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
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
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
Rare earth elements (REEs) are beneficial in developing modern technologies, especially electronics. Their extractions from natural deposits and their recycling require chemical processes that should be monitored rega...Rare earth elements (REEs) are beneficial in developing modern technologies, especially electronics. Their extractions from natural deposits and their recycling require chemical processes that should be monitored regarding efficiency and environmental sustainability. The purpose of this study is to develop impedimetric sensors for the sensitive detection of the rare earth elements La and Ce by modifying a platinum electrode with four isosorbide-based oligo (ether sulfone)s. These oligomers, functionalized with different end groups (hydroxyl, fluor, amine, maleimide), were obtained with satisfactory yields, starting from isosorbide and bis (4-fuorophenyl) sulphone monomers. The resulting oligomers were characterized by NMR, DSC, and ATG analysis. The dihydroxy-oligo (ether sulfone) modified sensor showed the highest analytical performance compared to the other oligomers. The detection limit is 10−9 M for La and 3 × 10−9 M for Ce which is lower than that of most of the published electrochemical sensors.展开更多
Polyethersulfone(PES) is widely used as biomaterials due to its thermal stability,mechanical strength,and chemical inertness.Nevertheless,their blood compatibility is still not adequate for hemodialysis and blood puri...Polyethersulfone(PES) is widely used as biomaterials due to its thermal stability,mechanical strength,and chemical inertness.Nevertheless,their blood compatibility is still not adequate for hemodialysis and blood purification.In this study,the sulfonated polyethersulfone(SPES) was synthesized through an electrophilic substitution reaction,and PES/SPES blending membranes were prepared.The characterization of the SPES was studied by FTIR.The water adsorption and water contact angle experiments show that the hydrophilicity of PES/SPES blend membrane was improved as for the sulfonate group existing in the SPES.Moreover,PES/SPES blend membrane could effectively reduce bovine serum albumin adsorption and prolong the blood coagulation time compared with the PES membrane,thereby improving blood compatibility.展开更多
Polysulfone （PSF） membranes have gained great attention in the fields of ultrafiltration, microfiltration, and thin film composite membranes for nanofiltration or reverse osmosis. For the first time, it is proposed ...Polysulfone （PSF） membranes have gained great attention in the fields of ultrafiltration, microfiltration, and thin film composite membranes for nanofiltration or reverse osmosis. For the first time, it is proposed to fabricate PSF membranes via thermally induced phase separation （TIPS） process using diphenyl sulfone （DPSO2） and polyethylene glycol （PEG） as mixed diluent. DPSO2 is chosen as a crystallizable diluent, while PEG is considered in terms of molecular weight （Mw） and dosage. We systematically investigate the interactions between PSF, DPSO2 and PEG based on the simulation calculations and solubility parameter theory. It is inferred that DPSO2 has an excellent compatibility with PSF, and the addition of PEG results in the ternary system thermodynamically less stable and then facilitates its liquid-liquid （L-L） phase separation. SEM images indicate that cellular-like pores are obvious throughout the membrane when the PEG content in the mixed diluent is 25 wt%-35 wt%. We can facilely manipulate the pore size, water flux and mechanical properties of PSF membranes with the dosage of PEG-200, the Mw of PEG or the cooling rate. The successful application of TIPS can provide a new approach for structure manipulation and performance enhancement of PSF membranes.展开更多
（E）-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd（PPh3）4 and 10 mol% of CuI to stereospecifically af...（E）-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd（PPh3）4 and 10 mol% of CuI to stereospecifically afford the corresponding （Z）-2-sulfonyl-substituted 1,3-enynes 3 in high yields.展开更多
Chloromethylated poly（phthalazinone ether sulfone ketone） （CMPPESK） was prepared from poly（phthalazinone ether sulfone ketone） （PPESK） using chloromethyl octyl ethers （CMOE） with lower toxicity as chlorometh...Chloromethylated poly（phthalazinone ether sulfone ketone） （CMPPESK） was prepared from poly（phthalazinone ether sulfone ketone） （PPESK） using chloromethyl octyl ethers （CMOE） with lower toxicity as chloromethylated regent. CMPPESK was soluble in N-methyl-2-pyrrolidone （NMP）, N,N-dimethylacetamide （DMAc） and chloroform. Quaternized poly（phthalazinone ether sulfone ketone） （QAPPESK） was prepared from CMPPESK by quaternization. QAPPESK had excellent solvent resistance, which was only partly soluble in sulfuric acid （98%） and swollen in N,N-dimethylformamide （DMF）. The vanadium redox flow battery （V-RFB） using QAPPESK anion-exchange membrane had better performance with 88.3% of overall energy efficiency.展开更多
