Donor-acceptor(D-A)compounds are particularly important in optoelectronic and biological applications.However,they are normally synthesized in the presence of transition metal catalysts.Herein,we report a metal-free m...Donor-acceptor(D-A)compounds are particularly important in optoelectronic and biological applications.However,they are normally synthesized in the presence of transition metal catalysts.Herein,we report a metal-free method by a complexmediated nucleophilic aromatic substitution of aryl nitriles with amines.The method can lead to rich D-A type aggregation-induced emission luminogens(AIEgens)with tunable properties.They emit from deep-blue to yellow-green and possess high photoluminescence quantum yields up to 70.5%in the aggregate state.Interestingly,the suppression of intramolecular flapping is proved to play an indispensable role in the AIE behavior,which is different from the mechanism met in other AIEgens.Moreover,the biocompatible AIEgens possess specific staining of lipid droplets in HeLa cells and the superiority of identifying fatty liver over traditional Oil Red O staining is exhibited.展开更多
Developing multifunctional spiropyran dyes is of particular importance in diverse applications.In the present study,we synthesized two 2,1,3-benzothiadiazole-conjugated spiropyrans(BT-SP-NO2and BTSP-NMe2)with distinct...Developing multifunctional spiropyran dyes is of particular importance in diverse applications.In the present study,we synthesized two 2,1,3-benzothiadiazole-conjugated spiropyrans(BT-SP-NO2and BTSP-NMe2)with distinct substituents.These donor-acceptor-structured spiropyrans exhibited typical twisted intramolecular charge transfer features and strong emissions in low-polarity solvents with fluorescence quantum yields(QYs)of up to 90.7%.Like traditional spiropyrans,the electron-acceptor-substituted BT-SP-NO2exhibited excellent photochromic behavior under multiple alternating UV—Vis irradiation,while the electron-donor-substituted BT-SP-NMe2was an acidochromic dye.In addition,the substituent groups distinctly affected the packing modes of these spiropyrans in the solid state.BTSP-NMe2showed a much stronger solid-state emission(QY of 59.0%)than BT-SP-NO2.Moreover,these two dyes were utilized as biocompatible probes for the specific light-up imaging of lipid droplets.展开更多
Lipid droplets(LDs)participate in many physiological processes,the abnormality of which will cause chronic diseases and pathologies such as diabetes and obesity.It is crucial to monitor the distribution of LDs at high...Lipid droplets(LDs)participate in many physiological processes,the abnormality of which will cause chronic diseases and pathologies such as diabetes and obesity.It is crucial to monitor the distribution of LDs at high spatial resolution and large depth.Herein,we carried three-photon imaging of LDs in fat liver.Owing to the large three-photon absorption cross-section of the luminogen named NAP-CF_(3)(1:67×10^(-79) cm^(6) s^(2)),three-photon fluorescence fat liver imaging reached the largest depth of 80μm.Fat liver diagnosis was successfully carried out with excellent performance,providing great potential for LDs-associated pathologies research.展开更多
As a new type of cancer treatment,photoacoustic(PA)therapy is based on PA shockwave for rapid,selective and effective killing of cancer cells.The nucleus has been widely used as a target for tumor therapy,which has ob...As a new type of cancer treatment,photoacoustic(PA)therapy is based on PA shockwave for rapid,selective and effective killing of cancer cells.The nucleus has been widely used as a target for tumor therapy,which has obtained a very considerable therapeutic effect.In situ destruction of tumor cell nucleus by photoacoustic therapy has not been studied.In this paper,a highly efficient nucleus-targeted photoacoustic theranostic polymer was developed for fluorescence and photoacoustic dual-mode imaging-guided PA therapy.The prepared polymer consists of nucleus targeting TAT peptide(TAT:YGRKKRRQRRR),hydrophilic chain poly(N,N-dimethylacrylamide)(PDMA),and near-infrared(NIR)light absorbing agent(hCyR),which can self-assemble to form nanoparticles of approximately 28 nm(denoted as TAT-PDMA-hCyR NPs).The designed nanoparticles show excellent nucleus targeting and tumor cell death(up to 80%)caused by DNA damage under pulsed laser irradiation compared to non-nucleus target counterpart PDMA-hCyR NPs without TAT peptide in vitro.As expected,the fluorescence and PA dual-mode imaging observed that TAT-PDMA-hCyR NPs were able to passively target and enrich in tumors,providing an experimental basis for in vivo treatment and thus ensuring a significant tumor inhibition rate(about 92%).In conclusion,this study provides a new and practicable method for the development of nucleus-targeting nanoparticles as potential theranostic agent for in vivo cancer imaging and therapy.展开更多
