The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by...The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by sulfonation of ASIBS with acetyl sulfate.The hydrophilic ionic channels were generated for proton exchange membranes(PEMs)by ion aggregation of-SO_(3)H groups and microphase separation between hydrophobic polyisobutylene and hydrophilic sulfonated poly(α-methyl styrene)segments in S-ASIBS.The proton transport ability was improved while oxidative stability was decreased by increasing SP in S-ASIBS.The appropriate SP of about 12.7 mol%in S-ASIBS provides the available PEMs with high proton transport ability,low methanol permeability and good oxidative stability.The absence of active tertiary hydrogen atoms along S-ASIBS copolymer chains avoids their attack by peroxy radicals.The residual rates of weight(RW)and proton conductivity(Rσ)of S-ASIBS-12.7 membrane after oxidation treatment for 916 h were 84.3%and 88.1%respectively,near to those of commercial Nafion 117(RW=87.9%,Rσ=90.3%).The membrane electrode assembly(MEA)could be prepared by using various S-ASIBS as PEMs for direct methanol fuel cell.The single cell with S-ASIBS-12.7 MEA behaves high performance of open circuit voltage(OCV)of 548 mV and peak power density(Pmax)of 36.1 mW·cm^(-2),which is similar to those of Nafion 117(OCV=506 mV,P_(max)=35.6 mW·cm^(-2)).To the best of our knowledge,this is the first example of advanced S-ASIBS membrane with high proton conductivity,excellent fuel barrier property and remarkable oxidative stability for promising PEMs.展开更多
Acidic-and alkalic-hydrolyses are selective in breaking functional bonds and falling off pharmacological moieties of antibiotics in production wastewater in comparison with advanced oxidation processes.Elevating tempe...Acidic-and alkalic-hydrolyses are selective in breaking functional bonds and falling off pharmacological moieties of antibiotics in production wastewater in comparison with advanced oxidation processes.Elevating temperature can accelerate hydrolytic kinetics and improve efficiency.In this work,magnetic sulfonated polypropylene resin(Fe_(3)O_(4)@PS-S)composites were reported for acidic-thermal hydrolysis of tylosin by employing the acidic feature of sulfonic group,the dielectric effect of resin,and the magnetic-loss effect of magnetite under microwave irradiation.As observed,a rapid and complete mitigation 100 mg/L of tylosin was achieved within 15 min by the catalysts.Acidic cleavage of tylosin was fulfilled by sulfonic groups in the composites,and microwave thermal accelerated the hydrolysis reactions due to the dielectric and magnetic-loss effects.Differentiating the dielectric and magnetic-loss effects through electromagnetic analyses indicated that the latter contributed more in converting microwave energy to heat.The interactions under multiple operational conditions were quantitatively fitted using the Behnajady model and visually demonstrated,which indicated that a synergic effect of microwave thermal-and acidichydrolyses contributed to the efficient mitigation of tylosin.The transformation products were identified and the pathways were supposed.Cleaving deoxyaminosugars groups and destructing lactone structures led to reduced antibacterial potential and toxicity reduction.The acute toxicity of tylosin and transformation products to fish,daphnia,and green algae were all classified as non-toxic.This work suggested that this synergistic acid-thermal hydrolytic method is attractive and promising in pretreating tylosin production wastewater in field.展开更多
Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by s...Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by side reactions and dendritic growth always severely worsens the long-term operation of AZIBs.Herein,a novel 3-cyclobutene sulfone(CS)additive was employed in the aqueous electrolyte to achieve a highly reversible Zn anode.The CS additive can offer strong electronegativity and high binding energy for the coordination with Zn^(2+),which enables its entry into the solvent sheath structure of Zn^(2+)and eliminates the free H_(2)O molecules from the solvated{Zn^(2+)-SO_(4)^(2-)-(H_(2)O)_(5)}.Thus,the occurrence of side reactions and dendritic growth can be effectively inhibited.Accordingly,the Zn anode achieves long cycle-life(1400 h at 1 m A cm^(-2),1 m Ah cm^(-2),and 400 h at 5 m A cm^(-2),5 m Ah cm^(-2))and high average coulombic efficiency(99.5% over 500 cycles at 10 m A cm^(-2),1 m Ah cm^(-2)).Besides,the assembled Zn||NH_(4)V_(4)O_(10)full cell suggests enhanced cycling reversibility(123.8 m Ah g^(-1)over 500 cycles at 2 A g^(-1),84.9 m Ah g^(-1)over 800 cycles at 5 A g^(-1))and improved rate capability(139.1 m Ah g^(-1)at 5 A g^(-1)).This work may exhibit the creative design and deep understanding of sulfone-based electrolyte additives for the achievement of high-performance AZIBs.展开更多
Reclaimed water for irrigation or hydroponic cultivation provides exposure pathways for per-and polyfluoroalkyl substances(PFAS)to enter the human food chain.This study employed hydroponic methods to investigate the b...Reclaimed water for irrigation or hydroponic cultivation provides exposure pathways for per-and polyfluoroalkyl substances(PFAS)to enter the human food chain.This study employed hydroponic methods to investigate the behavior of legacy PFAS and emerging chlorinated polyfluoroalkyl ether sulfonic acids(Cl-PFESAs)in lettuce grown under environment-related exposure levels and assessed the human exposure risks from consuming contaminated lettuce.Overall,PFAS in lettuce were concentration-dependent,with long-chain PFAS tending to accumulate in roots and short-chain PFAS accumulating more in shoots.The enrichment of PFAS in lettuce was jointly influenced by their chain length and polar functional groups.Specifically,the root concentration factors(RCFs)of PFAS generally increased with increasing chain length,and RCF values of most perfluoroalkanesulfonic acids(PFSAs)were significantly higher than those of perfluoroalkyl carboxylic acids(PFCAs)with the same chain length(p<0.01),while the translocation factors(TFs)exhibited opposite trends.RCF values of perfluorooctane sulfonate(PFOS)and its alternatives,Cl-PFESAs,were ranked as follows:8:2 Cl-PFESA(mean:139)>6:2 Cl-PFESA(28.6)>PFOS(25.7),which was attributed to the increased molecular size and hydrophobicity resulting from the insertion of ether bonds and additional CF2 in 8:2 Cl-PFESA.Notably,TF value of 8:2 Cl-PFESA(mean:0.007)was the smallest among all PFAS,indicating 8:2 Cl-PFESA was difficult to transfer to nutritional compartments.Adults and children would exceed the most conservative health-based reference dose(RfD)by consuming approximately 15.9–148 g and 7.92–74.0 g of contaminated lettuce per day,implying high health risks.展开更多
Photocatalytic technology has been proven to be a simple and effective method for degrading recalcitrant organic pollutants.In this study,a series of Z-scheme heterojunction nanocomposites composed of CeO_(2)and terep...Photocatalytic technology has been proven to be a simple and effective method for degrading recalcitrant organic pollutants.In this study,a series of Z-scheme heterojunction nanocomposites composed of CeO_(2)and terephthalic acid-modified WO_(3) was prepared and further used as photocatalysts for perfluorobutane sulfonate(PFBS)degradation.In this design,terephthalic acid was used as an electron recombination center and heterojunction mediator,which effectively enhances the migration ability of electron-hole pairs and the physicochemical stability of the catalyst.In addition,in situ synthesis of CeO_(2)onto the WO_(3) surface by the coordinate bond between terephthalic acid and Ce ions can avoid CeO_(2)agglomeration.As a result,the CeO_(2)@WO_(3) photocatalyst exhibits excellent PFBS degradation ability(94%for CeO_(2)@WO_(3) vs.19%for CeO_(2)).After the fifth cyclic degradation experiment,the CeO_(2)@WO_(3) photocatalyst still maintains stable degradation efficiency.Furthermore,the reaction mechanism of the PFBS in CeO_(2)@WO_(3) photocatalytic process was analyzed by free radical trapping experiment and liquid chromatography tandem mass spectrometry(LC-MS)technique.This study provides new insights for constructing Z-scheme heterojunction and demonstrates that CeO_(2)@WO_(3) photocatalysts possess a promising prospect for degrading PFBS pollutants.展开更多
