In this study,different loadings of x%Ni_(2)P/γ-Al_(2)O_(3)(x=6%,9%,12%,15%,18%)catalysts with aluminum oxide(Al_(2)O_(3))as the carrier,nickel chloride(NiCl2)as the nickel(Ni)source,and ammonium hypophosphite(NH_(4)...In this study,different loadings of x%Ni_(2)P/γ-Al_(2)O_(3)(x=6%,9%,12%,15%,18%)catalysts with aluminum oxide(Al_(2)O_(3))as the carrier,nickel chloride(NiCl2)as the nickel(Ni)source,and ammonium hypophosphite(NH_(4)H_(2)PO_(2))as the phosphorus(P)source were prepared by the equal volume impregnation method to investigate the effects of different loadings on the performance of the selective hydrogenation of diolefins and thiol etherification in LPG.The physicochemical properties of the catalysts were characterized by XRD,BET,SEM,TEM,H_(2)-TPR,and XPS,and the catalytic activity of the catalysts was evaluated in a fixed-bed microreactor.The results showed that a change in the loading affected the catalyst crystalline phase structure and size,specific surface area,P coverage,active phase dispersion,and catalytic activity.At 6%,9%,and 12%loadings the catalysts had an Ni phase but there was no obvious Ni_(2)P phase in the nickel phosphide;at 15%loading a single Ni_(2)P phase was obtained,and at 18%loading both Ni_(2)P and Ni1_(2)P_(5) phases appeared.There was a P enrichment on the catalyst surface,and the higher the loading the more P species were enriched on the surface,but some of the P was lost during the catalyst reduction process due to the production of phosphine(PH3)gas.The 15%Ni_(2)P/γ-Al_(2)O_(3) catalyst had the largest Ni/Al ratio and the best dispersion.The Ni_(2)P active phase size was small at about 4.25 nm and Ni_(2)P was uniformly dispersed on the catalyst surface without agglomeration.The 15%Ni_(2)P/γ-Al_(2)O_(3) catalyst had the best catalytic activity at a pressure of 2.0 MPa,a liquid hourly space velocity(LHSV)of 3.0 h-1,and a hydrogen to hydrocarbon ratio of 12.The 1,3-butadiene conversion was 97.45%and the methanethiol removal was 100%at a temperature of 140℃.展开更多
A novel tetra-europium(III)-containing antimonotungstate,Na_(8.2)[H_(2)N(CH_(3))_(2)]_(9)[Na_(10.8)(tar)_(4)(H_(2)O)_(20)(Eu_(2)Sb_(2)W_(21)O_(72))_(2)]·44.5H_(2)O(EuSbW,H_(4)tar=dl-tartaric acid),has been synthe...A novel tetra-europium(III)-containing antimonotungstate,Na_(8.2)[H_(2)N(CH_(3))_(2)]_(9)[Na_(10.8)(tar)_(4)(H_(2)O)_(20)(Eu_(2)Sb_(2)W_(21)O_(72))_(2)]·44.5H_(2)O(EuSbW,H_(4)tar=dl-tartaric acid),has been synthesized and characterized.The dimeric polyoxoanion of EuSbW consists of two Dawson-like{Eu_(2)Sb_(2)W_(21)}units bridged by four dl-tartaric acid ligands.The adjacent carboxyl and hydroxy groups in each tartaric acid simultaneously chelate with W and Eu atoms from different{Eu_(2)Sb_(2)W_(21)}units,thereby forming the dimeric structure.EuSbW represents an extremely rare polyoxometalate where four tartaric acid ligands function as connectors to bridge two{Eu_(2)Sb_(2)W_(21)}units.Additionally,EuSbW exhibits excellent catalytic activity and reusability in the oxidation of thioethers and alcohols,achieving 100%conversion and>99%selectivity for various thioethers,and 85–100%conversion with 90–99%selectivity for diverse alcohols under mild conditions.展开更多
Mercury ions(Hg^(2+))and bacteria are widely spread in water pollution and pose a great threat to human health and the environment.Herein,a multifunctional COF Dmta Tph with significant Hg^(2+)adsorption capability an...Mercury ions(Hg^(2+))and bacteria are widely spread in water pollution and pose a great threat to human health and the environment.Herein,a multifunctional COF Dmta Tph with significant Hg^(2+)adsorption capability and continuous sunlight-driven sterilization property is designed and synthesized by introducing thioether and photosensitive porphyrin in a single molecule.The obtained COF displays a high Hg^(2+)adsorption capacity of 657.9 mg/g at 298 K and a superior antibacterial effect toward Escherichia coli and Staphylococcus aureus under sunlight irradiation.Mechanistic studies reveal that the strong coordination between S species and Hg^(2+)is the main driving force for high Hg^(2+)adsorption capability.The sterilization mechanism clarifies that the inactivation of bacteria is caused by1O_(2)produced from Dmta Tph with the assistance of light irradiation.Noteworthy,when Dmta Tph is applied in the treatment of wastewater,it displays high Hg^(2+)removal efficiency and remarkable antibacterial effect under complex conditions.This study has demonstrated a promising strategy for designing multifunctional COF-based materials,offering great potential in tackling the problem of heavy metal ions and bacteria pollution in water.展开更多
The accompanied forge of C(sp^(3))–S and C(sp^(3))–C(sp^(3))bonds across alkene frameworks serves as a potent strategy to construct biologically important compounds.Here,we report a metal-free,photochemically mediat...The accompanied forge of C(sp^(3))–S and C(sp^(3))–C(sp^(3))bonds across alkene frameworks serves as a potent strategy to construct biologically important compounds.Here,we report a metal-free,photochemically mediated fluoroalkyl-mono/disulfuration of unactivated alkenes with high efficiency and high selectivity.A wide range of terminal and internal alkenes are good coupling partners,affording the expected products in moderate to good yields(>90 examples).The exceedingly mild reaction conditions,exceptional functional group tolerance,broad substrate scope,and the potential for late-stage modifications of pharmaceutical molecules highlight the utility of this method in the preparation of privileged motifs from readily available disulfides,tetrasulfides,and diselenides.Mechanistic studies suggest that a secondary alkyl radical intermediate undergoes efficient homolytic substitution with disulfides,facilitating the modular synthesis of a diverse array of unsymmetrical thioethers.展开更多
