An amphiphilic polymer bearing tetraphenylethene (TPE) moiety was synthesized by convenient reactions. The polymer exhibits unique aggregation-induced emission (AIE) characteristics and can self-assemble to size-tunab...An amphiphilic polymer bearing tetraphenylethene (TPE) moiety was synthesized by convenient reactions. The polymer exhibits unique aggregation-induced emission (AIE) characteristics and can self-assemble to size-tunable particles in DMF/water mixtures. The polymer nanoparticles can be used for cell imaging, which provides a potential stable fluorescent tool to monitor the distribution of drugs and bioconjugates in living cells.展开更多
We report a fluorescence "turn-on" method to detect the critical micelle concentration (CMC) of surfactants. This method works well for both cationic and anionic surfactants. It employs an unprecedented mech...We report a fluorescence "turn-on" method to detect the critical micelle concentration (CMC) of surfactants. This method works well for both cationic and anionic surfactants. It employs an unprecedented mechanism (aggregation-induced emission, or AIE) to determine the CMC values, and the results are consistent with the data obtained by the classical techniques. In addition, this method renders the convenient detection of the CMC values. Any large and professional instruments are unnecessary, instead, a portable UV lamp and an ultrasonic generator are enough to carry out the detection in an ordinary laboratory. Considering that micelles are interesting entities and have found applications in many important fields such as emulsion polymerization, template of nanosized materials synthesis, controllable drug delivery and macromolecular self-assembling. Our experimental results may offer a facile, sensitive and promising method to detect the formation of micelles constructed by the new amphiphilic molecules and macromolecules.展开更多
Regioseletive 1,3-dipolar polycycloadditions of 4,4'-isopropylidenediphenyl dipropiolate (1) and tetraphenylethene (TPE)-containing diazides (2) are carried out in polar solvents such as DMF/toluene at a moderate ...Regioseletive 1,3-dipolar polycycloadditions of 4,4'-isopropylidenediphenyl dipropiolate (1) and tetraphenylethene (TPE)-containing diazides (2) are carried out in polar solvents such as DMF/toluene at a moderate temperature of 100℃ for 6 h,producing poly(aroxycarbonyltriazole)s (PACTs) P3 with high molecular weights (Mw up to 23900) and regioregularities (F1,4 up to ~90%) in high yields (up to ~99%).These metal-free click polymerizations can propagate smoothly in an open atmosphere without protection from oxygen and moisture.The obtained polymers are soluble in common organic solvents and thermally stable at temperatures up to 375℃.Thanks to their contained TPE moieties,the PACTs show aggregation-induced emission and can serve as fluorescent chemosensors for superamplified detection of explosives.展开更多
The research on using thiol-ene click reaction to synthesize sulfur-containing polymers with topological structures and advanced functional properties is a hot topic. However, the application of the thiol-yne reaction...The research on using thiol-ene click reaction to synthesize sulfur-containing polymers with topological structures and advanced functional properties is a hot topic. However, the application of the thiol-yne reaction in the functional polymer preparation is limited and the thiol-yne click polymerization is to be further developed. In this review, we summarized recent research efforts on using thiol-yne click polymerization to synthesize polymers with topological structures. The sulfur-containing polymers were facilely prepared by photo-and thermo-initiated, amine-mediated, and transition-metal-catalyzed thiol-yne click polymerizations. These polymers are promising to be used as drug-delivery vehicles, high refractive index optical materials, photovoltaic materials, and biomaterials etc.展开更多