Nitroxyl(HNO)has been reported to possess unique biological and pharmacological performances,and emerged as a novel therapy for congestive heart failure.Recent studies also suggest that HNO may be produced and involve...Nitroxyl(HNO)has been reported to possess unique biological and pharmacological performances,and emerged as a novel therapy for congestive heart failure.Recent studies also suggest that HNO may be produced and involved in important metabolisms in mitochondria.However,due to its high reactivity and short life properties,fast,sensitive and selective observation and monitoring of HNO related dynamic changes in mitochondria still remains a great challenge.Herein,we synthesized a mitochondria-targeting near-infrared(NIR)fluorescent probe(DCMHNO)for rapid detection of HNO with remarkably high sensitivity,selectivity and photostability.DCMHNO shows fast response(about 4 min)towards HNO via 2-(diphenylphosphino)benzoyl group through the Staudinger reaction to boost the bright NIR emission(700 nm)with excellent sensitivity(detection limit of 13 nM),high p H stability and very low interference from other species.DCMHNO can selectively locate in mitochondria and visualize exogenous and endogenous HNO in live He La cells with high biocompatibility and photostability.The probe could also monitor the interaction between NO and H2 S that gives rise to the generation of HNO in live He La cells.In addition,DCMHNO was further utilized in ex vivo NIR imaging of HNO in live mouse liver tissues at the depth of about 50μm.In vivo imaging of HNO with high signal-to-noise ratio in live mice was also realized by using DCMHNO.These remarkable imaging performances could render NIR DCMNHNO as a useful tool to reveal HNO related dynamic changes in live samples.展开更多
Near-infrared(NIR)-Ⅱ fluorescence and photoacoustic(PA)dual-model imaging-guided photothermal therapy(PTT)can precisely diagnose and treat tumors and evaluate the therapeutic efficacy in real-time.Herein,we utilized ...Near-infrared(NIR)-Ⅱ fluorescence and photoacoustic(PA)dual-model imaging-guided photothermal therapy(PTT)can precisely diagnose and treat tumors and evaluate the therapeutic efficacy in real-time.Herein,we utilized a donor-π-acceptor(D-π-A)structured hemicyanine dye(named M1)with a large conjugated structure and strong intramolecular charge transfer effect and demonstrated that the aggregation of M1 could significantly enhance its photophysical performance by improving its photostability and photothermal conversion capability as compared with M1 in a single molecular state.Furthermore,we prepared water-dispersible NIR-Ⅱ fluorescent nanoparticles(M1 NPs)by wrapping M1 with DSPE-PEG2000-NH2.The obtained M1 NPs exhibit strong NIR-I absorption and NIR-Ⅱ fluorescence with their maxima at 734 and 1040 nm,respectively,with a fluorescence quantum yield of 2.84%.Moreover,M1 NPs also exhibit excellent biocompatibility,good photostability,and high photothermal conversion efficiency of 77.5%.In vitro and in vivo experiments reveal that M1 NPs can effectively image tumors through NIR-Ⅱ fluorescence and PA signals,inhibit DNA replication,trigger cytoskeleton collapse,and eventually induce tumor cell apoptosis under 808 nm laser irradiation.Based on these outstanding properties,the application of M1 NPs in PA and NIR-Ⅱ fluorescence imaging-guided PTT of tumors is demonstrated.展开更多
基金supported by the National Natural Science Foundation of China(22275072 and 62105184)the Natural Science Foundation of Guangdong Province(2020A1515010622)+1 种基金the Project of Science and Technology of Guangzhou(2024A04J3712)the Teli Young Scholar Program of Beijing Institute of Technology.
