Low-permeability dense reservoirs,including micro-fractured reservoirs,are commonly characterized by high content of clay substances,high original water saturation,high sensitivity to invasive fluids,high capillary pr...Low-permeability dense reservoirs,including micro-fractured reservoirs,are commonly characterized by high content of clay substances,high original water saturation,high sensitivity to invasive fluids,high capillary pressure,complicated structure and anisotropic,high flow-resistance and micro pore throats etc,.Generally they also have lots of natural micro fractures,probably leading to stress sensibility.Main damaging factors in such reservoirs are water-sensibility and water-blocking caused by invasive fluids during drilling and production operations.Once damaged,formation permeability can rarely recovered.Numerous studies have shown that damaging extent of water-blocking ranges from 70% to 90%.Main damaging mechanisms and influencing factors of water-blocking were systematically analyzed.Also some feasible precaution or treating approaches of water-blocking were put forward.In a laboratory setting,a new multi-functional drilling fluid composed mainly of amphion polymer,sulfonation polymer,high effectively preventive water-blocking surfactants,ideal packing temporary bridging agents(TBA) and film-forming agents,etc.,were developed.New low-damage drilling fluids has many advantages,such as good rheological properties,excellent effectiveness of water-blocking prevention,good temporary plugging effect,low filtration and ultra-low permeability(API filtration≤5 mL,HTHP filtration≤10 mL,mud cake frictional coefficient≤0.14,permeability recovery>81%),can efficiently prevent or minimize damage,preserve natural formation and enhance comprehensive development-investment effect in TUHA Jurassic dense sandstone reservoir formation with low-permeability,the only one developing integrated condense gas field.Some references can be provided to similar reservoir formations.展开更多
Our previous work proved that high adsorption capacity and uptake rate of lysozyme were achieved on alginate(Alg)-grafted re sin with an ionic capacity(IC) of 240 mmol·L^(-1)(Alg-FF-240).Moreover,the salt-toleran...Our previous work proved that high adsorption capacity and uptake rate of lysozyme were achieved on alginate(Alg)-grafted re sin with an ionic capacity(IC) of 240 mmol·L^(-1)(Alg-FF-240).Moreover,the salt-tolerant feature of Alg-FF-230 was improved by using sequential alginate grafting and sulfonation strategy.Inspired by the enhanced adsorption performance of lysozyme,we have herein proposed to investigate the static and dynamic adsorption behaviors of γ-globulin on a series of Alg-grafted resins with different grafting densities and sulfonation degrees.The adsorption ca pacity of γ-globulin decreased with increa sing alginate-grafting density(IC) from 160 to 230 mmol·L^(-1) at 0 mmol·L^(-1) NaCl because of the steric hindrance caused by the alginate-grafting layer.Effects of ionic strength(IS) indicated that the adsorption capacities of the resins with the IC value of 230-370 mmol·L^(-1) were much higher than CM Sepharose FF at 50-100 mmol·L^(-1) NaCl,and the uptake rate of Alg-FF-230 was about twice as much as that of CM Sepharose FF.This work demonstrated the important effects of alginate-grafting layer and IS in γ-globulin adsorption behavior,which would be helpful in the design of Alggrafted resins and the selection of proper IS condition for protein purification.展开更多
To enhance the blood compatibility of Polyvinyl Chloride (PVC) film, the film was modified by SO2/O2 gas plasma treatment. The effect of surface sulfonation of PVC treated by various SO2/O2 gas plasma depended on the ...To enhance the blood compatibility of Polyvinyl Chloride (PVC) film, the film was modified by SO2/O2 gas plasma treatment. The effect of surface sulfonation of PVC treated by various SO2/O2 gas plasma depended on the volume ratio O2/(SO2 +O2). When the volume ratio was 0.5, the effect of sulfonation was the best. Sulfonic acid groups were specifically and efficiently introduced onto the PVC surface, which was proved by X-ray photoelectron spectroscopy (XPS) and Attenuated Total Reflectance Fourier Transfer Infrared (ATR-FTIR) spectroscopy. The surface microstructure of modified PVC film was studied with scanning electron microscopy (SEM). The antithrombogenicity of the samples was determined by the activated partial thromboplastin time (APTT), prothrombin time (PT), thrombin time (TT) and plasma recalcification time (PRT) tests and platelet adhesion experiment. The results indicated that the antithrombogenicity of modified PVC was improved remarkably.展开更多
A series of multiblock sulfonated poly(arylene ether sulfone)s(SPAES)with various block lengths and predictable ion exchange capacity were synthesized from 4,4’-difluorodiphenyl sulfone,4,4’-dihydrodiphenyl sulfone ...A series of multiblock sulfonated poly(arylene ether sulfone)s(SPAES)with various block lengths and predictable ion exchange capacity were synthesized from 4,4’-difluorodiphenyl sulfone,4,4’-dihydrodiphenyl sulfone and 4,4’-biphenol by one-pot and two-pot polymerization.;H-NMR and FTIR spectra confirmed the structure that sulfonic acid groups were introduced precisely on the poly(arylene ether sulfone)s by post-sulfonation which resulted in controllable sulfonation degree.The proton exchange membranes(PEMs)-based SPAES displayed excellent dimensional,thermal,antioxidant stability,proton conductivity and mechanical properties(maximum tensile stress>35 MPa).Thermogravimetric analysis indicated the prepared SPAES began to degrade above 310℃.The effects of polymerization processes,those were,one-pot hydrophobic segment process,one-pot hydrophilic segment process and two-pot process,on the properties of polymers were investigated.The proton conductivity and microphase separation of SPAES PEMs increased in order of those prepared by one-pot hydrophobic segment process,two-pot process and one-pot hydrophilic segment process.The highest conductivities of SPAES synthesized by the above processes under 80℃ and 100%relative humidity were 213(MS4),297(MB3)and 360 mS·cm^(-1)(MQ2),respectively.展开更多
