its remarkable aggregation-induced emission(AIE)effect,into the macrocycle framework.Herein,this paper summarizes the combination strategies and synergistic approaches that achieve multi-functionality by integrating TPE and macrocyclic architectures.The emission characteristics of TPE-embedded macrocycles are elucidated,and it is anticipated that more AIE-type macrocycles with innovative backbones and broad applications will emerge.
基金funded by by National Natural Science Foundation of China (21890741,21827812)。
文摘Traditional fluorescent emitters cannot eff ectively utilize triplet excitons owing to the spin statistical limitation, thus their electrochemiluminescence(ECL) efficiency(Φ_(ECL)) is relatively low. Improving the utilization efficiency of triplet excitons is of great significance for developing efficient luminescent materials. Here we designed a hot exciton molecule(NZ2TPA) containing highly efficient chromophore naphthothiadiazole as an electron acceptor and triphenylamine(TPA) with aggregation induced emission(AIE) property as the strong electron donor to synthesize an ECL nanoemitter-NZ2TPA nanoparticles(NT NPs). The hybridized local and charge-transfer(HLCT) excited state of NZ2TPA achieved a high exciton utilization through the reverse intersystem crossing from higher triplet states( h RISC). The combination of HLCT and AIE characteristics endowed NT NPs with superior ΦECLover other nanoemitters, which provided an excellent material for the design of highly sensitive ECL biosensors. Using alkaline phosphatase(ALP) as an analyte model, a “signal-on” ECL biosensing approach was constructed by combining the quenching of manganese dioxide nanosheets(MnO_(2)NSs) on ECL emission of NT NPs and the reduction of MnO_(2)by ascorbic acid produced from ALP-catalyzed dephosphorylation, which showed a detectable range of 0.004-400 U/L with a detection limit of 0.57 mU/L. The excellent performance demonstrated the immense potential of organic nanomaterials through combining HLCT and AIE properties to improve ΦECL.
基金supported by the National Natural Science Foundation of China(21601087)the Natural Science Foundation of Jiangsu Province(BK20231296)+3 种基金the Open Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates,Guangzhou 510640,China(South China University of Technology[2023B1212060003])the Shenzhen Key Laboratory of Functional Aggregate Materials(ZDSYS20211021111400001)the Science Technology Innovation Commission of Shenzhen Municipality(KQTD20210811090142053)the Key Research and Development Project of Yunnan Province(202303AC100010).
文摘The aggregation process plays a significant role in regulating the aggregate structures from molecules toward macroscopic photophysical properties.Pyrene(Py),as the simplest dimer candidate,serves as a suitable model for studying the aggregation.Herein,a series of Py-based aggregation-induced emission(AIE)materials have been investigated by clarifying the comprehensive roles of oxygen,substituents,molecular motion,and packing during aggregation,initially realizing the aim of controlling aggregate structures.With a largely planar and conjugated conformation,Py shows anomalous AIE characteristics due to the oxygen quenching at the molecular level but turn-on fluorescence in the aggregate state because of the oxygen isolation.Although introducing substituents induces molecular motion and similarly weakened luminescence in the molecular state,the impact of substituents on the aggregate-state photophysical properties enormously differs,exhibiting from weak blue,strong cyan,and strong green to weak yellow emissions,due to variable aggregate structures.Interestingly,the natural alicycle-substituted Py-dehydroabietylamine(Py-DAA)exhibits both mechanochromism and acidichromism,which can be synergistically applied in dynamic encryption-decryption.This work not only elucidates the unique AIE property of Py for the first time but also clarifies the bridging role of aggregation between single-molecular and aggregate states,achieving preliminary control over the aggregate structures.
基金the National Natural Science Founda-tion(No.CHE-1665122)the National Institutes of Health(No.1R01GM 120240-01)for financial support.
文摘Fluorescence(FL)active 8-aryl guanosine derivatives were prepared and applied for cation mediated self-assembly to form the H-bonded G_(8)-quadruplexes.The p-cyano(p-CN)and 8-anthracene(8-An)substituted guanosines were identified to give the strongest fluorescence with the formation of G_(8)-octamers(G_(8))both in solution(NMR)and solid state(X-ray).This well-defined G_(8)-octamer system has provided the first direct evidence on the self-assembled G-quadruplex fluorescence emission with aggregation-induced emission(AIE),which could be applied as the foundation for FL molecular probe design toward G-quadruplex recognition.