Marine natural products offer a promising source in the development of new antibiotic drugs.Two previously undescribed compounds,including one sulfur-bearing alkaloid named quinosumycin(1)along with one chromone deriv...Marine natural products offer a promising source in the development of new antibiotic drugs.Two previously undescribed compounds,including one sulfur-bearing alkaloid named quinosumycin(1)along with one chromone derivative namely chromycone(2),were discovered from an ethyl acetate(EtOAc)extract of marine Streptomyces diastaticus NBU2966 through a bioactivity-guided isolation prioritized for antimicrobial potential.The analysis of nuclear magnetic resonance(NMR)spectroscopy,high resolution electrospray ionization mass spectroscopy(HRESIMS)data,and electronic circular dichroism(ECD)calculations enabled the elucidation of their structures and the determination of their absolute configurations.Quinosumycin(1)is the first heterodimer scaffold incorporating quinolinone and quinazolinone motifs coupled by a thioether bond.Interestingly,Compound 1 exhibited a relatively selective growth inhibition against methicillin-resistant Staphylococcus aureus(MRSA)with the minimal inhibitory concentration(MIC)value of 8μg/mL.展开更多
Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene...Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene(TCAET)was synthesized specifically for the capture of Au(Ⅲ)and Pd(Ⅱ)from HCl medium by liquid-liquid extraction.In a 0.1 mol·L^(-1)HCl medium,the transfer of Au(Ⅲ)and Pd(Ⅱ)from the aqueous phase to the organic phase was highly efficient,with a transfer ratio of 100%for Au(Ⅲ)and 98%for Pd(Ⅱ).Furthermore,the extraction equilibrium time for Au(Ⅲ)was just 5 min.Job's method data demonstrated that TCAET formed complexes with Au(Ⅲ)and Pd(Ⅱ)in a ratio of 2:3 and 1:1,respectively,during the extraction process.TCAET showed high selectivity toward Pd(Ⅱ)and Au(Ⅲ)over other competing metal ions.Moreover,both Au(Ⅲ)and Pd(Ⅱ)could be successfully stripped from the loaded organic phases with a 1.0 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl and 0.5 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl,respectively.Results obtained from five consecutive extraction-stripping cycles showed good reusability of TCAET toward Au(Ⅲ)and Pd(Ⅱ)recovery.The conclusion can provide a certain reference for thiacalixarene in the recovery of precious metal species.展开更多
Novel small sulfur heterocyclic quinones(6a,16adihydrobenzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,7,9,14,16,18-hexaone(4S6Q)and benzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,9,14,18-t...Novel small sulfur heterocyclic quinones(6a,16adihydrobenzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,7,9,14,16,18-hexaone(4S6Q)and benzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,9,14,18-tetraone(4S4Q))are developed by molecule structural design method and as cathode for aqueous zincorganic batteries.The conjugated thioether(–S–)bonds as connected units not only improve the conductivity of compounds but also inhibit their dissolution by both extendedπ-conjugated plane and constructed flexible molecular skeleton.Hence,the Zn//4S6Q and Zn//4S4Q batteries exhibit satisfactory electrochemical performance based on 3.5 mol L-1(M)Zn(ClO4)2electrolyte.For instance,the Zn//4S6Q battery obtains 240 and 208.6 mAh g^(-1)of discharge capacity at 150 mA g^(-1)and 30 A g^(-1),respectively.The excellent rate capability is ascribed to the fast reaction kinetics.This system displays a superlong life of 20,000 cycles with no capacity fading at 3 A g^(-1).Additionally,the H+-storage mechanism of the 4S6Q compound is demonstrated by ex situ analyses and density functional theory calculations.Impressively,the battery can normally work at-60℃benefiting from the anti-freezing electrolyte and maintain a high discharge capacity of 201.7 mAh g^(-1),which is 86.2%of discharge capacity at 25℃.The cutting-edge electrochemical performances of these novel compounds make them alternative electrode materials for Zn-organic batteries.展开更多
Stimuli-re sponsive polypeptides have been intensively investigated fo r controlled drug release,owing to their favorable biocompatibility and biodegradability.In this work,we designed and synthesized a new kind of po...Stimuli-re sponsive polypeptides have been intensively investigated fo r controlled drug release,owing to their favorable biocompatibility and biodegradability.In this work,we designed and synthesized a new kind of polypeptide bearing 1,4-dithiane pendants for reactive oxygen species(ROS)-responsive drug release.The polypeptide-based block copolymer was facilely synthesized by ring-opening polymerization(ROP)of 1,4-dithian-substituted L-glutamate N-carboxyanhydride(DTG-NCA)monomer using an amino-terminated poly(ethylene glycol)methyl ether(mPEG-NH2)as the macro molecular initiator.The resulta nt block copolyme r,mPEG-b-PDTG,could self-assemble into unifo rm micelles in aqueous medium owing to its amphiphilic structure.Then,the H2 O2-triggered oxidation behaviors of the mPEG-b-PDTG micelles were studied by dynamic light scattering(DLS),FT-IR and turbidimetric assay.It was revealed that the oxidation of thioether into sulfoxide in the side chains would result in disassembly of the micelles.Furthermore,the ROS-responsive drug release behavior of the mPEG-b-PDTG micelles was verified by using Nile Red as a model drug.MTT assay also proved that mPEG-b-PDTG was non-toxic in B16 F10 and L929 cells.Therefore,such a new class of oxidation-responsive polypeptide might provide a promising platform for ROS-responsive drug delivery.展开更多