The work herein employed a rotating packed bed(RPB)to intensify the sulfonation process of 1,4-diaminoanthraquinone leuco(DL)in an attempt to improve the yield of the product 1,4-diaminoanthra quinone-2-sulfonic acid(...The work herein employed a rotating packed bed(RPB)to intensify the sulfonation process of 1,4-diaminoanthraquinone leuco(DL)in an attempt to improve the yield of the product 1,4-diaminoanthra quinone-2-sulfonic acid(DSA).First,the effects of operating conditions in a stirred tank reactor(STR),including stirring speed,chlorosulfonic acid/DL molar ratio(η),solvent/DL mass ratio(ζ),reaction temperature and dropping speed of chlorosulfonic acid,on the yield of DSA were investigated.The yield of DSA can reach 87.34%under the optimal operating conditions:stirring speed of 500 r·min^(-1),ηof 4.5,ζof 7,reaction temperature of 150℃,dropping speed of 0.61 ml·min^(-1).In addition,the kinetics of the sulfonation process via the shrinking core model revealed that the reaction is controlled by diffusion via a product layer under the reaction temperature of 140℃.Furthermore,the RPB was employed to intensify the mass transfer between liquid and solid phases during the sulfonation reaction process.The results showed that the DSA yield of 92.69%obtained by RPB was 5.35%higher than that by STR,indicating that RPB can significantly intensify the mass transfer in the liquid-solid phase sulfonation reaction process.展开更多
A novel polyetheretherketone (PEK-C) prepared from phenolphthalein has been synthesized. In order to improve some of its properties for application in high performance membrane, the PEK-C has been sulfonated with conc...A novel polyetheretherketone (PEK-C) prepared from phenolphthalein has been synthesized. In order to improve some of its properties for application in high performance membrane, the PEK-C has been sulfonated with concentrated sulfuric acid. Degree of sulfonation can be regulated by controlling the temmperature and time of sulfonation. The characterization of the sulfonated PEK-C in sodium salt form has been made by IR, ~1H NMR and ^(13)C NMR etc. It is shown that the sulfonation appears to take place exclusively in the ortho position to phenolic ether of phenolphthalein unit. The result is in agreement with theoretical deduction. Some properties of the sulfonated PEK-C, such as solubility, transition temperature, thermal degradation and hydrophilicity have also been discussed.展开更多
This paper investigates the possibility of attaining sulphonated poly(phenylene oxide) (SPPO) with a relativelyhigher sulfonation degree. To achieve this aim, the approach we adopt is to improve the solubility of the ...This paper investigates the possibility of attaining sulphonated poly(phenylene oxide) (SPPO) with a relativelyhigher sulfonation degree. To achieve this aim, the approach we adopt is to improve the solubility of the final product in themixed solvent so that the sulfonation may take place between the bulk solutions and PPO powders even at higher sulfonationdegree. It is shown that the addition of a proper amount of dimethyl formide (DMF) to the conventional PPO-chloroformsystem can actually enhance the sulfonation effect. The solvent composition is then correlated with the sulfonation degreebased on the solubility parameters. It is interesting to find that solubility parameters between the mixed solvent and theprecipitated products keep an approximately unchanged value at about 4.9, which is just equal to that when pure chloroformis used, though the solubility parameters of both solvents increase with the content of DMF in solution. This may be the mainreason why the addition of DMF can reduce the precipitation and improve the ion exchange capacity (IEC) of SPPOpolymer.展开更多
3-Methylthio-5-hydroxy-1,2,4-triazine(1c)reacted with substituted benzenesulfonyl chloride to give 3-methylthio-5-oxy-1,2,4-triazin-6-yl pyridinium betaine(4)in anhydrous pyridine.But when NaOH/H_2O/CH_3COCH_3 or NaOH...3-Methylthio-5-hydroxy-1,2,4-triazine(1c)reacted with substituted benzenesulfonyl chloride to give 3-methylthio-5-oxy-1,2,4-triazin-6-yl pyridinium betaine(4)in anhydrous pyridine.But when NaOH/H_2O/CH_3COCH_3 or NaOH/CH_3OH were used as reactant and solvent,3-methylthio-4-substituted benzenesulfonyl-5-oxo-6-hydroxy-1,4,5,6-tetrahydro-1,2,4-triazine(6)or 1-tosyl-3-methylthio-5-oxo-6-methyloxy-1,4,5,6-tetrahydro-1,2,4-triazine(7)was obtained respectively.The above reactions show anomalous properties of nucleophilic attack on 6-carbon in 1,2,4-triazine ring.展开更多
