The detection of biothiols such as cysteine(Cys),homocysteine(Hcy),and glutathione(GSH)are critical for understanding their roles in biology and their involvement in various physiological and pathological processes.Re...The detection of biothiols such as cysteine(Cys),homocysteine(Hcy),and glutathione(GSH)are critical for understanding their roles in biology and their involvement in various physiological and pathological processes.Recently,significant progress has been made in constructing fluorescent probes capable of detecting and visualizing biothiols.This review provides an in-depth look at the latest advancements in simultaneous and selective molecular probes,focusing on developments over the last 5 years.We examine design techniques,sensing mechanisms,and imaging methods to assess their effectiveness and responsiveness to thiols.Additionally,we discuss the prevailing challenges and offer recommendations to address them.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
Lanthanide-doped upconversion nanoparticles(Ln-UCNPs)are a new type of nanomaterials with excellent fluorescence properties,which are well applied in fluorescent biosensing.Herein we developed a multifunctional probe ...Lanthanide-doped upconversion nanoparticles(Ln-UCNPs)are a new type of nanomaterials with excellent fluorescence properties,which are well applied in fluorescent biosensing.Herein we developed a multifunctional probe based on the surface engineering of core-shell structure UCNPs with polyacrylic acid(PAA).The developed PAA/UCNPs probe could be highly selective to detect and respond to Cu^(2+) at different pH.Cu^(2+) could easily combine with the carboxylate anion of PAA to quench the fluorescence of UCNPs.Therefore,we creatively proposed a fluorescent array sensor(PAA/UCNPs-Cu^(2+)),in which the same material acted as the sensing element by coupled with pH regulation for pattern recognition of 5 thiols.It could also easily identify the chiral enantiomer of cystine(L-Cys-and D-Cys),and distinguish their mixed samples with different concentrations,and more importantly,it could be combined with urine samples to detect actual level of homocysteine(Hcys)to provide a new solution for judging whether the human body suffers from homocystinuria.展开更多
In this work, we presented a fluorescent probe(MCQ-DNBS) for selective and sensitive detection of biothiols based on a methylated chromenoquinoline(MCQ) derivative. Probe MCQ-DNBS was constructed by masking the OH gro...In this work, we presented a fluorescent probe(MCQ-DNBS) for selective and sensitive detection of biothiols based on a methylated chromenoquinoline(MCQ) derivative. Probe MCQ-DNBS was constructed by masking the OH group in MCQ with a common sensing unit, 2,4-dinitrobezensulfonate group(DNBS) for biothiols. Due to the photo-induced electron transfer(PET) process between MCQ and DNBS, this probe was weekly fluorescent. Upon the addition of biothiols(Cys, Hcy and GSH), this probe emitted a strong red fluorescence(λ_(em max)=613 nm) with a large Stokes shift(115 nm). In addition,fluorescence imaging of biothiols in living cells was successfully realized using MCQ-DNBS as a detector.展开更多
A dual-site fluorescent probe with double bond and aldehyde as reactive sites, was designed for the selective detection of sulfite and biothiols. Sulfite reacts with conjugate bond selectively, while Cys responses wit...A dual-site fluorescent probe with double bond and aldehyde as reactive sites, was designed for the selective detection of sulfite and biothiols. Sulfite reacts with conjugate bond selectively, while Cys responses with aldehyde and GSH occurs substitution reaction. Different interactions cause different absorption and fluorescence responses. Moreover, it could be further applied in imaging in living cells.展开更多
Au or other metal nanostructures have the ability to strongly quench the fluorescence of fluorophores.This feature has made AuNP-conjugates attractive for the construction of platforms for various bioanalytes to overc...Au or other metal nanostructures have the ability to strongly quench the fluorescence of fluorophores.This feature has made AuNP-conjugates attractive for the construction of platforms for various bioanalytes to overcome the limitations of small molecule fluorophores(poor solubility,long reaction time).In this paper,an ultrafast"Turn-On"fluo rescent sensor for biothiols was constructed.The sensor is based on the fluorescent resonance energy transfer(FRET)effect between the fluorophore(PN)and AuNPs,which effectively quenches the fluorescence of the fluorophore.In the presence of thiols,PN is displaced and released from AuNP surfaces,and thus,the fluorescence is rapidly restored.The sensor features appreciable water solubility and ultrafast response time(a few seconds for Cys).In addition,it exhibits high selectivity and a detection limit as low as 12 nmol/L for Hcy.Moreover,the sensor presents good biocompatibility and has been successfully applied for imaging biothiols in living cells.展开更多
