Hydrogen peroxide(H2O2)plays a significant role in regulating a variety of biological processes.Dysregulation of H2O2 can lead to various diseases.Although numerous fluorescent imaging probes for H2O2 have been report...Hydrogen peroxide(H2O2)plays a significant role in regulating a variety of biological processes.Dysregulation of H2O2 can lead to various diseases.Although numerous fluorescent imaging probes for H2O2 have been reported,the development of H2O2 ratiometric fluorescent probe with large Stokes shift remains rather limited.Such probes have shown distinct advantages,such as minimized interference from environment and improved signal-to noise ratio.In this work,we reported a new pyrene-based compound Py-VPB as H2O2 fluorescent probe in vitro.The probe demonstrated ratiometric detection behavior,large Stokes shift and large emission shift.In addition,the probe showed high sensitivity and selectivity towards H2O2 in vitro.Based on these excellent properties,we successfully applied Py-VPB to the visualization of exogenous and endogenous H2O2 in living cells.Cell imaging study also showed that our probe was localized in the mitochondria.We envision that the probe can provide a useful tool for unmasking the biological roles of mitochondrial H2O2 in living systems.展开更多
Herein,the 2,4-dinitrophenyl functional group acting as the thiophenol reactive site was introduced into a carbazole-chalcone fluorophore to synthesize probe-CCF2,which could result in a remarkable increase in fluores...Herein,the 2,4-dinitrophenyl functional group acting as the thiophenol reactive site was introduced into a carbazole-chalcone fluorophore to synthesize probe-CCF2,which could result in a remarkable increase in fluorescence when reacting with thiophenols.The selectivity and accuracy of probe-CCF2 were investigated with thiophenols,hydrosulphide salt,aliphatic thiols,glutathione,cysteine,anions and metal cations.Probe-CCF2 exhibited a detection limit of 37 nmol/L(R^(2)=0.9951),a remarkable Stokes shift of approximately 130 nm,and a brief response time of 9 min with a remarkable increase in fluorescence of 90-fold.Probe-CCF2 was applied for thiophenol detection in water samples and imaging in living cells successfully,with high sensitivity and excellent selectivity.展开更多
Fluorescent probes have been widely employed in biological imaging and sensing.However,it is always a challenge to design probes with high sensitivity.In this work,based on rhodamine skeleton,we developed a general st...Fluorescent probes have been widely employed in biological imaging and sensing.However,it is always a challenge to design probes with high sensitivity.In this work,based on rhodamine skeleton,we developed a general strategy to construct sensitivity-enhanced fluorescent probe with the help of theoretical calculation for the first time.As a proof of concept,we synthesized a series of HOCl probes.Experiment results showed that with the C-9 of pyronin moiety of rhodamine stabilized by an electron donor group,probe DQF-S exhibited an importantly enhanced sensitivity(LOD:0.2 nmol/L)towards HOCl together with fast response time(<10 s).Moreover,due to the breaking symmetrical electron distribution by another electron donor group,the novel rhodamine probe DQF-S displayed a far red to near-infrared emission(>650 nm)and large Stokes shift.Bioimaging studies indicated that DQF-S can not only effectively detect basal HOCl in various types of cells,but also be successfully applied to image tumor tissue in vivo.These results demonstrate the potential of our design as a useful strategy to develop excellent fluorescent probes for bioimaging.展开更多
A simple, mild and efficient one-pot approach for the construction of 2-aryl-3-nitro-2,9-dihydrothiopyrano- [2,3-b]indole derivatives has been realized in CH2C12 medium at ambient temperature via three-component tande...A simple, mild and efficient one-pot approach for the construction of 2-aryl-3-nitro-2,9-dihydrothiopyrano- [2,3-b]indole derivatives has been realized in CH2C12 medium at ambient temperature via three-component tandem reaction of N-protected-2-chloro-3-formylindoles, sodium hydrosulfide and β-substituted nitroolefins/δ-substituted nitrodienes using DABCO (10 mol%) as an organocatalyst, followed by dehydration in the presence of activated molecular sieves (4 A). The significant advantages of this protocol are simple operation, shorter reaction time, high atom economy, good to high yields (73%-89%) and wider substrate scope. In addition, all the synthesized com- pounds have shown the large positive Stokes shift values (5632-6081 cm ^-1).展开更多