The objective of this study was to investigate the sulfonation of （1→6）-β-D-glucan （lasiodiplodan） as a potentiating mechanism for biological functionalities. Lasiodiplodan was sulfonated by the chlorosulfonic a...The objective of this study was to investigate the sulfonation of （1→6）-β-D-glucan （lasiodiplodan） as a potentiating mechanism for biological functionalities. Lasiodiplodan was sulfonated by the chlorosulfonic acid-pyridine method. The modified exopolysaccharide was characterized by FT-IR and 13C NMR spectroscopy, X-ray diffraction and SEM. Antioxidant activity was assessed by the methods of H2O2 and OH radical removal and reducing power. Antimicrobial potential was evaluated by the broth-microdilution method. Sulfonation resulted in a derivative with DS of 0.24. FT-IR analysis indicated the introduction of sulfonyl groups in the macromolecule structure through specific bands in the regions of 1,240 cm-1 and 810 cm-1. 13C NMR analysis suggested that sulfonation occurred at carbon 2 of the glucose residue. Sulfonation led to morphological changes in the structure of the biopolymer resulting in a heterogeneous structure with the presence of fibrils. Derivatization promoted an increase in the antioxidant ability of the macromolecule, with a high OH removal potential （74.32%）. Bacteriostatic activity against E. coli （Escherichia coli） and S. enterica （Salmonella enterica） typhimurium and fungicidal activity against C. albicans （Candida albicans） and C. tropicalis （Candida tropicalis） were found in the sulfonated sample. Sulfonation potentiated the antioxidant and antimicrobial activities of the biomacromolecule, suggesting that it is a potentiating mechanism of biological functions.展开更多
PGMEA is widely used as a solvent and diluent for photoresists,yet developing an efficient resin that simultaneously resists organic dissolution and removes trace metal ions presents a significant challenge.To overcom...PGMEA is widely used as a solvent and diluent for photoresists,yet developing an efficient resin that simultaneously resists organic dissolution and removes trace metal ions presents a significant challenge.To overcome this,a novel sulfonated hyper-cross-linked resin(2-CS-DVB-SO_(3)H)was synthesized through a multi-step process involving the preparation of a Cl^(-)functionalized gel polymer,followed by sulfonation and post-crosslinking.The effects of the monomers,crosslinking degree,sulfonation degree,dosage,adsorption temperature,and resin stability on its purity performance were discussed.The resulting resin demonstrated exceptional stability in organic media and effectively purified PGMEA under optimized conditions(30%crosslinking,4.69%S content,and 0.2 g mL^(−1)resin dosage),with Ti,Co,Ni,and Cu metal ion concentrations reduced below 10 ppb.This process elevated PGMEA purity from 98.90%to 99.48%.Thermodynamic analysis revealed the adsorption to be non-spontaneous.The resin maintained chemical stability in PGMEA within 18 h.FT-IR and XPS data identified ion exchange,electrostatic interactions and lone electron pair coordination between sulfonic acid groups and metal ions as the binding mechanisms.The hydrogen bonds formed between Cl−on the resin and hydroxyl groups in methanol(as organic impurities)were considered the primary factor responsible for enhancing the purity of PGMEA.These results collectively establish 2-CS-DVB-SO_(3)H as a robust and reliable material for metal ion removal in PGMEA purification,thereby improving the purity of photoresist solvents and potentially enhancing photoresist performance.展开更多
Fabricating a desired porous structure on the surface of biomedical polyetheretherketone(PEEK)implants for enhancing biological functions is crucial and difficult due to its inherent chemical inertness.In this study,a...Fabricating a desired porous structure on the surface of biomedical polyetheretherketone(PEEK)implants for enhancing biological functions is crucial and difficult due to its inherent chemical inertness.In this study,a porous surface of PEEK implants was fabricated by controllable sulfonation using gaseous sulfur trioxide(SO3)for different time(5,15,30,60 and 90 min).Micro-topological structure was generated on the surface of sulfonated PEEK implants preserving original mechanical properties.The protein absorption capacity and apatite forming ability was thus improved by the morphological and elemental change with higher degree of sulfonation.In combination of the appropriate micromorphology and bioactive sulfonate components,the cell adhesion,migration,proliferation and extracellular matrix secretion were obviously enhanced by the SPEEK-15 samples which were sulfonated for 15 min.Finding from this study revealed that controllable sulfonation by gaseous SO3 would be an extraordinarily strategy for improving osseointegration of PEEK implants by adjusting the microstructure and chemical composition while maintaining excellent mechanical properties.展开更多
It is well‑known that the sulfonation degree(DS)of aromatic syntan is an important factor affecting its retanning performances.But the quantitative relation between DS and syntan property and the influencing mechanism...It is well‑known that the sulfonation degree(DS)of aromatic syntan is an important factor affecting its retanning performances.But the quantitative relation between DS and syntan property and the influencing mechanism of DS on syntan property are not clarified.In this work,five phenolic formaldehyde syntans(PFSs)with the same polym‑erization degree but varying DS were prepared to investigate the effect of DS on the properties of syntan and crust leather.It was found that the absolute value of zeta potential and the particle size of PFS decreased with increasing DS in aqueous solution.Molecular dynamic simulation results proved that the DS of PFS was a major contributor to electrostatic interaction and hydrogen bonding in the PFS–water system and greatly affected the aggregation and dispersion of PFS in aqueous solution.The PFS with a low DS was prone to aggregate to large particles in aqueous solution because of low intermolecular electrostatic repulsion and less hydrogen bonds and therefore can be used to increase the thickness and tightness of leather.The PFS with a high DS presented a small particle size with more anionic groups in aqueous solution,thereby sharply decreasing the positive charge of leather surface and facilitat‑ing the penetration of the post‑tanning agents into the leather.These results might be scientifically valid for rational molecular design of syntans and more productive use of syntans in leather making.展开更多