High-temperature and high-salt reservoirs are often accompanied by serious gas channeling in gas flooding,which will greatly affect the effect of gas injection development,so in-situ foaming of temperature-resistant a...High-temperature and high-salt reservoirs are often accompanied by serious gas channeling in gas flooding,which will greatly affect the effect of gas injection development,so in-situ foaming of temperature-resistant and salt-resistant foaming agents is commonly used to control gas channeling.The feasibility of the compound system of dodecyl hydroxyl sulfobetaine(HSB12)andα-olefin sulfonate(AOS)as foaming agent for sandstone reservoir was studied at 130℃and 22×10^(4)mg/L.The results showed that the foaming agent(HSB12 and AOS were compounded in a 6:1 mass ratio,in this article,this foaming agent is simply referred to as SA61)had good solubility in 22×10^(4)mg/L simulated formation water.Besides,the foaming volume of SA61 and HSB12 was similar,but the foam decay half-life of SA61was 10-25 times higher than that of HSB12.The foaming performance of SA61 on the surface of quartz sand remained above 90%of that before adsorption.The strong interaction between HSB12 and AOS in the compound system SA61 was demonstrated by surface rheological measurements and NMR studies of surfactants.The results of co re flow test showed that SA61 had better mobility control ability than HSB12under the same surfactant concentration.In addition,SA61 showed a selective mobility reduction in2005.30 and 632.00 mD cores.The above research results can guide the selection and application of foaming agent in clastic reservoir.展开更多
Polyethylene oxide(PEO)-based solid polymer electrolytes are considered as promising material for solidstate sodium metallic batteries(SSMBs).However,their poor interfacial stability with high-voltage cathode limits t...Polyethylene oxide(PEO)-based solid polymer electrolytes are considered as promising material for solidstate sodium metallic batteries(SSMBs).However,their poor interfacial stability with high-voltage cathode limits their application in high-energy–density solid-state batteries.Herein,a uniform,sulfur-containing inorganic–organic composite cathode–electrolyte interphase layer was in situ formed by the addition of sodium polyvinyl sulfonate(NaPVS).The 5 wt%NaPVS-Na_(3)V_(2)(PO_(4))_(3)(NVP)|PEOsodium hexauorophosphate(NaPF6)|Na battery shows a higher initial capacity of 111.2 mAh.g^(-1)and an ultra-high capacity retention of 90.5%after 300 cycles.The 5 wt%NaPVS-Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)|PEO-NaPF_(6)|Na battery with the high cutoff voltage of 4.2 V showed a specific discharge capacity of 88.9 mAh.g^(-1)at 0.5C for 100 cycles with a capacity retention of 79%,which is much better than that of the pristine-NVPF(PR-NVPF)|PEO-NaPF_(6)|Na battery(33.2%).The addition of NaPVS not only enhances the diffusion kinetics at the interface but also improves the rate performance and stability of the battery,thus bolstering its viability for high-energy applications.In situ phase tracking further elucidates that NaPVS effectively mitigates self-discharge induced by the oxidative decomposition of PEO at high temperature.This work proposes a general strategy to maintain the structural stability of the cathode–electrolyte interface in PEO-based high-performance SSMBs.展开更多
Andrographolide sulfonate(AS)is a sulfonated derivative of andrographolide extracted from Andrographis paniculata(Burm.f.)Nees,and has been approved for several decades in China.The present study aimed to investigate ...Andrographolide sulfonate(AS)is a sulfonated derivative of andrographolide extracted from Andrographis paniculata(Burm.f.)Nees,and has been approved for several decades in China.The present study aimed to investigate the novel therapeutic application and possible mechanisms of AS in the treatment of rheumatoid arthritis.Results indicated that administration of AS by injection or gavage significantly reduced the paw swelling,improved body weights,and attenuated pathological changes in joints of rats with adjuvant-induced arthritis.Additionally,the levels of tumor necrosis factor-alpha(TNF-α),interleukin-6(IL-6),and IL-1β in the serum and ankle joints were reduced.Bioinformatics analysis,along with the spleen index and measurements of IL-17 and IL-10 levels,suggested a potential relationship between AS and Th17 cells under arthritic conditions.In vitro,AS was shown to block Th17 cell differentiation,as evidenced by the reduced percentages of CD4^(+)IL-17A^(+)T cells and decreased expression levels of RORγt,IL-17A,IL-17F,IL-21,and IL-22,without affecting the cell viability and apoptosis.This effect was attributed to the limited glycolysis,as indicated by metabolomics analysis,reduced glucose uptake,and p H measurements.Further investigation revealed that AS might bind to hexokinase2(HK2)to down-regulate the protein levels of HK2 but not glyceraldehyde-3-phosphate dehydrogenase(GAPDH)or pyruvate kinase M2(PKM2),and overexpression of HK2 reversed the inhibition of AS on Th17 cell differentiation.Furthermore,AS impaired the activation of phosphatidylinositol 3-kinase(PI3K)/protein kinase B(AKT)signals in vivo and in vitro,which was abolished by the addition of lactate.In conclusion,AS significantly improved adjuvant-induced arthritis(AIA)in rats by inhibiting glycolysis-mediated activation of PI3K/AKT to restrain Th17 cell differentiation.展开更多
The large-scale commercialization of proton exchange membrane fuel cells(PEMFCs)has been hindered by the high demand of platinum(Pt)in the cathode due to the sluggish kinetics of the oxygen reduction reaction.Reducing...The large-scale commercialization of proton exchange membrane fuel cells(PEMFCs)has been hindered by the high demand of platinum(Pt)in the cathode due to the sluggish kinetics of the oxygen reduction reaction.Reducing the amount of Pt would worsen the problems caused by the adsorption of perfluorinated sulfonic acid(PFSA)ionomers to Pt via the side chains,namely,blocking the active sites of Pt and inducing densely packed layers of fluorocarbon backbones on Pt surface to obstruct local O_(2)transport at the Pt/PFSA interfaces.This work aims at optimizing the Pt/ionomer interface to mitigate the sulfonate adsorption and in the meantime to reduce the local O_(2)transport resistance(R_(local)),by using a porous composite of 1-butyl-3-methylimidazolium hydrogen sulfate ionic liquid(IL)modified MOF-808(BMImHSO_(4)@MOF-808)as additive in cathodic catalyst layer(CCL).Through detailed physical,spectroscopic and electrochemical characterizations,we demonstrate a three-fold optimization mechanism of Pt/ionomer interface structure by BMImHSO_(4)@MOF-808:the unsaturated metal sites in MOF-808 effectively inhibit the sulfonate adsorption on Pt through coordination with the sulfonates of PFSA,thereby improving catalyst utilization;the pores in MOF-808 establish efficient transport channels for gaseous oxygen,significantly reducing R_(local);the IL modification layers facilitate the formation of continuous proton transport networks,increasing proton conductivity.The incorporation of BMImHSO_(4)@MOF-808 in a low-Pt CCL(0.1 mg_(Pt)cm^(-2))yields a peak power density of 1.9 W cm^(-2)for PEMFC under H_(2)-O_(2)condition,and ca.20%increase of power density under H_(2)-air condition as compared with conventional CCL,indicating the prospect of IL-MOF composites as an efficient additive to enhance the performance of PEMFCs.展开更多
Herein,an oxygen-doped porous g-C_(3)N_(4)photocatalyst modified with atomically dispersed Fe(Fe_(1)/OPCN)issuccessfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants f...Herein,an oxygen-doped porous g-C_(3)N_(4)photocatalyst modified with atomically dispersed Fe(Fe_(1)/OPCN)issuccessfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants fromwater via catalyst-contaminant interaction.The elimination performance of Fe_(1)/OPCN towards acid red 9,acidred 13 and amaranth containing similar azonaphthalene structure and increasing sulfonic acid groups increasesgradually.The amaranth degradation rate of Fe_(1)/OPCN is 17.7 and 6.1 times as that of homogeneous Fenton andOPCN,respectively.In addition,Fe_(1)/OPCN also has more outstanding removal activities towards other con-taminantswith sulfonic acid and azo groups alone.The considerable enhancement for removing sulfonic azocontaminants of Fe_(1)/OPCN is mainly ascribed to the following aspects:(1)The modified Fe could enhance theadsorption towards sulfonic azo compounds to accelerate the mass transfer,act as e^(-)acceptor to promoteinterfacial charge separation,and trigger the self-Fenton reaction to convert in-situ generated H_(2)O_(2)into·OH.(2)Fe(Ⅲ)could coordinate with-N=N-to form d-πconjugation,which could attract e^(-)transfer to attack-N=N-bond.Meanwhile,the inhibited charge recombination could release more free h^(þ)to oxidize sulfonicacid groups into SO4^(-)·.(3)Under the cooperation of abundant multiple active species(·O_(2)^(-),h^(þ),e^(-),·OH,SO4^(-)·)formed during the degradation reaction,sulfonic azo compounds could be completely mineralized into harmlesssmall molecules(CO_(2),H_(2)O,etc.)by means of-N=N-cleavage,hydroxyl substitution,and aromatic ringopening.This work offers a novel approach for effectively eliminating refractory sulfonic azo compounds fromwastewater.展开更多
