Self-assembly ofπ-conjugated compounds into supramolecular polymers has received considerable attention because of their intrinsic scientific interests and technological applications.As compared toπ-conjugated rods,...Self-assembly ofπ-conjugated compounds into supramolecular polymers has received considerable attention because of their intrinsic scientific interests and technological applications.As compared toπ-conjugated rods,discotics,and macrocycles,propeller-shapedπ-conjugated molecules have been less exploited to form long-range-ordered supramolecular polymers.Herein a novel type of supramolecular polymers has been constructed on the basis of propeller-shaped triphenylamine cyanostilbenes.The designed compound adopts nucleation-elongation cooperative mechanism for the supramolecular polymerization process,because of the participation of three-fold hydrogen bonds between the neighbouring monomers.The supramolecular polymeric state displays amplified chirality and enhanced emission than those in the monomeric state.The resulting supramolecular polymers exhibit severe emission quenching upon addition of 2,6-dinitrotoluene,ascribed to photoinduced electron transfer from the triphenylamine cyanostilbenes to the explosive analyte.The current study proves the feasibility to supramolecular polymerize propeller-likeπ-conjugated molecules,serving as a promising type of explosive sensor owing to their guest encapsulation and signal amplification capabilities.展开更多
Precisely optimizing the morphology of functional hybrid polymeric systems is crucial to improve its photophysical property and further extend their optoelectronic applications. The physic-chemical property of polymer...Precisely optimizing the morphology of functional hybrid polymeric systems is crucial to improve its photophysical property and further extend their optoelectronic applications. The physic-chemical property of polymeric matrix in electrospinning (ES) processing is a key factor to dominate the condensed structure of these hybrid microstructures and further improve its functionality. Herein, we set a flexible poly(ethylene oxide) (PEO) as the matrix to obtain a series of polydiarylfluorenes (including PHDPF, PODPF and PNDPF) electrospun hybrid microfibers with a robust deep-blue emission. Significantly different from the rough morphology of their poly(N-vinylcarbazole) (PVK) ES hybrid fibers, polydiarylfluorenes/PEO ES fibers showed a smooth morphology and small size with a diameter of 1∼2 µm. Besides, there is a relatively weak phase separation under rapid solvent evaporation during the ES processing, associated with the hydrogen-bonded-assisted network of PEO in ES fibers. These relative “homogeneous” ES fibers present efficient deep-blue emission (PLQY>50%), due to weak interchain aggregation. More interestingly, low fraction of planar (β) conformation appears in the uniform PODPF/PEO ES fibers, induced by the external traction force in ES processing. Meanwhile, PNDPF/PEO ES fibers present a highest sensitivity than those of other ES fibers, associated with the smallest diameter and large surface area. Finally, compared to PODPF/PVK fibers and PODPF/PEO amorphous ES fibers, PODPF/PEO ES fibers obtained from DCE solution exhibit an excellent quenching behavior toward a saturated DNT vapor, mainly due to the synergistic effect of small size, weak separation, β-conformation formation and high deep-blue emission efficiency.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
A number of electron-rich heterocycles are studied as potential reagents for visual colorimetric detection of FOX-7 due to colored charge-transfer complexes formation.The obtained results suggest that pyrrole and pyri...A number of electron-rich heterocycles are studied as potential reagents for visual colorimetric detection of FOX-7 due to colored charge-transfer complexes formation.The obtained results suggest that pyrrole and pyrimidine derivatives can form such complexes playing the role of electron donors despite a low electrophilicity of FOX-7.Density functional theory calculations,as well as quantum theory of atoms in molecules analysis,suggest stacking binding mode as the most preferable one with the binding energy of about 21-36 kJ/mol.All the complexes demonstrate a clear single charge-transfer absorption band in the visible region and the expected colors of the complexes are varying from violet and blue to red and orange.The calculations of the crystalline state of the studied complexes indicate high lattice energies,which are higher than that of pure FOX-7 and are close to the recently reported hydrogen-bonded complex of FOX-7 with 1,10-phenanthroline.Additional analysis of the studied charge-transfer complexes using properties based on density difference grids clearly suggests the acceptor role of FOX-7 in the complexes.This analysis can be effectively applied to identify the nature of other possible complexes of FOX-7,in which its role is unclear because of the specific reactivity,namely,both weak electrophilic and nucleophilic properties at the same time.展开更多