A sulfonated poly（ether ether ketone） （SPEEK） membrane with fairly high degree of sulfonation （DS） swells excessively and even dissolves at high temperature. To solve these problems, sulfonated phenolphthalein p...A sulfonated poly（ether ether ketone） （SPEEK） membrane with fairly high degree of sulfonation （DS） swells excessively and even dissolves at high temperature. To solve these problems, sulfonated phenolphthalein poly（ether sulfone） （SPES-C, DS= 53.7%） is blended with the SPEEK matrix （DS= 55.1%, 61.7%） to prepare SPEEKJSPES-C blend membrane. The decrease in swelling degree and methanol permeability of the membrane is dose-dependent. Pure SPEEK （DS = 61.7%） membrane dissolves completely in water at 70℃, whereas the swelling degree of the SPEEK （DS = 61.7%）/SPES-C （40%, by mass） membrane is 29.7% at 80℃. From room temperature to 80℃, the methanol permeability of all SPEEK （DS = 55.1%）/SPES-C blend membranes is about one order of magnitude lower than that of Nafion 115. At higher temperature, the addition of SPES-C polymer increases the dimensional stability and greater proton conductivity can be achieved. The SPEEK （DS = 55.1%）/SPES-C （40%, by mass） membrane can withstand temperatures up to 150℃. The proton conductivity of SPEEK （DS = 55.1%）/SPES-C （30%, by mass） membrane approaches 0.16 S·cm^-1, matching that of Nafion 115 at 140℃ and 100% RH, while pure SPEEK （DS = 55.1%） membrane dissolves at 90℃. The SPEEK/SPES-C blend membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.展开更多
A novel series of poly（aryl ether sulfone ketone）s （PPESKs） containing phthalazinone and biphenyl moieties were prepared by two-step nucleophilic polycondensation reaction. The ^-Mw values of these copolymers were...A novel series of poly（aryl ether sulfone ketone）s （PPESKs） containing phthalazinone and biphenyl moieties were prepared by two-step nucleophilic polycondensation reaction. The ^-Mw values of these copolymers were between 38,330 and 67,900. The glass transition temperatures （Tg） and 5% decomposition temperatures were ranged in 253-269 ℃ and 488-500 ℃, respectively, The structures of these copolymers were confirmed by FT-IR and ^1H NMR. Moreover, all the resultant copolymers were amorphous determined by wide angle X-ray diffraction （WAXD）.展开更多
The thermal degradation of poly（arylene sulfide sulfone）/N-methylpyrrolidone （PASS/NMP） crystal solvate was studied by thermogravimetric analysis （TGA） and was compared with pure PASS in order to determine the w...The thermal degradation of poly（arylene sulfide sulfone）/N-methylpyrrolidone （PASS/NMP） crystal solvate was studied by thermogravimetric analysis （TGA） and was compared with pure PASS in order to determine the way in which the formation of the crystal solvate affected the thermal properties of the polymer. The activation energy of the solid state process was determined using Kissinger＇s method, which does not require knowledge of the reaction mechanism （RM）, to be 174.18 kJ/mol which was lower than that for pure PASS （E = 214 kJ/mol）. The study of master curves together with interpretation of integral methods, allows confirmation that the thermal degradation mechanism for PASS in the crystal solvate system is a decelerated Rn type, which is a solid-state process based on a phase boundary controlled reaction, in the conversion range considered. Whereas, the pure PASS follows a decelerated Dn thermodegradation mechanism in the same conversion range.展开更多
Novel poly（aryl ether sulfone ketone）s （PAESK） were synthesized from bisphenol A （BPA）, 9,9＇-bis（4-hydroxyphenyl） fluorene （BHPF）, 4,4＇-dichlorodiphenylsulfone （DCS） and 4,4＇-difluorobenzophenone （DFB...Novel poly（aryl ether sulfone ketone）s （PAESK） were synthesized from bisphenol A （BPA）, 9,9＇-bis（4-hydroxyphenyl） fluorene （BHPF）, 4,4＇-dichlorodiphenylsulfone （DCS） and 4,4＇-difluorobenzophenone （DFB） via nucleophilic substitution polymerization, which were subsequently used to fabricate ultrafiltration membrane by phase-inversion method for high temperature condensed water treatment. The obtained high molecular weight co-polymers with fluorene group with good solubility and good thermal stability, can be easily cast into flexible, white and non-transparent fiat films. The influence of molar ratio of BPA and BHPF on the properties of the prepared co-polymers and membranes was investigated in detail. SEM study of the morphology of the membranes indicated that the prepared membranes possessed homogeneous pores on the top surface and were sponge-like or finger-like in cross-section. Pure water flux of the membranes increased from 71.87 L·m-2.h-1 to 247.65 L·m-2.h-1, while the retention of BSA decreased slightly, and the water contact angle decreased from 82.1 ° to 55.6° with the PVP concentration from 0 wt% to 10 wt%. With increasing concentration of PVP, the mechanical properties of membranes decreased, while the thermal stability increased. The permeate flux measurement showed that the PAESK membrane had the potential for high temperature condensed water treatment.展开更多