Sulfydryl-contained(-SH)substances including hydrogen sulfide(H_(2)S),cysteine(Cys),homocysteine(Hcy)and glutathione(GSH)play crucial roles in living systems,and their variations are closely associated with various di...Sulfydryl-contained(-SH)substances including hydrogen sulfide(H_(2)S),cysteine(Cys),homocysteine(Hcy)and glutathione(GSH)play crucial roles in living systems,and their variations are closely associated with various diseases.Herein,we developed a near-infrared intramolecular charge transfer(ICT)based fluorescent probe Y-NBD,achieving detection of Cys/Hcy and H_(2)S with different fluorescent signals(green-red for Cys/Hcy,red for H_(2)S),large Stokes shifts(∼100/105nm or 191 nm)and high signal-background-ratio,but not responding to GSH.Y-NBD was successfully applied to image exogenous/endogenous Cys/Hcy and H_(2)S in various living cancer cells(HeLa,A549,and HepG2)and in zebrafish.It not only visualized the transformation pathway of several thiols in HepG2 cells but also verified that the intestine is the main site for the activation and metabolism of Y-NBD in zebrafish,as well as realized to evaluate the degree of drug-induced liver injury.This work provides a promising tool for imaging Cys/Hcy and H_(2)S in living systems and shows great potency in evaluating drug-induced liver injury and its treatment.展开更多
Thiophenol(PhSH)is an important raw material for organic synthesis,while its high toxicity to organisms makes it an environmental pollutant.Therefore,it is crucial to accurately detect PhSH and explore its metabolic p...Thiophenol(PhSH)is an important raw material for organic synthesis,while its high toxicity to organisms makes it an environmental pollutant.Therefore,it is crucial to accurately detect PhSH and explore its metabolic process in the living system.Herein,a near-infrared(NIR)fluorescent probe TEM-FB was developed for sensing PhSH with a turn-on fluorescent signal at 719nm and a large Stokes shift(198 nm)based on generating the intramolecular charge transfer(ICT)process.TEM-FB shows high specificity and significant sensitivity towards PhSH(detection limit:10 nmol/L)via the aromatic nucleophilic substitution mechanism.Furthermore,it was successfully applied to image PhSH in multiple cell lines and in zebrafish.Notably,we revealed the oxidative stress process caused by PhSH and demonstrated that the hydrogen peroxide(H_(2)O_(2))in cells would alleviate the poisonousness from exogenous PhSH for the first time.This work provides a promising bioimaging tool for monitoring PhSH in living systems and visualizing the process of oxidative stress induced by PhSH.展开更多
Based on the coumarin skeleton, we deliberately designed two groups of fluorophores, termed as CoumR and Naph-Coum-R, using the diphenylamino group as the electron donor, which displayed longwavelength emissions(red s...Based on the coumarin skeleton, we deliberately designed two groups of fluorophores, termed as CoumR and Naph-Coum-R, using the diphenylamino group as the electron donor, which displayed longwavelength emissions(red spectral region), large Stokes shift(up to 204 nm), superior AIE performance,and large two-photon absorbance cross-sections(as high as 365 GM). The electron-withdrawing substituents at the 3-position of these dyes could induce a significant red-shift in their emission spectra.Preliminary imaging experiments demonstrated the capability of these dyes as two-photon fluorophores for specifically staining lipid droplets in living cells.展开更多