The broad class of explosives includes nitro aromatics as well as challenging aliphatic nitro-organics whose detection is important from counter-terrorism and national security perspectives.Here we report a turn-on fl...The broad class of explosives includes nitro aromatics as well as challenging aliphatic nitro-organics whose detection is important from counter-terrorism and national security perspectives.Here we report a turn-on fluorescent sensor array based on aggregation-induced emission(AIE)fluorophores as receptors.To achieve a good sensing system with fast response,good sensitivity and low detection limit,three receptors with abundant chemical diversities for target analytes were synthesized.The turn-on response of the individual receptor showed highly variable and cross-reactive analyte-dependent changes in fluorescence.The excellent ability to identify a variety of explosives,especially the challenging aliphatic nitro-organics(2,3-dimethyl-2,3-dinitrobutane(DMNB),1,3,5-trinitro-1,3,5-triazinane(RDX),cyclotetramethylene tetranitramine(HMX)and entaerythritol tetranitrate(PETN)),was demonstrated in qualitative and quantitative analyses with 100%accuracy.The fluorescence signal amplification in the presence of explosives allows for application of these receptors in a sensor microarray suitable for high-throughput screening.These results suggested that the cross-reactive sensor array based on AIE fluorophores could find a wide range of applications for sensing various analytes or complex mixtures.展开更多
The precise regulation of interactions provided by aggregation-induced emission(AIE)probes is of considerable significance for improving the sensing performance in the field of on-site detection.Here,a highly sensitiv...The precise regulation of interactions provided by aggregation-induced emission(AIE)probes is of considerable significance for improving the sensing performance in the field of on-site detection.Here,a highly sensitive perchlorate detection probe was designed by precisely modulating the van der Waals interactions by adjusting the length of the alkyl chain.The optimized AIE probe demonstrated superior perchlorate detection performance owing to its strong van der Waals interactions with perchlorate,including a low detection limit(53.81 nM),rapid response(<5 s),and excellent specificity even in the presence of 16 interfering anions.In addition,a hydrogel-based device loaded with the probe was constructed to achieve ultrasensitive recognition of perchlorate particles with a detection limit as low as 15 fg under a fluorescence microscope.Moreover,the practicality of the probe was further verified by employing a sensing chip in a portable detector,and thus the probe has been proven to be highly promising for trace perchlorate monitoring in real scenarios.We expect the present study to be of great value for the efficient design of high-performance fluorescent probes.展开更多
Organic light-emitting materials have attracted considerable attention because of their promising applications in diverse areas.Most fluorophores emit brightly in either dilute solutions or aggregate states;the former...Organic light-emitting materials have attracted considerable attention because of their promising applications in diverse areas.Most fluorophores emit brightly in either dilute solutions or aggregate states;the former generally suffer from aggregation-caused quenching problem,and the latter encounter intensity loss at low concentrations.Herein,we propose a new strategy to overcome these dilemmas by balancing the planar and distorted structures of terphenyl-based luminogens and obtain three luminogens,2PB-AC,2Me2PB-AC,and 2T2PB-AC,with bright emission in both solution and aggregate states.Among them,2PB-AC shows absolute photoluminescence quantum yields(ФPL)higher than 90%in both tetrahydrofuran solution(90.2%)and aggregate states(92.7%for powder and 95.3%for crystal).Thus,2PB-AC could be an efficient probe to realize dual-channel explosive detection in both solution and aggregate states.Moreover,it could be used to image live-cell lipid droplets at a wide range of concentrations.In addition,benefiting from its thermodynamically favorable intersystem crossing process,2Me2PB-AC could be doped in polymethyl methacrylate matrix to provide efficient room-temperature phosphorescence.Thus,this work provides a feasible strategy for the design of luminogens with highly efficient emission in both solution and aggregate states,greatly facilitating and broadening their practical applications.展开更多
Azide-alkyne click polymerization has become a powerful tool for polymer synthesis.However,the click polymerization between internal alkynes and azides is rarely utilized to prepare functional polymers.In this work,th...Azide-alkyne click polymerization has become a powerful tool for polymer synthesis.However,the click polymerization between internal alkynes and azides is rarely utilized to prepare functional polymers.In this work,the polymerization reactions of activated internal alkyne monomers of tris(2-butynoate)s(1)with tetraphenylethene-containing diazides(2)were performed in dimethylformamide(DMF)under simple heating,affording four hyperbranched poly(methyltriazolylcarboxylate)s(hb-PMTCs)with high molecular weights(A4W up to 2.4 x 104)and regioregularities(up to 83.9%)in good yields.The hb-PMTCs are soluble in common organic solvents,and thermally stable with 5%weight loss temperatures up to 400℃.They are non-emissive in dilute solution,but become highly emissive in aggregated state,exhibiting aggregationinduced emission characteristics.The polymers can generate fluorescent photopatterns with high resolution,and can work as fluorescent sensors to detect nitroaromatic explosive with high sensitivity.展开更多
Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX) is one of the most widely used powerful explosives. The direct and selective detection of HMX, without the requirement of specialized equipment, remains a great ch...Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX) is one of the most widely used powerful explosives. The direct and selective detection of HMX, without the requirement of specialized equipment, remains a great challenge due to its extremely low volatility, unfavorable reduction potential and lack of aromatic rings. Here, we report the first chemical probe of direct identification of HMX at ppb sensitivity based on a designed metal-organic cage(MOC). The cage features two unsaturated dicopper units and four electron donating amino groups inside the cavity, providing multiple binding sites to selectively enhance host-guest events. It was found that compared to other explosive molecules the capture of HMX inside the cavity would strongly modulate the emissive behavior of the host cage, resulting in highly induced fluorescence “turn-on”(160 folds). Based on the density functional theory(DFT) simulation, the mutual fit of both size and binding sites between host and guest leads to the synergistic effects that perturb the ligand-to-metal charge-transfer(LMCT) process, which is probably the origin of such selective HMX-induced turn-on behavior.展开更多
基金the National Natural Science Foundation of China(Nos.21922110 and 21871245)the Collaborative Innovation Program of Hefei Science Center,CAS(No.2022HSC-CIP014)the Fundamental Research Funds for the Central Universities(No.WK3450000005).
文摘Self-assembly ofπ-conjugated compounds into supramolecular polymers has received considerable attention because of their intrinsic scientific interests and technological applications.As compared toπ-conjugated rods,discotics,and macrocycles,propeller-shapedπ-conjugated molecules have been less exploited to form long-range-ordered supramolecular polymers.Herein a novel type of supramolecular polymers has been constructed on the basis of propeller-shaped triphenylamine cyanostilbenes.The designed compound adopts nucleation-elongation cooperative mechanism for the supramolecular polymerization process,because of the participation of three-fold hydrogen bonds between the neighbouring monomers.The supramolecular polymeric state displays amplified chirality and enhanced emission than those in the monomeric state.The resulting supramolecular polymers exhibit severe emission quenching upon addition of 2,6-dinitrotoluene,ascribed to photoinduced electron transfer from the triphenylamine cyanostilbenes to the explosive analyte.The current study proves the feasibility to supramolecular polymerize propeller-likeπ-conjugated molecules,serving as a promising type of explosive sensor owing to their guest encapsulation and signal amplification capabilities.
基金supported by the National Natural Science Foundation of China(Nos.22075136 and 61874053)the open research fund from Anhui Province Key Laboratory of Environment-friendly Polymer Materials,Anhui Province Key Laboratory of Optoelectronic Materials Science and Technologythe State Key Laboratory of Luminescent Materials and Devices(South China University of Technology).
文摘Precisely optimizing the morphology of functional hybrid polymeric systems is crucial to improve its photophysical property and further extend their optoelectronic applications. The physic-chemical property of polymeric matrix in electrospinning (ES) processing is a key factor to dominate the condensed structure of these hybrid microstructures and further improve its functionality. Herein, we set a flexible poly(ethylene oxide) (PEO) as the matrix to obtain a series of polydiarylfluorenes (including PHDPF, PODPF and PNDPF) electrospun hybrid microfibers with a robust deep-blue emission. Significantly different from the rough morphology of their poly(N-vinylcarbazole) (PVK) ES hybrid fibers, polydiarylfluorenes/PEO ES fibers showed a smooth morphology and small size with a diameter of 1∼2 µm. Besides, there is a relatively weak phase separation under rapid solvent evaporation during the ES processing, associated with the hydrogen-bonded-assisted network of PEO in ES fibers. These relative “homogeneous” ES fibers present efficient deep-blue emission (PLQY>50%), due to weak interchain aggregation. More interestingly, low fraction of planar (β) conformation appears in the uniform PODPF/PEO ES fibers, induced by the external traction force in ES processing. Meanwhile, PNDPF/PEO ES fibers present a highest sensitivity than those of other ES fibers, associated with the smallest diameter and large surface area. Finally, compared to PODPF/PVK fibers and PODPF/PEO amorphous ES fibers, PODPF/PEO ES fibers obtained from DCE solution exhibit an excellent quenching behavior toward a saturated DNT vapor, mainly due to the synergistic effect of small size, weak separation, β-conformation formation and high deep-blue emission efficiency.