A novel type of crosslinkable poly（aryl ether sulfone）（PAES） bearing an allyl pendant（PES-OAllyl） was synthesized by a grafting reaction of hydrophenyl-containing PAES（PES-OH） and allyl bromide. PES-OH was pre...A novel type of crosslinkable poly（aryl ether sulfone）（PAES） bearing an allyl pendant（PES-OAllyl） was synthesized by a grafting reaction of hydrophenyl-containing PAES（PES-OH） and allyl bromide. PES-OH was prepared by a demethylation reaction of a methoxyphenylated PAES（PES-OCH3） in the presence of pyridine/hydrochlo- ride. The PES-OCH3 was synthesized by an aromatic nucleophilic substitution of bis（4-chlorophenyl）sulfone and （p-methoxy）phenylhydroquinone. Both DSC and solubility investigation were used to study the crosslinking behavior of PES-OAllyl. After heat treatment, the glass transition temperature（Tg） value of PES-OAllyl sharply increased from 165 ℃ to 227 ℃. Meanwhile, PES-OAllyl changed from a soluble polymer to an insoluble thermoset. In addition, TGA（thermogravimetric analysis） result suggests that the thermal stability of the crosslinked product was improved. All the data prove that the crosslinked PES-OAllyl could be a potential solvent-resistance high-performance material.展开更多
The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted.The sulfoxides and sulfones could be obtained by simply switching the reaction media,i.e.,bis(2-butoxyethyl)ethe...The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted.The sulfoxides and sulfones could be obtained by simply switching the reaction media,i.e.,bis(2-butoxyethyl)ether(BBE)or poly(ethylene glycol)dimethyl ether(PEGDME).The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents.This strategy represents an economic and eco-friendly method that could find potential applications.展开更多
A series of cardo poly（aryl ether sulfone） copolymers bearing pendent sulfonic acid groups （SPES-X） have been prepared by a facile chemical graft method. The structure was confirmed by 1H-NMR spectra. The side-cha...A series of cardo poly（aryl ether sulfone） copolymers bearing pendent sulfonic acid groups （SPES-X） have been prepared by a facile chemical graft method. The structure was confirmed by 1H-NMR spectra. The side-chain-type SPES-X membranes show significantly reduced swelling behavior and excellent mechanical properties as well as appropriate proton conductivity compared to the main-chain-type sulfonated polymers with similar ion exchange capacity （IEC） value. Moreover, they show methanol permeability in the range of 0.6 × 10^-7-5.7 × 10^-7 cmE/s which is lower than that of Nafion 117. All the results indicate that the SPES-Xmembranes are promising candidates for the direct methanol fuel cells.展开更多
Owing to the excellent filtration performance and low energy cost,polymeric nanofibers microfiltration(MF)membranes have attracted increasing attentions.Poly(arylene sulfide sulfone)(PASS),as one of the structurally m...Owing to the excellent filtration performance and low energy cost,polymeric nanofibers microfiltration(MF)membranes have attracted increasing attentions.Poly(arylene sulfide sulfone)(PASS),as one of the structurally modified polymers based on poly-(phenylene sulfide)(PPS),has been selected as the raw material to fabricate nanofibers MF membranes via electrospun techniques.The effects of PASS solution and the electrospinning processing parameters on the structural morphology of nanofibers were investigated in detail.The average diameter of PASS nanofibers was(296±46)nm under the optimal condition:polymer concentration of 0.27 g·m L^–1 PASS/DMI,applied voltage of 20 kV,and speed of collector drum of 300 r·min^–1.And then the multi-layer PASS nanofibers MF membranes were fabricated from cold-pressing the optimized PASS nanofibers(as-prepared PASS nanofibers)membrane.The morphology,porosity,pore size,mechanical properties,and surface wettability of the multi-layer PASS nanofibers MF membranes could be tuned by the layers of as-prepared nanofibers membrane.The results demonstrated that the membrane with 6 layers(marked as PASS-6)exhibited the smallest porosity,smallest pore size,highest mechanical property,and best surface wettability.Meanwhile,the multi-layer PASS nanofibers MF membranes showed that the rejection ratio gradually increased,while the pure water flux decreased with increasing membranes thickness.The PASS-6 membrane exhibited large water flux of 747.76 L·m^–2·h^–1 and high separation efficiency of 99.9%to 0.2μm particles,making it a promising candidate for microfilter.展开更多
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 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.