The research on aggregation-induced emission (AIE) has drawn increasing interests in the past decade. With the efforts scientists paid, a variety of AIE systems have been developed, among which the tetraphenylethelene...The research on aggregation-induced emission (AIE) has drawn increasing interests in the past decade. With the efforts scientists paid, a variety of AIE systems have been developed, among which the tetraphenylethelene and silole derivatives are the most studied. Development of new AIE systems could further enrich the AIE molecules and promote the development of AIE area. In this communication, we prepared a new AIE system based on 1,2,4,6-tetraphenylpyridinium ions according to the restriction of intramolecular rotation mechanism. These molecules could be facilely synthesized via one-step and one-pot reaction. The ionic AIE-active molecules could find wide application in sensing and optoelectronic areas.展开更多
We report a novel strategy to study the chain dynamics of poly(acrylic acid) (PAA) in a relative concentrated solution (1.0 g/L). The strategy is based on the fluorescent probe (DCTPE) with unique aggregation-induced ...We report a novel strategy to study the chain dynamics of poly(acrylic acid) (PAA) in a relative concentrated solution (1.0 g/L). The strategy is based on the fluorescent probe (DCTPE) with unique aggregation-induced emission (AIE) characteristics. Free DCTPE molecules are non-emissive in aqueous solution, but they become highly emissive when trapped in polymer coils. The fluorescence intensity is proportional to the efficiency of trapping DCTPE molecules in polymer coils. By correlation the change of fluorescence intensity with the variation of pH value (from 1.78 to 12.06), the PAA chain's dynamics in the relatively concentrated solution have been elucidated into three processes. In the pH range from 12.06 to 6.0, PAA chains take an extended and non-folding conformation. Changing pH from 6.0 to 3.86, PAA chains are partially protonated and loosely packed polymer coils are formed. Further lowering the pH value of the solution (from 3.86 to 1.78), protonated segments dominate the PAA chains, and at the same time, the intermolecular hydrogen bonding takes effect, thus the polymer chains posses in the conformation of more compact coils.展开更多
Planarized intramolecular charge transfer(PLICT)state can facilitate the fluorescence process thanks to the relative excellent planarity.Recently,we have discovered that the excited state quinone-conformation induced ...Planarized intramolecular charge transfer(PLICT)state can facilitate the fluorescence process thanks to the relative excellent planarity.Recently,we have discovered that the excited state quinone-conformation induced planarization(ESQIP)occurring on tetraphenylpyrazine(TPP)based derivatives could furnish them with PLICT feature.Unlike to the well-known intramolecular charge transfer,strengthening the electron-donating nature on the donor(D)moiety did not impair the PLICT.The calculation results showed that planarization of the TPP based compounds scarcely accompanied with energy wastage while amount of energy was required for the torsion on geometries.In the polar solvents,the energy consumption for planarization could further decrease,but that for twisting structure would increase.To take advantage of the transformation of the frontier orbitals'distribution,the PLICT type materials would perform a potential application on organic light-emitting diodes(OLEDs).展开更多
We report a novel strategy to study the chain dynamics of poly(acrylic acid)(PAA)in a relative concentrated solution(1.0 g/L).The strategy is based on the fluorescent probe(DCTPE)with unique aggregation-induced emissi...We report a novel strategy to study the chain dynamics of poly(acrylic acid)(PAA)in a relative concentrated solution(1.0 g/L).The strategy is based on the fluorescent probe(DCTPE)with unique aggregation-induced emission(AIE)characteristics.Free DCTPE molecules are non-emissive in aqueous solution,but they become highly emissive when trapped in polymer coils.The fluorescence intensity is proportional to the efficiency of trapping DCTPE molecules in polymer coils.By correlation the change of fluorescence intensity with the variation of pH value(from1.78 to 12.06),the PAA chain’s dynamics in the relatively concentrated solution have been elucidated into three processes.In the pH range from 12.06 to 6.0,PAA chains take an extended and non-folding conformation.Changing pH from 6.0 to 3.86,PAA chains are partially protonated and loosely packed polymer coils are formed.Further lowering the pH value of the solution(from 3.86 to 1.78),protonated segments dominate the PAA chains,and at the same time,the intermolecular hydrogen bonding takes effect,thus the polymer chains posses in the conformation of more compact coils.展开更多