文摘Donor-acceptor(D-A)compounds are particularly important in optoelectronic and biological applications.However,they are normally synthesized in the presence of transition metal catalysts.Herein,we report a metal-free method by a complexmediated nucleophilic aromatic substitution of aryl nitriles with amines.The method can lead to rich D-A type aggregation-induced emission luminogens(AIEgens)with tunable properties.They emit from deep-blue to yellow-green and possess high photoluminescence quantum yields up to 70.5%in the aggregate state.Interestingly,the suppression of intramolecular flapping is proved to play an indispensable role in the AIE behavior,which is different from the mechanism met in other AIEgens.Moreover,the biocompatible AIEgens possess specific staining of lipid droplets in HeLa cells and the superiority of identifying fatty liver over traditional Oil Red O staining is exhibited.
基金supported by the National Natural Science Foundation of China(62105184)the Natural Science Foundation of Shandong Province,China(2022HWYQ-007 and ZR2021QB043)the Special Fund of Taishan Scholars Project of Shandong Province,China(tsqn201909012)。
文摘Developing multifunctional spiropyran dyes is of particular importance in diverse applications.In the present study,we synthesized two 2,1,3-benzothiadiazole-conjugated spiropyrans(BT-SP-NO2and BTSP-NMe2)with distinct substituents.These donor-acceptor-structured spiropyrans exhibited typical twisted intramolecular charge transfer features and strong emissions in low-polarity solvents with fluorescence quantum yields(QYs)of up to 90.7%.Like traditional spiropyrans,the electron-acceptor-substituted BT-SP-NO2exhibited excellent photochromic behavior under multiple alternating UV—Vis irradiation,while the electron-donor-substituted BT-SP-NMe2was an acidochromic dye.In addition,the substituent groups distinctly affected the packing modes of these spiropyrans in the solid state.BTSP-NMe2showed a much stronger solid-state emission(QY of 59.0%)than BT-SP-NO2.Moreover,these two dyes were utilized as biocompatible probes for the specific light-up imaging of lipid droplets.
基金supported by National Natural Science Foundation of China (61975172,82001874,62105184)the Guangdong Basic and Applied Basic Research Foundation (2020A1515110578).
文摘Lipid droplets(LDs)participate in many physiological processes,the abnormality of which will cause chronic diseases and pathologies such as diabetes and obesity.It is crucial to monitor the distribution of LDs at high spatial resolution and large depth.Herein,we carried three-photon imaging of LDs in fat liver.Owing to the large three-photon absorption cross-section of the luminogen named NAP-CF_(3)(1:67×10^(-79) cm^(6) s^(2)),three-photon fluorescence fat liver imaging reached the largest depth of 80μm.Fat liver diagnosis was successfully carried out with excellent performance,providing great potential for LDs-associated pathologies research.
基金This work was supported by the National Natural Science Foundation of China(No.81630046)the Science and Technology Planning Project of Guangdong Province(Nos.2015B020233016 and 2014B020215003)。
文摘As a new type of cancer treatment,photoacoustic(PA)therapy is based on PA shockwave for rapid,selective and effective killing of cancer cells.The nucleus has been widely used as a target for tumor therapy,which has obtained a very considerable therapeutic effect.In situ destruction of tumor cell nucleus by photoacoustic therapy has not been studied.In this paper,a highly efficient nucleus-targeted photoacoustic theranostic polymer was developed for fluorescence and photoacoustic dual-mode imaging-guided PA therapy.The prepared polymer consists of nucleus targeting TAT peptide(TAT:YGRKKRRQRRR),hydrophilic chain poly(N,N-dimethylacrylamide)(PDMA),and near-infrared(NIR)light absorbing agent(hCyR),which can self-assemble to form nanoparticles of approximately 28 nm(denoted as TAT-PDMA-hCyR NPs).The designed nanoparticles show excellent nucleus targeting and tumor cell death(up to 80%)caused by DNA damage under pulsed laser irradiation compared to non-nucleus target counterpart PDMA-hCyR NPs without TAT peptide in vitro.As expected,the fluorescence and PA dual-mode imaging observed that TAT-PDMA-hCyR NPs were able to passively target and enrich in tumors,providing an experimental basis for in vivo treatment and thus ensuring a significant tumor inhibition rate(about 92%).In conclusion,this study provides a new and practicable method for the development of nucleus-targeting nanoparticles as potential theranostic agent for in vivo cancer imaging and therapy.