A novel integrated film of sulfonated polysulfone/graphene/potassium copper ferricyanide(KCuFC/SPSG)was used for selectively extracting rubidium ion(Rb^(+))from brine.To form KCuFC/SPSG,the precursor film of sulfonate...A novel integrated film of sulfonated polysulfone/graphene/potassium copper ferricyanide(KCuFC/SPSG)was used for selectively extracting rubidium ion(Rb^(+))from brine.To form KCuFC/SPSG,the precursor film of sulfonated polysulfone/graphene(SPSG)was synthesized by phase conversion process,which was alternately immersed in 0.1 mol·L^(-1)CuSO_(4)/K_(4)[Fe(CN)_(6)]by in-situ adsorption coupled co-precipitation method.Various data such as nuclear magnetic resonance spectrometer,Fourier transform infrared spectroscope,X-ray photoelectron spectroscope,X-ray diffraction,scanning electron microscope,and energy dispersive spectroscopy all verified that abundant KCuFC were uniformly located on the film.The resulting KCuFC/SPSG was used in film separation system.As the solution was fed into the system,the Rb^(+)could be selectively adsorption by KCuFC/SPSG.After the saturation adsorption,0.5 mol·L^(-1)NH_(4)Cl/HCl was fed into the film cell,Rb^(+)could be quickly desorbed by ion-exchange between Rb^(+)and NH_(4)^(+)in the lattice of KCuFC.The purpose of separating and recovering Rb^(+)from the brine can be achieved after the repeated operation.The effects of pH,adsorption time,and interferential ions on the adsorption capacity of Rb^(+)were investigated by batch experiments.The adsorption behavior fits the pseudo-second order kinetic process,while KCuFC has a higher adsorption capacity(Langmuir maximum sorption 165.4 mg·g^(-1)).In addition,KCuFC/SPSG shows excellent selectivity for Rb^(+)even in complex brine systems.KCuFC/SPSG could maintain 93.5%extraction efficiency after five adsorption/desorption cycles.展开更多
The occurrence of ultrafiltration(UF)membrane fouling frequently hampers the sustainable advancement of UF technology.Reactive self-cleaning UF membranes can effectively alleviate the problem of membrane fouling.Never...The occurrence of ultrafiltration(UF)membrane fouling frequently hampers the sustainable advancement of UF technology.Reactive self-cleaning UF membranes can effectively alleviate the problem of membrane fouling.Nevertheless,the self-cleaning process may accelerate membrane aging.Addressing these concerns,we present an innovative design concept for composite self-healing materials based on self-cleaning UF membranes.To begin,TiO_(2)nanoparticles were incorporated into the polymer molecular structure via molecular design,resulting in the synthesis of TiO_(2)/carboxyl-polyether sulfone(PES)hybrid materials.Subsequently,the nonsolvent-induced phase inversion technique was employed to prepare a novel of UF membrane.Lastly,a polyvinyl alcohol(PVA)hydrogel coating was applied to the hybrid UF membrane surface to create PVA@TiO_(2)/carboxyl-PES self-healing reactive UF membranes.By establishing a covalent bond,the TiO_(2)nanoparticles were effectively and uniformly dispersed within the UF membrane,leading to exceptional self-cleaning properties.Furthermore,the water-absorbing and swelling properties of PVA hydrogel,along with its capacity to form hydrogen bonds with water molecules,resulted in UF membranes with improved hydrophilicity and active self-healing abilities.The results demonstrated that the water contact angle of PVA@5%TiO_(2)/carboxyl-PES UF membrane was 43.1°.Following a 1-h exposure to simulated solar exposure,the water flux recovery ratio increased from 48.16%to 81.03%.Moreover,even after undergoing five cycles of 12-h simulated sunlight exposure,the UF membranes exhibited a consistent retention rate of over 97%,thus fully demonstrating their exceptional self-cleaning,antifouling,and selfhealing capabilities.We anticipate that the self-healing reactive UF membrane system will serve as a pioneering and comprehensive solution for the self-cleaning antifouling challenges encountered in UF membranes while also effectively mitigating the aging effects of reactive UF membranes.展开更多
In order to prolong the service time and enhance the biocompatibility of magnesium(Mg)alloys used for cardiovascular scaffolds,the composite coatings of Schiff base(corrosion inhibitor)and sulfonated hyaluronic acid(S...In order to prolong the service time and enhance the biocompatibility of magnesium(Mg)alloys used for cardiovascular scaffolds,the composite coatings of Schiff base(corrosion inhibitor)and sulfonated hyaluronic acid(S-HA)nanoparticles(NP@S-HA)with different sulfur content(10.02 wt%and 11.55wt%)were prepared on ZE21B alloy by means of electrostatic spraying with spraying time of 0.5 min,1.0 min and 1.5 min in this paper.Through a series of representations including corrosion experiments and biological characterization,the composite coatings with a sulfur content of 11.55wt%and a spray time of 1.0 min were finally picked due to its better comprehensive performances,which provides a new possibility for the surface modification of degradable Mg alloy cardiovascular scaffolds.展开更多
Transition-metal-catalyzed remote sp^(2)C-H functionalization of aryl sulfonic acids was hardly ever real-ized owing to competitive ortho-C-H functionalization of aryl sulfonates and electron-deficient nature of pheny...Transition-metal-catalyzed remote sp^(2)C-H functionalization of aryl sulfonic acids was hardly ever real-ized owing to competitive ortho-C-H functionalization of aryl sulfonates and electron-deficient nature of phenyl ring.Herein,with the assistance of a practical biaryl indolyl directing template,palladium-catalyzed remote sp^(2)C-H alkylation of aryl sulfonic acids have been achieved in moderate to good yields with exclusive meta selectivity.Moreover,remote meta-selective C-H alkynylation of aryl sulfonic acids was also accomplished with a rhodium catalyst.These meta-C-H functionalized products proved to be the superior synthetic precursors,which are difficult to access using the conventional strategy.展开更多
Photothermal therapy(PTT)is a cutting-edge cancer treatment that can kill cancer cells in hypoxic environments without relying on oxygen.Seeking of the ideal photothermal agents with a high absorption coefficient in t...Photothermal therapy(PTT)is a cutting-edge cancer treatment that can kill cancer cells in hypoxic environments without relying on oxygen.Seeking of the ideal photothermal agents with a high absorption coefficient in the near-infrared region,and a high excellent photothermal conversion efficiency is of great significance.Sulfone-Rhodanmine dye has showed an impressive absorption wavelength over 700 nm,but suffered from a stability issue.In this study,we synthesized five sulfone rhodamines and investigated the substitution effects on stability.SO_(2)R2 showed high stability and strong absorbance at 714 nm with an excellent photothermal conversion efficiency of 53.06%,making it suitable for accurate photoacoustic imaging-guided photothermal therapy in vivo.展开更多
A new,four component copper(Ⅰ)-catalyzed interrupted click/radical relay cascade has been developed.This unprecedented interrupted click reaction provides a rapid modular synthesis of triazole sulfones,important priv...A new,four component copper(Ⅰ)-catalyzed interrupted click/radical relay cascade has been developed.This unprecedented interrupted click reaction provides a rapid modular synthesis of triazole sulfones,important privileged heterocyclic pharmacophores which cannot be accessed by a traditional click reaction.Radical interception of cuprate-triazole,the key reaction intermediate formed in situ,is an important feature of this process.展开更多
