Redox dyshomeostasis is a critical factor in the initiation of numerous diseases,making the accurate evaluation of the redox status of the cellular environment an important aspect of physiological research.However,mai...Redox dyshomeostasis is a critical factor in the initiation of numerous diseases,making the accurate evaluation of the redox status of the cellular environment an important aspect of physiological research.However,maintaining redox homeostasis relies on a complex and dynamic physiological system involving multiple substrate-enzyme interactions,so its accurately detection remains a challenge.With this research,we developed an activable fiuorescence switching platform by incorporating different conjugate acceptors to a fiuorophore using ester bonds and resulting in fiuorescence quenching due to donor-excited photo-induced electron transfer(d-Pe T),which was confirmed through density functional theory calculations.The reaction-based probe was deployed for recognizing all major intracellular reducing sulfur species(RSS),including H_(2)S,cysteine(Cys),homocysteine(Hcy),glutathione(GSH),and protein free thiols.The quenched fiuorescence was significantly recovered by RSS,through releasing the fiuorophore and diminishing the d-Pe T effect.Furthermore,the fiuorescent probe was used for the sensing and imaging RSS in living cells,demonstrating good cell-permeability,low cytotoxicity,and negative correlation with reactive oxygen species content,enabling the evaluating of global thiols redox state in Hep G2 cellular lines during ferroptosis processes.展开更多
The vicinal dithiol motif is widely present in proteins, and is critical for proteins’ structures and functions.In recent years, a variety of fluorescent probes with high specificity and outstanding optical propertie...The vicinal dithiol motif is widely present in proteins, and is critical for proteins’ structures and functions.In recent years, a variety of fluorescent probes with high specificity and outstanding optical properties for sensing protein vicinal dithiols have been developed. In this review, we summarized the fluorescent probes of protein vicinal dithiols in literature. These probes are classified into four types based on their acceptor sites, i.e., biarsenical probes, monoarsenical probes, dimaleimide probes and diacrylate probes.Through analyzing the properties of different probes, we expect that this review would help readers further understand the structural factors of these probes and provide the design strategy for novel fluorescent probes with improved properties.展开更多
Fe（NO3）3-9H2O/Fe（HSO4）3 was used as an efficient reagent system for the oxidation of alcohols to their corresponding carbonyl compounds. All reactions were performed in the absence of solvent in good to high yield...Fe（NO3）3-9H2O/Fe（HSO4）3 was used as an efficient reagent system for the oxidation of alcohols to their corresponding carbonyl compounds. All reactions were performed in the absence of solvent in good to high yields. Under the same reaction conditions, thiols and sulfides were also converted to their corresponding disulfides and sulfoxides, respectively. 2007 Farhad Shirini. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
A Michael addition is usually taken as a base-catalysed reaction. However, our synthesized 2-（quinolin-2-ylmethylene） malonic acid （QMA） as a Michael-type thiol fluorescent probe is acid-active in its sensing reac...A Michael addition is usually taken as a base-catalysed reaction. However, our synthesized 2-（quinolin-2-ylmethylene） malonic acid （QMA） as a Michael-type thiol fluorescent probe is acid-active in its sensing reaction. In this work, based on theoretic calculation and experimental study on 7-hydroxy-2-（quinolin-2-ylmethylene） malonic acid, we demonstrated that QMA as a Michael acceptor is acid-activatable, i.e., it works only in solutions at pH〈7, and the lower the pH of solutions is, the higher reactivity QMA has. In alkaline solution, the malonate QMA[-2H＋]2- cannot react with both RSand RSH. In contrast, 2-（quinolin-2- ylmethylene） malonic ester （QME）, the ester of QMA, reveal a contrary pH effect on its sensing reaction, that is, it can sense thiols in alkaline solutions but not in acidic solutions, like a normal base-catalysed Michael addition. The values of activation enthalpies from theoretic calculation support the above sensing behavior of two probes under different pH conditions. In acidic solutions, the protonated QMA is more highly reactive towards electrophilic attack over its other ionized states in neutral and alkaline solutions, and so can react with lowly reactive RSH. In contrast, there is a big energy barrier in the interaction of QME with RSH （acidic solutions）, and the reaction of QME with the highly reactive nucleophile RS- is a low activation energy process （in alkaline solutions）. Theoretic calculation reveals that the sensing reaction of QMA undergoes a 1,4-addition process with neutral thiols （RSH）, and a 1,2-addition pathway for the sensing reaction of QME with RS-. Therefore, the sensing reaction of QMA is an acid-catalysed Michael addition via a 1,4-addition, and a normal base-catalysed Michael addition via a 1,2-addition.展开更多
An efficient and convenient tert-butyl nitrite-catalyzed selective aerobic oxidation of thiols has been developed. Under the optimal reaction conditions, a number of thiol derivatives including aromatic thiols, hetero...An efficient and convenient tert-butyl nitrite-catalyzed selective aerobic oxidation of thiols has been developed. Under the optimal reaction conditions, a number of thiol derivatives including aromatic thiols, heteroaromatic thiols and aliphatic thiols can be converted into their corresponding disulfides in good to excellent yields.展开更多