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supported by the Ministry of Education and Science of Ukraine(No.0122U000760)。
文摘A number of electron-rich heterocycles are studied as potential reagents for visual colorimetric detection of FOX-7 due to colored charge-transfer complexes formation.The obtained results suggest that pyrrole and pyrimidine derivatives can form such complexes playing the role of electron donors despite a low electrophilicity of FOX-7.Density functional theory calculations,as well as quantum theory of atoms in molecules analysis,suggest stacking binding mode as the most preferable one with the binding energy of about 21-36 kJ/mol.All the complexes demonstrate a clear single charge-transfer absorption band in the visible region and the expected colors of the complexes are varying from violet and blue to red and orange.The calculations of the crystalline state of the studied complexes indicate high lattice energies,which are higher than that of pure FOX-7 and are close to the recently reported hydrogen-bonded complex of FOX-7 with 1,10-phenanthroline.Additional analysis of the studied charge-transfer complexes using properties based on density difference grids clearly suggests the acceptor role of FOX-7 in the complexes.This analysis can be effectively applied to identify the nature of other possible complexes of FOX-7,in which its role is unclear because of the specific reactivity,namely,both weak electrophilic and nucleophilic properties at the same time.
基金the National Natural Science Foundation of China(50873051,205333050)National High Technology Research and Development Program of China(2007AA03Z307)Transregional Project(TRR61)
文摘The broad class of explosives includes nitro aromatics as well as challenging aliphatic nitro-organics whose detection is important from counter-terrorism and national security perspectives.Here we report a turn-on fluorescent sensor array based on aggregation-induced emission(AIE)fluorophores as receptors.To achieve a good sensing system with fast response,good sensitivity and low detection limit,three receptors with abundant chemical diversities for target analytes were synthesized.The turn-on response of the individual receptor showed highly variable and cross-reactive analyte-dependent changes in fluorescence.The excellent ability to identify a variety of explosives,especially the challenging aliphatic nitro-organics(2,3-dimethyl-2,3-dinitrobutane(DMNB),1,3,5-trinitro-1,3,5-triazinane(RDX),cyclotetramethylene tetranitramine(HMX)and entaerythritol tetranitrate(PETN)),was demonstrated in qualitative and quantitative analyses with 100%accuracy.The fluorescence signal amplification in the presence of explosives allows for application of these receptors in a sensor microarray suitable for high-throughput screening.These results suggested that the cross-reactive sensor array based on AIE fluorophores could find a wide range of applications for sensing various analytes or complex mixtures.
基金Natural Science Foundation of Xinjiang,Grant/Award Number:2022D01E03West Light Foundation of the Chinese Academy of Sciences,Grant/Award Number:2021-XBQNXZ-023+1 种基金National Natural Science Foundation of China,Grant/Award Numbers:52172168,22104152Key Research Program of Frontier Sciences,CAS,。
文摘The precise regulation of interactions provided by aggregation-induced emission(AIE)probes is of considerable significance for improving the sensing performance in the field of on-site detection.Here,a highly sensitive perchlorate detection probe was designed by precisely modulating the van der Waals interactions by adjusting the length of the alkyl chain.The optimized AIE probe demonstrated superior perchlorate detection performance owing to its strong van der Waals interactions with perchlorate,including a low detection limit(53.81 nM),rapid response(<5 s),and excellent specificity even in the presence of 16 interfering anions.In addition,a hydrogel-based device loaded with the probe was constructed to achieve ultrasensitive recognition of perchlorate particles with a detection limit as low as 15 fg under a fluorescence microscope.Moreover,the practicality of the probe was further verified by employing a sensing chip in a portable detector,and thus the probe has been proven to be highly promising for trace perchlorate monitoring in real scenarios.We expect the present study to be of great value for the efficient design of high-performance fluorescent probes.
