Glutathione(GSH)-activated prodrugs are promising for overcoming the limitations of conventional anti-tumor drugs.However,current GSH-responsive disulfide groups exhibit unregulated reactivity,making it impossible to ...Glutathione(GSH)-activated prodrugs are promising for overcoming the limitations of conventional anti-tumor drugs.However,current GSH-responsive disulfide groups exhibit unregulated reactivity,making it impossible to precisely control the drug release rate.We herein report a series of GSH-responsive prodrugs with a“three-in-one”molecular design by integrating a fluorescence report unit,stimuliresponsive unit and chemodrug into one scaffold with tunable aromatic nucleophilic substitution(SNAr)reactivity.The drug release rate of these prodrugs is tailored by modification of substituent groups with different electron-withdrawing or-donating abilities on the BODIPY core.Furthermore,the prodrugs self-assemble in water to form nanoparticles that serve as photosensitizers to produce reactive oxygen species upon irradiation for photodynamic therapy(PDT).The PDT process also increases the concentration of GSH in cells,further promoting the release of drugs for chemotherapy.This strategy provides a powerful platform for sequential photodynamic and chemotherapy with tunable drug release rates and synergistic therapeutic effects.展开更多
Biothiols,including cysteine(Cys),homocysteine(Hey),and glutathione(GSH) play important roles in physiological processes,and the detection of thiol using fluorescent probes has attracted attention due to their high se...Biothiols,including cysteine(Cys),homocysteine(Hey),and glutathione(GSH) play important roles in physiological processes,and the detection of thiol using fluorescent probes has attracted attention due to their high sensitivity and selectively and invasive on-time imaging.However,the similar structures and reactivity of these biothiols present great challenges for selective detection.This review focused on the the "aromatic nucleophilic substitution-rearrangement(SNAr-rearrangement) mechanism",which provided a powerful tool to design fluorescent probes for the discrimination between biothiols.We classify the fluorescent probes according to types of fluorophores,such as difluoroboron dipyrromethene(BODIPY),nitrobenzoxadiazole(NBD),cyanine,pyronin,naphthalimide,coumarin,and so on.We hope this review will inspire exploration of new fluorescent probes for biothiols and other relevant analytes.展开更多
We report a turn-on fluorescent probe for H2S through a cascade reaction using a new trap group 4- （bromomethyl）benzoate, based on excited-state intramolecular proton transfer （ESIPT） sensing mechanism. The probe ...We report a turn-on fluorescent probe for H2S through a cascade reaction using a new trap group 4- （bromomethyl）benzoate, based on excited-state intramolecular proton transfer （ESIPT） sensing mechanism. The probe showed good selectivity and high sensitivity towards H2S and it was capable of detecting and imaging H2S in living HeLa cells, indicating its potential biological applications.展开更多
Evaluating the correlation between hypoxia inducible factor 1(HIF-1) and nitric oxide(NO) generated under hypoxia is of great significance. In this work, we developed a fluorescent probe for the monitor of HIF-1 activ...Evaluating the correlation between hypoxia inducible factor 1(HIF-1) and nitric oxide(NO) generated under hypoxia is of great significance. In this work, we developed a fluorescent probe for the monitor of HIF-1 activity influenced by NO under hypoxia in hepatoma cells with dual-targeting for hepatocyte and lipid droplet(LD). The probe shows excellent selectivity to NO and high sensitivity with 6000-fold fluorescence enhancement. Live cell imaging experiments revealed the probe’s capability of imaging exogenous and endogenous NO with specific in LDs of Hep G2 cells. For cells under hypoxia, HIF-1 induced LD level is observed to correlate with NO level. This work provides the in-situ visualization of NO-dependent HIF-1 upregulation through LD accumulation.展开更多