Organoseleniums are a class of compounds attracting attention across the globe owing to their Glutathione peroxidase(GPx)mimicry,which confers on them a strong antioxidant activity.Diphenyl diselenide(DPDS)is an Organ...Organoseleniums are a class of compounds attracting attention across the globe owing to their Glutathione peroxidase(GPx)mimicry,which confers on them a strong antioxidant activity.Diphenyl diselenide(DPDS)is an Organoselenium whose GPx mimetic property has been suggested to rely on the oxidation of non-protein or protein thiols critical to the activities of some sulfhydryl enzymes.This study,therefore investigated the GPx mimic/antioxidant property of DPDS as well as the role of thiols of two key sulfhydryl enzymes,cerebral Na^(+)/K^(+)-ATPase(sodium pump)and hepatic delta-aminolevulinic acid dehydratase(δ-ALAD)in the GPx mimicry of DPDS.Albino Wistar rats were euthanized,and the liver and brain were removed and used to assay for the effect of DPDS on lipid peroxidation induced by two prooxidants[Fe2^(+)(10μM)and H2O2,(1 mM)]as well as the activities of the sulfhydryl enzymes.The results revealed that DPDS profoundly(P<0.05)counteracted Fe2^(+)and H2O2-induced lipid peroxidation in the rats’hepatic and cerebral tissues.Furthermore,the results of assay systems for lipid peroxidation and sodium pump revealed that DPDS inhibited Na^(+)/K^(+)-ATPase and lipid peroxidation in the brain tissue homogenates in the same reaction system.A similar result was obtained in the assay system for lipid peroxidation and hepaticδ-ALAD as DPDS simultaneously inhibited the enzyme’s activity and lipid peroxidation.This suggests that the GPx mimetic property of DPDS may be linked to the enzymes’loss of activity,which further validates the suggestions that the enzymes’inhibition,as well as the antioxidant action of DPDS,rely on the oxidation of critical thiols of the enzymes.However,the GPx mimicry of DPDS should be investigated in the presence of thiol-blocking or oxidizing agents in biological systems in order to further ascertain the role of protein thiols.展开更多
Plasmonicnanoparticles(PNPs)with stable nanogaps are important to achieve strong,uniform and quantitative gap-enhanced Raman scattering(GERS)signals.Chiral PNPs with plasmonic circular dichroism(PCD)responses have bee...Plasmonicnanoparticles(PNPs)with stable nanogaps are important to achieve strong,uniform and quantitative gap-enhanced Raman scattering(GERS)signals.Chiral PNPs with plasmonic circular dichroism(PCD)responses have been discovered to be suitable for applications in enantiomeric recognition,cancer therapy and activation of immune system.Herein,two-thiolsmodulated growth was demonstrated to result in the acquisition of PNPs with synergistically enhanced GERS and PCD signals.4-Aminothiophenol(4-ATP)and cysteine(Cys)played the role of Raman reporter and chiral stimulus,respectively.At a fixed 4-ATP concentration,the GERS signal of PNPs was significantly enhanced with the increase of the concentration of Cys.Simultaneously,at a fixed concentration of Cys,an increase in PCD response was observed by elevating the concentration of 4-ATP.Both aforementioned molecules acted as morphology controllers,leading to the formation of helical shell.It is suggested that the giant GERS and PCD response were contributed by the‘‘hot spots''within the PNPs and more perfect helical shells.Our research pointed out a novel synthetic guideline to obtain PNPs with multiple functionalities by incorporating multi-ligands into the growth stages.展开更多
The photocatalytic oxidative coupling of thiols is one of the most popular methods to synthesize the disulfides.Triphenylamine and its derivatives(TPAs)are promising for the above reaction,but suffer from the easy pol...The photocatalytic oxidative coupling of thiols is one of the most popular methods to synthesize the disulfides.Triphenylamine and its derivatives(TPAs)are promising for the above reaction,but suffer from the easy polymerization and difficult separation.To overcome these obstacles while controlling the photogenerated electrons transfer directly to target substrates,herein,we constructed one TPA-based metal-organic framework(MOF),(Me_(2)NH_(2))[Sr(TCBPA)]·DMA·3H_(2)O(1),by direct self-assembly of tris(4′-carboxybiphenyl)amine(H_(3)TCBPA)and photoredox inert strontium ion(Sr^(2+)).DFT calculations revealed that the valence band maximum(VBM)and the conduction band minimum(CBM)are mainly located on TCBPA^(3-),successfully inhibiting the undesirable electron migration to metal nodes.Experimental results indicated that 1 displays superior performance than homogeneous H_(3)TCBPA,which may result from the abundant π…π and C—H…π interactions between the well-arranged TCBPA^(3-)and the build-in electric field between the anionic framework and the Me_(2)NH^(2+).This work highlights that immobilizing TPAs into MOFs is one promising approach to designing heterogeneous photocatalysts for the synthesis of disulfides by oxidative coupling of thiols.展开更多
Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical p...Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical properties[1-3].While transition metals such as Au,Ag,Pt,and Pd dominate the core composition,surface ligands are predominantly limited to phosphines,thiols,alkynes,and carbenes.Among these,N-heterocyclic carbenes(NHCs)have emerged as a superior ligand class due to their dual capacity for strongσ-donation andπ-back bonding,which stabilizes diverse metal oxidation states and enhances metal-ligand interactions.Notably,NHC-protected clusters exhibit exceptional thermal stability attributed to CH-π/π-πinteractions and enlarged HOMO-LUMO gaps compared to thiol or phosphine analogues.Despite progress,synthetic limitations persist due to NHCs'sensitivity under harsh conditions.Current methods rely on direct reduction of metal-carbene precursors or ligand exchange reactions,with heterogeneous NHC-capped systems remaining unexplored.展开更多
Photocatalytic water splitting for hydrogen evolution reaction(HER)has emerged as one of the most promising approaches for solar energy utilization.Porous easily functionalized metal-organic framework(MOF)represents a...Photocatalytic water splitting for hydrogen evolution reaction(HER)has emerged as one of the most promising approaches for solar energy utilization.Porous easily functionalized metal-organic framework(MOF)represents a rising crystalline material for photocatalytic application.Yet,most MOFs still face challenges like chemical instability in solution media,no photosensitization,and ambiguous active sites.Herein,thiol-dense Hf-or Zr-based porous frameworks(Hf-,Zr-TBAPy-8SH)were prepared as platforms for facile construction of HER active sites by anchoring transition metal(TM)ions as well as forming heterojunction with nanoscale semiconductor(CdS).The highest HER rate of 8.15mmol g^(-1) h^(-1) by Co(Ⅱ)-loaded Hf-based composite highlight(1)[S^(-)-Co]motifs as competent HER site,(2)match heterojunction outweighing traditional photosensitizer-mediated HER,(3)regulating electron density of metal-oxo cluster as a way to harness HER activity.This study firstly demonstrates synergy of Hf-oxo clusters,thiol functionalities and heterojunction as an easy yet controllable strategy to form integrated photocatalyst.展开更多