基金Ministry of Education Academic Research Fund Tier 1,Grant/Award Number:A-0009304-00-00Sichuan Science and Technology Program,Grant/Award Number:2022NSFSC1269。
文摘The development of novel photosensitizers(PSs)with aggregation-induced emission(AIE)properties has emerged as a crucial advancement in the field of photodynamic therapy(PDT).However,the versatile applications of AIE PSs are limited by low encapsulation efficiency and inadequate target tissue permeability.Biomimetic technology stands out as a promising strategy to overcome these challenges,aiming to enhance AIE PSs tumor penetration efficacy,and their association with antitumor immune responses.In this review,recent advancements in biomimetic AIE PSs for PDT and immunotherapy are summarized.We start with introducing strategies involving biomimetic AIE PSs based on cell membranes and extracellular vesicles for the combined application of PDT and immunotherapy.We then discuss the preparation of biomimetic AIE PSs nanoparticles.Finally,we briefly outline the challenges and prospects associated with biomimetic AIE PSs.
基金supported by the National Natural Science Foundation of China(Nos.52173137 and 51873163).
文摘AIEgens can serve as an effective platform for the construction of photosensitizer-based immunogenic cell death(ICD)inducers.To date,several mitochondria or endoplasmic reticulum(ER)-targeted aggregationinduced emission(AIE)molecules have been developed and have evoked massive ICD in cells.However,due to the complex physicochemical environment in cells,these small AIE molecules cannot maintain a stable aggregate state,which not only affects the fluorescence intensity of the photosensitizer but also decreases the generation of reactive oxygen species(ROS),and thus reducing the effect of the photosensitizer to elicit ICD.AIEgen-based nanomicelles,which maintain a stable micellar structure,can prevent defects of AIE molecules in photodynamic therapy(PDT)applications.Therefore,in this study,a mitochondria-targeted AIE nanophotosensitizer was synthesized and used as a highly potent ICD inducer for vaccine preparation and tumor prevention.
基金supported by the National Natural Science Foundation of China(No.51973007).
文摘Parathyroid hormone (PTH) is an important factor in maintaining blood calcium levels in the human body. Therefore, monitoring PTH levels is essential for assessing the various diseases progression and managing overall health. In this study, a fluorescence and optical sensor based on an aggregation-induced emissive liquid crystal photopolymer (AIE-LC-Poly) film was established for the qualitative and quantitative detection of PTH. The specific interaction between PTH and anti-PTH on the substrate surface was utilized, and variations in orientation and aggregation state of the fluorescent LCs were evaluated by both optic and fluorescent means. The detection limit for PTH using optical image was above 10 µg/mL, while fluorescence detection achieved a much lower limit of 1 ng/mL. Additionally, the photopolymer further amplified the detection signals by strengthening the AIE effect of the fluorescent LCs in initiate state, and enhancing the disturbance of LCs ordered orientation upon PTH addition. Ultimately, the detection limits for PTH were reduced to 0.01 µg/mL for optical detection and 50 pg/mL for fluorescence detection. The quantitative and sensitive AIE-LC-Poly biosensing technology presented here sets the stage to develop LC-based sensor for biomedical applications without labeling.
基金the National Natural Science Foundation of China(Grant Nos.52272052,51972315,21873110,and 61720106014).
文摘Comprehensive Summary Currently,solid-state fluorescent carbonized polymer dots(CPDs)have attracted attention increasingly due to their applications for optoelectronic display.However,designing CPDs possessing solid-state fluorescence and clarifying the fluorescence mechanism remain challenging.Herein,we initially synthesized a novel type of polythiophene derivatives CPDs,poly-4,4’-(thiophene-3,4-diyl)dibenzoic acid carbonized polymer dots(PDBA-CPDs)with solid-state fluorescence.Subsequently,the structural and optical characterization revealed that the solid-state fluorescence originated from the aggregation induced emission of the CPDs.In brief,in aggregation state,the remaining polymer structure groups on the surface of the CPDs overlapped and weakened the non-radiative transition,enhancing solid-state fluorescence emission.Thirdly,three polythiophene-derived CPDs were designed to further demonstrate the aggregation induced solid-state fluorescence mechanism.Finally,owing to their unique properties of solid-state fluorescence,the white LEDs(light emitting diodes)were fabricated with high color rendering index(CRI)of 82.7 and CIE coordinates of(0.37,0.39)using commercial 460 nm chip.