In recent decades, peptides as potential drugs were more and more explored with the development of non-oral medicine. There into, sulfur-containing peptide is one of the most popular aspects in peptide drugs due to th...In recent decades, peptides as potential drugs were more and more explored with the development of non-oral medicine. There into, sulfur-containing peptide is one of the most popular aspects in peptide drugs due to the introduction of sulfur atoms leading unique properties.The purpose of the present review is to focus on the discovery of various sulfur-containing peptides with particular emphasis on their pharmacological mechanisms. This review is organized according to the structures of the sulfurcontaining peptides.展开更多
An efficient, practical, highly selective and environmentally benign method is reported for the synthesis of aryl thioethers via the coupling of thiols with aryl boronic acids in the presence of NaOH and a catalytic a...An efficient, practical, highly selective and environmentally benign method is reported for the synthesis of aryl thioethers via the coupling of thiols with aryl boronic acids in the presence of NaOH and a catalytic amount of CuSO4 at 130 ℃ using water as a green solvent. The products were obtained in moderate to excellent yields;more importantly, the use of toxic ligands and solvents was avoided. A broad range of aryl boronic acids and scalable processes make this methodology valuable and versatile for the synthesis of a broad range of aryl sulfides.展开更多
Covalent organic frameworks(COFs)have lately emerged as a blooming class of potential materials for photocatalytic water splitting because of their high crystallinity,huge surface areas,and structural versatility.Howe...Covalent organic frameworks(COFs)have lately emerged as a blooming class of potential materials for photocatalytic water splitting because of their high crystallinity,huge surface areas,and structural versatility.However,the photocatalytic performance for most pure COFs face some limitations factors,such as the significant recombination of photogenerated carriers and slow charge transfer.Herein,a novel thioether-functionalized pyrene-based COF(S_(4)-COF)was effectively produced and chosen as a support for the immobilization of ultrafine gold nanoparticles(Au NPs).S_(4)-COF photocatalyst with Au as cocatalyst demonstrates remarkable photocatalytic activity with a H_(2) generation rate of 1377μmol g^(−1) h^(−1) under visible light(>420 nm),which is ca.4.5-fold increase comparing to that of pure S_(4)-COF(302μmol g^(−1) h^(−1)).Au NPs anchored on S_(4)-COF possess an ultrafine size distribution ranging from 1.75 to 6.25 nm with an average size centered at 3.8 nm,which benefits from the coordination interaction between thioether groups and Au.Meanwhile,the produced Au@S_(4)-COF can generate a stable photocatalytic H_(2) generation during the four recycles and preserve its crystallinity structure after the stability testing.The Au NPs anchored on the S_(4)-COF photocatalyst can greatly accelerate the separation of photogenerated carriers and increase charge transfer because of the combined function of Au NPs and thioether groups.Such a method can not only prevent the aggregation of Au NPs onto thioether-containing COFs to achieve long-term photostability but also allow uniform dispersion for an ordered structure of photocatalysts.This work provides a rational strategy for designing and preparing COF-based photocatalysts for solar-driven H_(2) production.展开更多
An effective method for the synthesis of vinyl thioethers through the conjugate addition of ethanethiol to electron-deficient alkynes promoted by BF3.Et20 has been developed. Electron-deficient internal alkynes react ...An effective method for the synthesis of vinyl thioethers through the conjugate addition of ethanethiol to electron-deficient alkynes promoted by BF3.Et20 has been developed. Electron-deficient internal alkynes react with ethanethiol in this system to yield mainly Z-isomer of vinyl thioether adducts, while electron-deficient terminal alkynes afford mainly E-isomer of vinyl thioether adducts.展开更多
The title compound 3-methyl-l-（4-methylphenyl）-4-（N-4-trifluoromethylphenyl） aminomethyl-5-（4-methoxyphenylthio）-lH-pyrazole has been synthesized via a four-step reaction and characterized by IR, 1H NMR, element...The title compound 3-methyl-l-（4-methylphenyl）-4-（N-4-trifluoromethylphenyl） aminomethyl-5-（4-methoxyphenylthio）-lH-pyrazole has been synthesized via a four-step reaction and characterized by IR, 1H NMR, elemental analysis and X-ray crystallography. The compound crystallizes in monoclinic, space group P21/c with a = 8.7170（15）, b = 18.355（3）, c = 15.292（3） A, fl = 103.445（3）°, V= 2379.7（7） A3, Dc = 1.350 g/cm3, Z = 4, p = 0.184, F（000） = 1008, and the final R = 0.0491 and wR = 0.1339 for 4160 observed reflections （I 〉 2a（/））. The results demonstrate that there is a face-to-face π-π stacking interaction between one benzene ring （C（19）-C（24）） and another （C（I 3）-C（! 8）） at a plane-plane distance of 3.3539 A. The ring normal and vector between the ring centroids form an angle of 18.2° up to the centroid-to-centroid distance of 3.5273 A. The crystal structure is stabilized by the intermolecular hydrogen bond of N（3）-H（3A）...N（2） （symmetry code： A -x＋l, -y＋l, -z）. The preliminary biological test shows that the title compound has a moderate antifungal activity.展开更多
