Poly(ester amide)s(PEAs)represent promising biomaterials because of their well-balanced mechanical properties,biodegradability,and biocompatibility.However,practical applications of PEAs are still limited by challenge...Poly(ester amide)s(PEAs)represent promising biomaterials because of their well-balanced mechanical properties,biodegradability,and biocompatibility.However,practical applications of PEAs are still limited by challenges in functional versatility and environmental adaptability.Here,we present the first synthesis of periodic selenium-incorporated PEAs(Se-PEAs)via a rapid,catalyst-free selenol-yne click polymerization process.By harnessing the versatility of selenium,we achieved precise modulation of material properties.The resulting Se-PEAs demonstrated tunable mechanical behavior,spanning rigid plastics to elastomers,alongside exceptional thermal stability and high optical clarity.Programmable degradation profiles ensure long-term stability in physiological environments while facilitating rapid oxidative degradation at the end of the lifecycle.Surface selenoniumization further conferred robust antibacterial efficacy without compromising mechanical integrity.This multifunctionality positions Se-PEAs as transformative materials for biomedical implants,sustainable packaging,and high-refractiveindex optics.Our work advanced functional polymer design and underscored the potential of selenium chemistry in addressing global challenges in terms of plastic waste and ecological sustainability.展开更多
This study uses all-atom molecular dynamics simulations to investigate the dislocation propagation, stress transmission, and mechanical properties in poly(p-phenylene terephthalamide) fibers under uniaxial tension. Th...This study uses all-atom molecular dynamics simulations to investigate the dislocation propagation, stress transmission, and mechanical properties in poly(p-phenylene terephthalamide) fibers under uniaxial tension. The results indicate that the dislocation propagates and the stress transfers not only along the fiber axis but also between adjacent molecular chains through hydrogen bonds, demonstrating their influence on the yield behavior. As the degree of polymerization increases, breakage of covalent bonds and interchain slippage contribute to the yield of fibers together. This work provides theoretical guidance for the design and manufacturing of high-performance fibers.展开更多
Poly(m-phenylene isophthalamide)(PMIA),a key aromatic polyamide,is widely used for its outstanding mechanical strength,high thermal stability,and excellent insulation properties.However,different applications demand v...Poly(m-phenylene isophthalamide)(PMIA),a key aromatic polyamide,is widely used for its outstanding mechanical strength,high thermal stability,and excellent insulation properties.However,different applications demand varying dielectric properties,so tailoring its dielectric per-formance is essential.PMIA was first synthesized in this study,followed by introducing pores and developing porous PMIA films and PMIA-based composites with reduced dielectric constants.Porous PMIA films were fabricated using the wet phase inversion process with N,N-dimethylac-etamide(DMAC)solvent and water as the non-solvent.The impact of casting solution composi-tion and coagulation bath temperature on pore structures was analyzed.A film produced with 18%PMIA and 5%LiCl in a 35℃coagulation bath achieved the lowest dielectric constant of 1.76 at 1 Hz,48%lower than the standard PMIA film,which had a tensile strength of 18.5 MPa and an initial degradation temperature of 320℃.展开更多
Aqueous zinc metal batteries(ZMBs)are vital to potable electronics and electric energy infrastructures because of their high energy conversion efficiency,high energy density,and environmental friendliness.However,ramp...Aqueous zinc metal batteries(ZMBs)are vital to potable electronics and electric energy infrastructures because of their high energy conversion efficiency,high energy density,and environmental friendliness.However,rampant zinc dendrite growth and side reactions on the Zn anode seriously impede the practical application of ZMBs.In this work,morpholine-crosslinked polyacrylamide hydrogel electrolytes(ploy(acrylamide),6m-PAM)are successfully developed to simultaneously regulate solvation shell to suppress side reactions and homogenize Zn^(2+)ion migration for dendrite-free ZMBs.Notably,the 6m-PAM electrolyte exhibits excellent mechanical strength of 50.6 kPa,high Zn^(2+)ion conductivity of 52 mS cm^(-1)at room temperature,and fast self-healing ability,providing stable and adaptable electrolyte-anode interfaces.Experimental and theoretical calculation results reveal that Zn^(2+)-N(morpholine)coordination interaction effectively reshapes the primary solvation shell of Zn^(2+),suppressing the activity of free water and Zn dendrites.As a result,the 6m-PAM electrolyte endows symmetric zinc cells with a long-term cycling life of 2000 h at 7.5 mA cm^(-2).Notably,Zn/Polyaniline(PANI)batteries equipped with 6m-PAM electrolytes also exhibit a high capacity of 124 mA h g^(-1)at 1 A g^(-1)and a long cycling life of 4000 times with a high-capacity retention of 98.3%,This functional crosslinked hydrogel electrolyte paves a new way to construct durable dendrite-free ZMBs.展开更多