Aqueous zinc ion batteries(AZIBs)are one of the promising energy storage devices.However,uncontrolled dendrite and side reactions have seriously hindered its further application.In this study,the metal-organic framewo...Aqueous zinc ion batteries(AZIBs)are one of the promising energy storage devices.However,uncontrolled dendrite and side reactions have seriously hindered its further application.In this study,the metal-organic framework(MOF)functionalized glass fiber separator(GF-PFC-31)was used to regulate interfacial behavior of zinc metal anode,enabling the development of high-performance AZIBs.In PFC-31,there areπ-πinteractions between two adjacent benzene rings with a spacing of 3.199 A.This spacing can block the passage of[Zn(H_(2)O)_6]^(2+)(8.6 A in diameter)through the GF-PFC-31 separator to a certain extent,which promotes the deposition process of Zn ions.In addition,the sulfonic acid group(-S03H)contained in GF-PFC-31 can form a hydrogen bonding network with H_(2)O,which can provide a desolvation effect and reduce the side reaction.Consequently,GF-PFC-31 separator achieves uniform deposition of Zn ions.The Zn‖GF-PFC-31‖Zn symmetric cell exhibits stable cycle life(3000 h at 1.2 mA cm^(-2),2000 h at 0.3 mA cm^(-2),and 2000 h at 5.0 mA cm^(-2)),and Zn‖GF-PFC-31‖MnO_(2) full cell with GF-PFC-31 separator can cycle for 1000 cycles at 1.2 A g^(-1)with capacity retention rate of 82.5%.This work provides a promising method to achieve high-performance AZIBs.展开更多
This is the first study to report the co-occurrence of per-and polyfluoroalkyl substances(PFASs),heavy metals,and polycyclic aromatic hydrocarbons(PAHs)and their impacts on the native microbial consortium in soil due ...This is the first study to report the co-occurrence of per-and polyfluoroalkyl substances(PFASs),heavy metals,and polycyclic aromatic hydrocarbons(PAHs)and their impacts on the native microbial consortium in soil due to the long-term exposure.The PFASs,heavy metals,and PAHs were detected in soil samples collected at 2–6 m below the ground surface at different sampling locations in a steel-making factory.The total concentrations of PFASs varied from 6.55 to 19.79 ng g^(-1),with perfluorooctane sulfonate(PFOS),perfluorobutane sulfonate,and 6:2 chlorinated polyfluorinated ether sulfonate(alternative of PFOS)being the predominant PFASs.The concentrations of arsenic,cadmium,and lead were detected in the ranges of 4.40–1270.00,0.01–8.67,and 18.00–647.00 mg kg^(-1),respectively,and the concentration of total PAHs was detected in the range of 1.02–131.60 mg kg^(-1).The long-term exposure to mixed contaminants of PFASs,heavy metals,and PAHs led to lower richness and diversity of microbial communities in soil.The soil bacterial communities were mainly composed of Pseudomonas,norank_p_GAL15,Leptothrix,norank_o_Rokubacteriales,and Acinetobacter.Correlations between soil environmental factors and microbial communities indicated that cation exchange capacity and total phosphorus were two key factors in shaping the composition of native microbial communities.Furthermore,Arthrobacter,Leptothrix,and Sphingobium were found to be significantly positively correlated with PFAS concentrations,indicating that these genera could tolerate the stress exerted by PFASs,along with the stress imposed due to the presence of heavy metals or/and PAHs.展开更多
The potential association between colorectal cancer(CRC)and environmental pollutants is worrisome.Previous studies have found that some perfluoroalkyl acids,including perfluorooctane sulfonate(PFOS),induced colorectal...The potential association between colorectal cancer(CRC)and environmental pollutants is worrisome.Previous studies have found that some perfluoroalkyl acids,including perfluorooctane sulfonate(PFOS),induced colorectal tumors in experimental animals and promoted the migration of and invasion by CRC cells in vitro,but the underlying mechanism is unclear.Here,we investigated the effects of PFOS on the proliferation and migration of CRC cells and the potentialmechanisms involving activating the PI3K/Akt-NF-κB signal pathway and epithelial-mesenchymal transition(EMT).It was found that PFOS promoted the growth andmigration of HCT116 cells at non-cytotoxic concentrations and increased the mRNA expression of the migration-related angiogenic cytokines vascular endothelial growth factor(VEGF)and interleukin-8(IL-8).In a mechanistic investigation,the up-stream signal pathway PI3K/Akt-NF-κB was activated by PFOS,and the process was suppressed by LY294002(PI3K/Akt inhibitor)and BAY11-7082(NF-κB inhibitor)respectively,leading to less proliferation of HCT116 cells.Furthermore,matrix metalloproteinases(MMP)and EMT-related markers were up-regulated after PFOS exposure,and were also suppressed respectively by LY294002 and BAY11-7082.Moreover,the up-regulation of EMT markers was suppressed by a MMP inhibitor GM6001.Taken together,our results indicated that PFOS promotes colorectal cancer cell migration and proliferation by activating the PI3K/Akt-NF-κB signal pathway and epithelial-mesenchymal transition.This could be a potential toxicological mechanism of PFOS-induced malignant development of colorectal cancer.展开更多
PPMG-based composite electrolytes were fabricated via the solution method using the polyvinyl alcohol and polyvinylpyrrolidone blend reinforced with various contents of sulfonated inorganic filler.Sulfuric acid was em...PPMG-based composite electrolytes were fabricated via the solution method using the polyvinyl alcohol and polyvinylpyrrolidone blend reinforced with various contents of sulfonated inorganic filler.Sulfuric acid was employed as the sulfonating agent to functionalize the external surface of the inorganic filler,i.e.,graphene oxide.The proton conductivities of the newly prepared proton exchange membranes(PEMs)were increased by increasing the temperature and content of sulfonated graphene oxide(SGO),i.e.,ranging from 0.025 S/cm to 0.060 S/cm.The induction of the optimum level of SGO is determined to be an excellent route to enhance ionic conductivity.The single-cell performance test was conducted by sandwiching the newly prepared PEMs between an anode(0.2 mg/cm^(2) Pt/Ru)and a cathode(0.2 mg/cm^(2) Pt)to prepare membrane electrode assemblies,followed by hot pressing under a pressure of approximately 100 kg/cm^(2) at 60℃for 5–10 min.The highest power densities achieved with PPMG PEMs were 14.9 and 35.60 mW/cm^(2) at 25℃and 70℃,respectively,at ambient pressure with 100%relative humidity.Results showed that the newly prepared PEMs exhibit good electrochemical performance.The results indicated that the prepared composite membrane with 6 wt%filler can be used as an alternative membrane for applications of high-performance proton exchange membrane fuel cell.展开更多
基金financially supported by the National Natural Science Foundation of China (No. 21774006)
文摘The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by sulfonation of ASIBS with acetyl sulfate.The hydrophilic ionic channels were generated for proton exchange membranes(PEMs)by ion aggregation of-SO_(3)H groups and microphase separation between hydrophobic polyisobutylene and hydrophilic sulfonated poly(α-methyl styrene)segments in S-ASIBS.The proton transport ability was improved while oxidative stability was decreased by increasing SP in S-ASIBS.The appropriate SP of about 12.7 mol%in S-ASIBS provides the available PEMs with high proton transport ability,low methanol permeability and good oxidative stability.The absence of active tertiary hydrogen atoms along S-ASIBS copolymer chains avoids their attack by peroxy radicals.The residual rates of weight(RW)and proton conductivity(Rσ)of S-ASIBS-12.7 membrane after oxidation treatment for 916 h were 84.3%and 88.1%respectively,near to those of commercial Nafion 117(RW=87.9%,Rσ=90.3%).The membrane electrode assembly(MEA)could be prepared by using various S-ASIBS as PEMs for direct methanol fuel cell.The single cell with S-ASIBS-12.7 MEA behaves high performance of open circuit voltage(OCV)of 548 mV and peak power density(Pmax)of 36.1 mW·cm^(-2),which is similar to those of Nafion 117(OCV=506 mV,P_(max)=35.6 mW·cm^(-2)).To the best of our knowledge,this is the first example of advanced S-ASIBS membrane with high proton conductivity,excellent fuel barrier property and remarkable oxidative stability for promising PEMs.