To develop the high-performance fluorescent bio-sensors, the metal nanoparticles were employed as nanoquenchers and at- tracted reasonable attention in the design of fluorescent biosensors. In this work, silver nanopa...To develop the high-performance fluorescent bio-sensors, the metal nanoparticles were employed as nanoquenchers and at- tracted reasonable attention in the design of fluorescent biosensors. In this work, silver nanoparticles （AgNPs） were obtained via reduction of Ag＋ on FAM-labeled DNA template. For the tight binding between AgNPs and DNA, the tem- plate-synthesized AgNPs turned out high quenching efficiency and could be applied as super nanoquenchers to establish the biosensing platform for fluorescent detection. As an example, the template-synthesized DNA-AgNPs conjugates were em- ployed in sensing thiols. By forming S-Ag bonds, thiols interact intensely with AgNPs and replace the FAM-labeled DNA off from the surface of AgNPs, resulting in a fluorescence enhancement. Besides the advantages of lower background and higher signal-to-background ratio （S/B）, the conjugates present better stability, making them applicable in complicated biological fluids. To further evidence the feasibility of sensing thiols in real samples, the thiols in human urine were detected. The total amount of free thiols found in human urine was ranging from 229 μM to 302μM with the proposed sensor. To conclude the reliability, low content of Cys was added and the recovery was 98%-103%.展开更多
Epoxy resin is widely used in electronic packaging due to its exceptional performance,particularly the low-temperature curable thiol/epoxy system,which effectively minimizes thermal damage to sensitive electronic comp...Epoxy resin is widely used in electronic packaging due to its exceptional performance,particularly the low-temperature curable thiol/epoxy system,which effectively minimizes thermal damage to sensitive electronic components.However,the majority of commercial thiol curing agents contain hydrolysable ester bonds and lack rigid structures,which induces most of thiol/epoxy systems still suffering from unsatisfactory heat resistance and hygrothermal resistance,significantly hindering their application in electronic packaging.In this study,we synthesized a tetrafunctional thiol compound,bis[3-(3-sulfanylpropyl)-4-(3-sulfanylpropoxy)phenyl]sulfone(TMBPS)with rigid and ester-free structures to replace traditional commercial thiol curing agents,pentaerythritol tetra(3-mercaptopropionate)(PETMP).Compared to the PETMP/epoxy system,the TMBPS/epoxy system exhibited superior comprehensive properties.The rigid structures of bisphenol S-type tetrathiol enhanced the heat resistance and mechanical properties of TMBPS/epoxy resin cured products,outperforming those of PETMP/epoxy resin cured products.Notably,the glass transition temperature of TMBPS/epoxy resin cured products was 74.2℃which was 11.8°C higher than that of PETMP cured products.Moreover,the ester-free structure in TMBPS contributed to its enhanced resistance to chemicals and hygrothermal conditions.After undergoing 1000 h of hightemperature and high-humidity aging,the tensile strength and adhesion strength of TMBPS-cured products were 73.33 MPa and 3.39 MPa,respectively exceeding 100%and 40%of their initial values,while PETMP-cured products exhibited a complete loss of both tensile strength and adhesion strength.This study provides a strategy for obtaining thermosetting polymers that can be cured at low temperatures and exhibit excellent comprehensive properties.展开更多
Metal-organic frameworks(MOFs)attract broad interests in mercury(Hg)ion adsorption field,while unreasonable distribution of active groups commonly restricts their utilization efficiency.In this work,we constructed a n...Metal-organic frameworks(MOFs)attract broad interests in mercury(Hg)ion adsorption field,while unreasonable distribution of active groups commonly restricts their utilization efficiency.In this work,we constructed a new MOF(TYUST-6)with dense thiol-rich traps in the 1D pore wall.This accessible channel and rational distribution of thiols allow the smooth diffusion of Hg ions and thereby result in a high Langmuir adsorption capacity of 1347.6 mg/g,almost reaching the theoretical maximum(1444.3 mg/g).Adsorption equilibrium needs 10 and 30 min at the initial concentrations of 10 and 100 mg/L,respectively.Common co-existing ions and solution pH show almost negligible interferences on the adsorption,and adsorbent regeneration can be well achieved.Combining experimental characterizations and theoretical calculations,the thiol groups in the pore wall are proved to be the dominant interaction sites.Thus,this work reports a novel high-capacity adsorbent for Hg^(2+),and proposes a feasible guideline for designing effective adsorbents.展开更多
The thiol-imidazole functionalized(p-triphenyl-pentafluorobenzaldehyde)polymer(IMPTP)was prepared and quaternized with different side chains to obtain imidazolium-modified Me-IMPTP,He-IMPTP and BIM-IMPTP membranes for...The thiol-imidazole functionalized(p-triphenyl-pentafluorobenzaldehyde)polymer(IMPTP)was prepared and quaternized with different side chains to obtain imidazolium-modified Me-IMPTP,He-IMPTP and BIM-IMPTP membranes for application in high-temperature proton exchange membrane fuel cells(HT-PEMFCs).The presence of the thioether group in the polymers enabled radical scavenging for antioxidant properties,while imidazolium cations interacted strongly with H_(2)PO_(4) to prevent phosphoric acid(PA)leaching.The prepared BIM-IMPTP membrane incorporating bisimidazolium cation string with a long alkyl spacer demonstrated the highest mass retention of 82.93%after being immersed in Fenton's reagent for 24 h.Additionally,the PA-doped BIM-IMPTP membranes exhibited excellent PA retention under high-humidity conditions(80℃/100%RH).The single cell equipped with the BIM-IMPTP/320%PA membrane achieved a maximum power density(PDmax)of 945 mW cm^(-2)at 160℃.Among the four membranes with a similar acid doping content(ADC),the BIM-IMPTP/163%PA membrane with bis-cation pairs in the side chains exhibited a well-developed microphase-separated structure and high proton conductivity(119.0 mS cm^(-1)at 180℃).The single cell assembled with BIM-IMPTP/163%PA membrane maintained a PDmax of 613 mW cm^(-2)at 160℃ and demonstrated long-term operational stability under both 150/400 mA cm^(-2)and 80℃/200 mA cm^(-2)conditions.These results indicate that the introduction of thioether and bis-cation pairs in the structural design of polymers contributes significantly to the long-term stability of HT-PEMs.展开更多
A visible-light-induced metal-free desulfurization method for thiols and disulfides has been explored.This radical desulfurization features mild conditions,robustness,and excellent functionality compatibility.It was s...A visible-light-induced metal-free desulfurization method for thiols and disulfides has been explored.This radical desulfurization features mild conditions,robustness,and excellent functionality compatibility.It was successfully applied not only to the desulfurization of small molecules,but also to peptides.展开更多