α-Chiral amides are common in pharmaceuticals,agrochemicals,natural products,and peptides,prompting the need for new synthetic methods.Here,we introduce a nickel-catalyzed asymmetric reductive amidation method to syn...α-Chiral amides are common in pharmaceuticals,agrochemicals,natural products,and peptides,prompting the need for new synthetic methods.Here,we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesizeα-chiral amides from benzyl ammonium salts and isocyanates.The key to success is using a chiral 2,2-bipyridine ligand(-)-Ph-SBpy,enabling high yield(up to 95%)and enantiomeric ratio(up to 98:2 er)under mild conditions.Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate,enhancing selectivity and efficiency.The synthetic utility is showcased through transformations of the enantioenriched amides,and the mechanism and enantioselectivity are supported by experimental and computational studies.展开更多
Herein,manganese(Mn)‑doped poly(1,5‑diaminonaphthalene)(PN)electrode material(Mn@PN)was synthesized via chemical oxidative polymerization.The material′s distinctive vesicular architecture enables rapid ion transport ...Herein,manganese(Mn)‑doped poly(1,5‑diaminonaphthalene)(PN)electrode material(Mn@PN)was synthesized via chemical oxidative polymerization.The material′s distinctive vesicular architecture enables rapid ion transport while maintaining the structural stability of the electrode under continuous charge‑discharge cycles.Electrochemical characterization under a three‑electrode system revealed exceptional rate capability:Mn@PN delivered an ultrahigh specific capacitance of 10318 F·g^(-1) at a low current density of 3 A·g^(-1) and retained 9415 F·g^(-1)(91.2%retention compared to the value at 3 A·g^(-1))even at an ultrahigh current density of 50 A·g^(-1).Moreover,the material exhibited 97.4%capacitance retention after 9000 cycles at 30 A·g^(-1),corresponding with a low capacitance decay rate of 0.003‰per cycle,significantly outperforming conventional conductive polymers like polyaniline(PANI).An asymmetric supercapacitor assembled with Mn@PN as the positive electrode(Mn@PN||AC)achieved an energy density of 328 Wh·kg^(-1) at 15 A·g^(-1) and retained 80.7%of its initial specific capacitance after 4000 cycles at 20 A·g^(-1).展开更多
Polymer-electrolyte-based solid-state Li metal batteries with high-voltage Ni-rich cathodes are promising energy storage technologies owing to their favorable security and high energy densities.However,operating in wi...Polymer-electrolyte-based solid-state Li metal batteries with high-voltage Ni-rich cathodes are promising energy storage technologies owing to their favorable security and high energy densities.However,operating in wide temperature range and at high voltage is a tough challenge for them.Herein,F/N donating fluorinated-amide-based plasticizers regulated polymer electrolyte capable of enabling high-voltage Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)batteries with excellent performance in wide temperature range is developed.F/N donating fluorinated-amide-based plasticizers significantly improve ionic conductivity(1.52 mS/cm at 30℃),enhance oxidation stability(5.0 V vs.Li^(+)/Li)and fabricate robust LiF/Li_(3)N-rich electrode-electrolyte interphases,which significantly improve the interface stability of Li metal anode and NCM811 cathode.The designed polymer electrolyte is nonflammable and has excellent dimensional stability at 200℃.Capitalizing on these advantageous attributes,the Li||NCM811 cells show excellent cycle stability and rate capability from−20℃ to 60℃ at high voltages(∼4.6 V),and under high-loading full cell condition,which display impressive capacity retention of 84.4%after 1000 cycles and ultrahigh capacity of 154.8 mAh/g at 10 C.This work provides a rational design strategy of polymer electrolytes for wide-temperature high-energy solid-state Li metal batteries.展开更多
Conductive polymers have recently drawn tremendous attention due to their promising applications in electronic and energy-related devices.While p-type conductive polymers such as poly(3,4-ethylenedioxythiophene):poly(...Conductive polymers have recently drawn tremendous attention due to their promising applications in electronic and energy-related devices.While p-type conductive polymers such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)have achieved commercialization,the development of stable,high-performance n-type polymers has lagged.Recently,the discovery of n-type polymer poly(benzodifurandione)(PBFDO)has greatly promoted the development and application of n-type conductive polymers.However,the synthesis process involves cumbersome post-processing,which greatly increases the cost and difficulty of mass production.Herein,a novel synthesis method for PBFDO has been developed,which was promoted by the combination of solvent dimethyl sulfoxide(DMSO)and acetic anhydride(Ac_(2)O).This method exploits the oxidative capability of DMSO,activated by Ac_(2)O,which can promote the keto-enol tautomerism of 3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione(BFDO)and induce the rapid polymerization.The resulting PBFDO ink exhibits a high electronic conductivity of more than 2000 S cm^(-1)and excellent ambient stability.Significantly,the additives and by-products remain in a liquid state during the polymerization process and possess low boiling points,allowing for the production of pure PBFDO films through straightforward heating and drying.Furthermore,this approach holds considerable promise for in situ polymerization,as functional conductive films can be prepared by merely combining the monomers with the DMSO/Ac_(2)O mixture and applying heat.This efficient,purification-free strategy represents a significant step toward the industrial application of the highperformance n-type conductive polymer PBFDO.展开更多