To valorize kraft lignin,hydroxymethylation and sulfonation were applied on this under-utilized,but vastly available,material.The hydroxymethylation pretreatment was conducted as means to improve the reactivity of lig...To valorize kraft lignin,hydroxymethylation and sulfonation were applied on this under-utilized,but vastly available,material.The hydroxymethylation pretreatment was conducted as means to improve the reactivity of lignin.The sulfonation of hydroxymethylated kraft lignin was investigated by sulfuric acid and sodium sulfite treatments under various conditions.The modified lignin samples were characterized for their charge density,solubility,elemental components,and molecular weights.The results showed that the hydroxymethylation facilitated the sulfonation by sodium sulfite,yielding a product(SSH-lignin)with the charge density of-1.2 meq/g and water solubility of 10 g/L under the conditions of Ns_(2)SO_(3)/lignin molar ratio of 0.49 mol/mol,95℃and 3 h.On the other hand,hydroxymethylation hindered the sulfonation of lignin by sulfuric acid,yielding a product(SAH-lignin)with the charge density of–0.46 meq/g and solubility of 0.9 g/L under the conditions of H_(2)SO_(4)/lignin molar ratio of 14.8 mol/mol,80℃and 1 h.The SSH-lignin had a high adsorption on kaolinite(17 mg/g)at a lignin concentration of 40 g/L.The sulfonated lignins were also found to be effective coagulant for the cationic dye ethyl violet.展开更多
Carbon-based solid acids have been successfully employed as acidic catalysts for pollutant mitigation in wastewater.To fully tap the potentials of commercially viable carbons for the preparation of solid acids and enh...Carbon-based solid acids have been successfully employed as acidic catalysts for pollutant mitigation in wastewater.To fully tap the potentials of commercially viable carbons for the preparation of solid acids and enhance their catalytic performances is a challenging problem.In this work,three commercialized carbons including biochar,activated carbon and graphite were preprocessed(ball-milling,Hummer exfoliation,HNO3 soaking,and microwave heating in HNO_(3),etc.),sulfonated,and evaluated as solid-acid catalysts for tylosin mitigation.Graphite-originated solid acid performed the best through a balling-milling preprocess,while biochar-originated solid acids behaved well under all preprocessing treatments,in which 40 mg L^(−1) of tylosin was mitigated within 8 min by 1 g L^(−1) of biochar-originated solid acids.The biochar solid acid through the ball-milling preprocess presented high total acidity and large amounts of-SO_(3)H groups,due to dramatically increased surface area and the rise of activation groups(hydroxyl,alkyl and alkoxy groups,etc.)facilitating electrophilic reaction.In addition,decreased particle size and aromaticity and increased structural defects also contributed.Theoretical calculation of average local ionization energy(ALIE)of condensed aromatic model molecules with substituted activation groups confirmed the promoting effects on sulfonation from strong to weak were 8.40-9.06 eV.These findings have deepened the knowledge in tuning carbon surface chemistry for better sulfonation,thus strengthening catalytic degradation of tylosin.The value of this study is in pulling a clear thread for maneuvering solid-acid catalysts using carbons,which holds a novel promise for rationally functionalizing biochar-based catalysts for the remediation of macrolide antibiotics in polluted water.展开更多
Modular free-assembly construction of mono-,di-,and tri-fluoromethyl sulfones was comprehensively achieved by a combination of halides,a sulfur dioxide surrogate,and halofluorocarbons.The industrial raw material thiou...Modular free-assembly construction of mono-,di-,and tri-fluoromethyl sulfones was comprehensively achieved by a combination of halides,a sulfur dioxide surrogate,and halofluorocarbons.The industrial raw material thiourea dioxide served as the sulfur dioxide source,combined with readily available fluorocarbon sources such as 2-bromo-2-fluoroacetate and chlorodifluoromethane(ClCF_(2)H,Freon)employed as fluoromethyl reagents.Notably,four methyl sulfone-containing pharmaceuticals were modified into three types of fluoromethyl sulfones,displaying their great potential for drug discovery via the current strategy.Mechanistic studies further demonstrated that C-F…H-N interactions between thiourea dioxide and halofluorocarbons play a key role in stabilizing monofluoromethyl electrophiles and difluorocarbene species.展开更多
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