By the suspended condensation reaction of poly(choloromethylthiirane)with o-tolidine and o- dianisidine respectively, two newmicrobeads chelating resins were synthesized by usingγ-Fe_2O_3 asmagnetic core. Their adsor...By the suspended condensation reaction of poly(choloromethylthiirane)with o-tolidine and o- dianisidine respectively, two newmicrobeads chelating resins were synthesized by usingγ-Fe_2O_3 asmagnetic core. Their adsorption properties for Hg(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Pb(Ⅱ), Au(Ⅲ), Pd(Ⅱ), Pt (Ⅳ)and Ag(Ⅰ)were investigated. Themicrobeads posses excellent adsorbability for Hg(Ⅱ) and noble metalions, and predominantly adsorbed Pd(Ⅱ)or Hg(Ⅱ)in the coexistence ofCu(Ⅱ), Zn(Ⅱ)and Mg(Ⅱ).展开更多
Tetrabutylammonium fluoride （TBAF） effectively facilitated a denitrative substitution reaction of electron-deficient nitroarenes with phenylthiotrimethylsilane （PhSTMS） under mild and base-free neutral conditions ...Tetrabutylammonium fluoride （TBAF） effectively facilitated a denitrative substitution reaction of electron-deficient nitroarenes with phenylthiotrimethylsilane （PhSTMS） under mild and base-free neutral conditions at room temperature, providing a practical and efficient synthesis of useful unsymmetrical diaryl thioethers. Nitroarenes bearing ortho- and para-positioned electron-withdrawing groups are the most reactive substrates, indicating that this reaction most possibly proceeded via the nucleophilic aromatic substitution （SNAr） mechanism.展开更多
Dielectric elastomers(DEs)have drawn much attention owing to their application prospects in artificial muscles and soft robotics,it is still a big challenge to prepare DEs with high electromechanical performances.This...Dielectric elastomers(DEs)have drawn much attention owing to their application prospects in artificial muscles and soft robotics,it is still a big challenge to prepare DEs with high electromechanical performances.This work reports a highly stretchable poly(thioether)-b-polysiloxane-b-poly(thioether)triblock copolymer based homogenous DEs with high electromechanical properties.The triblock copolymer(PSiPGE)was synthesized through the ring-opening polymerization(ROP)of phenyl glycidyl ether(PGE)and carbonyl sulfide(COS)catalyzed by silicon alkoxides.The dipoles(benzene rings)on the side groups of PSiPGE improved the dipole polarizations and the phase separation structure of this triblock copolymer enhanced the interfacial polarizations between poly(thioether)and polysiloxane,and thus improving the dielectric constant(ε',up to 5.8).In addition,the PSiPGE exhibited low elastic modulus(Y,0.04 MPa),and thus possessed high electromechanical sensitivity(β,~145 MPa^(-1)) which is much higher than that of most homogenous DEs.This work provides a new strategy to construct homogenous DEs with excellent electromechanical performances,leading to a greater application aspect in the actuated devices.展开更多
The synthesis of a thioether inserted, core-shell structured polymer from the scaffold of hyperbranched polyglycerol (PG) was described. PG was first allyl functionalized, and in the presence of AlBN, the allyl groups...The synthesis of a thioether inserted, core-shell structured polymer from the scaffold of hyperbranched polyglycerol (PG) was described. PG was first allyl functionalized, and in the presence of AlBN, the allyl groups further underwent radical addition to thiol compounds, thus thiol functional polyethylene oxide monomether (MPEO) were grafted onto PG. Similarly, 2-mercaptoethylammonium chloride was introduced onto PG via thiol addition, and the residual amino groups were further quaternized with decyl bromide, leading to an amphiphilic core-shell structure polymer. (c) 2007 De Cheng Wan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
A stereoselective and effective method for the synthesis of vinyl thioethers has been developed.This method is based on the Michael addition of ethanethiol to various alkynyl ketones using 10 mol%of tributylphosphine ...A stereoselective and effective method for the synthesis of vinyl thioethers has been developed.This method is based on the Michael addition of ethanethiol to various alkynyl ketones using 10 mol%of tributylphosphine as catalyst.Most of alkynyl ketones react with ethanethiol in this system to yield mainly Z-isomer of vinyl thioether adducts,only in one case mainly E-isomer of vinyl thioether adducts was observed.展开更多
The catalytic desulfurization of a model organic sulfurous compound n-butyl-sulfide in a fixed bed microreactor is studied in the presence of catalyst and a hydrogen provider. The experimental results show that the ap...The catalytic desulfurization of a model organic sulfurous compound n-butyl-sulfide in a fixed bed microreactor is studied in the presence of catalyst and a hydrogen provider. The experimental results show that the appropriate reaction conditions are： a mixed catalyst of HZSM-5 zeolite and Co-Mo/Al2O3-TiO2, a reaction temperature of 300℃, atmosphere pressure, a feed speed of 50 mL/h and a mass hourly space velocity of 3.0 h^-1 A higher catalytic property and desulfurization efficiency of the mixed catalyst of HZSM-5 zeolite and Co-Mo/Al2O3-TiO2 is achieved. The adsorption and desulfurization efficiency of the FCC gasoline from Shenghua Refinery, which is affiliated to China University of Petroleum （East China）, is 53.0 %.展开更多
The disulfides reacted with zinc in DMF, followed by alkyl halides, giving unsymmetrical thioether in excellent yields. This reaction takes place under mild and neutral conditions.