The interaction between citrate capped silver nanoparticles and two different thiols, mercaptohexanol （MH） and cysteine, was investigated. The thiols interacted with silver nanoparticles in a significantly contrasti...The interaction between citrate capped silver nanoparticles and two different thiols, mercaptohexanol （MH） and cysteine, was investigated. The thiols interacted with silver nanoparticles in a significantly contrasting manner. With MH, a sparingly soluble silver（1） thiolate complex AgSRm （Rm = -（CH2）6OH） was formed on the silver nanoparticle surface. Cyclic voltammograms and UV-vis spectra were used to infer that the AgSRm complex on the nanoparticle surface undergoes a phase transition to give a mixture of AgSRm and Ag2S-like complexes. In contrast, when silver nanoparticles were exposed to cysteine, the citrate cap- ping agent on the silver nanoparticles was replaced by cysteine to give cysteine capped nanoparticles. As cysteine capped nanoparticles form, the electrochemical data displayed a decrease in oxidative peak charge but the UV-vis spectra showed a constant signal. Therefore, cysteine capped nanoparticles were suggested to have either inactivated the silver surface or else pro- moted detachment from the electrode surface.展开更多
Pyridine-N-oxide serves as an efficient catalyst for the ring-opening reactions of N-tosylaziridines with various aryl thiols under mild conditions. This transformation is highly effective, which gives rise to the cor...Pyridine-N-oxide serves as an efficient catalyst for the ring-opening reactions of N-tosylaziridines with various aryl thiols under mild conditions. This transformation is highly effective, which gives rise to the corresponding β-amino sulfides in good to excellent yields.展开更多
Photochromic molecules can achieve reversible isomerization upon alternate light irradiations, which offers a great opportunity to improve the precision of analytes detection and imaging in complicated biological envi...Photochromic molecules can achieve reversible isomerization upon alternate light irradiations, which offers a great opportunity to improve the precision of analytes detection and imaging in complicated biological environments. Previous reported photochromic probe exhibited only mono-color switching and an initially fluorescence-ON state that may cause high background signal and impose an adverse impact on the desired sensing precision. To overcome this set-back, we developed a novel photochromic probe with an analyte-activation mode for ratiometric sensing of toxic thiols in both real water samples and live cells. The dynamic dual-fluorescence signal is released only after the fast and selective cleavage of the 2,4-dinitrophenyl sulfonate by the targeted thiophenol derivatives. Consequently, a "double-check" with synchronized dual-fluorescence blinking for analyte detection is successfully employed upon alternate light triggers with rapid response(k=7.2×10^(-2) s^(-1)), high sensitivity(LOD=6.1 nM) as well as selectivity of thiophenol derivatives over other common thiol species(e.g., GSH, Cys and Hcy). The photochromic probe was successfully introduced to the fast and on-site detection of highly toxic thiophenols in real waste water samples. Moreover, by using confocal laser-scanning microscopy(CLSM) and flow cytometric analysis, the potential applications of this ratiometric photochromic probe for trace toxic thiol sensing in live cells are examined.展开更多
An efficient and practical method is described for the ring-opening reactions of N-tosylaziridines with various thiols in water under mild conditions. Various surfactants have been evaluated to optimize the reactions....An efficient and practical method is described for the ring-opening reactions of N-tosylaziridines with various thiols in water under mild conditions. Various surfactants have been evaluated to optimize the reactions. Under optimal conditions, these reactions gave rise to the corresponding β-amino sulfides in good to excellent yields.展开更多
The simultaneous binding/dissociation of multiple bonds in a one-pot manner by multicomponent reactions provide an important approach for developing novel and sustainable pathway in the drug discovery process.Herein w...The simultaneous binding/dissociation of multiple bonds in a one-pot manner by multicomponent reactions provide an important approach for developing novel and sustainable pathway in the drug discovery process.Herein we develop an electrocatalytic three-component reaction to construct multifunctional and valuable isothiourea compounds,which uses thiols,isocyanides and amines as substrates.Compared with the previous work,the organic electrosynthesis technique can avoid the requirement of heavy metal catalysts and stoichiometric oxidants.In addition,using thiol as a substrate to participate in the three-component reaction broadens the source of sulfur,which can also construct more abundant isothiourea derivatives.展开更多
基金the National Natural Science Foundation of China(Nos.21907080,22278330)Youth Innovative Team(No.xtr052022012)+3 种基金Fundamental Research Funds for the Central University(No.xzy012023010)from Xi’an Jiaotong Universitysupported by Natural Science Basic Research Program of Shaanxi(No.2023-JC-QN-0246)China/Shaanxi Postdoctoral Science Foundation(Nos.2023M732811,2023BSHEDZZ20)the University of Bath and the Open Research Fund of the School of Chemistry and Chemical Engineering,Henan Normal University(No.2020ZD01)for support。
文摘Redox dyshomeostasis is a critical factor in the initiation of numerous diseases,making the accurate evaluation of the redox status of the cellular environment an important aspect of physiological research.However,maintaining redox homeostasis relies on a complex and dynamic physiological system involving multiple substrate-enzyme interactions,so its accurately detection remains a challenge.With this research,we developed an activable fiuorescence switching platform by incorporating different conjugate acceptors to a fiuorophore using ester bonds and resulting in fiuorescence quenching due to donor-excited photo-induced electron transfer(d-Pe T),which was confirmed through density functional theory calculations.The reaction-based probe was deployed for recognizing all major intracellular reducing sulfur species(RSS),including H_(2)S,cysteine(Cys),homocysteine(Hcy),glutathione(GSH),and protein free thiols.The quenched fiuorescence was significantly recovered by RSS,through releasing the fiuorophore and diminishing the d-Pe T effect.Furthermore,the fiuorescent probe was used for the sensing and imaging RSS in living cells,demonstrating good cell-permeability,low cytotoxicity,and negative correlation with reactive oxygen species content,enabling the evaluating of global thiols redox state in Hep G2 cellular lines during ferroptosis processes.