We report for the first time a practical and simple supramolecular approach to turn fluorophores into photosensitizers(PSs).Using boron dipyrromethene(BODIPY)as a proof-of-concept,eight BODIPY derivatives manifest bri...We report for the first time a practical and simple supramolecular approach to turn fluorophores into photosensitizers(PSs).Using boron dipyrromethene(BODIPY)as a proof-of-concept,eight BODIPY derivatives manifest bright fluorescence and generate negligible singlet oxygen in solution.In contrast,aggregation fails to emit fluorescence and enhances singlet oxygen generation.Experimentally,these aggregates have excellent photodynamic therapy(PDT)performance,and one even exhibits much stronger photocytotoxicity than the commercialized PS Ce6 under identical conditions.Theoretical studies show that this property originated from significantly reduced energy gaps between relevant excited singlet and triplet states,leading to considerably improved intersystem-crossing efficiency.Importantly,a simple disaggregation recovers the original properties of the fluorophores.This reversible switching property between fluorophores and PSs assists the development of smart PDT systems,in which singlet oxygen generation in tumors can be controlled in an intelligent manner after PDT treatment.The present work provides a novel strategy to design heavy-atom-free PSs and may pave the way to the development of smart PDT systems.展开更多
Structural modifications are a successful and commonly used approach to tune the emission properties of diverse fluorophores,but extending this approach to heavy-atom-free persistent luminophores has so far been unsuc...Structural modifications are a successful and commonly used approach to tune the emission properties of diverse fluorophores,but extending this approach to heavy-atom-free persistent luminophores has so far been unsuccessful.Here we employed a novel strategy to demonstrate triplet–triplet energy transfer from an organic room-temperature phosphor(RTP)with persistent luminescence to an organic molecule with thermally activated delayed fluorescence(TADF).We illustrated this approach by preparing heavy-atom-free composite crystals of an RTP with a long-lifetime emission and a red emissive organic fluorophore with TADF to yield materials with emission above 650 nm.The emission arose from the triplet excited state of an acceptor undergoing thermally activated reverse intersystem crossing(RISC)to the emissive S1 state.Such composite crystal is the first organic material with persistent TADF,achieved by triplet–triplet energy transfer.展开更多
We reported a new monofunctionalized pillar[5]arene bearing imidazolium moiety that formed stable [1]pseudorotaxane even at high concentration （100 mmol/L） in chloroform. The self-assembly was detailed investigated ...We reported a new monofunctionalized pillar[5]arene bearing imidazolium moiety that formed stable [1]pseudorotaxane even at high concentration （100 mmol/L） in chloroform. The self-assembly was detailed investigated by multiple methods, including varying concentration 1H NMR, 2D COSY NMR, 2D NOESY NMR, viscosity measurements, 2D DOSY NMR, and HR-ESI-MS analysis. [llRotaxane was obtained efficiently through photo thiol-ene reaction which further confirmed the formation of [l]pseudorotaxane.展开更多
The introduction of hydroxy group to the 3- or 5-position of 4,4-difluoro-4-bora-3aAa-diazaindacene （BODIPY） results in unexpected tautomerization to BDPONa with interesting structural and photophysical properties. ...The introduction of hydroxy group to the 3- or 5-position of 4,4-difluoro-4-bora-3aAa-diazaindacene （BODIPY） results in unexpected tautomerization to BDPONa with interesting structural and photophysical properties. The core of BDPONa is an anion with sodium cation as counter-ion. BDPONa displays strong fluorescence in organic solvents.展开更多
Difluoroboronβ-diketonate(BF2bdk)complexes have attracted much attention due to their outstanding photophysical properties.However,BF2bdk with near-infrared fluorescence usually suffer from emission quenching in soli...Difluoroboronβ-diketonate(BF2bdk)complexes have attracted much attention due to their outstanding photophysical properties.However,BF2bdk with near-infrared fluorescence usually suffer from emission quenching in solid state due to theπ-πstacking in aggregation.Herein,we report a BF2bdk dye exhibiting donor-acceptor(D-A)structure with the difluoroboron moiety acting as the electron acceptor and the aminonaphthalene as the electron donor.It processes intense molar extinction coefficient,large Stokes shift and strong fluorescence in red/NIR region in both solution and aggregations.It was used for NIR imaging in living cells.展开更多
基金support from the National Natural Science Foundation of China(22177014,22231001 and 21971023)the Fundamental Research Funds for the Central Universities and Key Laboratory of Photochemical Conversion and Optoelectronic Materials,TIPC,CAS.