文摘In this study,different loadings of x%Ni_(2)P/γ-Al_(2)O_(3)(x=6%,9%,12%,15%,18%)catalysts with aluminum oxide(Al_(2)O_(3))as the carrier,nickel chloride(NiCl2)as the nickel(Ni)source,and ammonium hypophosphite(NH_(4)H_(2)PO_(2))as the phosphorus(P)source were prepared by the equal volume impregnation method to investigate the effects of different loadings on the performance of the selective hydrogenation of diolefins and thiol etherification in LPG.The physicochemical properties of the catalysts were characterized by XRD,BET,SEM,TEM,H_(2)-TPR,and XPS,and the catalytic activity of the catalysts was evaluated in a fixed-bed microreactor.The results showed that a change in the loading affected the catalyst crystalline phase structure and size,specific surface area,P coverage,active phase dispersion,and catalytic activity.At 6%,9%,and 12%loadings the catalysts had an Ni phase but there was no obvious Ni_(2)P phase in the nickel phosphide;at 15%loading a single Ni_(2)P phase was obtained,and at 18%loading both Ni_(2)P and Ni1_(2)P_(5) phases appeared.There was a P enrichment on the catalyst surface,and the higher the loading the more P species were enriched on the surface,but some of the P was lost during the catalyst reduction process due to the production of phosphine(PH3)gas.The 15%Ni_(2)P/γ-Al_(2)O_(3) catalyst had the largest Ni/Al ratio and the best dispersion.The Ni_(2)P active phase size was small at about 4.25 nm and Ni_(2)P was uniformly dispersed on the catalyst surface without agglomeration.The 15%Ni_(2)P/γ-Al_(2)O_(3) catalyst had the best catalytic activity at a pressure of 2.0 MPa,a liquid hourly space velocity(LHSV)of 3.0 h-1,and a hydrogen to hydrocarbon ratio of 12.The 1,3-butadiene conversion was 97.45%and the methanethiol removal was 100%at a temperature of 140℃.
基金supported by the Natural Science Foundation of Jiangxi Province(20232ACB213005).
文摘A novel tetra-europium(III)-containing antimonotungstate,Na_(8.2)[H_(2)N(CH_(3))_(2)]_(9)[Na_(10.8)(tar)_(4)(H_(2)O)_(20)(Eu_(2)Sb_(2)W_(21)O_(72))_(2)]·44.5H_(2)O(EuSbW,H_(4)tar=dl-tartaric acid),has been synthesized and characterized.The dimeric polyoxoanion of EuSbW consists of two Dawson-like{Eu_(2)Sb_(2)W_(21)}units bridged by four dl-tartaric acid ligands.The adjacent carboxyl and hydroxy groups in each tartaric acid simultaneously chelate with W and Eu atoms from different{Eu_(2)Sb_(2)W_(21)}units,thereby forming the dimeric structure.EuSbW represents an extremely rare polyoxometalate where four tartaric acid ligands function as connectors to bridge two{Eu_(2)Sb_(2)W_(21)}units.Additionally,EuSbW exhibits excellent catalytic activity and reusability in the oxidation of thioethers and alcohols,achieving 100%conversion and>99%selectivity for various thioethers,and 85–100%conversion with 90–99%selectivity for diverse alcohols under mild conditions.
基金financially supported by the National Natural Science Foundation of China(Nos.22106078,62105175)High-end Foreign Experts Recruitment Plan(No.G2023024007L)+1 种基金Shandong Provincial Natural Science Foundation(Nos.ZR2022YQ12,ZR2021QB031,ZR2021QF058)the Science,Education,and Industry Integration Pilot Project for Talent Research at Qilu University of Technology(Shandong Academy of Sciences)(No.2024RCKY028)。
文摘Mercury ions(Hg^(2+))and bacteria are widely spread in water pollution and pose a great threat to human health and the environment.Herein,a multifunctional COF Dmta Tph with significant Hg^(2+)adsorption capability and continuous sunlight-driven sterilization property is designed and synthesized by introducing thioether and photosensitive porphyrin in a single molecule.The obtained COF displays a high Hg^(2+)adsorption capacity of 657.9 mg/g at 298 K and a superior antibacterial effect toward Escherichia coli and Staphylococcus aureus under sunlight irradiation.Mechanistic studies reveal that the strong coordination between S species and Hg^(2+)is the main driving force for high Hg^(2+)adsorption capability.The sterilization mechanism clarifies that the inactivation of bacteria is caused by1O_(2)produced from Dmta Tph with the assistance of light irradiation.Noteworthy,when Dmta Tph is applied in the treatment of wastewater,it displays high Hg^(2+)removal efficiency and remarkable antibacterial effect under complex conditions.This study has demonstrated a promising strategy for designing multifunctional COF-based materials,offering great potential in tackling the problem of heavy metal ions and bacteria pollution in water.