基金financial supports from the National Natural Science Foundation of China (Nos. 21572093 & 21778028)the 111 Project
文摘The vicinal dithiol motif is widely present in proteins, and is critical for proteins’ structures and functions.In recent years, a variety of fluorescent probes with high specificity and outstanding optical properties for sensing protein vicinal dithiols have been developed. In this review, we summarized the fluorescent probes of protein vicinal dithiols in literature. These probes are classified into four types based on their acceptor sites, i.e., biarsenical probes, monoarsenical probes, dimaleimide probes and diacrylate probes.Through analyzing the properties of different probes, we expect that this review would help readers further understand the structural factors of these probes and provide the design strategy for novel fluorescent probes with improved properties.
文摘Fe（NO3）3-9H2O/Fe（HSO4）3 was used as an efficient reagent system for the oxidation of alcohols to their corresponding carbonyl compounds. All reactions were performed in the absence of solvent in good to high yields. Under the same reaction conditions, thiols and sulfides were also converted to their corresponding disulfides and sulfoxides, respectively. 2007 Farhad Shirini. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
基金This work is supported by the National Natural Science Foundation of China （No.21272224）, the Open Research Fund of State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University （No.201410）, and the Open Research Fund of Key Laboratory of Advanced Scientific Computation, Xihua University （No.szjj2013-024）.
文摘A Michael addition is usually taken as a base-catalysed reaction. However, our synthesized 2-（quinolin-2-ylmethylene） malonic acid （QMA） as a Michael-type thiol fluorescent probe is acid-active in its sensing reaction. In this work, based on theoretic calculation and experimental study on 7-hydroxy-2-（quinolin-2-ylmethylene） malonic acid, we demonstrated that QMA as a Michael acceptor is acid-activatable, i.e., it works only in solutions at pH〈7, and the lower the pH of solutions is, the higher reactivity QMA has. In alkaline solution, the malonate QMA[-2H＋]2- cannot react with both RSand RSH. In contrast, 2-（quinolin-2- ylmethylene） malonic ester （QME）, the ester of QMA, reveal a contrary pH effect on its sensing reaction, that is, it can sense thiols in alkaline solutions but not in acidic solutions, like a normal base-catalysed Michael addition. The values of activation enthalpies from theoretic calculation support the above sensing behavior of two probes under different pH conditions. In acidic solutions, the protonated QMA is more highly reactive towards electrophilic attack over its other ionized states in neutral and alkaline solutions, and so can react with lowly reactive RSH. In contrast, there is a big energy barrier in the interaction of QME with RSH （acidic solutions）, and the reaction of QME with the highly reactive nucleophile RS- is a low activation energy process （in alkaline solutions）. Theoretic calculation reveals that the sensing reaction of QMA undergoes a 1,4-addition process with neutral thiols （RSH）, and a 1,2-addition pathway for the sensing reaction of QME with RS-. Therefore, the sensing reaction of QMA is an acid-catalysed Michael addition via a 1,4-addition, and a normal base-catalysed Michael addition via a 1,2-addition.
基金financially supported by the National Natural Science Foundation of China (Nos. 21376224, 21206147)
文摘An efficient and convenient tert-butyl nitrite-catalyzed selective aerobic oxidation of thiols has been developed. Under the optimal reaction conditions, a number of thiol derivatives including aromatic thiols, heteroaromatic thiols and aliphatic thiols can be converted into their corresponding disulfides in good to excellent yields.