文摘Glutathione(GSH)-activated prodrugs are promising for overcoming the limitations of conventional anti-tumor drugs.However,current GSH-responsive disulfide groups exhibit unregulated reactivity,making it impossible to precisely control the drug release rate.We herein report a series of GSH-responsive prodrugs with a“three-in-one”molecular design by integrating a fluorescence report unit,stimuliresponsive unit and chemodrug into one scaffold with tunable aromatic nucleophilic substitution(SNAr)reactivity.The drug release rate of these prodrugs is tailored by modification of substituent groups with different electron-withdrawing or-donating abilities on the BODIPY core.Furthermore,the prodrugs self-assemble in water to form nanoparticles that serve as photosensitizers to produce reactive oxygen species upon irradiation for photodynamic therapy(PDT).The PDT process also increases the concentration of GSH in cells,further promoting the release of drugs for chemotherapy.This strategy provides a powerful platform for sequential photodynamic and chemotherapy with tunable drug release rates and synergistic therapeutic effects.
基金financially supported by the National Natural Science Foundation of China (No. 21525206)
文摘Biothiols,including cysteine(Cys),homocysteine(Hey),and glutathione(GSH) play important roles in physiological processes,and the detection of thiol using fluorescent probes has attracted attention due to their high sensitivity and selectively and invasive on-time imaging.However,the similar structures and reactivity of these biothiols present great challenges for selective detection.This review focused on the the "aromatic nucleophilic substitution-rearrangement(SNAr-rearrangement) mechanism",which provided a powerful tool to design fluorescent probes for the discrimination between biothiols.We classify the fluorescent probes according to types of fluorophores,such as difluoroboron dipyrromethene(BODIPY),nitrobenzoxadiazole(NBD),cyanine,pyronin,naphthalimide,coumarin,and so on.We hope this review will inspire exploration of new fluorescent probes for biothiols and other relevant analytes.
基金financially supported by the 973 Program (No.2013CB933800)National Natural Science Foundation of China (Nos.21525206,21402216,21272243)the Fundamental Research Funds for the Central Universities and Beijing Municipal Commission of Education
文摘We report a turn-on fluorescent probe for H2S through a cascade reaction using a new trap group 4- （bromomethyl）benzoate, based on excited-state intramolecular proton transfer （ESIPT） sensing mechanism. The probe showed good selectivity and high sensitivity towards H2S and it was capable of detecting and imaging H2S in living HeLa cells, indicating its potential biological applications.
基金financially supported by National Natural Science Foundation of China (Nos. 21971023, 22074007 and 21525206)。
文摘Evaluating the correlation between hypoxia inducible factor 1(HIF-1) and nitric oxide(NO) generated under hypoxia is of great significance. In this work, we developed a fluorescent probe for the monitor of HIF-1 activity influenced by NO under hypoxia in hepatoma cells with dual-targeting for hepatocyte and lipid droplet(LD). The probe shows excellent selectivity to NO and high sensitivity with 6000-fold fluorescence enhancement. Live cell imaging experiments revealed the probe’s capability of imaging exogenous and endogenous NO with specific in LDs of Hep G2 cells. For cells under hypoxia, HIF-1 induced LD level is observed to correlate with NO level. This work provides the in-situ visualization of NO-dependent HIF-1 upregulation through LD accumulation.
基金This research was made possible as a result of generous grants from the National Natural Science Foundation of China(nos.22177014,21971023,21688102 and 21525206).