Per-and polyfluoroalkyl substances(PFAS)are persistent environmental contaminants that often show an adverse impact on human health.Rational design of porous adsorbents for selective and reversible removal of PFAS,suc...Per-and polyfluoroalkyl substances(PFAS)are persistent environmental contaminants that often show an adverse impact on human health.Rational design of porous adsorbents for selective and reversible removal of PFAS,such as perfluorooctane sulfonate(PFOS),is imperative and challenging.Herein,a Janus strategy based on an ionic covalent organic framework(iCOF-DGCl)composed of the alternately hydrophobic aromatic domains and hydrophilic guanidinium moieites has been proposed to meet the requirement of high-performance adsorbents.iCOF-DGCl shows fast adsorption kinetics(970.9 mg g^(−1)min^(−1))and ultrahigh uptake capacity(2491 mg g^(−1))toward PFOS,making it one of the most effective materials among the reported PFOS adsorbents.Moreover,the PFOS removal by iCOF-DGCl remains highly selective in the presence of disturbing anions,and the adsorbent could be well recovered for reuse.Mechanism studies have demonstrated that the Janus structure units of iCOF-DGCl form both hydrophobic and electrostatic interactions with the amphiphilic PFOS,thus achieving cooperative adsorption of PFOS.This work provides a facile approach based on Janus structure of COFs adsorbent for wastewater remediation.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
基金Project(50574061) supported by the National Natural Science Foundation of China
文摘Low-permeability dense reservoirs,including micro-fractured reservoirs,are commonly characterized by high content of clay substances,high original water saturation,high sensitivity to invasive fluids,high capillary pressure,complicated structure and anisotropic,high flow-resistance and micro pore throats etc,.Generally they also have lots of natural micro fractures,probably leading to stress sensibility.Main damaging factors in such reservoirs are water-sensibility and water-blocking caused by invasive fluids during drilling and production operations.Once damaged,formation permeability can rarely recovered.Numerous studies have shown that damaging extent of water-blocking ranges from 70% to 90%.Main damaging mechanisms and influencing factors of water-blocking were systematically analyzed.Also some feasible precaution or treating approaches of water-blocking were put forward.In a laboratory setting,a new multi-functional drilling fluid composed mainly of amphion polymer,sulfonation polymer,high effectively preventive water-blocking surfactants,ideal packing temporary bridging agents(TBA) and film-forming agents,etc.,were developed.New low-damage drilling fluids has many advantages,such as good rheological properties,excellent effectiveness of water-blocking prevention,good temporary plugging effect,low filtration and ultra-low permeability(API filtration≤5 mL,HTHP filtration≤10 mL,mud cake frictional coefficient≤0.14,permeability recovery>81%),can efficiently prevent or minimize damage,preserve natural formation and enhance comprehensive development-investment effect in TUHA Jurassic dense sandstone reservoir formation with low-permeability,the only one developing integrated condense gas field.Some references can be provided to similar reservoir formations.
基金supported by the National Natural Science Foundation of China (Nos. 21878222 and 21621004)。
文摘Our previous work proved that high adsorption capacity and uptake rate of lysozyme were achieved on alginate(Alg)-grafted re sin with an ionic capacity(IC) of 240 mmol·L^(-1)(Alg-FF-240).Moreover,the salt-tolerant feature of Alg-FF-230 was improved by using sequential alginate grafting and sulfonation strategy.Inspired by the enhanced adsorption performance of lysozyme,we have herein proposed to investigate the static and dynamic adsorption behaviors of γ-globulin on a series of Alg-grafted resins with different grafting densities and sulfonation degrees.The adsorption ca pacity of γ-globulin decreased with increa sing alginate-grafting density(IC) from 160 to 230 mmol·L^(-1) at 0 mmol·L^(-1) NaCl because of the steric hindrance caused by the alginate-grafting layer.Effects of ionic strength(IS) indicated that the adsorption capacities of the resins with the IC value of 230-370 mmol·L^(-1) were much higher than CM Sepharose FF at 50-100 mmol·L^(-1) NaCl,and the uptake rate of Alg-FF-230 was about twice as much as that of CM Sepharose FF.This work demonstrated the important effects of alginate-grafting layer and IS in γ-globulin adsorption behavior,which would be helpful in the design of Alggrafted resins and the selection of proper IS condition for protein purification.
基金The project supported by the Natural Science Foundation of Shanxi Province ( No. 2001H18) and the Research Foundation of Shanxi Province for Abroad Returnee (No. 200177)
文摘To enhance the blood compatibility of Polyvinyl Chloride (PVC) film, the film was modified by SO2/O2 gas plasma treatment. The effect of surface sulfonation of PVC treated by various SO2/O2 gas plasma depended on the volume ratio O2/(SO2 +O2). When the volume ratio was 0.5, the effect of sulfonation was the best. Sulfonic acid groups were specifically and efficiently introduced onto the PVC surface, which was proved by X-ray photoelectron spectroscopy (XPS) and Attenuated Total Reflectance Fourier Transfer Infrared (ATR-FTIR) spectroscopy. The surface microstructure of modified PVC film was studied with scanning electron microscopy (SEM). The antithrombogenicity of the samples was determined by the activated partial thromboplastin time (APTT), prothrombin time (PT), thrombin time (TT) and plasma recalcification time (PRT) tests and platelet adhesion experiment. The results indicated that the antithrombogenicity of modified PVC was improved remarkably.