文摘Organoseleniums are a class of compounds attracting attention across the globe owing to their Glutathione peroxidase(GPx)mimicry,which confers on them a strong antioxidant activity.Diphenyl diselenide(DPDS)is an Organoselenium whose GPx mimetic property has been suggested to rely on the oxidation of non-protein or protein thiols critical to the activities of some sulfhydryl enzymes.This study,therefore investigated the GPx mimic/antioxidant property of DPDS as well as the role of thiols of two key sulfhydryl enzymes,cerebral Na^(+)/K^(+)-ATPase(sodium pump)and hepatic delta-aminolevulinic acid dehydratase(δ-ALAD)in the GPx mimicry of DPDS.Albino Wistar rats were euthanized,and the liver and brain were removed and used to assay for the effect of DPDS on lipid peroxidation induced by two prooxidants[Fe2^(+)(10μM)and H2O2,(1 mM)]as well as the activities of the sulfhydryl enzymes.The results revealed that DPDS profoundly(P<0.05)counteracted Fe2^(+)and H2O2-induced lipid peroxidation in the rats’hepatic and cerebral tissues.Furthermore,the results of assay systems for lipid peroxidation and sodium pump revealed that DPDS inhibited Na^(+)/K^(+)-ATPase and lipid peroxidation in the brain tissue homogenates in the same reaction system.A similar result was obtained in the assay system for lipid peroxidation and hepaticδ-ALAD as DPDS simultaneously inhibited the enzyme’s activity and lipid peroxidation.This suggests that the GPx mimetic property of DPDS may be linked to the enzymes’loss of activity,which further validates the suggestions that the enzymes’inhibition,as well as the antioxidant action of DPDS,rely on the oxidation of critical thiols of the enzymes.However,the GPx mimicry of DPDS should be investigated in the presence of thiol-blocking or oxidizing agents in biological systems in order to further ascertain the role of protein thiols.
基金financially supported by the National Natural Science Foundation of China (Nos.22072032 and21902148)the Key Science and Technology Program of Henan Province (No.192102210004)+2 种基金the Research Initiated Project of Chengdu University (No.2081921109)Chengdu University Graduate Talent Training Quality and Teaching Reform Project (No.cdjgy2022034)Chengdu University Talent Training Quality and Teaching Reform Project (No.cdjgb2022103)。
文摘Plasmonicnanoparticles(PNPs)with stable nanogaps are important to achieve strong,uniform and quantitative gap-enhanced Raman scattering(GERS)signals.Chiral PNPs with plasmonic circular dichroism(PCD)responses have been discovered to be suitable for applications in enantiomeric recognition,cancer therapy and activation of immune system.Herein,two-thiolsmodulated growth was demonstrated to result in the acquisition of PNPs with synergistically enhanced GERS and PCD signals.4-Aminothiophenol(4-ATP)and cysteine(Cys)played the role of Raman reporter and chiral stimulus,respectively.At a fixed 4-ATP concentration,the GERS signal of PNPs was significantly enhanced with the increase of the concentration of Cys.Simultaneously,at a fixed concentration of Cys,an increase in PCD response was observed by elevating the concentration of 4-ATP.Both aforementioned molecules acted as morphology controllers,leading to the formation of helical shell.It is suggested that the giant GERS and PCD response were contributed by the‘‘hot spots''within the PNPs and more perfect helical shells.Our research pointed out a novel synthetic guideline to obtain PNPs with multiple functionalities by incorporating multi-ligands into the growth stages.
基金supported by NSFC(22101160)the"1331"Project of Shanxi ProvinceResearch Project Supported by Shanxi Scholarship Council of China(2020-088).
文摘The photocatalytic oxidative coupling of thiols is one of the most popular methods to synthesize the disulfides.Triphenylamine and its derivatives(TPAs)are promising for the above reaction,but suffer from the easy polymerization and difficult separation.To overcome these obstacles while controlling the photogenerated electrons transfer directly to target substrates,herein,we constructed one TPA-based metal-organic framework(MOF),(Me_(2)NH_(2))[Sr(TCBPA)]·DMA·3H_(2)O(1),by direct self-assembly of tris(4′-carboxybiphenyl)amine(H_(3)TCBPA)and photoredox inert strontium ion(Sr^(2+)).DFT calculations revealed that the valence band maximum(VBM)and the conduction band minimum(CBM)are mainly located on TCBPA^(3-),successfully inhibiting the undesirable electron migration to metal nodes.Experimental results indicated that 1 displays superior performance than homogeneous H_(3)TCBPA,which may result from the abundant π…π and C—H…π interactions between the well-arranged TCBPA^(3-)and the build-in electric field between the anionic framework and the Me_(2)NH^(2+).This work highlights that immobilizing TPAs into MOFs is one promising approach to designing heterogeneous photocatalysts for the synthesis of disulfides by oxidative coupling of thiols.
文摘Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical properties[1-3].While transition metals such as Au,Ag,Pt,and Pd dominate the core composition,surface ligands are predominantly limited to phosphines,thiols,alkynes,and carbenes.Among these,N-heterocyclic carbenes(NHCs)have emerged as a superior ligand class due to their dual capacity for strongσ-donation andπ-back bonding,which stabilizes diverse metal oxidation states and enhances metal-ligand interactions.Notably,NHC-protected clusters exhibit exceptional thermal stability attributed to CH-π/π-πinteractions and enlarged HOMO-LUMO gaps compared to thiol or phosphine analogues.Despite progress,synthetic limitations persist due to NHCs'sensitivity under harsh conditions.Current methods rely on direct reduction of metal-carbene precursors or ligand exchange reactions,with heterogeneous NHC-capped systems remaining unexplored.
基金supported by the National Natural Science Foundation of China(Nos.22371054,22301045)the Foundation of Basic and Applied Basic Research of Guangdong Province(Nos.2020B1515120024,2024A1515012801)Science and Technology Planning Project of Guangdong Province(Nos.2021A0505030066,2023A0505050164).
文摘Photocatalytic water splitting for hydrogen evolution reaction(HER)has emerged as one of the most promising approaches for solar energy utilization.Porous easily functionalized metal-organic framework(MOF)represents a rising crystalline material for photocatalytic application.Yet,most MOFs still face challenges like chemical instability in solution media,no photosensitization,and ambiguous active sites.Herein,thiol-dense Hf-or Zr-based porous frameworks(Hf-,Zr-TBAPy-8SH)were prepared as platforms for facile construction of HER active sites by anchoring transition metal(TM)ions as well as forming heterojunction with nanoscale semiconductor(CdS).The highest HER rate of 8.15mmol g^(-1) h^(-1) by Co(Ⅱ)-loaded Hf-based composite highlight(1)[S^(-)-Co]motifs as competent HER site,(2)match heterojunction outweighing traditional photosensitizer-mediated HER,(3)regulating electron density of metal-oxo cluster as a way to harness HER activity.This study firstly demonstrates synergy of Hf-oxo clusters,thiol functionalities and heterojunction as an easy yet controllable strategy to form integrated photocatalyst.