Biothiols such as cysteine(Cys),homocysteine(Hcy)and glutathione(GSH)act as critical roles in maintaining biological redox homeostasis,which is crucial for a plenty of physiological and pathological processes.Therefor...Biothiols such as cysteine(Cys),homocysteine(Hcy)and glutathione(GSH)act as critical roles in maintaining biological redox homeostasis,which is crucial for a plenty of physiological and pathological processes.Therefore,the detection of biothiols is very important and beneficial for many applications.Herein,we have designed and developed a new crystal dimethyl 4-(2,4-dinitrophenylsulfonyloxy)pyridine-2,6-dicarboxylate(P)with 2,4-dinitrobenzene-1-sulfonyl(DNBS)pendant for light-up and detection of biothiols(Cys was selected as the analyte model).The fluorescence"off-on"switch is triggered by the cleavage of DNBS unit by the interaction with biothiols via nucleophilic aromatic substitution reaction.The turn-on fluorescent probe exhibited excellent selectivity and sensitivity toward biothiols.展开更多
4-Fluoro-7-nitrobenzo-2-oxa-1,3-diazole（NBD-F） was employed as a colorimetric probe for differential detection of biothiols in different media. The spectral response and the selectivity of NBD-F toward thiols were s...4-Fluoro-7-nitrobenzo-2-oxa-1,3-diazole（NBD-F） was employed as a colorimetric probe for differential detection of biothiols in different media. The spectral response and the selectivity of NBD-F toward thiols were significantly improved by surfactant micelles. Mercapto group exhibited high reactivity in all the solvents（including Tris–HCl buffer solution, CTAB and SDS micelles）. The 4-thioether derivatives of NBDF reacting with Cys and Hcy but not GSH could transfer to the corresponding 4-amino-substituents via intramolecular nucleophilic aromatic substitution, thus, GSH could be discriminated from Cys/Hcy. In CTAB micelles, the reaction product of NBD-F with Cys is non-fluorescent and it absorbs in longwavelength region. According to the spectral responses of NBD-F toward different low-molecularweight thiols, we could identify Cys, Hcy and GSH from each other.展开更多
In this study,a biothiol-sensitive near-infrared(NIR)fluorescent sensor,BDP-CYS,based on a coumarinhemicyanine skeleton,was designed and developed based on thiol−halogen SNAr nucleophilic substitution.BDP-CYS was succ...In this study,a biothiol-sensitive near-infrared(NIR)fluorescent sensor,BDP-CYS,based on a coumarinhemicyanine skeleton,was designed and developed based on thiol−halogen SNAr nucleophilic substitution.BDP-CYS was successfully implemented to ratiometrically monitor endogenous and exogenous Cys,Hcy,and GSH in living cells as well as to distinguish between normal and cancer cells.Furthermore,the probe was utilized to detect changes of biothiols in drug-induced hepatotoxicity and evaluate the treatment effectiveness of diabetes-associated liver injury in vivo.The advantages of BDP-CYS’s Cys,Hcy,and GSH include practical sensitivity,high selectivity,rapidity of reaction,and stability across a range of pH and temperature conditions,thus introducing a new tool to better understand the roles of biothiols in oxidative stress.展开更多
Biothiols are important species in physiological processes such as regulating protein structures, redox homeostasis and cell signalling. Alternation in the biothiol levels is associated with various pathological proce...Biothiols are important species in physiological processes such as regulating protein structures, redox homeostasis and cell signalling. Alternation in the biothiol levels is associated with various pathological processes, therefore non-invasive fluorescent probes with high specificity to biothiols are highly desirable research utilities. Meanwhile, fluorescent probes with aggregationinduced emission properties(AIEgens) possess unique photophysical properties that allow modulation of the sensing process through controlling the aggregation-disaggregation or the intramolecular rotational motions of the fluorophores. Herein we review the recent progress in the development of biothiol-specific AIEgens. In particular, the molecular design principles to target different types of biothiols and the corresponding sensing mechanisms are discussed, along with the potential of the future design and development of multi-functional bioprobes.展开更多