基金supported by the National Natural Science Foundation of China(Nos.51978052 and 22306012)the National Key Research and Development Program of China(No.2023YFC3711300)the Guangdong Basic and Applied Basic Research Foundation(No.2022A1515110578).
文摘Acidic-and alkalic-hydrolyses are selective in breaking functional bonds and falling off pharmacological moieties of antibiotics in production wastewater in comparison with advanced oxidation processes.Elevating temperature can accelerate hydrolytic kinetics and improve efficiency.In this work,magnetic sulfonated polypropylene resin(Fe_(3)O_(4)@PS-S)composites were reported for acidic-thermal hydrolysis of tylosin by employing the acidic feature of sulfonic group,the dielectric effect of resin,and the magnetic-loss effect of magnetite under microwave irradiation.As observed,a rapid and complete mitigation 100 mg/L of tylosin was achieved within 15 min by the catalysts.Acidic cleavage of tylosin was fulfilled by sulfonic groups in the composites,and microwave thermal accelerated the hydrolysis reactions due to the dielectric and magnetic-loss effects.Differentiating the dielectric and magnetic-loss effects through electromagnetic analyses indicated that the latter contributed more in converting microwave energy to heat.The interactions under multiple operational conditions were quantitatively fitted using the Behnajady model and visually demonstrated,which indicated that a synergic effect of microwave thermal-and acidichydrolyses contributed to the efficient mitigation of tylosin.The transformation products were identified and the pathways were supposed.Cleaving deoxyaminosugars groups and destructing lactone structures led to reduced antibacterial potential and toxicity reduction.The acute toxicity of tylosin and transformation products to fish,daphnia,and green algae were all classified as non-toxic.This work suggested that this synergistic acid-thermal hydrolytic method is attractive and promising in pretreating tylosin production wastewater in field.
基金the financial support from the Foshan Talents Special Foundation(BKBS202003)。
文摘Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by side reactions and dendritic growth always severely worsens the long-term operation of AZIBs.Herein,a novel 3-cyclobutene sulfone(CS)additive was employed in the aqueous electrolyte to achieve a highly reversible Zn anode.The CS additive can offer strong electronegativity and high binding energy for the coordination with Zn^(2+),which enables its entry into the solvent sheath structure of Zn^(2+)and eliminates the free H_(2)O molecules from the solvated{Zn^(2+)-SO_(4)^(2-)-(H_(2)O)_(5)}.Thus,the occurrence of side reactions and dendritic growth can be effectively inhibited.Accordingly,the Zn anode achieves long cycle-life(1400 h at 1 m A cm^(-2),1 m Ah cm^(-2),and 400 h at 5 m A cm^(-2),5 m Ah cm^(-2))and high average coulombic efficiency(99.5% over 500 cycles at 10 m A cm^(-2),1 m Ah cm^(-2)).Besides,the assembled Zn||NH_(4)V_(4)O_(10)full cell suggests enhanced cycling reversibility(123.8 m Ah g^(-1)over 500 cycles at 2 A g^(-1),84.9 m Ah g^(-1)over 800 cycles at 5 A g^(-1))and improved rate capability(139.1 m Ah g^(-1)at 5 A g^(-1)).This work may exhibit the creative design and deep understanding of sulfone-based electrolyte additives for the achievement of high-performance AZIBs.
基金supported by the Fundamental Research Funds for Central Non-profit Scientific Institution(No.1610132022015)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0750200)the National Natural Science Foundation of China(No.22176198).
文摘Reclaimed water for irrigation or hydroponic cultivation provides exposure pathways for per-and polyfluoroalkyl substances(PFAS)to enter the human food chain.This study employed hydroponic methods to investigate the behavior of legacy PFAS and emerging chlorinated polyfluoroalkyl ether sulfonic acids(Cl-PFESAs)in lettuce grown under environment-related exposure levels and assessed the human exposure risks from consuming contaminated lettuce.Overall,PFAS in lettuce were concentration-dependent,with long-chain PFAS tending to accumulate in roots and short-chain PFAS accumulating more in shoots.The enrichment of PFAS in lettuce was jointly influenced by their chain length and polar functional groups.Specifically,the root concentration factors(RCFs)of PFAS generally increased with increasing chain length,and RCF values of most perfluoroalkanesulfonic acids(PFSAs)were significantly higher than those of perfluoroalkyl carboxylic acids(PFCAs)with the same chain length(p<0.01),while the translocation factors(TFs)exhibited opposite trends.RCF values of perfluorooctane sulfonate(PFOS)and its alternatives,Cl-PFESAs,were ranked as follows:8:2 Cl-PFESA(mean:139)>6:2 Cl-PFESA(28.6)>PFOS(25.7),which was attributed to the increased molecular size and hydrophobicity resulting from the insertion of ether bonds and additional CF2 in 8:2 Cl-PFESA.Notably,TF value of 8:2 Cl-PFESA(mean:0.007)was the smallest among all PFAS,indicating 8:2 Cl-PFESA was difficult to transfer to nutritional compartments.Adults and children would exceed the most conservative health-based reference dose(RfD)by consuming approximately 15.9–148 g and 7.92–74.0 g of contaminated lettuce per day,implying high health risks.
基金Project supported by the National Natural Science Foundation of China(52300206)the Natural Science Foundation of Jiangsu Province(BK20230705)+2 种基金Industry-University Research Cooperation Project of Jiangsu Province,China(BY20221227)Natural Science Foundation of the Jiangsu Higher Education Institutions of China(22KJB610014)the Talent-Recruiting Program of Nanjing Institute of Technology(YKJ202124)。
文摘Photocatalytic technology has been proven to be a simple and effective method for degrading recalcitrant organic pollutants.In this study,a series of Z-scheme heterojunction nanocomposites composed of CeO_(2)and terephthalic acid-modified WO_(3) was prepared and further used as photocatalysts for perfluorobutane sulfonate(PFBS)degradation.In this design,terephthalic acid was used as an electron recombination center and heterojunction mediator,which effectively enhances the migration ability of electron-hole pairs and the physicochemical stability of the catalyst.In addition,in situ synthesis of CeO_(2)onto the WO_(3) surface by the coordinate bond between terephthalic acid and Ce ions can avoid CeO_(2)agglomeration.As a result,the CeO_(2)@WO_(3) photocatalyst exhibits excellent PFBS degradation ability(94%for CeO_(2)@WO_(3) vs.19%for CeO_(2)).After the fifth cyclic degradation experiment,the CeO_(2)@WO_(3) photocatalyst still maintains stable degradation efficiency.Furthermore,the reaction mechanism of the PFBS in CeO_(2)@WO_(3) photocatalytic process was analyzed by free radical trapping experiment and liquid chromatography tandem mass spectrometry(LC-MS)technique.This study provides new insights for constructing Z-scheme heterojunction and demonstrates that CeO_(2)@WO_(3) photocatalysts possess a promising prospect for degrading PFBS pollutants.