基金financially supported by the National Natural Science Foundation of China(No.21306010)。
文摘A series of multiblock sulfonated poly(arylene ether sulfone)s(SPAES)with various block lengths and predictable ion exchange capacity were synthesized from 4,4’-difluorodiphenyl sulfone,4,4’-dihydrodiphenyl sulfone and 4,4’-biphenol by one-pot and two-pot polymerization.;H-NMR and FTIR spectra confirmed the structure that sulfonic acid groups were introduced precisely on the poly(arylene ether sulfone)s by post-sulfonation which resulted in controllable sulfonation degree.The proton exchange membranes(PEMs)-based SPAES displayed excellent dimensional,thermal,antioxidant stability,proton conductivity and mechanical properties(maximum tensile stress>35 MPa).Thermogravimetric analysis indicated the prepared SPAES began to degrade above 310℃.The effects of polymerization processes,those were,one-pot hydrophobic segment process,one-pot hydrophilic segment process and two-pot process,on the properties of polymers were investigated.The proton conductivity and microphase separation of SPAES PEMs increased in order of those prepared by one-pot hydrophobic segment process,two-pot process and one-pot hydrophilic segment process.The highest conductivities of SPAES synthesized by the above processes under 80℃ and 100%relative humidity were 213(MS4),297(MB3)and 360 mS·cm^(-1)(MQ2),respectively.
基金financially supported by the National Key Research and Development Program of China(2016YFB0301500)the National Natural Science Foundation of China(21878009)。
文摘The work herein employed a rotating packed bed(RPB)to intensify the sulfonation process of 1,4-diaminoanthraquinone leuco(DL)in an attempt to improve the yield of the product 1,4-diaminoanthra quinone-2-sulfonic acid(DSA).First,the effects of operating conditions in a stirred tank reactor(STR),including stirring speed,chlorosulfonic acid/DL molar ratio(η),solvent/DL mass ratio(ζ),reaction temperature and dropping speed of chlorosulfonic acid,on the yield of DSA were investigated.The yield of DSA can reach 87.34%under the optimal operating conditions:stirring speed of 500 r·min^(-1),ηof 4.5,ζof 7,reaction temperature of 150℃,dropping speed of 0.61 ml·min^(-1).In addition,the kinetics of the sulfonation process via the shrinking core model revealed that the reaction is controlled by diffusion via a product layer under the reaction temperature of 140℃.Furthermore,the RPB was employed to intensify the mass transfer between liquid and solid phases during the sulfonation reaction process.The results showed that the DSA yield of 92.69%obtained by RPB was 5.35%higher than that by STR,indicating that RPB can significantly intensify the mass transfer in the liquid-solid phase sulfonation reaction process.
文摘A novel polyetheretherketone (PEK-C) prepared from phenolphthalein has been synthesized. In order to improve some of its properties for application in high performance membrane, the PEK-C has been sulfonated with concentrated sulfuric acid. Degree of sulfonation can be regulated by controlling the temmperature and time of sulfonation. The characterization of the sulfonated PEK-C in sodium salt form has been made by IR, ~1H NMR and ^(13)C NMR etc. It is shown that the sulfonation appears to take place exclusively in the ortho position to phenolic ether of phenolphthalein unit. The result is in agreement with theoretical deduction. Some properties of the sulfonated PEK-C, such as solubility, transition temperature, thermal degradation and hydrophilicity have also been discussed.
基金The authors graefully acknowledge financial support from the National Natural Science Foundation of China (29976040), Natural Science Foundation of Anhui Province (99045431), Key Foundation of Anhui Educational Comrnittee (2000j1255zd), the Foundation of
文摘This paper investigates the possibility of attaining sulphonated poly(phenylene oxide) (SPPO) with a relativelyhigher sulfonation degree. To achieve this aim, the approach we adopt is to improve the solubility of the final product in themixed solvent so that the sulfonation may take place between the bulk solutions and PPO powders even at higher sulfonationdegree. It is shown that the addition of a proper amount of dimethyl formide (DMF) to the conventional PPO-chloroformsystem can actually enhance the sulfonation effect. The solvent composition is then correlated with the sulfonation degreebased on the solubility parameters. It is interesting to find that solubility parameters between the mixed solvent and theprecipitated products keep an approximately unchanged value at about 4.9, which is just equal to that when pure chloroformis used, though the solubility parameters of both solvents increase with the content of DMF in solution. This may be the mainreason why the addition of DMF can reduce the precipitation and improve the ion exchange capacity (IEC) of SPPOpolymer.
基金Director of the project supported by National Natural Science foundation of China.
文摘3-Methylthio-5-hydroxy-1,2,4-triazine(1c)reacted with substituted benzenesulfonyl chloride to give 3-methylthio-5-oxy-1,2,4-triazin-6-yl pyridinium betaine(4)in anhydrous pyridine.But when NaOH/H_2O/CH_3COCH_3 or NaOH/CH_3OH were used as reactant and solvent,3-methylthio-4-substituted benzenesulfonyl-5-oxo-6-hydroxy-1,4,5,6-tetrahydro-1,2,4-triazine(6)or 1-tosyl-3-methylthio-5-oxo-6-methyloxy-1,4,5,6-tetrahydro-1,2,4-triazine(7)was obtained respectively.The above reactions show anomalous properties of nucleophilic attack on 6-carbon in 1,2,4-triazine ring.