基金This work was financially supported by the National Natural Science Foundation of China(grant no.21788102)the Natural Science Foundation of Guangdong Province(grant nos.2019B030301003 and 2016A030312002)the Innovation and Technology Commission of Hong Kong(grant no.ITC-CNERC14S01).
文摘Organic light-emitting materials have attracted considerable attention because of their promising applications in diverse areas.Most fluorophores emit brightly in either dilute solutions or aggregate states;the former generally suffer from aggregation-caused quenching problem,and the latter encounter intensity loss at low concentrations.Herein,we propose a new strategy to overcome these dilemmas by balancing the planar and distorted structures of terphenyl-based luminogens and obtain three luminogens,2PB-AC,2Me2PB-AC,and 2T2PB-AC,with bright emission in both solution and aggregate states.Among them,2PB-AC shows absolute photoluminescence quantum yields(ФPL)higher than 90%in both tetrahydrofuran solution(90.2%)and aggregate states(92.7%for powder and 95.3%for crystal).Thus,2PB-AC could be an efficient probe to realize dual-channel explosive detection in both solution and aggregate states.Moreover,it could be used to image live-cell lipid droplets at a wide range of concentrations.In addition,benefiting from its thermodynamically favorable intersystem crossing process,2Me2PB-AC could be doped in polymethyl methacrylate matrix to provide efficient room-temperature phosphorescence.Thus,this work provides a feasible strategy for the design of luminogens with highly efficient emission in both solution and aggregate states,greatly facilitating and broadening their practical applications.
基金the National Natural Science Foundation of China(Nos.21875152 and 21404077)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.17KJB150034)+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)(No.2019B030301003)the Priority Academic Program Development of Jiangsu High Education Institutions(PAPD).M.N.L.and Q.Z.Z.thank the financial support from Undergraduate Training Program for Innovation and Entrepreneurship,Soochow University(No.2018xj032)H.K.L.acknowledges the supports from Jiangsu Planned Projects for Postdoctoral Research Funds(No.1501023B)China Postdoctoral Science Foundation(No.2016M591906).
文摘Azide-alkyne click polymerization has become a powerful tool for polymer synthesis.However,the click polymerization between internal alkynes and azides is rarely utilized to prepare functional polymers.In this work,the polymerization reactions of activated internal alkyne monomers of tris(2-butynoate)s(1)with tetraphenylethene-containing diazides(2)were performed in dimethylformamide(DMF)under simple heating,affording four hyperbranched poly(methyltriazolylcarboxylate)s(hb-PMTCs)with high molecular weights(A4W up to 2.4 x 104)and regioregularities(up to 83.9%)in good yields.The hb-PMTCs are soluble in common organic solvents,and thermally stable with 5%weight loss temperatures up to 400℃.They are non-emissive in dilute solution,but become highly emissive in aggregated state,exhibiting aggregationinduced emission characteristics.The polymers can generate fluorescent photopatterns with high resolution,and can work as fluorescent sensors to detect nitroaromatic explosive with high sensitivity.
基金the National Natural Science Foundation of China (NSFC, Nos. 21773135, 22032003, 21821001)the Ministry of Science and Technology (MOST, No. 2017YFA0204501)the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation, No. TRR61)。
文摘Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX) is one of the most widely used powerful explosives. The direct and selective detection of HMX, without the requirement of specialized equipment, remains a great challenge due to its extremely low volatility, unfavorable reduction potential and lack of aromatic rings. Here, we report the first chemical probe of direct identification of HMX at ppb sensitivity based on a designed metal-organic cage(MOC). The cage features two unsaturated dicopper units and four electron donating amino groups inside the cavity, providing multiple binding sites to selectively enhance host-guest events. It was found that compared to other explosive molecules the capture of HMX inside the cavity would strongly modulate the emissive behavior of the host cage, resulting in highly induced fluorescence “turn-on”(160 folds). Based on the density functional theory(DFT) simulation, the mutual fit of both size and binding sites between host and guest leads to the synergistic effects that perturb the ligand-to-metal charge-transfer(LMCT) process, which is probably the origin of such selective HMX-induced turn-on behavior.