基金financial support from the Major Scientific and Technological Projects of CNPC(Award No.ZD2019-183-007)。
文摘High-temperature and high-salt reservoirs are often accompanied by serious gas channeling in gas flooding,which will greatly affect the effect of gas injection development,so in-situ foaming of temperature-resistant and salt-resistant foaming agents is commonly used to control gas channeling.The feasibility of the compound system of dodecyl hydroxyl sulfobetaine(HSB12)andα-olefin sulfonate(AOS)as foaming agent for sandstone reservoir was studied at 130℃and 22×10^(4)mg/L.The results showed that the foaming agent(HSB12 and AOS were compounded in a 6:1 mass ratio,in this article,this foaming agent is simply referred to as SA61)had good solubility in 22×10^(4)mg/L simulated formation water.Besides,the foaming volume of SA61 and HSB12 was similar,but the foam decay half-life of SA61was 10-25 times higher than that of HSB12.The foaming performance of SA61 on the surface of quartz sand remained above 90%of that before adsorption.The strong interaction between HSB12 and AOS in the compound system SA61 was demonstrated by surface rheological measurements and NMR studies of surfactants.The results of co re flow test showed that SA61 had better mobility control ability than HSB12under the same surfactant concentration.In addition,SA61 showed a selective mobility reduction in2005.30 and 632.00 mD cores.The above research results can guide the selection and application of foaming agent in clastic reservoir.
基金supported by the Natural Science Foundation of China(No.22109079)the Natural Science Foundation of China(No.21973008)+2 种基金the Natural Science Foundation of China(No.22179010)the National Key R&D Program of China(No.2021YFB2400200)Taishan Scholars of Shandong Province(No.tsqnz20231212)。
文摘Polyethylene oxide(PEO)-based solid polymer electrolytes are considered as promising material for solidstate sodium metallic batteries(SSMBs).However,their poor interfacial stability with high-voltage cathode limits their application in high-energy–density solid-state batteries.Herein,a uniform,sulfur-containing inorganic–organic composite cathode–electrolyte interphase layer was in situ formed by the addition of sodium polyvinyl sulfonate(NaPVS).The 5 wt%NaPVS-Na_(3)V_(2)(PO_(4))_(3)(NVP)|PEOsodium hexauorophosphate(NaPF6)|Na battery shows a higher initial capacity of 111.2 mAh.g^(-1)and an ultra-high capacity retention of 90.5%after 300 cycles.The 5 wt%NaPVS-Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)|PEO-NaPF_(6)|Na battery with the high cutoff voltage of 4.2 V showed a specific discharge capacity of 88.9 mAh.g^(-1)at 0.5C for 100 cycles with a capacity retention of 79%,which is much better than that of the pristine-NVPF(PR-NVPF)|PEO-NaPF_(6)|Na battery(33.2%).The addition of NaPVS not only enhances the diffusion kinetics at the interface but also improves the rate performance and stability of the battery,thus bolstering its viability for high-energy applications.In situ phase tracking further elucidates that NaPVS effectively mitigates self-discharge induced by the oxidative decomposition of PEO at high temperature.This work proposes a general strategy to maintain the structural stability of the cathode–electrolyte interface in PEO-based high-performance SSMBs.
基金supported by the project of Central Funds Guiding the Local Science and Technology Development(No.20212ZDD02010)。
文摘Andrographolide sulfonate(AS)is a sulfonated derivative of andrographolide extracted from Andrographis paniculata(Burm.f.)Nees,and has been approved for several decades in China.The present study aimed to investigate the novel therapeutic application and possible mechanisms of AS in the treatment of rheumatoid arthritis.Results indicated that administration of AS by injection or gavage significantly reduced the paw swelling,improved body weights,and attenuated pathological changes in joints of rats with adjuvant-induced arthritis.Additionally,the levels of tumor necrosis factor-alpha(TNF-α),interleukin-6(IL-6),and IL-1β in the serum and ankle joints were reduced.Bioinformatics analysis,along with the spleen index and measurements of IL-17 and IL-10 levels,suggested a potential relationship between AS and Th17 cells under arthritic conditions.In vitro,AS was shown to block Th17 cell differentiation,as evidenced by the reduced percentages of CD4^(+)IL-17A^(+)T cells and decreased expression levels of RORγt,IL-17A,IL-17F,IL-21,and IL-22,without affecting the cell viability and apoptosis.This effect was attributed to the limited glycolysis,as indicated by metabolomics analysis,reduced glucose uptake,and p H measurements.Further investigation revealed that AS might bind to hexokinase2(HK2)to down-regulate the protein levels of HK2 but not glyceraldehyde-3-phosphate dehydrogenase(GAPDH)or pyruvate kinase M2(PKM2),and overexpression of HK2 reversed the inhibition of AS on Th17 cell differentiation.Furthermore,AS impaired the activation of phosphatidylinositol 3-kinase(PI3K)/protein kinase B(AKT)signals in vivo and in vitro,which was abolished by the addition of lactate.In conclusion,AS significantly improved adjuvant-induced arthritis(AIA)in rats by inhibiting glycolysis-mediated activation of PI3K/AKT to restrain Th17 cell differentiation.
文摘The large-scale commercialization of proton exchange membrane fuel cells(PEMFCs)has been hindered by the high demand of platinum(Pt)in the cathode due to the sluggish kinetics of the oxygen reduction reaction.Reducing the amount of Pt would worsen the problems caused by the adsorption of perfluorinated sulfonic acid(PFSA)ionomers to Pt via the side chains,namely,blocking the active sites of Pt and inducing densely packed layers of fluorocarbon backbones on Pt surface to obstruct local O_(2)transport at the Pt/PFSA interfaces.This work aims at optimizing the Pt/ionomer interface to mitigate the sulfonate adsorption and in the meantime to reduce the local O_(2)transport resistance(R_(local)),by using a porous composite of 1-butyl-3-methylimidazolium hydrogen sulfate ionic liquid(IL)modified MOF-808(BMImHSO_(4)@MOF-808)as additive in cathodic catalyst layer(CCL).Through detailed physical,spectroscopic and electrochemical characterizations,we demonstrate a three-fold optimization mechanism of Pt/ionomer interface structure by BMImHSO_(4)@MOF-808:the unsaturated metal sites in MOF-808 effectively inhibit the sulfonate adsorption on Pt through coordination with the sulfonates of PFSA,thereby improving catalyst utilization;the pores in MOF-808 establish efficient transport channels for gaseous oxygen,significantly reducing R_(local);the IL modification layers facilitate the formation of continuous proton transport networks,increasing proton conductivity.The incorporation of BMImHSO_(4)@MOF-808 in a low-Pt CCL(0.1 mg_(Pt)cm^(-2))yields a peak power density of 1.9 W cm^(-2)for PEMFC under H_(2)-O_(2)condition,and ca.20%increase of power density under H_(2)-air condition as compared with conventional CCL,indicating the prospect of IL-MOF composites as an efficient additive to enhance the performance of PEMFCs.
基金supported by the Natural Science Foundation of Jiangsu Province(BK20221541)National Natural Science Foundation of China(21707052)Jiangsu Agriculture Science and Technology Innovation Fund(CX(20)3108).