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National Key R&D Program of China,Grant/Award Number:2020YFA0211200)National Natural Science Foundation of China,Grant/Award Numbers:21722507,21525523,21974128,21874121,52003257Natural Science Foundation of Hubei Province,Grant/Award Number:2019CFA043。
文摘Theranostic systems by integrating the tumor imaging and tumor therapeutic capabilities into one platform have attracted numerous attentions from worldwide researchers.Despite the great developments,their clinical application is still in the nascent stage,owing to the unsatisfied imaging quality and limited therapeutic efficacy.Fortunately,the emerging of aggregation-induced emission(AIE)molecules with unique fluorescence property offers an opportunity to solve the imaging problem.Besides,further utilizing the tumor microenvironments and external triggers to design the stimuli-responsive imaging-guided therapy could enhance the therapeutic efficacy and reduce the side effects.In this review,the advancements in stimuli-responsive theranostic systems with AIE characteristics are summarized.Theranostic systems are first classified according to their treatment modes,and then subdivided based on various stimuli,including pH,redox,enzyme,and light.In each section,the design strategies and application examples are introduced.At last,the current state of the art,limitations,as well as prospects are also discussed.
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 National Natural Science Foundation of China(NSFC,Nos.21788102,21722603 and 21871083)Shanghai Municipal Science and Technology Major Project(No.2018SHZDZX03)+2 种基金‘Shu Guang’Project supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation(No.19SG26)the Innovation Program of Shanghai Municipal Education Commission(No.2017-01-07-00-02-E00010)the Fundamental Research Funds for the Central Universities。
文摘A new chiral bromobinaphthol-pyrene compound was developed to achieve a green circularly polarized luminescence(CPL)from its excimer with a dissymmetry factor(|glum|)value of 4.3×10^-3 and a high quantum yieldΦF,solid up to 55.9%,while no CPL signals could be observed for the blue luminescence from unimolecule.Meanwhile,reversal CPL signals can be observed from both concentrated solution and solid.
基金financially supported by the National Natural Science Foundation of China(Nos.52173102,21774070 and 21602124)Fluorine Silicone Materials Collaborative Fund of Shandong Provincial Natural Science Foundation(Nos.ZR2021LFG001,ZR2021LFG007)the Young Scholars Program of Shandong University(No.2018WLJH40)。
文摘Since the discovery of aggregation induced emission(AIE)phenomenon,various stimuli-responsive materials have been rapidly developed,but there are still great challenges in the application of ink printing due to the bad water solubility.In this research,a new cationic amphiphilic TPE-functionalized pyridine salt(TPE-OTs)was designed,which shows good water solubility and hydrochromic properties.The optical properties of the compound have been studied,which is equipped with the typical AIEE characteristics and TICT effect.The compound can self-assemble to form aggregates with a particle size of about 30 nm in water.What is more,the compound is responsive to the environmental humidity,whose fluorescent color changes from green to yellow as the humidity gradually increased.Based on this characteristic,we applied it to the fluorescent anti-counterfeiting ink,realizing the protection and encryption of information.
基金the support from the National Natural Science Foundation of China(Nos.22165027,22061039,22001214)Key R&D program of Gansu Province(No.21YF5GA066)Gansu Provincial Department of Education:Excellent Postgraduate“Innovation Star”Project(No.2021CXZX-184)。
文摘Supramolecular chemistry has received considerable attention in host-vip recognition.The structureresponse relationship of host-vip recognition system is a meaningful issue.Herein,a series of tripodal nitrogen mustard derivatives(TMs)have been developed in this paper.By rationally design the intramolecular alkyl chain lengths of host,the host-vip binding model have been successfully tuned,which underwent a transformation fromπ-πto multiple hydrogen bonds.This process enhances the host-vip binding force and recognition efficiency.