Two novel thieno-[3,4-b]-pyrazine-based molecules, TP-E and TP-O, were designed and synthesized for potential application as red fluorescent emitters. The bulky tetraphenylethylene groups were attached at the peripher...Two novel thieno-[3,4-b]-pyrazine-based molecules, TP-E and TP-O, were designed and synthesized for potential application as red fluorescent emitters. The bulky tetraphenylethylene groups were attached at the periphery of the thieno-[3,4-b]-pyrazine core to form the non-planar molecules, as efficient solid- state emitting materials. The peripheral groups were grafted to the emissive core through either a conjugated acetylene bond, or a non-conjugated ether bond. These molecules exhibit strnng red fluorescence in both dilute solutions and in thin films with large Stokes shifts of over 100 nm. The cyclic voltammetry measurements showed the reversible oxidation and reduction behavior for both compounds. All these properties indicate the two compounds are possible functional materials for use in ontoelectronic devices.展开更多
Herein,we presented a brand-new concept to construct the Forster resonance energy transfer(FRET)based cassette by integrating a vibration-induced emission(VIE)chromophore as the donor.Different from traditional donors...Herein,we presented a brand-new concept to construct the Forster resonance energy transfer(FRET)based cassette by integrating a vibration-induced emission(VIE)chromophore as the donor.Different from traditional donors only with a single emission,the VIE donor possessed well-separated dual emission bands by altering the excited state molecular configuration from the bent state to the planar state.By linking an acceptor such as a cyanine dye(Cy5),a novel VIE-FRET cassette(PPCy5)was prepared.The planar emission profile of the VIE donor moiety could fully cover the absorption of Cy5,and thus the complete FRET process enabled the excellent bimodal spectra difference of 142 nm and ultra-large pseudo-Stokes shift of up to 300 nm.Benefiting from the viscosity-dependent characteristic of the VIE donor,PPCy5 could clearly and intuitively reveal the different viscosity regions in vivo by dual-color and high-resolution imaging.The VIE-FRET paradigm provides an optional platform for developing donor-acceptor-based dual-color fluorescent probes with high-resolution imaging ability.展开更多
基金This work was supported by the Science Technology and Innovation Committee of Shenzhen Municipality(JCYJ20180507181654823)the National Natural Science Foundation of China(21778044)and Sichuan Science and Technology Program(2018JY0360).
文摘Hydrogen peroxide(H2O2)plays a significant role in regulating a variety of biological processes.Dysregulation of H2O2 can lead to various diseases.Although numerous fluorescent imaging probes for H2O2 have been reported,the development of H2O2 ratiometric fluorescent probe with large Stokes shift remains rather limited.Such probes have shown distinct advantages,such as minimized interference from environment and improved signal-to noise ratio.In this work,we reported a new pyrene-based compound Py-VPB as H2O2 fluorescent probe in vitro.The probe demonstrated ratiometric detection behavior,large Stokes shift and large emission shift.In addition,the probe showed high sensitivity and selectivity towards H2O2 in vitro.Based on these excellent properties,we successfully applied Py-VPB to the visualization of exogenous and endogenous H2O2 in living cells.Cell imaging study also showed that our probe was localized in the mitochondria.We envision that the probe can provide a useful tool for unmasking the biological roles of mitochondrial H2O2 in living systems.
基金supported by Natural Science Foundation of Zhejiang Province(LQ21C200002)Zhejiang Provincial Key Research and Development Program(2021CO2062,2022C02028)Key Research and Development Program of Ningbo(2021Z056,2022S163)
文摘Herein,the 2,4-dinitrophenyl functional group acting as the thiophenol reactive site was introduced into a carbazole-chalcone fluorophore to synthesize probe-CCF2,which could result in a remarkable increase in fluorescence when reacting with thiophenols.The selectivity and accuracy of probe-CCF2 were investigated with thiophenols,hydrosulphide salt,aliphatic thiols,glutathione,cysteine,anions and metal cations.Probe-CCF2 exhibited a detection limit of 37 nmol/L(R^(2)=0.9951),a remarkable Stokes shift of approximately 130 nm,and a brief response time of 9 min with a remarkable increase in fluorescence of 90-fold.Probe-CCF2 was applied for thiophenol detection in water samples and imaging in living cells successfully,with high sensitivity and excellent selectivity.