基金supported by the National Natural Foundation of China (21075032 & 21005026)National Key Basic Research Program (2011CB911000)Hunan Province Key Project of Scientific & Tech-nical Programs (2010TP4013-1)
文摘To develop the high-performance fluorescent bio-sensors, the metal nanoparticles were employed as nanoquenchers and at- tracted reasonable attention in the design of fluorescent biosensors. In this work, silver nanoparticles （AgNPs） were obtained via reduction of Ag＋ on FAM-labeled DNA template. For the tight binding between AgNPs and DNA, the tem- plate-synthesized AgNPs turned out high quenching efficiency and could be applied as super nanoquenchers to establish the biosensing platform for fluorescent detection. As an example, the template-synthesized DNA-AgNPs conjugates were em- ployed in sensing thiols. By forming S-Ag bonds, thiols interact intensely with AgNPs and replace the FAM-labeled DNA off from the surface of AgNPs, resulting in a fluorescence enhancement. Besides the advantages of lower background and higher signal-to-background ratio （S/B）, the conjugates present better stability, making them applicable in complicated biological fluids. To further evidence the feasibility of sensing thiols in real samples, the thiols in human urine were detected. The total amount of free thiols found in human urine was ranging from 229 μM to 302μM with the proposed sensor. To conclude the reliability, low content of Cys was added and the recovery was 98%-103%.
基金the support of the Science and Technology Commission of Shanghai Municipality(STCSM,No.20dz1203600)the Experimental Center of Materials Science and Engineering in Tongji University。
文摘Epoxy resin is widely used in electronic packaging due to its exceptional performance,particularly the low-temperature curable thiol/epoxy system,which effectively minimizes thermal damage to sensitive electronic components.However,the majority of commercial thiol curing agents contain hydrolysable ester bonds and lack rigid structures,which induces most of thiol/epoxy systems still suffering from unsatisfactory heat resistance and hygrothermal resistance,significantly hindering their application in electronic packaging.In this study,we synthesized a tetrafunctional thiol compound,bis[3-(3-sulfanylpropyl)-4-(3-sulfanylpropoxy)phenyl]sulfone(TMBPS)with rigid and ester-free structures to replace traditional commercial thiol curing agents,pentaerythritol tetra(3-mercaptopropionate)(PETMP).Compared to the PETMP/epoxy system,the TMBPS/epoxy system exhibited superior comprehensive properties.The rigid structures of bisphenol S-type tetrathiol enhanced the heat resistance and mechanical properties of TMBPS/epoxy resin cured products,outperforming those of PETMP/epoxy resin cured products.Notably,the glass transition temperature of TMBPS/epoxy resin cured products was 74.2℃which was 11.8°C higher than that of PETMP cured products.Moreover,the ester-free structure in TMBPS contributed to its enhanced resistance to chemicals and hygrothermal conditions.After undergoing 1000 h of hightemperature and high-humidity aging,the tensile strength and adhesion strength of TMBPS-cured products were 73.33 MPa and 3.39 MPa,respectively exceeding 100%and 40%of their initial values,while PETMP-cured products exhibited a complete loss of both tensile strength and adhesion strength.This study provides a strategy for obtaining thermosetting polymers that can be cured at low temperatures and exhibit excellent comprehensive properties.
基金supported by the National Natural Science Foundation of China(No.22208230)Fundamental Research Program of Shanxi Province(No.202103021223281)。
文摘Metal-organic frameworks(MOFs)attract broad interests in mercury(Hg)ion adsorption field,while unreasonable distribution of active groups commonly restricts their utilization efficiency.In this work,we constructed a new MOF(TYUST-6)with dense thiol-rich traps in the 1D pore wall.This accessible channel and rational distribution of thiols allow the smooth diffusion of Hg ions and thereby result in a high Langmuir adsorption capacity of 1347.6 mg/g,almost reaching the theoretical maximum(1444.3 mg/g).Adsorption equilibrium needs 10 and 30 min at the initial concentrations of 10 and 100 mg/L,respectively.Common co-existing ions and solution pH show almost negligible interferences on the adsorption,and adsorbent regeneration can be well achieved.Combining experimental characterizations and theoretical calculations,the thiol groups in the pore wall are proved to be the dominant interaction sites.Thus,this work reports a novel high-capacity adsorbent for Hg^(2+),and proposes a feasible guideline for designing effective adsorbents.
基金supported by the National Natural Science Foundation of China(No.22179047)the Development of Scientific and Technological Project of Jilin Province(20230201139GX).
文摘The thiol-imidazole functionalized(p-triphenyl-pentafluorobenzaldehyde)polymer(IMPTP)was prepared and quaternized with different side chains to obtain imidazolium-modified Me-IMPTP,He-IMPTP and BIM-IMPTP membranes for application in high-temperature proton exchange membrane fuel cells(HT-PEMFCs).The presence of the thioether group in the polymers enabled radical scavenging for antioxidant properties,while imidazolium cations interacted strongly with H_(2)PO_(4) to prevent phosphoric acid(PA)leaching.The prepared BIM-IMPTP membrane incorporating bisimidazolium cation string with a long alkyl spacer demonstrated the highest mass retention of 82.93%after being immersed in Fenton's reagent for 24 h.Additionally,the PA-doped BIM-IMPTP membranes exhibited excellent PA retention under high-humidity conditions(80℃/100%RH).The single cell equipped with the BIM-IMPTP/320%PA membrane achieved a maximum power density(PDmax)of 945 mW cm^(-2)at 160℃.Among the four membranes with a similar acid doping content(ADC),the BIM-IMPTP/163%PA membrane with bis-cation pairs in the side chains exhibited a well-developed microphase-separated structure and high proton conductivity(119.0 mS cm^(-1)at 180℃).The single cell assembled with BIM-IMPTP/163%PA membrane maintained a PDmax of 613 mW cm^(-2)at 160℃ and demonstrated long-term operational stability under both 150/400 mA cm^(-2)and 80℃/200 mA cm^(-2)conditions.These results indicate that the introduction of thioether and bis-cation pairs in the structural design of polymers contributes significantly to the long-term stability of HT-PEMs.