文摘The objective of this study was to investigate the sulfonation of （1→6）-β-D-glucan （lasiodiplodan） as a potentiating mechanism for biological functionalities. Lasiodiplodan was sulfonated by the chlorosulfonic acid-pyridine method. The modified exopolysaccharide was characterized by FT-IR and 13C NMR spectroscopy, X-ray diffraction and SEM. Antioxidant activity was assessed by the methods of H2O2 and OH radical removal and reducing power. Antimicrobial potential was evaluated by the broth-microdilution method. Sulfonation resulted in a derivative with DS of 0.24. FT-IR analysis indicated the introduction of sulfonyl groups in the macromolecule structure through specific bands in the regions of 1,240 cm-1 and 810 cm-1. 13C NMR analysis suggested that sulfonation occurred at carbon 2 of the glucose residue. Sulfonation led to morphological changes in the structure of the biopolymer resulting in a heterogeneous structure with the presence of fibrils. Derivatization promoted an increase in the antioxidant ability of the macromolecule, with a high OH removal potential （74.32%）. Bacteriostatic activity against E. coli （Escherichia coli） and S. enterica （Salmonella enterica） typhimurium and fungicidal activity against C. albicans （Candida albicans） and C. tropicalis （Candida tropicalis） were found in the sulfonated sample. Sulfonation potentiated the antioxidant and antimicrobial activities of the biomacromolecule, suggesting that it is a potentiating mechanism of biological functions.
基金supported by the National Key Research and Development Program of China(No.2020YFA0710204)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA0390503)the National Natural Science Foundation of China(No.22278408).
文摘PGMEA is widely used as a solvent and diluent for photoresists,yet developing an efficient resin that simultaneously resists organic dissolution and removes trace metal ions presents a significant challenge.To overcome this,a novel sulfonated hyper-cross-linked resin(2-CS-DVB-SO_(3)H)was synthesized through a multi-step process involving the preparation of a Cl^(-)functionalized gel polymer,followed by sulfonation and post-crosslinking.The effects of the monomers,crosslinking degree,sulfonation degree,dosage,adsorption temperature,and resin stability on its purity performance were discussed.The resulting resin demonstrated exceptional stability in organic media and effectively purified PGMEA under optimized conditions(30%crosslinking,4.69%S content,and 0.2 g mL^(−1)resin dosage),with Ti,Co,Ni,and Cu metal ion concentrations reduced below 10 ppb.This process elevated PGMEA purity from 98.90%to 99.48%.Thermodynamic analysis revealed the adsorption to be non-spontaneous.The resin maintained chemical stability in PGMEA within 18 h.FT-IR and XPS data identified ion exchange,electrostatic interactions and lone electron pair coordination between sulfonic acid groups and metal ions as the binding mechanisms.The hydrogen bonds formed between Cl−on the resin and hydroxyl groups in methanol(as organic impurities)were considered the primary factor responsible for enhancing the purity of PGMEA.These results collectively establish 2-CS-DVB-SO_(3)H as a robust and reliable material for metal ion removal in PGMEA purification,thereby improving the purity of photoresist solvents and potentially enhancing photoresist performance.
基金financially supported by the National Natural Science Foundation of China(Projects.51673186 , 81672263)the Special Fund for Industrialization of Science and Technology Cooperation between Jilin Province and Chinese Academy of Sciences(2017SYHZ0021).
文摘Fabricating a desired porous structure on the surface of biomedical polyetheretherketone(PEEK)implants for enhancing biological functions is crucial and difficult due to its inherent chemical inertness.In this study,a porous surface of PEEK implants was fabricated by controllable sulfonation using gaseous sulfur trioxide(SO3)for different time(5,15,30,60 and 90 min).Micro-topological structure was generated on the surface of sulfonated PEEK implants preserving original mechanical properties.The protein absorption capacity and apatite forming ability was thus improved by the morphological and elemental change with higher degree of sulfonation.In combination of the appropriate micromorphology and bioactive sulfonate components,the cell adhesion,migration,proliferation and extracellular matrix secretion were obviously enhanced by the SPEEK-15 samples which were sulfonated for 15 min.Finding from this study revealed that controllable sulfonation by gaseous SO3 would be an extraordinarily strategy for improving osseointegration of PEEK implants by adjusting the microstructure and chemical composition while maintaining excellent mechanical properties.
基金This work was supported by the National Natural Science Foundation of China(21978176).
文摘It is well‑known that the sulfonation degree(DS)of aromatic syntan is an important factor affecting its retanning performances.But the quantitative relation between DS and syntan property and the influencing mechanism of DS on syntan property are not clarified.In this work,five phenolic formaldehyde syntans(PFSs)with the same polym‑erization degree but varying DS were prepared to investigate the effect of DS on the properties of syntan and crust leather.It was found that the absolute value of zeta potential and the particle size of PFS decreased with increasing DS in aqueous solution.Molecular dynamic simulation results proved that the DS of PFS was a major contributor to electrostatic interaction and hydrogen bonding in the PFS–water system and greatly affected the aggregation and dispersion of PFS in aqueous solution.The PFS with a low DS was prone to aggregate to large particles in aqueous solution because of low intermolecular electrostatic repulsion and less hydrogen bonds and therefore can be used to increase the thickness and tightness of leather.The PFS with a high DS presented a small particle size with more anionic groups in aqueous solution,thereby sharply decreasing the positive charge of leather surface and facilitat‑ing the penetration of the post‑tanning agents into the leather.These results might be scientifically valid for rational molecular design of syntans and more productive use of syntans in leather making.