文摘The accompanied forge of C(sp^(3))–S and C(sp^(3))–C(sp^(3))bonds across alkene frameworks serves as a potent strategy to construct biologically important compounds.Here,we report a metal-free,photochemically mediated fluoroalkyl-mono/disulfuration of unactivated alkenes with high efficiency and high selectivity.A wide range of terminal and internal alkenes are good coupling partners,affording the expected products in moderate to good yields(>90 examples).The exceedingly mild reaction conditions,exceptional functional group tolerance,broad substrate scope,and the potential for late-stage modifications of pharmaceutical molecules highlight the utility of this method in the preparation of privileged motifs from readily available disulfides,tetrasulfides,and diselenides.Mechanistic studies suggest that a secondary alkyl radical intermediate undergoes efficient homolytic substitution with disulfides,facilitating the modular synthesis of a diverse array of unsymmetrical thioethers.
基金Supported by the National Natural Science Foundation of China(No.42176101)the Ningbo Youth Science and Technology Innovation Leading Project(No.2024QL063)+2 种基金the National 111 Project of China(No.D16013)the Scientific Research Fund of Zhejiang Provincial Education Department(No.Y202250186)the Li Dak Sum Yip Yio Chin Kenneth Li Marine Biopharmaceutical Development Fund。
文摘Marine natural products offer a promising source in the development of new antibiotic drugs.Two previously undescribed compounds,including one sulfur-bearing alkaloid named quinosumycin(1)along with one chromone derivative namely chromycone(2),were discovered from an ethyl acetate(EtOAc)extract of marine Streptomyces diastaticus NBU2966 through a bioactivity-guided isolation prioritized for antimicrobial potential.The analysis of nuclear magnetic resonance(NMR)spectroscopy,high resolution electrospray ionization mass spectroscopy(HRESIMS)data,and electronic circular dichroism(ECD)calculations enabled the elucidation of their structures and the determination of their absolute configurations.Quinosumycin(1)is the first heterodimer scaffold incorporating quinolinone and quinazolinone motifs coupled by a thioether bond.Interestingly,Compound 1 exhibited a relatively selective growth inhibition against methicillin-resistant Staphylococcus aureus(MRSA)with the minimal inhibitory concentration(MIC)value of 8μg/mL.
基金supported by the National Natural Science Foundation of China(U20A20268)Natural Science Foundation of Hunan Province(2020JJ1004)Hunan Provincial Innovation Foundation for Postgraduate(CX20211190)。
文摘Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene(TCAET)was synthesized specifically for the capture of Au(Ⅲ)and Pd(Ⅱ)from HCl medium by liquid-liquid extraction.In a 0.1 mol·L^(-1)HCl medium,the transfer of Au(Ⅲ)and Pd(Ⅱ)from the aqueous phase to the organic phase was highly efficient,with a transfer ratio of 100%for Au(Ⅲ)and 98%for Pd(Ⅱ).Furthermore,the extraction equilibrium time for Au(Ⅲ)was just 5 min.Job's method data demonstrated that TCAET formed complexes with Au(Ⅲ)and Pd(Ⅱ)in a ratio of 2:3 and 1:1,respectively,during the extraction process.TCAET showed high selectivity toward Pd(Ⅱ)and Au(Ⅲ)over other competing metal ions.Moreover,both Au(Ⅲ)and Pd(Ⅱ)could be successfully stripped from the loaded organic phases with a 1.0 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl and 0.5 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl,respectively.Results obtained from five consecutive extraction-stripping cycles showed good reusability of TCAET toward Au(Ⅲ)and Pd(Ⅱ)recovery.The conclusion can provide a certain reference for thiacalixarene in the recovery of precious metal species.
基金the National Natural Science Foundation of China(22279063 and 21835004)the National Key R&D Program of China(2016YFB0901500)+1 种基金Ministry of Education of China(B12015 and IRT13R30)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Novel small sulfur heterocyclic quinones(6a,16adihydrobenzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,7,9,14,16,18-hexaone(4S6Q)and benzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,9,14,18-tetraone(4S4Q))are developed by molecule structural design method and as cathode for aqueous zincorganic batteries.The conjugated thioether(–S–)bonds as connected units not only improve the conductivity of compounds but also inhibit their dissolution by both extendedπ-conjugated plane and constructed flexible molecular skeleton.Hence,the Zn//4S6Q and Zn//4S4Q batteries exhibit satisfactory electrochemical performance based on 3.5 mol L-1(M)Zn(ClO4)2electrolyte.For instance,the Zn//4S6Q battery obtains 240 and 208.6 mAh g^(-1)of discharge capacity at 150 mA g^(-1)and 30 A g^(-1),respectively.The excellent rate capability is ascribed to the fast reaction kinetics.This system displays a superlong life of 20,000 cycles with no capacity fading at 3 A g^(-1).Additionally,the H+-storage mechanism of the 4S6Q compound is demonstrated by ex situ analyses and density functional theory calculations.Impressively,the battery can normally work at-60℃benefiting from the anti-freezing electrolyte and maintain a high discharge capacity of 201.7 mAh g^(-1),which is 86.2%of discharge capacity at 25℃.The cutting-edge electrochemical performances of these novel compounds make them alternative electrode materials for Zn-organic batteries.