基金supported by the National Natural Science Foundation of China(21663005,21871060,21672220,81501591)the Natural Science Foundation of Jiangxi Province(2018ACB21009,20181BAB213007)+1 种基金the Science and Technology Plan of Shenzhen(JCYJ20170818113851132)the Research Grants Council of Hong Kong(16301614,16305015,AoE/P-03/08,Ao E/P-02/12,A-HKUST 605/16,N_HKUST604/14)
文摘Nitroxyl(HNO)has been reported to possess unique biological and pharmacological performances,and emerged as a novel therapy for congestive heart failure.Recent studies also suggest that HNO may be produced and involved in important metabolisms in mitochondria.However,due to its high reactivity and short life properties,fast,sensitive and selective observation and monitoring of HNO related dynamic changes in mitochondria still remains a great challenge.Herein,we synthesized a mitochondria-targeting near-infrared(NIR)fluorescent probe(DCMHNO)for rapid detection of HNO with remarkably high sensitivity,selectivity and photostability.DCMHNO shows fast response(about 4 min)towards HNO via 2-(diphenylphosphino)benzoyl group through the Staudinger reaction to boost the bright NIR emission(700 nm)with excellent sensitivity(detection limit of 13 nM),high p H stability and very low interference from other species.DCMHNO can selectively locate in mitochondria and visualize exogenous and endogenous HNO in live He La cells with high biocompatibility and photostability.The probe could also monitor the interaction between NO and H2 S that gives rise to the generation of HNO in live He La cells.In addition,DCMHNO was further utilized in ex vivo NIR imaging of HNO in live mouse liver tissues at the depth of about 50μm.In vivo imaging of HNO with high signal-to-noise ratio in live mice was also realized by using DCMHNO.These remarkable imaging performances could render NIR DCMNHNO as a useful tool to reveal HNO related dynamic changes in live samples.
基金supported by National Natural Science Foundation of China(No.62175262)Fundamental Research Funds for the Central South University(No.2020CX021)The Science and Technology Innovation Program of Hunan Province(No.2022RC1201).
文摘Near-infrared(NIR)-Ⅱ fluorescence and photoacoustic(PA)dual-model imaging-guided photothermal therapy(PTT)can precisely diagnose and treat tumors and evaluate the therapeutic efficacy in real-time.Herein,we utilized a donor-π-acceptor(D-π-A)structured hemicyanine dye(named M1)with a large conjugated structure and strong intramolecular charge transfer effect and demonstrated that the aggregation of M1 could significantly enhance its photophysical performance by improving its photostability and photothermal conversion capability as compared with M1 in a single molecular state.Furthermore,we prepared water-dispersible NIR-Ⅱ fluorescent nanoparticles(M1 NPs)by wrapping M1 with DSPE-PEG2000-NH2.The obtained M1 NPs exhibit strong NIR-I absorption and NIR-Ⅱ fluorescence with their maxima at 734 and 1040 nm,respectively,with a fluorescence quantum yield of 2.84%.Moreover,M1 NPs also exhibit excellent biocompatibility,good photostability,and high photothermal conversion efficiency of 77.5%.In vitro and in vivo experiments reveal that M1 NPs can effectively image tumors through NIR-Ⅱ fluorescence and PA signals,inhibit DNA replication,trigger cytoskeleton collapse,and eventually induce tumor cell apoptosis under 808 nm laser irradiation.Based on these outstanding properties,the application of M1 NPs in PA and NIR-Ⅱ fluorescence imaging-guided PTT of tumors is demonstrated.