A simple and sensitive electrogenerated chemiluminescence(ECL)sensor array was developed for the discrimination of three biothiols,including homocysteine(Hcy),cysteine(Cys)and glutathione(GSH)using two bis-cyclometala...A simple and sensitive electrogenerated chemiluminescence(ECL)sensor array was developed for the discrimination of three biothiols,including homocysteine(Hcy),cysteine(Cys)and glutathione(GSH)using two bis-cyclometalated Ir(Ⅲ)complexes as ECL probes.Two aldehyde groups bearing bis-cyclometalated Ir(Ⅲ)complexes were selected as ECL probes,including[(bt)2Ir(phen-CHO)]PF_(6)(bt=2-phenylbenzothiazole,phen-CHO=1,10-phenanthroline-5-carboxaldehyde,probe 1)and[(ppy)_(2)Ir(phen-CHO)]PF_(6)(ppy=2-phenylpyridine,probe 2).A“signal on”ECL method was proposed for biothiols assay based on the increase in ECL intensity of two ECL probes by biothiols.Three biothiols can be detected with detection limits of 0.8,0.7 and 0.8μM by probe 1 and 0.3,0.4 and 0.5μM by probe 2 for Cys,Hcy and GSH,respectively.Two-element sensor array was assembled for the detection of three biothiols due to the different enhancement effects of biothiols on the ECL intensity of two ECL probes.The ECL sensor array combining with the principal component analysis was applied to discriminate three biothiols.This study demonstrates that the ECL sensor array using dual ECL reagents provides a promis-ing way for the discrimination of multiple biothiols with good sensitivity and simpleness.展开更多
The content of biothiols in cells is highly associated with the occurrence and development of several diseases.However,due to their active chemical properties,thiol-contained molecules are normally volatile during the...The content of biothiols in cells is highly associated with the occurrence and development of several diseases.However,due to their active chemical properties,thiol-contained molecules are normally volatile during the detection process,rendering precise analysis of intracellular biothiols challenging.In this study,5,5’-dithiobis-(2-nitrobenzoic acid)(DTNB)is covalently modified on the surface of gold nanorods(AuNRs),constructing sensing substrates for in situ Raman imaging analysis of biothiols in cells.Au NRs are able to serve as ideal surface-enhanced Raman scattering substrates,and thus Raman signals of DTNB are greatly amplified by AuNRs.Meanwhile,the disulfide bond of DTNB can be broken by thiols,thereby releasing part of DTNB from the surface of AuNRs.As a result,three kinds of main biothiols are sensitively quantified with DTNB-modified AuNRs according to the variation of Raman signals,and DTNB-modified Au NRs exhibit far better analytical performance than a commercial probe.In addition,the sensing substrates can be readily delivered to cytoplasm with the transmembrane of Au NRs,and are capable of responding to biothiols in cells.Notably,the Raman approach is established by the breaking of chemical bonds rather than the aggregation of substrates,which is more inclined to analyze intracellular biothiols with a desirable spatial resolution.Therefore,fluctuation of biothiols in glioma cells is evidently observed via Raman imaging.Overall,this work provides an alternative strategy for designing Raman sensors to visualize active molecules in cells.展开更多
The abnormal changes of biothiols are directly related to health condition of human body,and the effective identification and quantification of biothiols is of great significance for screening and diagnosis of disease...The abnormal changes of biothiols are directly related to health condition of human body,and the effective identification and quantification of biothiols is of great significance for screening and diagnosis of disease.This study described the development of a p H-regulated colorimetric sensor array for discrimination of five kinds of biothiols including cysteine(Cys),glutathione(GSH),homocysteine(Hcy),cysteamine(CA)and N-acetylcysteine(NAC).The proposed sensor array was established using 5-nm-and 20-nm-sizedβ-cyclodextrin-functionalized gold nanoparticles(β-CD@Au NPs)as nonspecific receptor and signal transduction elements.Due to the different binding affinity between biothiols andβ-CD@Au NPs in various p H environments,the different aggregation behaviors of nanoparticles produced unique colorimetric response patterns,which were able to be distinguished by bare eyes and UV-vis spectrophotometer.Accordingly,principal component analysis(PCA)and hierarchical cluster analysis(HCA)were employed for pattern recognition and generated a clustering map for a clear differentiation of biothiols at the level ofμmol/L.Furthermore,it can be proved that the method was successfully applied to the analysis of biothiols in human urine samples.展开更多
基金XLS thanks the National Natural Science Foundation of China(No.21907080,22278330)the Youth Innovative Team(No.xtr052022012)from Xi'an Jiaotong Universitysupported by the Natural Science Basic Research Program of Shaanxi(Program No.2023-JC-QN-0246).