基金financially supported by National Key Research and Development Program of China(No.2016YFC1100701)the National Natural Science Foundation of China(Nos.51573184,51520105004 and 51833010)the Youth Innovation Promotion Association of Chinese Academy of Sciences(No.2017266)。
文摘Stimuli-re sponsive polypeptides have been intensively investigated fo r controlled drug release,owing to their favorable biocompatibility and biodegradability.In this work,we designed and synthesized a new kind of polypeptide bearing 1,4-dithiane pendants for reactive oxygen species(ROS)-responsive drug release.The polypeptide-based block copolymer was facilely synthesized by ring-opening polymerization(ROP)of 1,4-dithian-substituted L-glutamate N-carboxyanhydride(DTG-NCA)monomer using an amino-terminated poly(ethylene glycol)methyl ether(mPEG-NH2)as the macro molecular initiator.The resulta nt block copolyme r,mPEG-b-PDTG,could self-assemble into unifo rm micelles in aqueous medium owing to its amphiphilic structure.Then,the H2 O2-triggered oxidation behaviors of the mPEG-b-PDTG micelles were studied by dynamic light scattering(DLS),FT-IR and turbidimetric assay.It was revealed that the oxidation of thioether into sulfoxide in the side chains would result in disassembly of the micelles.Furthermore,the ROS-responsive drug release behavior of the mPEG-b-PDTG micelles was verified by using Nile Red as a model drug.MTT assay also proved that mPEG-b-PDTG was non-toxic in B16 F10 and L929 cells.Therefore,such a new class of oxidation-responsive polypeptide might provide a promising platform for ROS-responsive drug delivery.
基金financial support provided by The National Key Research and Development Program of China (No. 2017YFD0200500)the National Natural Science Foundation of China (Nos. 21722202, 21672069, 21472050)+3 种基金S&TCSM of Shanghai (No. 18JC1415600),S&TCSM of Shanghai(No.18JC1415600)Fok Ying Tung Education Foundation(No. 141011)DFMEC(No. 20130076110023)Professor of Special Appointment(Eastern Scholar) at Shanghai Institutions of Higher Learning,National Program for Support of Top-Notch Young Professionals
文摘In recent decades, peptides as potential drugs were more and more explored with the development of non-oral medicine. There into, sulfur-containing peptide is one of the most popular aspects in peptide drugs due to the introduction of sulfur atoms leading unique properties.The purpose of the present review is to focus on the discovery of various sulfur-containing peptides with particular emphasis on their pharmacological mechanisms. This review is organized according to the structures of the sulfurcontaining peptides.
基金Funded by the National Natural Science Foundation of China(No.21571144)
文摘An efficient, practical, highly selective and environmentally benign method is reported for the synthesis of aryl thioethers via the coupling of thiols with aryl boronic acids in the presence of NaOH and a catalytic amount of CuSO4 at 130 ℃ using water as a green solvent. The products were obtained in moderate to excellent yields;more importantly, the use of toxic ligands and solvents was avoided. A broad range of aryl boronic acids and scalable processes make this methodology valuable and versatile for the synthesis of a broad range of aryl sulfides.
文摘Covalent organic frameworks(COFs)have lately emerged as a blooming class of potential materials for photocatalytic water splitting because of their high crystallinity,huge surface areas,and structural versatility.However,the photocatalytic performance for most pure COFs face some limitations factors,such as the significant recombination of photogenerated carriers and slow charge transfer.Herein,a novel thioether-functionalized pyrene-based COF(S_(4)-COF)was effectively produced and chosen as a support for the immobilization of ultrafine gold nanoparticles(Au NPs).S_(4)-COF photocatalyst with Au as cocatalyst demonstrates remarkable photocatalytic activity with a H_(2) generation rate of 1377μmol g^(−1) h^(−1) under visible light(>420 nm),which is ca.4.5-fold increase comparing to that of pure S_(4)-COF(302μmol g^(−1) h^(−1)).Au NPs anchored on S_(4)-COF possess an ultrafine size distribution ranging from 1.75 to 6.25 nm with an average size centered at 3.8 nm,which benefits from the coordination interaction between thioether groups and Au.Meanwhile,the produced Au@S_(4)-COF can generate a stable photocatalytic H_(2) generation during the four recycles and preserve its crystallinity structure after the stability testing.The Au NPs anchored on the S_(4)-COF photocatalyst can greatly accelerate the separation of photogenerated carriers and increase charge transfer because of the combined function of Au NPs and thioether groups.Such a method can not only prevent the aggregation of Au NPs onto thioether-containing COFs to achieve long-term photostability but also allow uniform dispersion for an ordered structure of photocatalysts.This work provides a rational strategy for designing and preparing COF-based photocatalysts for solar-driven H_(2) production.
基金the National Natural Science Foundation of China(No.21102179)Fundamental Research Funds for the Central Universities(No.JKZ2011011) for the financial support
文摘An effective method for the synthesis of vinyl thioethers through the conjugate addition of ethanethiol to electron-deficient alkynes promoted by BF3.Et20 has been developed. Electron-deficient internal alkynes react with ethanethiol in this system to yield mainly Z-isomer of vinyl thioether adducts, while electron-deficient terminal alkynes afford mainly E-isomer of vinyl thioether adducts.