文摘To valorize kraft lignin,hydroxymethylation and sulfonation were applied on this under-utilized,but vastly available,material.The hydroxymethylation pretreatment was conducted as means to improve the reactivity of lignin.The sulfonation of hydroxymethylated kraft lignin was investigated by sulfuric acid and sodium sulfite treatments under various conditions.The modified lignin samples were characterized for their charge density,solubility,elemental components,and molecular weights.The results showed that the hydroxymethylation facilitated the sulfonation by sodium sulfite,yielding a product(SSH-lignin)with the charge density of-1.2 meq/g and water solubility of 10 g/L under the conditions of Ns_(2)SO_(3)/lignin molar ratio of 0.49 mol/mol,95℃and 3 h.On the other hand,hydroxymethylation hindered the sulfonation of lignin by sulfuric acid,yielding a product(SAH-lignin)with the charge density of–0.46 meq/g and solubility of 0.9 g/L under the conditions of H_(2)SO_(4)/lignin molar ratio of 14.8 mol/mol,80℃and 1 h.The SSH-lignin had a high adsorption on kaolinite(17 mg/g)at a lignin concentration of 40 g/L.The sulfonated lignins were also found to be effective coagulant for the cationic dye ethyl violet.
基金National Natural Science Foundation of China(51978052,42207456)State Key Joint Laboratory of Environmental Simulation and Pollution(19K01ESPCR).
文摘Carbon-based solid acids have been successfully employed as acidic catalysts for pollutant mitigation in wastewater.To fully tap the potentials of commercially viable carbons for the preparation of solid acids and enhance their catalytic performances is a challenging problem.In this work,three commercialized carbons including biochar,activated carbon and graphite were preprocessed(ball-milling,Hummer exfoliation,HNO3 soaking,and microwave heating in HNO_(3),etc.),sulfonated,and evaluated as solid-acid catalysts for tylosin mitigation.Graphite-originated solid acid performed the best through a balling-milling preprocess,while biochar-originated solid acids behaved well under all preprocessing treatments,in which 40 mg L^(−1) of tylosin was mitigated within 8 min by 1 g L^(−1) of biochar-originated solid acids.The biochar solid acid through the ball-milling preprocess presented high total acidity and large amounts of-SO_(3)H groups,due to dramatically increased surface area and the rise of activation groups(hydroxyl,alkyl and alkoxy groups,etc.)facilitating electrophilic reaction.In addition,decreased particle size and aromaticity and increased structural defects also contributed.Theoretical calculation of average local ionization energy(ALIE)of condensed aromatic model molecules with substituted activation groups confirmed the promoting effects on sulfonation from strong to weak were 8.40-9.06 eV.These findings have deepened the knowledge in tuning carbon surface chemistry for better sulfonation,thus strengthening catalytic degradation of tylosin.The value of this study is in pulling a clear thread for maneuvering solid-acid catalysts using carbons,which holds a novel promise for rationally functionalizing biochar-based catalysts for the remediation of macrolide antibiotics in polluted water.
基金financial support provided by the NSFC(nos.22071057,21971065,and 21871089)STCSM(nos.20XD1421500,20JC1416800,and 18JC1415600)+1 种基金the Innovative Research Team of High-Level Local Universities in Shanghai(no.SSMU-ZLCX20180501)the Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning.
文摘Modular free-assembly construction of mono-,di-,and tri-fluoromethyl sulfones was comprehensively achieved by a combination of halides,a sulfur dioxide surrogate,and halofluorocarbons.The industrial raw material thiourea dioxide served as the sulfur dioxide source,combined with readily available fluorocarbon sources such as 2-bromo-2-fluoroacetate and chlorodifluoromethane(ClCF_(2)H,Freon)employed as fluoromethyl reagents.Notably,four methyl sulfone-containing pharmaceuticals were modified into three types of fluoromethyl sulfones,displaying their great potential for drug discovery via the current strategy.Mechanistic studies further demonstrated that C-F…H-N interactions between thiourea dioxide and halofluorocarbons play a key role in stabilizing monofluoromethyl electrophiles and difluorocarbene species.
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the financial support from National Key Research and Development Program(2019YFA0210403)National Natural Science Foundation of China(22001178,21975259)+1 种基金Natural Science Foundation of Hebei Province(B2021202077,B2022202039,C20220313)S&T Program of Hebei(236Z4308G).The authors extend their gratitude to Shiyanjia Lab(www.shiyanjia.com)for XPS measurement.
文摘Per-and polyfluoroalkyl substances(PFAS)are persistent environmental contaminants that often show an adverse impact on human health.Rational design of porous adsorbents for selective and reversible removal of PFAS,such as perfluorooctane sulfonate(PFOS),is imperative and challenging.Herein,a Janus strategy based on an ionic covalent organic framework(iCOF-DGCl)composed of the alternately hydrophobic aromatic domains and hydrophilic guanidinium moieites has been proposed to meet the requirement of high-performance adsorbents.iCOF-DGCl shows fast adsorption kinetics(970.9 mg g^(−1)min^(−1))and ultrahigh uptake capacity(2491 mg g^(−1))toward PFOS,making it one of the most effective materials among the reported PFOS adsorbents.Moreover,the PFOS removal by iCOF-DGCl remains highly selective in the presence of disturbing anions,and the adsorbent could be well recovered for reuse.Mechanism studies have demonstrated that the Janus structure units of iCOF-DGCl form both hydrophobic and electrostatic interactions with the amphiphilic PFOS,thus achieving cooperative adsorption of PFOS.This work provides a facile approach based on Janus structure of COFs adsorbent for wastewater remediation.
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.