文摘The detection of biothiols such as cysteine(Cys),homocysteine(Hcy),and glutathione(GSH)are critical for understanding their roles in biology and their involvement in various physiological and pathological processes.Recently,significant progress has been made in constructing fluorescent probes capable of detecting and visualizing biothiols.This review provides an in-depth look at the latest advancements in simultaneous and selective molecular probes,focusing on developments over the last 5 years.We examine design techniques,sensing mechanisms,and imaging methods to assess their effectiveness and responsiveness to thiols.Additionally,we discuss the prevailing challenges and offer recommendations to address them.
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supported by the National Natural Science Foundation of China(No.21775044)the Shanghai Science and Technology Committee(Nos.19ZR1473300 and 18DZ1112700)the Fundamental Research Funds for the Central Universities。
文摘Lanthanide-doped upconversion nanoparticles(Ln-UCNPs)are a new type of nanomaterials with excellent fluorescence properties,which are well applied in fluorescent biosensing.Herein we developed a multifunctional probe based on the surface engineering of core-shell structure UCNPs with polyacrylic acid(PAA).The developed PAA/UCNPs probe could be highly selective to detect and respond to Cu^(2+) at different pH.Cu^(2+) could easily combine with the carboxylate anion of PAA to quench the fluorescence of UCNPs.Therefore,we creatively proposed a fluorescent array sensor(PAA/UCNPs-Cu^(2+)),in which the same material acted as the sensing element by coupled with pH regulation for pattern recognition of 5 thiols.It could also easily identify the chiral enantiomer of cystine(L-Cys-and D-Cys),and distinguish their mixed samples with different concentrations,and more importantly,it could be combined with urine samples to detect actual level of homocysteine(Hcys)to provide a new solution for judging whether the human body suffers from homocystinuria.
基金supported by the National Natural Science Foundation of China (No.U1608222)Special Fund for Agroscientific Research in the Public Interest of China(No.201503108)+1 种基金Fundamental Research Funds for the Central Universities of Central South University (No. 2018zzts109)the State Key Laboratory of Chemo/Biosensing and Chemometrics (No. 2016005)
文摘In this work, we presented a fluorescent probe(MCQ-DNBS) for selective and sensitive detection of biothiols based on a methylated chromenoquinoline(MCQ) derivative. Probe MCQ-DNBS was constructed by masking the OH group in MCQ with a common sensing unit, 2,4-dinitrobezensulfonate group(DNBS) for biothiols. Due to the photo-induced electron transfer(PET) process between MCQ and DNBS, this probe was weekly fluorescent. Upon the addition of biothiols(Cys, Hcy and GSH), this probe emitted a strong red fluorescence(λ_(em max)=613 nm) with a large Stokes shift(115 nm). In addition,fluorescence imaging of biothiols in living cells was successfully realized using MCQ-DNBS as a detector.
基金financially supported by the National Natural Science Foundation of China (Nos.21572147, 21232005 and J1103315)
文摘A dual-site fluorescent probe with double bond and aldehyde as reactive sites, was designed for the selective detection of sulfite and biothiols. Sulfite reacts with conjugate bond selectively, while Cys responses with aldehyde and GSH occurs substitution reaction. Different interactions cause different absorption and fluorescence responses. Moreover, it could be further applied in imaging in living cells.
基金the support from the National Natural Science Foundation of China(Nos.81971678 and 81671756)Key Research Project of Science and Technology Foundation of Hunan Province(Nos.2017SK2093,2018GK5004 and 2019SK2211)Projects of Medical and Health Technology Development Program in Shandong Province(No.2018WS471)。
文摘Au or other metal nanostructures have the ability to strongly quench the fluorescence of fluorophores.This feature has made AuNP-conjugates attractive for the construction of platforms for various bioanalytes to overcome the limitations of small molecule fluorophores(poor solubility,long reaction time).In this paper,an ultrafast"Turn-On"fluo rescent sensor for biothiols was constructed.The sensor is based on the fluorescent resonance energy transfer(FRET)effect between the fluorophore(PN)and AuNPs,which effectively quenches the fluorescence of the fluorophore.In the presence of thiols,PN is displaced and released from AuNP surfaces,and thus,the fluorescence is rapidly restored.The sensor features appreciable water solubility and ultrafast response time(a few seconds for Cys).In addition,it exhibits high selectivity and a detection limit as low as 12 nmol/L for Hcy.Moreover,the sensor presents good biocompatibility and has been successfully applied for imaging biothiols in living cells.