The research on aggregation-induced emission(AIE)has drawn increasing interests in the past decade.With the efforts scientists paid,a variety of AIE systems have been developed,among which the tetraphenylethelene and ...The research on aggregation-induced emission(AIE)has drawn increasing interests in the past decade.With the efforts scientists paid,a variety of AIE systems have been developed,among which the tetraphenylethelene and silole derivatives are the most studied.Development of new AIE systems could further enrich the AIE molecules and promote the development of AIE area.In this communication,we prepared a new AIE system based on1,2,4,6-tetraphenylpyridinium ions according to the restriction of intramolecular rotation mechanism.These molecules could be facilely synthesized via one-step and one-pot reaction.The ionic AIE-active molecules could find wide application in sensing and optoelectronic areas.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
We report a synthetic design and the experimental exploration of preparation of disubstituted polyacetylenes (PAs, P3) through 1,3-dipolar cycloaddition of azides with precursor PA bearing alkyne pendants. The precu...We report a synthetic design and the experimental exploration of preparation of disubstituted polyacetylenes (PAs, P3) through 1,3-dipolar cycloaddition of azides with precursor PA bearing alkyne pendants. The precursor PA (P2) was derived by desilylation of the pristine PA with trimethylethynylsilane side chains (P1). P1 was obtained by polymerization of a dual-alkyne containing monomer with one of the alkynes end-capping by trimethylsilane (M) under the promotion of WC16-Ph4Sn catalyst. Two synthetic routes, i.e. two-steps (from P1 to P3 via precursor P2) and one-pot (from P1 to P3 without separation and purification of P2) were tried and the results indicated that one-pot strategy is more facile and resultant P3-1 showed higher purity and higher molecular weight than the resultant of P3-2. By using the techniques such as GPC, FTIR and 1H NMR spectroscopy the polymerization behavior and the structures of the polymers were well characterized.展开更多
基金supported by the National Natural Science Foundation of China (20974028, 20974098, and 21174120)the National Basic Research Program of China (2009CB623605)+1 种基金the Research Grants Council of Hong Kong (603509, HKUST2/CRF/10, 604711, and N_HKUST620/11)B.Z.T. thanks the support from the Cao Guangbiao Foundation of Zhejiang University
文摘An amphiphilic polymer bearing tetraphenylethene (TPE) moiety was synthesized by convenient reactions. The polymer exhibits unique aggregation-induced emission (AIE) characteristics and can self-assemble to size-tunable particles in DMF/water mixtures. The polymer nanoparticles can be used for cell imaging, which provides a potential stable fluorescent tool to monitor the distribution of drugs and bioconjugates in living cells.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 50573065 & 50873086)the Natural Science Foundation of Zhejiang Province (Grant No. Z406018)
文摘We report a fluorescence "turn-on" method to detect the critical micelle concentration (CMC) of surfactants. This method works well for both cationic and anionic surfactants. It employs an unprecedented mechanism (aggregation-induced emission, or AIE) to determine the CMC values, and the results are consistent with the data obtained by the classical techniques. In addition, this method renders the convenient detection of the CMC values. Any large and professional instruments are unnecessary, instead, a portable UV lamp and an ultrasonic generator are enough to carry out the detection in an ordinary laboratory. Considering that micelles are interesting entities and have found applications in many important fields such as emulsion polymerization, template of nanosized materials synthesis, controllable drug delivery and macromolecular self-assembling. Our experimental results may offer a facile, sensitive and promising method to detect the formation of micelles constructed by the new amphiphilic molecules and macromolecules.