文摘Rare earth elements (REEs) are beneficial in developing modern technologies, especially electronics. Their extractions from natural deposits and their recycling require chemical processes that should be monitored regarding efficiency and environmental sustainability. The purpose of this study is to develop impedimetric sensors for the sensitive detection of the rare earth elements La and Ce by modifying a platinum electrode with four isosorbide-based oligo (ether sulfone)s. These oligomers, functionalized with different end groups (hydroxyl, fluor, amine, maleimide), were obtained with satisfactory yields, starting from isosorbide and bis (4-fuorophenyl) sulphone monomers. The resulting oligomers were characterized by NMR, DSC, and ATG analysis. The dihydroxy-oligo (ether sulfone) modified sensor showed the highest analytical performance compared to the other oligomers. The detection limit is 10−9 M for La and 3 × 10−9 M for Ce which is lower than that of most of the published electrochemical sensors.
基金Supported by the Special Fund for International Cooperation Projects of China (2005DFA50160)
文摘Polyethersulfone(PES) is widely used as biomaterials due to its thermal stability,mechanical strength,and chemical inertness.Nevertheless,their blood compatibility is still not adequate for hemodialysis and blood purification.In this study,the sulfonated polyethersulfone(SPES) was synthesized through an electrophilic substitution reaction,and PES/SPES blending membranes were prepared.The characterization of the SPES was studied by FTIR.The water adsorption and water contact angle experiments show that the hydrophilicity of PES/SPES blend membrane was improved as for the sulfonate group existing in the SPES.Moreover,PES/SPES blend membrane could effectively reduce bovine serum albumin adsorption and prolong the blood coagulation time compared with the PES membrane,thereby improving blood compatibility.
基金supported by the National Natural Science Foundation of China(Nos.21174124 and 21534009)
文摘Polysulfone （PSF） membranes have gained great attention in the fields of ultrafiltration, microfiltration, and thin film composite membranes for nanofiltration or reverse osmosis. For the first time, it is proposed to fabricate PSF membranes via thermally induced phase separation （TIPS） process using diphenyl sulfone （DPSO2） and polyethylene glycol （PEG） as mixed diluent. DPSO2 is chosen as a crystallizable diluent, while PEG is considered in terms of molecular weight （Mw） and dosage. We systematically investigate the interactions between PSF, DPSO2 and PEG based on the simulation calculations and solubility parameter theory. It is inferred that DPSO2 has an excellent compatibility with PSF, and the addition of PEG results in the ternary system thermodynamically less stable and then facilitates its liquid-liquid （L-L） phase separation. SEM images indicate that cellular-like pores are obvious throughout the membrane when the PEG content in the mixed diluent is 25 wt%-35 wt%. We can facilely manipulate the pore size, water flux and mechanical properties of PSF membranes with the dosage of PEG-200, the Mw of PEG or the cooling rate. The successful application of TIPS can provide a new approach for structure manipulation and performance enhancement of PSF membranes.
基金the National Natural Science Foundation of China(No.20462002)Natural Science Foundation of Jiangxi Province(No.0420015)for financial support.
文摘（E）-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd（PPh3）4 and 10 mol% of CuI to stereospecifically afford the corresponding （Z）-2-sulfonyl-substituted 1,3-enynes 3 in high yields.
基金partly financed by the Major State Basic Research Development Program of China(No.2003 CB615700)the National Natural Science Foundation of China(No.20604005).