基金supported by Research Fund for the Doctoral Program of Zunyi Medical College(F-564)Natural Science Foundation of Guizhou Province(No.J2011[2083])
文摘The title compound 3-methyl-l-（4-methylphenyl）-4-（N-4-trifluoromethylphenyl） aminomethyl-5-（4-methoxyphenylthio）-lH-pyrazole has been synthesized via a four-step reaction and characterized by IR, 1H NMR, elemental analysis and X-ray crystallography. The compound crystallizes in monoclinic, space group P21/c with a = 8.7170（15）, b = 18.355（3）, c = 15.292（3） A, fl = 103.445（3）°, V= 2379.7（7） A3, Dc = 1.350 g/cm3, Z = 4, p = 0.184, F（000） = 1008, and the final R = 0.0491 and wR = 0.1339 for 4160 observed reflections （I 〉 2a（/））. The results demonstrate that there is a face-to-face π-π stacking interaction between one benzene ring （C（19）-C（24）） and another （C（I 3）-C（! 8）） at a plane-plane distance of 3.3539 A. The ring normal and vector between the ring centroids form an angle of 18.2° up to the centroid-to-centroid distance of 3.5273 A. The crystal structure is stabilized by the intermolecular hydrogen bond of N（3）-H（3A）...N（2） （symmetry code： A -x＋l, -y＋l, -z）. The preliminary biological test shows that the title compound has a moderate antifungal activity.
基金Funded by Natural Science Foundation of Hubei Province (NO.2000J022)
文摘By the suspended condensation reaction of poly(choloromethylthiirane)with o-tolidine and o- dianisidine respectively, two newmicrobeads chelating resins were synthesized by usingγ-Fe_2O_3 asmagnetic core. Their adsorption properties for Hg(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Pb(Ⅱ), Au(Ⅲ), Pd(Ⅱ), Pt (Ⅳ)and Ag(Ⅰ)were investigated. Themicrobeads posses excellent adsorbability for Hg(Ⅱ) and noble metalions, and predominantly adsorbed Pd(Ⅱ)or Hg(Ⅱ)in the coexistence ofCu(Ⅱ), Zn(Ⅱ)and Mg(Ⅱ).
基金the National Natural Science Foundation of China(No.20902070)Natural Science Foundation of Zhejiang Province(No.Y4100579)Qianjiang Talents Program of Zhejiang Province(No.QJD0902004) for financial supports
文摘Tetrabutylammonium fluoride （TBAF） effectively facilitated a denitrative substitution reaction of electron-deficient nitroarenes with phenylthiotrimethylsilane （PhSTMS） under mild and base-free neutral conditions at room temperature, providing a practical and efficient synthesis of useful unsymmetrical diaryl thioethers. Nitroarenes bearing ortho- and para-positioned electron-withdrawing groups are the most reactive substrates, indicating that this reaction most possibly proceeded via the nucleophilic aromatic substitution （SNAr） mechanism.
基金National Natural Science Foundation of China(Nos.51973190 and 21774108)Zhejiang Provincial Department of Science and Technology(No.2020R52006)for financial supports。
文摘Dielectric elastomers(DEs)have drawn much attention owing to their application prospects in artificial muscles and soft robotics,it is still a big challenge to prepare DEs with high electromechanical performances.This work reports a highly stretchable poly(thioether)-b-polysiloxane-b-poly(thioether)triblock copolymer based homogenous DEs with high electromechanical properties.The triblock copolymer(PSiPGE)was synthesized through the ring-opening polymerization(ROP)of phenyl glycidyl ether(PGE)and carbonyl sulfide(COS)catalyzed by silicon alkoxides.The dipoles(benzene rings)on the side groups of PSiPGE improved the dipole polarizations and the phase separation structure of this triblock copolymer enhanced the interfacial polarizations between poly(thioether)and polysiloxane,and thus improving the dielectric constant(ε',up to 5.8).In addition,the PSiPGE exhibited low elastic modulus(Y,0.04 MPa),and thus possessed high electromechanical sensitivity(β,~145 MPa^(-1)) which is much higher than that of most homogenous DEs.This work provides a new strategy to construct homogenous DEs with excellent electromechanical performances,leading to a greater application aspect in the actuated devices.
文摘The synthesis of a thioether inserted, core-shell structured polymer from the scaffold of hyperbranched polyglycerol (PG) was described. PG was first allyl functionalized, and in the presence of AlBN, the allyl groups further underwent radical addition to thiol compounds, thus thiol functional polyethylene oxide monomether (MPEO) were grafted onto PG. Similarly, 2-mercaptoethylammonium chloride was introduced onto PG via thiol addition, and the residual amino groups were further quaternized with decyl bromide, leading to an amphiphilic core-shell structure polymer. (c) 2007 De Cheng Wan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
基金support from National Natural Science Foundation of China(No.30973609)
文摘A stereoselective and effective method for the synthesis of vinyl thioethers has been developed.This method is based on the Michael addition of ethanethiol to various alkynyl ketones using 10 mol%of tributylphosphine as catalyst.Most of alkynyl ketones react with ethanethiol in this system to yield mainly Z-isomer of vinyl thioether adducts,only in one case mainly E-isomer of vinyl thioether adducts was observed.
文摘The catalytic desulfurization of a model organic sulfurous compound n-butyl-sulfide in a fixed bed microreactor is studied in the presence of catalyst and a hydrogen provider. The experimental results show that the appropriate reaction conditions are： a mixed catalyst of HZSM-5 zeolite and Co-Mo/Al2O3-TiO2, a reaction temperature of 300℃, atmosphere pressure, a feed speed of 50 mL/h and a mass hourly space velocity of 3.0 h^-1 A higher catalytic property and desulfurization efficiency of the mixed catalyst of HZSM-5 zeolite and Co-Mo/Al2O3-TiO2 is achieved. The adsorption and desulfurization efficiency of the FCC gasoline from Shenghua Refinery, which is affiliated to China University of Petroleum （East China）, is 53.0 %.
文摘The disulfides reacted with zinc in DMF, followed by alkyl halides, giving unsymmetrical thioether in excellent yields. This reaction takes place under mild and neutral conditions.