基金supported by the National Natural Science Foundation of China (20634020,50703033,20974098 and 20974028)the Ministry of Science and Technology of China (2009CB623605)+4 种基金the University Grants Committee of Hong Kong ( AoE/P-03/08)the Research Grants Council of Hong Kong (603509,601608 and 602707)the Innovation and Technology Fund of Hong Kong (ITS/168/09). A.J.Q. and B.Z.T acknowledge the supports from the Postdoctoral Research Foundation of China (20081461)the Fundamental Research Funds for the Central Universities (2010KYJD005)the CAO GuangBiao Foundation of Zhejiang University,respectively
文摘Regioseletive 1,3-dipolar polycycloadditions of 4,4'-isopropylidenediphenyl dipropiolate (1) and tetraphenylethene (TPE)-containing diazides (2) are carried out in polar solvents such as DMF/toluene at a moderate temperature of 100℃ for 6 h,producing poly(aroxycarbonyltriazole)s (PACTs) P3 with high molecular weights (Mw up to 23900) and regioregularities (F1,4 up to ~90%) in high yields (up to ~99%).These metal-free click polymerizations can propagate smoothly in an open atmosphere without protection from oxygen and moisture.The obtained polymers are soluble in common organic solvents and thermally stable at temperatures up to 375℃.Thanks to their contained TPE moieties,the PACTs show aggregation-induced emission and can serve as fluorescent chemosensors for superamplified detection of explosives.
基金supported by the National Natural Science Foundation of China(21222402,21174120)the National Basic Research Program of China(2009CB623605,2013CB834702)the Research Grants Council of Hong Kong(603509,HKUST2/CRF/10,604711,N_HKUST620/11)
文摘The research on using thiol-ene click reaction to synthesize sulfur-containing polymers with topological structures and advanced functional properties is a hot topic. However, the application of the thiol-yne reaction in the functional polymer preparation is limited and the thiol-yne click polymerization is to be further developed. In this review, we summarized recent research efforts on using thiol-yne click polymerization to synthesize polymers with topological structures. The sulfur-containing polymers were facilely prepared by photo-and thermo-initiated, amine-mediated, and transition-metal-catalyzed thiol-yne click polymerizations. These polymers are promising to be used as drug-delivery vehicles, high refractive index optical materials, photovoltaic materials, and biomaterials etc.
基金the National Science Foundation of China (21222402, 21174120, 20974098)the National Basic Research Program of China (2013CB834702, 2009CB623605)the Research Grants Council of Hong Kong (603509, HKUST2/CRF/10, 604711, NHKUST620/11)
文摘The research on aggregation-induced emission (AIE) has drawn increasing interests in the past decade. With the efforts scientists paid, a variety of AIE systems have been developed, among which the tetraphenylethelene and silole derivatives are the most studied. Development of new AIE systems could further enrich the AIE molecules and promote the development of AIE area. In this communication, we prepared a new AIE system based on 1,2,4,6-tetraphenylpyridinium ions according to the restriction of intramolecular rotation mechanism. These molecules could be facilely synthesized via one-step and one-pot reaction. The ionic AIE-active molecules could find wide application in sensing and optoelectronic areas.
基金the National Science Foundation of China (21074113)the Key Project of the Natural Science Foundation of Zhejiang Province (Z4110056)
文摘We report a novel strategy to study the chain dynamics of poly(acrylic acid) (PAA) in a relative concentrated solution (1.0 g/L). The strategy is based on the fluorescent probe (DCTPE) with unique aggregation-induced emission (AIE) characteristics. Free DCTPE molecules are non-emissive in aqueous solution, but they become highly emissive when trapped in polymer coils. The fluorescence intensity is proportional to the efficiency of trapping DCTPE molecules in polymer coils. By correlation the change of fluorescence intensity with the variation of pH value (from 1.78 to 12.06), the PAA chain's dynamics in the relatively concentrated solution have been elucidated into three processes. In the pH range from 12.06 to 6.0, PAA chains take an extended and non-folding conformation. Changing pH from 6.0 to 3.86, PAA chains are partially protonated and loosely packed polymer coils are formed. Further lowering the pH value of the solution (from 3.86 to 1.78), protonated segments dominate the PAA chains, and at the same time, the intermolecular hydrogen bonding takes effect, thus the polymer chains posses in the conformation of more compact coils.