文摘Herein,an oxygen-doped porous g-C_(3)N_(4)photocatalyst modified with atomically dispersed Fe(Fe_(1)/OPCN)issuccessfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants fromwater via catalyst-contaminant interaction.The elimination performance of Fe_(1)/OPCN towards acid red 9,acidred 13 and amaranth containing similar azonaphthalene structure and increasing sulfonic acid groups increasesgradually.The amaranth degradation rate of Fe_(1)/OPCN is 17.7 and 6.1 times as that of homogeneous Fenton andOPCN,respectively.In addition,Fe_(1)/OPCN also has more outstanding removal activities towards other con-taminantswith sulfonic acid and azo groups alone.The considerable enhancement for removing sulfonic azocontaminants of Fe_(1)/OPCN is mainly ascribed to the following aspects:(1)The modified Fe could enhance theadsorption towards sulfonic azo compounds to accelerate the mass transfer,act as e^(-)acceptor to promoteinterfacial charge separation,and trigger the self-Fenton reaction to convert in-situ generated H_(2)O_(2)into·OH.(2)Fe(Ⅲ)could coordinate with-N=N-to form d-πconjugation,which could attract e^(-)transfer to attack-N=N-bond.Meanwhile,the inhibited charge recombination could release more free h^(þ)to oxidize sulfonicacid groups into SO4^(-)·.(3)Under the cooperation of abundant multiple active species(·O_(2)^(-),h^(þ),e^(-),·OH,SO4^(-)·)formed during the degradation reaction,sulfonic azo compounds could be completely mineralized into harmlesssmall molecules(CO_(2),H_(2)O,etc.)by means of-N=N-cleavage,hydroxyl substitution,and aromatic ringopening.This work offers a novel approach for effectively eliminating refractory sulfonic azo compounds fromwastewater.
基金supported by the Ministry of Science and Technology of China(Science and Technology to Boost Economy 2020 Key Project,SQ2020YFF0412719 and SQ2020YFF0404901)The Key Research and Development and Transformation Program Funding in Qinghai Province(2021-GX-105)Major projects of Anhui Province and Anhui Province Key Research and Development Plan(202104e11020005)。
文摘A novel integrated film of sulfonated polysulfone/graphene/potassium copper ferricyanide(KCuFC/SPSG)was used for selectively extracting rubidium ion(Rb^(+))from brine.To form KCuFC/SPSG,the precursor film of sulfonated polysulfone/graphene(SPSG)was synthesized by phase conversion process,which was alternately immersed in 0.1 mol·L^(-1)CuSO_(4)/K_(4)[Fe(CN)_(6)]by in-situ adsorption coupled co-precipitation method.Various data such as nuclear magnetic resonance spectrometer,Fourier transform infrared spectroscope,X-ray photoelectron spectroscope,X-ray diffraction,scanning electron microscope,and energy dispersive spectroscopy all verified that abundant KCuFC were uniformly located on the film.The resulting KCuFC/SPSG was used in film separation system.As the solution was fed into the system,the Rb^(+)could be selectively adsorption by KCuFC/SPSG.After the saturation adsorption,0.5 mol·L^(-1)NH_(4)Cl/HCl was fed into the film cell,Rb^(+)could be quickly desorbed by ion-exchange between Rb^(+)and NH_(4)^(+)in the lattice of KCuFC.The purpose of separating and recovering Rb^(+)from the brine can be achieved after the repeated operation.The effects of pH,adsorption time,and interferential ions on the adsorption capacity of Rb^(+)were investigated by batch experiments.The adsorption behavior fits the pseudo-second order kinetic process,while KCuFC has a higher adsorption capacity(Langmuir maximum sorption 165.4 mg·g^(-1)).In addition,KCuFC/SPSG shows excellent selectivity for Rb^(+)even in complex brine systems.KCuFC/SPSG could maintain 93.5%extraction efficiency after five adsorption/desorption cycles.
基金supported by the National Natural Science Foundation of China(51978133,52100026,U20A20322,52170151,51978132)the Fundamental Research Funds for the Central Universities of China(2412021QD022)+1 种基金the Key Research and Development Project of Hainan Province(ZDYF2022SHFZ298)the Industrialization Cultivation Project of Jilin Provincial Department of Education(JJKH20221174CY)。
文摘The occurrence of ultrafiltration(UF)membrane fouling frequently hampers the sustainable advancement of UF technology.Reactive self-cleaning UF membranes can effectively alleviate the problem of membrane fouling.Nevertheless,the self-cleaning process may accelerate membrane aging.Addressing these concerns,we present an innovative design concept for composite self-healing materials based on self-cleaning UF membranes.To begin,TiO_(2)nanoparticles were incorporated into the polymer molecular structure via molecular design,resulting in the synthesis of TiO_(2)/carboxyl-polyether sulfone(PES)hybrid materials.Subsequently,the nonsolvent-induced phase inversion technique was employed to prepare a novel of UF membrane.Lastly,a polyvinyl alcohol(PVA)hydrogel coating was applied to the hybrid UF membrane surface to create PVA@TiO_(2)/carboxyl-PES self-healing reactive UF membranes.By establishing a covalent bond,the TiO_(2)nanoparticles were effectively and uniformly dispersed within the UF membrane,leading to exceptional self-cleaning properties.Furthermore,the water-absorbing and swelling properties of PVA hydrogel,along with its capacity to form hydrogen bonds with water molecules,resulted in UF membranes with improved hydrophilicity and active self-healing abilities.The results demonstrated that the water contact angle of PVA@5%TiO_(2)/carboxyl-PES UF membrane was 43.1°.Following a 1-h exposure to simulated solar exposure,the water flux recovery ratio increased from 48.16%to 81.03%.Moreover,even after undergoing five cycles of 12-h simulated sunlight exposure,the UF membranes exhibited a consistent retention rate of over 97%,thus fully demonstrating their exceptional self-cleaning,antifouling,and selfhealing capabilities.We anticipate that the self-healing reactive UF membrane system will serve as a pioneering and comprehensive solution for the self-cleaning antifouling challenges encountered in UF membranes while also effectively mitigating the aging effects of reactive UF membranes.
基金Joint Fund of the National Natural Science Foundation of China(U2004164)Key Scientific and Technological Research Projects in Henan Province(grant number 232102311155 and 232102230106)+1 种基金Zhengzhou University College Student Innovation and Entrepreneurship Training Program(13210022)Natural Science Foundation of the Jiangsu Higher Education Institutions of China(grant number 21KJB430013)。
文摘In order to prolong the service time and enhance the biocompatibility of magnesium(Mg)alloys used for cardiovascular scaffolds,the composite coatings of Schiff base(corrosion inhibitor)and sulfonated hyaluronic acid(S-HA)nanoparticles(NP@S-HA)with different sulfur content(10.02 wt%and 11.55wt%)were prepared on ZE21B alloy by means of electrostatic spraying with spraying time of 0.5 min,1.0 min and 1.5 min in this paper.Through a series of representations including corrosion experiments and biological characterization,the composite coatings with a sulfur content of 11.55wt%and a spray time of 1.0 min were finally picked due to its better comprehensive performances,which provides a new possibility for the surface modification of degradable Mg alloy cardiovascular scaffolds.
基金Financial support from the National Natural Science Foundation of China(No.22171145 to Z.Jin,32072440 to X.Xu)is gratefully acknowledged.
文摘Transition-metal-catalyzed remote sp^(2)C-H functionalization of aryl sulfonic acids was hardly ever real-ized owing to competitive ortho-C-H functionalization of aryl sulfonates and electron-deficient nature of phenyl ring.Herein,with the assistance of a practical biaryl indolyl directing template,palladium-catalyzed remote sp^(2)C-H alkylation of aryl sulfonic acids have been achieved in moderate to good yields with exclusive meta selectivity.Moreover,remote meta-selective C-H alkynylation of aryl sulfonic acids was also accomplished with a rhodium catalyst.These meta-C-H functionalized products proved to be the superior synthetic precursors,which are difficult to access using the conventional strategy.