基金the National Natural Science Foundation of China(Nos.21877029,21735001)the National Key R&D Program of China(No.2019YFA0210103)+1 种基金the National Postdoctoral Program for Innovative Talents(No.BX20190110)the China Postdoctoral Science Foundation(No.2019M662758)。
文摘Fluorescent probes have been widely employed in biological imaging and sensing.However,it is always a challenge to design probes with high sensitivity.In this work,based on rhodamine skeleton,we developed a general strategy to construct sensitivity-enhanced fluorescent probe with the help of theoretical calculation for the first time.As a proof of concept,we synthesized a series of HOCl probes.Experiment results showed that with the C-9 of pyronin moiety of rhodamine stabilized by an electron donor group,probe DQF-S exhibited an importantly enhanced sensitivity(LOD:0.2 nmol/L)towards HOCl together with fast response time(<10 s).Moreover,due to the breaking symmetrical electron distribution by another electron donor group,the novel rhodamine probe DQF-S displayed a far red to near-infrared emission(>650 nm)and large Stokes shift.Bioimaging studies indicated that DQF-S can not only effectively detect basal HOCl in various types of cells,but also be successfully applied to image tumor tissue in vivo.These results demonstrate the potential of our design as a useful strategy to develop excellent fluorescent probes for bioimaging.
文摘A simple, mild and efficient one-pot approach for the construction of 2-aryl-3-nitro-2,9-dihydrothiopyrano- [2,3-b]indole derivatives has been realized in CH2C12 medium at ambient temperature via three-component tandem reaction of N-protected-2-chloro-3-formylindoles, sodium hydrosulfide and β-substituted nitroolefins/δ-substituted nitrodienes using DABCO (10 mol%) as an organocatalyst, followed by dehydration in the presence of activated molecular sieves (4 A). The significant advantages of this protocol are simple operation, shorter reaction time, high atom economy, good to high yields (73%-89%) and wider substrate scope. In addition, all the synthesized com- pounds have shown the large positive Stokes shift values (5632-6081 cm ^-1).
基金supported by the National Natural Science Foundation of China(Nos.22077099 and 22171223)the Innovation Capability Support Program of Shaanxi(Nos.2023-CX-TD-75 and 2022KJXX-32)+4 种基金the Technology Innovation Leading Program of Shaanxi(Program No.2023KXJ-209)the Natural Science Basic Research Program of Shaanxi(Nos.2022JQ-151 and 2023-JC-YB-141)Young Talent Fund of Association for Science and Technology in Shaanxi,China(No.SWYY202206)the Shaanxi Fundamental Science Research Project for Chemistry&Biology(Nos.22JHZ010 and 22JHQ080)the Yan’an City Science and Technology Project(No.2022SLZDCY-002).
文摘Sulfydryl-contained(-SH)substances including hydrogen sulfide(H_(2)S),cysteine(Cys),homocysteine(Hcy)and glutathione(GSH)play crucial roles in living systems,and their variations are closely associated with various diseases.Herein,we developed a near-infrared intramolecular charge transfer(ICT)based fluorescent probe Y-NBD,achieving detection of Cys/Hcy and H_(2)S with different fluorescent signals(green-red for Cys/Hcy,red for H_(2)S),large Stokes shifts(∼100/105nm or 191 nm)and high signal-background-ratio,but not responding to GSH.Y-NBD was successfully applied to image exogenous/endogenous Cys/Hcy and H_(2)S in various living cancer cells(HeLa,A549,and HepG2)and in zebrafish.It not only visualized the transformation pathway of several thiols in HepG2 cells but also verified that the intestine is the main site for the activation and metabolism of Y-NBD in zebrafish,as well as realized to evaluate the degree of drug-induced liver injury.This work provides a promising tool for imaging Cys/Hcy and H_(2)S in living systems and shows great potency in evaluating drug-induced liver injury and its treatment.
基金supported by the National Natural Science Foundation of China(Nos.22077099 and 22171223)the Technology Innovation Leading Program of Shaanxi(No.2020TG-031)+3 种基金the Innovation Capability Support Program of Shaanxi(Nos.2023-CXTD-75 and 2022KJXX-32)the Natural Science Basic Research Program of Shaanxi(No.2023-JC-YB-141)Young Talent Fund of Association for Science and Technology in Shaanxi,China(No.SWYY202206)the Natural Science Basic Research Plan in Shaanxi Province of China(Nos.2022JQ-151 and 2022JQ-125).