基金supported financially by the National Natural Science Foundation of Henan(162300410200)Key Scientific Research Projects of Higher Education of He’nan Province(17A150016)
文摘Biothiols such as cysteine(Cys),homocysteine(Hcy)and glutathione(GSH)act as critical roles in maintaining biological redox homeostasis,which is crucial for a plenty of physiological and pathological processes.Therefore,the detection of biothiols is very important and beneficial for many applications.Herein,we have designed and developed a new crystal dimethyl 4-(2,4-dinitrophenylsulfonyloxy)pyridine-2,6-dicarboxylate(P)with 2,4-dinitrobenzene-1-sulfonyl(DNBS)pendant for light-up and detection of biothiols(Cys was selected as the analyte model).The fluorescence"off-on"switch is triggered by the cleavage of DNBS unit by the interaction with biothiols via nucleophilic aromatic substitution reaction.The turn-on fluorescent probe exhibited excellent selectivity and sensitivity toward biothiols.
基金financially supported by Shanghai Municipal Natural Science Foundation(No.15ZR1409000)the open fund of Shanghai Key Laboratory of Chemical Biology(No.SKLCB-2013-03)
文摘4-Fluoro-7-nitrobenzo-2-oxa-1,3-diazole（NBD-F） was employed as a colorimetric probe for differential detection of biothiols in different media. The spectral response and the selectivity of NBD-F toward thiols were significantly improved by surfactant micelles. Mercapto group exhibited high reactivity in all the solvents（including Tris–HCl buffer solution, CTAB and SDS micelles）. The 4-thioether derivatives of NBDF reacting with Cys and Hcy but not GSH could transfer to the corresponding 4-amino-substituents via intramolecular nucleophilic aromatic substitution, thus, GSH could be discriminated from Cys/Hcy. In CTAB micelles, the reaction product of NBD-F with Cys is non-fluorescent and it absorbs in longwavelength region. According to the spectral responses of NBD-F toward different low-molecularweight thiols, we could identify Cys, Hcy and GSH from each other.
基金supported by grants from the National Natural Science Foundation of China(Grant No.22106008)Basic Research Project(General Program)of Xuzhou(KC23055,KC22296)+1 种基金The Scientific Research Project of Health Commission of Jiangsu Province(Z2023016)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX24_3067).
文摘In this study,a biothiol-sensitive near-infrared(NIR)fluorescent sensor,BDP-CYS,based on a coumarinhemicyanine skeleton,was designed and developed based on thiol−halogen SNAr nucleophilic substitution.BDP-CYS was successfully implemented to ratiometrically monitor endogenous and exogenous Cys,Hcy,and GSH in living cells as well as to distinguish between normal and cancer cells.Furthermore,the probe was utilized to detect changes of biothiols in drug-induced hepatotoxicity and evaluate the treatment effectiveness of diabetes-associated liver injury in vivo.The advantages of BDP-CYS’s Cys,Hcy,and GSH include practical sensitivity,high selectivity,rapidity of reaction,and stability across a range of pH and temperature conditions,thus introducing a new tool to better understand the roles of biothiols in oxidative stress.
基金supported by Australian Research Council (DE170100058)Rebecca L. Cooper Medical Research Foundation
文摘Biothiols are important species in physiological processes such as regulating protein structures, redox homeostasis and cell signalling. Alternation in the biothiol levels is associated with various pathological processes, therefore non-invasive fluorescent probes with high specificity to biothiols are highly desirable research utilities. Meanwhile, fluorescent probes with aggregationinduced emission properties(AIEgens) possess unique photophysical properties that allow modulation of the sensing process through controlling the aggregation-disaggregation or the intramolecular rotational motions of the fluorophores. Herein we review the recent progress in the development of biothiol-specific AIEgens. In particular, the molecular design principles to target different types of biothiols and the corresponding sensing mechanisms are discussed, along with the potential of the future design and development of multi-functional bioprobes.