文摘Chloromethylated poly（phthalazinone ether sulfone ketone） （CMPPESK） was prepared from poly（phthalazinone ether sulfone ketone） （PPESK） using chloromethyl octyl ethers （CMOE） with lower toxicity as chloromethylated regent. CMPPESK was soluble in N-methyl-2-pyrrolidone （NMP）, N,N-dimethylacetamide （DMAc） and chloroform. Quaternized poly（phthalazinone ether sulfone ketone） （QAPPESK） was prepared from CMPPESK by quaternization. QAPPESK had excellent solvent resistance, which was only partly soluble in sulfuric acid （98%） and swollen in N,N-dimethylformamide （DMF）. The vanadium redox flow battery （V-RFB） using QAPPESK anion-exchange membrane had better performance with 88.3% of overall energy efficiency.
基金Supported by the State Key Development Program for Basic Research of China （2008CB617502）, the National Natural Science Foundation of China （20606025）, and Program for Changjiang Scholars and Innovative Research Team in University of China （IRT0641）.
文摘A sulfonated poly（ether ether ketone） （SPEEK） membrane with fairly high degree of sulfonation （DS） swells excessively and even dissolves at high temperature. To solve these problems, sulfonated phenolphthalein poly（ether sulfone） （SPES-C, DS= 53.7%） is blended with the SPEEK matrix （DS= 55.1%, 61.7%） to prepare SPEEKJSPES-C blend membrane. The decrease in swelling degree and methanol permeability of the membrane is dose-dependent. Pure SPEEK （DS = 61.7%） membrane dissolves completely in water at 70℃, whereas the swelling degree of the SPEEK （DS = 61.7%）/SPES-C （40%, by mass） membrane is 29.7% at 80℃. From room temperature to 80℃, the methanol permeability of all SPEEK （DS = 55.1%）/SPES-C blend membranes is about one order of magnitude lower than that of Nafion 115. At higher temperature, the addition of SPES-C polymer increases the dimensional stability and greater proton conductivity can be achieved. The SPEEK （DS = 55.1%）/SPES-C （40%, by mass） membrane can withstand temperatures up to 150℃. The proton conductivity of SPEEK （DS = 55.1%）/SPES-C （30%, by mass） membrane approaches 0.16 S·cm^-1, matching that of Nafion 115 at 140℃ and 100% RH, while pure SPEEK （DS = 55.1%） membrane dissolves at 90℃. The SPEEK/SPES-C blend membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.
文摘A novel series of poly（aryl ether sulfone ketone）s （PPESKs） containing phthalazinone and biphenyl moieties were prepared by two-step nucleophilic polycondensation reaction. The ^-Mw values of these copolymers were between 38,330 and 67,900. The glass transition temperatures （Tg） and 5% decomposition temperatures were ranged in 253-269 ℃ and 488-500 ℃, respectively, The structures of these copolymers were confirmed by FT-IR and ^1H NMR. Moreover, all the resultant copolymers were amorphous determined by wide angle X-ray diffraction （WAXD）.
基金supported by the 863 program of China(No.2007AA 03Z561)
文摘The thermal degradation of poly（arylene sulfide sulfone）/N-methylpyrrolidone （PASS/NMP） crystal solvate was studied by thermogravimetric analysis （TGA） and was compared with pure PASS in order to determine the way in which the formation of the crystal solvate affected the thermal properties of the polymer. The activation energy of the solid state process was determined using Kissinger＇s method, which does not require knowledge of the reaction mechanism （RM）, to be 174.18 kJ/mol which was lower than that for pure PASS （E = 214 kJ/mol）. The study of master curves together with interpretation of integral methods, allows confirmation that the thermal degradation mechanism for PASS in the crystal solvate system is a decelerated Rn type, which is a solid-state process based on a phase boundary controlled reaction, in the conversion range considered. Whereas, the pure PASS follows a decelerated Dn thermodegradation mechanism in the same conversion range.
基金financial support under Heilongjiang Postdoctoral Fund (No.LBH-Z09175)
文摘Novel poly（aryl ether sulfone ketone）s （PAESK） were synthesized from bisphenol A （BPA）, 9,9＇-bis（4-hydroxyphenyl） fluorene （BHPF）, 4,4＇-dichlorodiphenylsulfone （DCS） and 4,4＇-difluorobenzophenone （DFB） via nucleophilic substitution polymerization, which were subsequently used to fabricate ultrafiltration membrane by phase-inversion method for high temperature condensed water treatment. The obtained high molecular weight co-polymers with fluorene group with good solubility and good thermal stability, can be easily cast into flexible, white and non-transparent fiat films. The influence of molar ratio of BPA and BHPF on the properties of the prepared co-polymers and membranes was investigated in detail. SEM study of the morphology of the membranes indicated that the prepared membranes possessed homogeneous pores on the top surface and were sponge-like or finger-like in cross-section. Pure water flux of the membranes increased from 71.87 L·m-2.h-1 to 247.65 L·m-2.h-1, while the retention of BSA decreased slightly, and the water contact angle decreased from 82.1 ° to 55.6° with the PVP concentration from 0 wt% to 10 wt%. With increasing concentration of PVP, the mechanical properties of membranes decreased, while the thermal stability increased. The permeate flux measurement showed that the PAESK membrane had the potential for high temperature condensed water treatment.