文摘Thiophenol(PhSH)is an important raw material for organic synthesis,while its high toxicity to organisms makes it an environmental pollutant.Therefore,it is crucial to accurately detect PhSH and explore its metabolic process in the living system.Herein,a near-infrared(NIR)fluorescent probe TEM-FB was developed for sensing PhSH with a turn-on fluorescent signal at 719nm and a large Stokes shift(198 nm)based on generating the intramolecular charge transfer(ICT)process.TEM-FB shows high specificity and significant sensitivity towards PhSH(detection limit:10 nmol/L)via the aromatic nucleophilic substitution mechanism.Furthermore,it was successfully applied to image PhSH in multiple cell lines and in zebrafish.Notably,we revealed the oxidative stress process caused by PhSH and demonstrated that the hydrogen peroxide(H_(2)O_(2))in cells would alleviate the poisonousness from exogenous PhSH for the first time.This work provides a promising bioimaging tool for monitoring PhSH in living systems and visualizing the process of oxidative stress induced by PhSH.
基金supported by the National Natural Science Foundation of China (No. 22178395)。
文摘Based on the coumarin skeleton, we deliberately designed two groups of fluorophores, termed as CoumR and Naph-Coum-R, using the diphenylamino group as the electron donor, which displayed longwavelength emissions(red spectral region), large Stokes shift(up to 204 nm), superior AIE performance,and large two-photon absorbance cross-sections(as high as 365 GM). The electron-withdrawing substituents at the 3-position of these dyes could induce a significant red-shift in their emission spectra.Preliminary imaging experiments demonstrated the capability of these dyes as two-photon fluorophores for specifically staining lipid droplets in living cells.
基金the National Natural Science Foundation of China(Nos.21274016 and 21072026)Fundamental Research Funds for the Central Universities(No.DUT13LK06)for financial support to this work
文摘Two novel thieno-[3,4-b]-pyrazine-based molecules, TP-E and TP-O, were designed and synthesized for potential application as red fluorescent emitters. The bulky tetraphenylethylene groups were attached at the periphery of the thieno-[3,4-b]-pyrazine core to form the non-planar molecules, as efficient solid- state emitting materials. The peripheral groups were grafted to the emissive core through either a conjugated acetylene bond, or a non-conjugated ether bond. These molecules exhibit strnng red fluorescence in both dilute solutions and in thin films with large Stokes shifts of over 100 nm. The cyclic voltammetry measurements showed the reversible oxidation and reduction behavior for both compounds. All these properties indicate the two compounds are possible functional materials for use in ontoelectronic devices.
基金This work was supported by the National Natural Science Foundation of China(21788102,21905090,21790361,22004036,91859205)Shanghai Municipal Science and Technology Major Project(2018SHZDZX03)+2 种基金the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning,Programme of Introducing Talents of Discipline to Universities(B16017)Shanghai Science and Technology Committee(17520750100)Natural Science Foundation of Shanghai(19ZR1412200),and the Fundamental Research Funds for the Central Universities.
文摘Herein,we presented a brand-new concept to construct the Forster resonance energy transfer(FRET)based cassette by integrating a vibration-induced emission(VIE)chromophore as the donor.Different from traditional donors only with a single emission,the VIE donor possessed well-separated dual emission bands by altering the excited state molecular configuration from the bent state to the planar state.By linking an acceptor such as a cyanine dye(Cy5),a novel VIE-FRET cassette(PPCy5)was prepared.The planar emission profile of the VIE donor moiety could fully cover the absorption of Cy5,and thus the complete FRET process enabled the excellent bimodal spectra difference of 142 nm and ultra-large pseudo-Stokes shift of up to 300 nm.Benefiting from the viscosity-dependent characteristic of the VIE donor,PPCy5 could clearly and intuitively reveal the different viscosity regions in vivo by dual-color and high-resolution imaging.The VIE-FRET paradigm provides an optional platform for developing donor-acceptor-based dual-color fluorescent probes with high-resolution imaging ability.