基金We thank Shanghai Jiao Tong University and the National"1000-Youth Talents Plan"for financial support.
文摘A visible-light-induced metal-free desulfurization method for thiols and disulfides has been explored.This radical desulfurization features mild conditions,robustness,and excellent functionality compatibility.It was successfully applied not only to the desulfurization of small molecules,but also to peptides.
基金supported by the National Research Foundation Singapore under its National Research Foundation(NRF)Environmental and Water Technologies(EWT)PhD Scholarship Programme and administered by the Environment and Water Industry Programme Office(EWI)supported by a Marie Curie Intra European Fellowshipfunding from the European Union’s Seventh Framework Programme(FP/2007-2013)/ERC Grant Agreement n.[320403]
文摘The interaction between citrate capped silver nanoparticles and two different thiols, mercaptohexanol （MH） and cysteine, was investigated. The thiols interacted with silver nanoparticles in a significantly contrasting manner. With MH, a sparingly soluble silver（1） thiolate complex AgSRm （Rm = -（CH2）6OH） was formed on the silver nanoparticle surface. Cyclic voltammograms and UV-vis spectra were used to infer that the AgSRm complex on the nanoparticle surface undergoes a phase transition to give a mixture of AgSRm and Ag2S-like complexes. In contrast, when silver nanoparticles were exposed to cysteine, the citrate cap- ping agent on the silver nanoparticles was replaced by cysteine to give cysteine capped nanoparticles. As cysteine capped nanoparticles form, the electrochemical data displayed a decrease in oxidative peak charge but the UV-vis spectra showed a constant signal. Therefore, cysteine capped nanoparticles were suggested to have either inactivated the silver surface or else pro- moted detachment from the electrode surface.
基金Project supported by the National Natural Science Foundation of China （Nos. 20862009 and 20962010） and the Natural Science Foundation of Jiangxi Province （No. 2008GQH0026）.
文摘Pyridine-N-oxide serves as an efficient catalyst for the ring-opening reactions of N-tosylaziridines with various aryl thiols under mild conditions. This transformation is highly effective, which gives rise to the corresponding β-amino sulfides in good to excellent yields.
基金supported by the National Natural Science Foundation of China(21788102,21420102004,21878086)the Shanghai Rising-Star Program(19QA1402500)+2 种基金Shanghai Municipal Science and Technology Major Project(2018SHZDZX03)the Program of Introducing Talents of Discipline to Universities(B16017)financially supported by an award from China Scholarship Council
文摘Photochromic molecules can achieve reversible isomerization upon alternate light irradiations, which offers a great opportunity to improve the precision of analytes detection and imaging in complicated biological environments. Previous reported photochromic probe exhibited only mono-color switching and an initially fluorescence-ON state that may cause high background signal and impose an adverse impact on the desired sensing precision. To overcome this set-back, we developed a novel photochromic probe with an analyte-activation mode for ratiometric sensing of toxic thiols in both real water samples and live cells. The dynamic dual-fluorescence signal is released only after the fast and selective cleavage of the 2,4-dinitrophenyl sulfonate by the targeted thiophenol derivatives. Consequently, a "double-check" with synchronized dual-fluorescence blinking for analyte detection is successfully employed upon alternate light triggers with rapid response(k=7.2×10^(-2) s^(-1)), high sensitivity(LOD=6.1 nM) as well as selectivity of thiophenol derivatives over other common thiol species(e.g., GSH, Cys and Hcy). The photochromic probe was successfully introduced to the fast and on-site detection of highly toxic thiophenols in real waste water samples. Moreover, by using confocal laser-scanning microscopy(CLSM) and flow cytometric analysis, the potential applications of this ratiometric photochromic probe for trace toxic thiol sensing in live cells are examined.
基金Project supported by the National Natural Science Foundation of China （Nos. ＇20862009, 20962010）, Jiangxi Educational Committee （No. G J J10386） and the National Natural Science Foundation of Jiangxi Province （No. 2008GQH0026）.
文摘An efficient and practical method is described for the ring-opening reactions of N-tosylaziridines with various thiols in water under mild conditions. Various surfactants have been evaluated to optimize the reactions. Under optimal conditions, these reactions gave rise to the corresponding β-amino sulfides in good to excellent yields.
基金We thank the financial support from the National Natural Science Foundation of China(Nos.22061003 and 22161008)the Natural Science Foundation of Guangxi Province(Nos.2021GXNSFFA220005 and 2021GXNSFBA196041).
文摘The simultaneous binding/dissociation of multiple bonds in a one-pot manner by multicomponent reactions provide an important approach for developing novel and sustainable pathway in the drug discovery process.Herein we develop an electrocatalytic three-component reaction to construct multifunctional and valuable isothiourea compounds,which uses thiols,isocyanides and amines as substrates.Compared with the previous work,the organic electrosynthesis technique can avoid the requirement of heavy metal catalysts and stoichiometric oxidants.In addition,using thiol as a substrate to participate in the three-component reaction broadens the source of sulfur,which can also construct more abundant isothiourea derivatives.