基金Supported by the National Natural Science Foundation of China(No.50973040)the Science and Technology Development Plan of Jilin Province, China(No.20090322)
文摘A novel type of crosslinkable poly（aryl ether sulfone）（PAES） bearing an allyl pendant（PES-OAllyl） was synthesized by a grafting reaction of hydrophenyl-containing PAES（PES-OH） and allyl bromide. PES-OH was prepared by a demethylation reaction of a methoxyphenylated PAES（PES-OCH3） in the presence of pyridine/hydrochlo- ride. The PES-OCH3 was synthesized by an aromatic nucleophilic substitution of bis（4-chlorophenyl）sulfone and （p-methoxy）phenylhydroquinone. Both DSC and solubility investigation were used to study the crosslinking behavior of PES-OAllyl. After heat treatment, the glass transition temperature（Tg） value of PES-OAllyl sharply increased from 165 ℃ to 227 ℃. Meanwhile, PES-OAllyl changed from a soluble polymer to an insoluble thermoset. In addition, TGA（thermogravimetric analysis） result suggests that the thermal stability of the crosslinked product was improved. All the data prove that the crosslinked PES-OAllyl could be a potential solvent-resistance high-performance material.
文摘The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted.The sulfoxides and sulfones could be obtained by simply switching the reaction media,i.e.,bis(2-butoxyethyl)ether(BBE)or poly(ethylene glycol)dimethyl ether(PEGDME).The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents.This strategy represents an economic and eco-friendly method that could find potential applications.
基金financially supported by the National Natural Science Foundation of China(No.51203151)the Program of Jilin Education Department(No.93201201)
文摘A series of cardo poly（aryl ether sulfone） copolymers bearing pendent sulfonic acid groups （SPES-X） have been prepared by a facile chemical graft method. The structure was confirmed by 1H-NMR spectra. The side-chain-type SPES-X membranes show significantly reduced swelling behavior and excellent mechanical properties as well as appropriate proton conductivity compared to the main-chain-type sulfonated polymers with similar ion exchange capacity （IEC） value. Moreover, they show methanol permeability in the range of 0.6 × 10^-7-5.7 × 10^-7 cmE/s which is lower than that of Nafion 117. All the results indicate that the SPES-Xmembranes are promising candidates for the direct methanol fuel cells.
文摘Owing to the excellent filtration performance and low energy cost,polymeric nanofibers microfiltration(MF)membranes have attracted increasing attentions.Poly(arylene sulfide sulfone)(PASS),as one of the structurally modified polymers based on poly-(phenylene sulfide)(PPS),has been selected as the raw material to fabricate nanofibers MF membranes via electrospun techniques.The effects of PASS solution and the electrospinning processing parameters on the structural morphology of nanofibers were investigated in detail.The average diameter of PASS nanofibers was(296±46)nm under the optimal condition:polymer concentration of 0.27 g·m L^–1 PASS/DMI,applied voltage of 20 kV,and speed of collector drum of 300 r·min^–1.And then the multi-layer PASS nanofibers MF membranes were fabricated from cold-pressing the optimized PASS nanofibers(as-prepared PASS nanofibers)membrane.The morphology,porosity,pore size,mechanical properties,and surface wettability of the multi-layer PASS nanofibers MF membranes could be tuned by the layers of as-prepared nanofibers membrane.The results demonstrated that the membrane with 6 layers(marked as PASS-6)exhibited the smallest porosity,smallest pore size,highest mechanical property,and best surface wettability.Meanwhile,the multi-layer PASS nanofibers MF membranes showed that the rejection ratio gradually increased,while the pure water flux decreased with increasing membranes thickness.The PASS-6 membrane exhibited large water flux of 747.76 L·m^–2·h^–1 and high separation efficiency of 99.9%to 0.2μm particles,making it a promising candidate for microfilter.