基金the National Natural Science Foundation of China(Nos.21762045,21911540466)Shandong Provincial Natural Science Foundation(No.ZR2019YQ12)+1 种基金China Postdoctoral Science Foundation(No.219M652306)Taishan Scholar Project(No.tsqn201812049)for supporting this work。
文摘Photothermal therapy(PTT)is a cutting-edge cancer treatment that can kill cancer cells in hypoxic environments without relying on oxygen.Seeking of the ideal photothermal agents with a high absorption coefficient in the near-infrared region,and a high excellent photothermal conversion efficiency is of great significance.Sulfone-Rhodanmine dye has showed an impressive absorption wavelength over 700 nm,but suffered from a stability issue.In this study,we synthesized five sulfone rhodamines and investigated the substitution effects on stability.SO_(2)R2 showed high stability and strong absorbance at 714 nm with an excellent photothermal conversion efficiency of 53.06%,making it suitable for accurate photoacoustic imaging-guided photothermal therapy in vivo.
基金financial support from the Natural Science Foundation of China and Shandong Province(Nos.21971149,92156007,ZR2019ZD45,ZR2020KB005)the Fundamental Research Funds of Shandong University。
文摘A new,four component copper(Ⅰ)-catalyzed interrupted click/radical relay cascade has been developed.This unprecedented interrupted click reaction provides a rapid modular synthesis of triazole sulfones,important privileged heterocyclic pharmacophores which cannot be accessed by a traditional click reaction.Radical interception of cuprate-triazole,the key reaction intermediate formed in situ,is an important feature of this process.
基金financially supported by National Natural Science Foundation of China(No.82204604,22304055)Youth Talent Program of Hebei Provincial Education Department(No.BJ2018020)+1 种基金Natural Science Foundation of Hebei Province(No.E2020209151,E2022209158,H2022209012)Science and Technology Project of Hebei Education Department(No.JZX2024026)。
文摘Aqueous zinc ion batteries(AZIBs)are one of the promising energy storage devices.However,uncontrolled dendrite and side reactions have seriously hindered its further application.In this study,the metal-organic framework(MOF)functionalized glass fiber separator(GF-PFC-31)was used to regulate interfacial behavior of zinc metal anode,enabling the development of high-performance AZIBs.In PFC-31,there areπ-πinteractions between two adjacent benzene rings with a spacing of 3.199 A.This spacing can block the passage of[Zn(H_(2)O)_6]^(2+)(8.6 A in diameter)through the GF-PFC-31 separator to a certain extent,which promotes the deposition process of Zn ions.In addition,the sulfonic acid group(-S03H)contained in GF-PFC-31 can form a hydrogen bonding network with H_(2)O,which can provide a desolvation effect and reduce the side reaction.Consequently,GF-PFC-31 separator achieves uniform deposition of Zn ions.The Zn‖GF-PFC-31‖Zn symmetric cell exhibits stable cycle life(3000 h at 1.2 mA cm^(-2),2000 h at 0.3 mA cm^(-2),and 2000 h at 5.0 mA cm^(-2)),and Zn‖GF-PFC-31‖MnO_(2) full cell with GF-PFC-31 separator can cycle for 1000 cycles at 1.2 A g^(-1)with capacity retention rate of 82.5%.This work provides a promising method to achieve high-performance AZIBs.
基金supported by the National Natural Science Foundation of China(Nos.41991335 and 42277029)the Eco-Environmental Engineering Research Center,China State Construction Engineering Corp.Ltd.(CSCEC)(Soil Remediation Technology and Equipment)(No.CSCEC-PT-009).
文摘This is the first study to report the co-occurrence of per-and polyfluoroalkyl substances(PFASs),heavy metals,and polycyclic aromatic hydrocarbons(PAHs)and their impacts on the native microbial consortium in soil due to the long-term exposure.The PFASs,heavy metals,and PAHs were detected in soil samples collected at 2–6 m below the ground surface at different sampling locations in a steel-making factory.The total concentrations of PFASs varied from 6.55 to 19.79 ng g^(-1),with perfluorooctane sulfonate(PFOS),perfluorobutane sulfonate,and 6:2 chlorinated polyfluorinated ether sulfonate(alternative of PFOS)being the predominant PFASs.The concentrations of arsenic,cadmium,and lead were detected in the ranges of 4.40–1270.00,0.01–8.67,and 18.00–647.00 mg kg^(-1),respectively,and the concentration of total PAHs was detected in the range of 1.02–131.60 mg kg^(-1).The long-term exposure to mixed contaminants of PFASs,heavy metals,and PAHs led to lower richness and diversity of microbial communities in soil.The soil bacterial communities were mainly composed of Pseudomonas,norank_p_GAL15,Leptothrix,norank_o_Rokubacteriales,and Acinetobacter.Correlations between soil environmental factors and microbial communities indicated that cation exchange capacity and total phosphorus were two key factors in shaping the composition of native microbial communities.Furthermore,Arthrobacter,Leptothrix,and Sphingobium were found to be significantly positively correlated with PFAS concentrations,indicating that these genera could tolerate the stress exerted by PFASs,along with the stress imposed due to the presence of heavy metals or/and PAHs.
基金supported by the National Natural Science Foundation of China(No.U20A20133)the Key Laboratory of Pollution Exposure and Health Intervention of Zhejiang Province(No.20220207)the Fundamental Research Funds for the Provincial Universities of Zhejiang(No.2021YW63).
文摘The potential association between colorectal cancer(CRC)and environmental pollutants is worrisome.Previous studies have found that some perfluoroalkyl acids,including perfluorooctane sulfonate(PFOS),induced colorectal tumors in experimental animals and promoted the migration of and invasion by CRC cells in vitro,but the underlying mechanism is unclear.Here,we investigated the effects of PFOS on the proliferation and migration of CRC cells and the potentialmechanisms involving activating the PI3K/Akt-NF-κB signal pathway and epithelial-mesenchymal transition(EMT).It was found that PFOS promoted the growth andmigration of HCT116 cells at non-cytotoxic concentrations and increased the mRNA expression of the migration-related angiogenic cytokines vascular endothelial growth factor(VEGF)and interleukin-8(IL-8).In a mechanistic investigation,the up-stream signal pathway PI3K/Akt-NF-κB was activated by PFOS,and the process was suppressed by LY294002(PI3K/Akt inhibitor)and BAY11-7082(NF-κB inhibitor)respectively,leading to less proliferation of HCT116 cells.Furthermore,matrix metalloproteinases(MMP)and EMT-related markers were up-regulated after PFOS exposure,and were also suppressed respectively by LY294002 and BAY11-7082.Moreover,the up-regulation of EMT markers was suppressed by a MMP inhibitor GM6001.Taken together,our results indicated that PFOS promotes colorectal cancer cell migration and proliferation by activating the PI3K/Akt-NF-κB signal pathway and epithelial-mesenchymal transition.This could be a potential toxicological mechanism of PFOS-induced malignant development of colorectal cancer.
文摘PPMG-based composite electrolytes were fabricated via the solution method using the polyvinyl alcohol and polyvinylpyrrolidone blend reinforced with various contents of sulfonated inorganic filler.Sulfuric acid was employed as the sulfonating agent to functionalize the external surface of the inorganic filler,i.e.,graphene oxide.The proton conductivities of the newly prepared proton exchange membranes(PEMs)were increased by increasing the temperature and content of sulfonated graphene oxide(SGO),i.e.,ranging from 0.025 S/cm to 0.060 S/cm.The induction of the optimum level of SGO is determined to be an excellent route to enhance ionic conductivity.The single-cell performance test was conducted by sandwiching the newly prepared PEMs between an anode(0.2 mg/cm^(2) Pt/Ru)and a cathode(0.2 mg/cm^(2) Pt)to prepare membrane electrode assemblies,followed by hot pressing under a pressure of approximately 100 kg/cm^(2) at 60℃for 5–10 min.The highest power densities achieved with PPMG PEMs were 14.9 and 35.60 mW/cm^(2) at 25℃and 70℃,respectively,at ambient pressure with 100%relative humidity.Results showed that the newly prepared PEMs exhibit good electrochemical performance.The results indicated that the prepared composite membrane with 6 wt%filler can be used as an alternative membrane for applications of high-performance proton exchange membrane fuel cell.