基金the National Natural Science Foundation of China(Nos.21775097,21775098)the Fundamental Research Funds for the Central Universities(GK201801006)。
文摘A simple and sensitive electrogenerated chemiluminescence(ECL)sensor array was developed for the discrimination of three biothiols,including homocysteine(Hcy),cysteine(Cys)and glutathione(GSH)using two bis-cyclometalated Ir(Ⅲ)complexes as ECL probes.Two aldehyde groups bearing bis-cyclometalated Ir(Ⅲ)complexes were selected as ECL probes,including[(bt)2Ir(phen-CHO)]PF_(6)(bt=2-phenylbenzothiazole,phen-CHO=1,10-phenanthroline-5-carboxaldehyde,probe 1)and[(ppy)_(2)Ir(phen-CHO)]PF_(6)(ppy=2-phenylpyridine,probe 2).A“signal on”ECL method was proposed for biothiols assay based on the increase in ECL intensity of two ECL probes by biothiols.Three biothiols can be detected with detection limits of 0.8,0.7 and 0.8μM by probe 1 and 0.3,0.4 and 0.5μM by probe 2 for Cys,Hcy and GSH,respectively.Two-element sensor array was assembled for the detection of three biothiols due to the different enhancement effects of biothiols on the ECL intensity of two ECL probes.The ECL sensor array combining with the principal component analysis was applied to discriminate three biothiols.This study demonstrates that the ECL sensor array using dual ECL reagents provides a promis-ing way for the discrimination of multiple biothiols with good sensitivity and simpleness.
基金supported by the National Natural Science Foundation of China(22234005,21974070,22222407,22176099)the Natural Science Foundation of Jiangsu Province(BK20192008)the State Key Laboratory of Analytical Chemistry for Life Science(SKLACLS2220)。
文摘The content of biothiols in cells is highly associated with the occurrence and development of several diseases.However,due to their active chemical properties,thiol-contained molecules are normally volatile during the detection process,rendering precise analysis of intracellular biothiols challenging.In this study,5,5’-dithiobis-(2-nitrobenzoic acid)(DTNB)is covalently modified on the surface of gold nanorods(AuNRs),constructing sensing substrates for in situ Raman imaging analysis of biothiols in cells.Au NRs are able to serve as ideal surface-enhanced Raman scattering substrates,and thus Raman signals of DTNB are greatly amplified by AuNRs.Meanwhile,the disulfide bond of DTNB can be broken by thiols,thereby releasing part of DTNB from the surface of AuNRs.As a result,three kinds of main biothiols are sensitively quantified with DTNB-modified AuNRs according to the variation of Raman signals,and DTNB-modified Au NRs exhibit far better analytical performance than a commercial probe.In addition,the sensing substrates can be readily delivered to cytoplasm with the transmembrane of Au NRs,and are capable of responding to biothiols in cells.Notably,the Raman approach is established by the breaking of chemical bonds rather than the aggregation of substrates,which is more inclined to analyze intracellular biothiols with a desirable spatial resolution.Therefore,fluctuation of biothiols in glioma cells is evidently observed via Raman imaging.Overall,this work provides an alternative strategy for designing Raman sensors to visualize active molecules in cells.
基金the financial support from the National Natural Science Foundation of China(82073603)Jilin Province Science and Technology Development Plan Item(20200602010ZP)+1 种基金Health Commission of Jilin Province(2020Q011)Norman Bethune Health Science Center of Jilin University(2020B39)
文摘The abnormal changes of biothiols are directly related to health condition of human body,and the effective identification and quantification of biothiols is of great significance for screening and diagnosis of disease.This study described the development of a p H-regulated colorimetric sensor array for discrimination of five kinds of biothiols including cysteine(Cys),glutathione(GSH),homocysteine(Hcy),cysteamine(CA)and N-acetylcysteine(NAC).The proposed sensor array was established using 5-nm-and 20-nm-sizedβ-cyclodextrin-functionalized gold nanoparticles(β-CD@Au NPs)as nonspecific receptor and signal transduction elements.Due to the different binding affinity between biothiols andβ-CD@Au NPs in various p H environments,the different aggregation behaviors of nanoparticles produced unique colorimetric response patterns,which were able to be distinguished by bare eyes and UV-vis spectrophotometer.Accordingly,principal component analysis(PCA)and hierarchical cluster analysis(HCA)were employed for pattern recognition and generated a clustering map for a clear differentiation of biothiols at the level ofμmol/L.Furthermore,it can be proved that the method was successfully applied to the analysis of biothiols in human urine samples.