基金Supported by the National Natural Science Foundation of China(Nos.21788102,51673118,21975077)the Science&Technology Program of Guangzhou Province,China(Nos.201804010218,201804020027)+2 种基金the Project of the Innovation and Technology Commission of Hong Kong,China(No.ITC-CNERC14S01)the Fundamental Research Funds for the Central Universities,China(No.2019ZD04)the Fund of Key Laboratory of Luminescence from Molecular Aggregates of Guangdong Province,China(No.2019B030301003).
文摘Planarized intramolecular charge transfer(PLICT)state can facilitate the fluorescence process thanks to the relative excellent planarity.Recently,we have discovered that the excited state quinone-conformation induced planarization(ESQIP)occurring on tetraphenylpyrazine(TPP)based derivatives could furnish them with PLICT feature.Unlike to the well-known intramolecular charge transfer,strengthening the electron-donating nature on the donor(D)moiety did not impair the PLICT.The calculation results showed that planarization of the TPP based compounds scarcely accompanied with energy wastage while amount of energy was required for the torsion on geometries.In the polar solvents,the energy consumption for planarization could further decrease,but that for twisting structure would increase.To take advantage of the transformation of the frontier orbitals'distribution,the PLICT type materials would perform a potential application on organic light-emitting diodes(OLEDs).
文摘We report a novel strategy to study the chain dynamics of poly(acrylic acid)(PAA)in a relative concentrated solution(1.0 g/L).The strategy is based on the fluorescent probe(DCTPE)with unique aggregation-induced emission(AIE)characteristics.Free DCTPE molecules are non-emissive in aqueous solution,but they become highly emissive when trapped in polymer coils.The fluorescence intensity is proportional to the efficiency of trapping DCTPE molecules in polymer coils.By correlation the change of fluorescence intensity with the variation of pH value(from1.78 to 12.06),the PAA chain’s dynamics in the relatively concentrated solution have been elucidated into three processes.In the pH range from 12.06 to 6.0,PAA chains take an extended and non-folding conformation.Changing pH from 6.0 to 3.86,PAA chains are partially protonated and loosely packed polymer coils are formed.Further lowering the pH value of the solution(from 3.86 to 1.78),protonated segments dominate the PAA chains,and at the same time,the intermolecular hydrogen bonding takes effect,thus the polymer chains posses in the conformation of more compact coils.
文摘The research on aggregation-induced emission(AIE)has drawn increasing interests in the past decade.With the efforts scientists paid,a variety of AIE systems have been developed,among which the tetraphenylethelene and silole derivatives are the most studied.Development of new AIE systems could further enrich the AIE molecules and promote the development of AIE area.In this communication,we prepared a new AIE system based on1,2,4,6-tetraphenylpyridinium ions according to the restriction of intramolecular rotation mechanism.These molecules could be facilely synthesized via one-step and one-pot reaction.The ionic AIE-active molecules could find wide application in sensing and optoelectronic areas.
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partially supported by the National Natural Science Foundation of China (21074113,20634020 & 20974028)the National Basic Research Program of China (973 Program,2009CB623605)+1 种基金the Research Grants Council of Hong Kong (603509 & HKUST2/CRF/10)the University Grants Committee of Hong Kong (AoE/P-03/08)
文摘We report a synthetic design and the experimental exploration of preparation of disubstituted polyacetylenes (PAs, P3) through 1,3-dipolar cycloaddition of azides with precursor PA bearing alkyne pendants. The precursor PA (P2) was derived by desilylation of the pristine PA with trimethylethynylsilane side chains (P1). P1 was obtained by polymerization of a dual-alkyne containing monomer with one of the alkynes end-capping by trimethylsilane (M) under the promotion of WC16-Ph4Sn catalyst. Two synthetic routes, i.e. two-steps (from P1 to P3 via precursor P2) and one-pot (from P1 to P3 without separation and purification of P2) were tried and the results indicated that one-pot strategy is more facile and resultant P3-1 showed higher purity and higher molecular weight than the resultant of P3-2. By using the techniques such as GPC, FTIR and 1H NMR spectroscopy the polymerization behavior and the structures of the polymers were well characterized.