文摘We report for the first time a practical and simple supramolecular approach to turn fluorophores into photosensitizers(PSs).Using boron dipyrromethene(BODIPY)as a proof-of-concept,eight BODIPY derivatives manifest bright fluorescence and generate negligible singlet oxygen in solution.In contrast,aggregation fails to emit fluorescence and enhances singlet oxygen generation.Experimentally,these aggregates have excellent photodynamic therapy(PDT)performance,and one even exhibits much stronger photocytotoxicity than the commercialized PS Ce6 under identical conditions.Theoretical studies show that this property originated from significantly reduced energy gaps between relevant excited singlet and triplet states,leading to considerably improved intersystem-crossing efficiency.Importantly,a simple disaggregation recovers the original properties of the fluorophores.This reversible switching property between fluorophores and PSs assists the development of smart PDT systems,in which singlet oxygen generation in tumors can be controlled in an intelligent manner after PDT treatment.The present work provides a novel strategy to design heavy-atom-free PSs and may pave the way to the development of smart PDT systems.
基金This study was financially supported by the National Natural Science Foundation of China(nos.21525206 and 21971023)Q.-Z.Y.and by the EPSRC Early Career Fellowship(no.EP/L000075/1)to R.B.
文摘Structural modifications are a successful and commonly used approach to tune the emission properties of diverse fluorophores,but extending this approach to heavy-atom-free persistent luminophores has so far been unsuccessful.Here we employed a novel strategy to demonstrate triplet–triplet energy transfer from an organic room-temperature phosphor(RTP)with persistent luminescence to an organic molecule with thermally activated delayed fluorescence(TADF).We illustrated this approach by preparing heavy-atom-free composite crystals of an RTP with a long-lifetime emission and a red emissive organic fluorophore with TADF to yield materials with emission above 650 nm.The emission arose from the triplet excited state of an acceptor undergoing thermally activated reverse intersystem crossing(RISC)to the emissive S1 state.Such composite crystal is the first organic material with persistent TADF,achieved by triplet–triplet energy transfer.
基金the financial support from the 973 Program (No. 2013CB933800)the National Natural Science Foundation of China (Nos. 21222210, 21474124, 21472202)
文摘We reported a new monofunctionalized pillar[5]arene bearing imidazolium moiety that formed stable [1]pseudorotaxane even at high concentration （100 mmol/L） in chloroform. The self-assembly was detailed investigated by multiple methods, including varying concentration 1H NMR, 2D COSY NMR, 2D NOESY NMR, viscosity measurements, 2D DOSY NMR, and HR-ESI-MS analysis. [llRotaxane was obtained efficiently through photo thiol-ene reaction which further confirmed the formation of [l]pseudorotaxane.
基金financially supported by the 973 program (Nos.2013CB933800,2013CB834505)National Natural Science Foundation of China (Nos.21222210,21102155,91027041)the Chinese Academy of Sciences (100 Talents Program)
文摘The introduction of hydroxy group to the 3- or 5-position of 4,4-difluoro-4-bora-3aAa-diazaindacene （BODIPY） results in unexpected tautomerization to BDPONa with interesting structural and photophysical properties. The core of BDPONa is an anion with sodium cation as counter-ion. BDPONa displays strong fluorescence in organic solvents.
基金financially supported by National Natural Science Foundation of China(No.21525206)
文摘Difluoroboronβ-diketonate(BF2bdk)complexes have attracted much attention due to their outstanding photophysical properties.However,BF2bdk with near-infrared fluorescence usually suffer from emission quenching in solid state due to theπ-πstacking in aggregation.Herein,we report a BF2bdk dye exhibiting donor-acceptor(D-A)structure with the difluoroboron moiety acting as the electron acceptor and the aminonaphthalene as the electron donor.It processes intense molar extinction coefficient,large Stokes shift and strong fluorescence in red/NIR region in both solution and aggregations.It was used for NIR imaging in living cells.