基金the National Natural Science Foundation of China(Nos.21902057 and 21773088)the China Postdoctoral Science Foundation(No.2021M691201)+1 种基金the Interdisciplinary Scientific Research Team Project of Jilin University(No.419021420367)the Special Project from MOST of China.
文摘Chiral metal nanoclusters(MNCs)are competitive candidates for fabricating circularly polarized light-emitting diodes(CPLEDs),but the device performance is greatly limited by the poor emission of MNCs in solid thin films.Herein,host molecule enhanced aggregation induced emission(AIE)of MNCs is demonstrated for fabricating highly efficient CPLEDs.Namely,on the basis of the AIE effect of atomically precise enantiomeric(R/S)-4-phenylthiazolidine-2-thione capped silver(R/S-Ag_(6)(PTLT)_(6))NCs in solid thin films,1,3-bis(carbazol-9-yl)benzene(mCP)is introduced as a host molecule to control the orientation and packing arrangements of R/S-Ag_(6)(PTLT)_(6) NCs throughπ–πinteractions with the R/S-Ag_(6)(PTLT)_(6) NCs and further enhance the AIE.The as-fabricated Ag_(6)(PTLT)_(6) NC/mCP hybrid solid thin film shows a high photoluminescence quantum yield of 71.0%close to that of Ag_(6)(PTLT)_(6) NC single crystal.As the hybrid films are employed as the active emission layers of CPLEDs,mCP also suppresses the triplettriplet annihilation and balances the charge transport.Thus,the CPLEDs exhibit a maximum brightness of 3,906 cd/m^(2),peak external quantum efficiency of 10.0%,electroluminescence dissymmetry factors of−5.3×10^(−3)and 4.7×10^(−3).
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11374195 and 21403133)Taishan Scholar Project of Shandong Normal University,China+1 种基金the Promotive Research Fund for Excellent Young and Middle-aged Scientists of Shandong Province,China(Grant No.BS2014cl001)the China Postdoctoral Science Foundation(Grant No.2014M560571)
文摘Influence of intramolecular π-π interaction on the luminescent properties of thermally activated delayed fluorescence（TADF） molecule（3, 5-bis（3,6-di-tert-butyl-9 H-carbazol-9-yl）-phenyl）（pyridin-4-yl） methanone（DTCBPY） is theoretically studied by using the density functional theory（DFT） and time-dependent density functional theory（TD-DFT）.Four conformations（named as A, B, C, and D） of the DTCBPY can be found by relax scanning, and the configuration C corresponds to the luminescent molecule detected experimentally. Besides, we calculate the proportion of each conformation by Boltzmann distribution, high configuration ratios（44% and 52%） can be found for C and D. Moreover, C and D are found to exist with an intramolecular π-π interaction between one donor and the acceptor; the intramolecular interaction brings a smaller Huang-Rhys factor and reduced reorganization energy. Our work presents a rational explanation for the experimental results and demonstrates the importance of the intramolecular π-π interaction to the photophysical properties of TADF molecules.
基金JSPSKAKENHI Grant-in-Aid for Scientific Research(C),Grant/Award Number:JP20K05475(Tomohiko Nishiuchi)Scientific Research(B),Grant/Award Number:JP21H01887(Kenji Kamada)。
文摘Since the discovery of the triphenylmethyl(trityl)cation 120 years ago,a variety of aromatic cations having various colors and luminescence properties have been rigorously studied.Many,differently substituted trityl cations have been synthesized,and their optical properties have been elucidated.However,the optical properties of the parent,non-substituted and highly reactive trityl cation,which was observed to be very weakly luminescent,have not been subjected to detailed investigation.In the effort described herein,we explored the optical nature of non-substituted trityl hexafluorophosphate(PF_(6))in the crystalline state.Trityl PF_(6) was found to exist as two crystal polymorphs including a yellow(Y)and an orange(O)form.Moreover,we observed that these crystalline forms display crystalline-state emission with different colors.The results of X-ray crystallographic analysis showed that the two polymorphs have totally different molecular packing arrangements.Furthermore,an investigation of their optical properties revealed that the O-crystal undergoes a distinct color change to yellow upon cooling as a consequence of a change in the nature of the charge transfer interaction between the cation and PF6 anion,and that both the Y-and O-crystal exhibit phosphorescence.