In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still face...In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still faced with defects such as low intrinsic ionic conductivity,a narrow electrochemical window,and poor thermal stability.A crosslinking and fluorination molecular design strategy toward PDOL is proposed to tackle the issues above.The amorphous crosslinked structure effectively improves ionic conductivity by inhibiting long-chain crystallization.Especially,the antioxidant–CF_(3)groups,stable crosslinked structure,and reduced terminal hydroxyl groups significantly enhance the electrochemical oxidation stability with a superb high-voltage window of 4.7 V.In addition,the designed electrolyte also exhibits obviously improved thermal stability with no deformation at 120°C for 5 min.Furthermore,the semi-solid NCM811||Li batteries exhibit a favourable capacity retention of 88.8%after 150 cycles at 0.5 C.Even assembled with NCM622 cathode working at 4.5 V,the semi-solid batteries can still show a satisfactory capacity retention of 85.3%after 100 cycles at 0.5 C.Also,a 0.1 Ah NCM811||Li pouch cell with active materials loading of 9 mg/cm2 demonstrates satisfactory cycling stability and working ability,which shows promising practical application prospects.展开更多
Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this stu...Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this study,a novel p H/glutathione dual-responsive pesticide delivery system was constructed through the synthesis of disulfide-bridged hollow mesoporous organosilica nanospheres(HMONs)via the St??ber method,followed by poly(acrylic acid)(PAA)coating through distillation-precipitation polymerization to form HMONs@PAA nanocomposites.The resulting abamectin-loaded system(Abamectin-HMONs@PAA)demonstrated a 12.73% pesticide loading capacity and significantly improved photostability,retaining twice as much active ingredient as free abamectin after 250 h of UV irradiation(36 W).Release studies revealed p H-and glutathione-dependent characteristics,with cumulative releases in acidic conditions exceeding those in neutral and alkaline environments by 18.66% and 40.98%,respectively,and a 14.2% increase in glutathione-containing solution(0.2 mmol·L^(-1) in 70% ethanol)after 97 h.Bioassays showed superior performance against Plutella xylostella,with a 13.33% reduction in survival rate compared to conventional suspension at equivalent dosage(40 mg·L^(-1)),while maintaining efficacy after extensive rainfall simulation(20 events over 10 days).This study provides a promising approach for developing environmentally responsive nanopesticides with enhanced durability and controlled-release properties,offering significant potential for sustainable crop protection.展开更多
Poly(phenylene oxide)(PPO)exhibits excellent dielectric properties,making it an ideal substrate for high-frequency,high-speed copper-clad laminates.The phenolic hydroxyl group at the end of PPO plays a key role in its...Poly(phenylene oxide)(PPO)exhibits excellent dielectric properties,making it an ideal substrate for high-frequency,high-speed copper-clad laminates.The phenolic hydroxyl group at the end of PPO plays a key role in its reactivity.Accurately quantifying the phenolic hydroxyl content in PPO is essential but challenging.In this study,we proposed a method for measuring the phenolic hydroxyl content of PPO using differential UV absorption spectroscopy.In alkaline solutions,the phenolic hydroxyl in PPO completely ionizes to form phenoxide ions,leading to a significant increase in UV absorbance at approximately 250 and 300 nm.Notably,the differential UV absorbance at approximately 300 nm was directly proportional to the phenolic hydroxyl concentration.Using 2,6-dimethylphenol as a standard,a calibration curve was established to relate the phenolic hydroxyl concentration to differential UV absorbance at approximately 300 nm,providing a precise and straightforward method for phenolic hydroxyl quantification in PPO with distinct advantages over conventional techniques.展开更多
Although poly(urethane-urea)elastomers(PUEs)possess excellent mechanical properties and durability,their inherent flammability and inability to self-repair after damage significantly limits their applications in high-...Although poly(urethane-urea)elastomers(PUEs)possess excellent mechanical properties and durability,their inherent flammability and inability to self-repair after damage significantly limits their applications in high-end fields.To address this challenge,this study employs a supramolecular chemistry approach by simultaneously incorporating multiple hydrogen bonds as dynamic cross-linking points and a phosphorus-nitrogen synergistic flame-retardant structure into the poly(urethane-urea)network.The multiple hydrogen bonds endow the material with efficient intrinsic self-healing capability,while the phosphorus-nitrogen flame retardant ensures outstanding thermal stability and flame resistance,leading to the successful synthesis of a high-performance multifunctional poly(urethane-urea)elastomer.Experimental results demonstrated that when the content of the flame retardant diethyl(2-((2-aminoethyl)amino)ethyl)phosphoramidate(DEPTA)was 10 wt%,the resulting PUE/10%DEPTA achieved a V-0 rating in the vertical burning test,with a limiting oxygen index(LOI)of 30%.Concurrently,the elastomer maintained good toughness,exhibiting a tensile strength of 27.3 MPa,an elongation at break of 601%,and a self-healing efficiency of up to 94.46%.This breakthrough shows significant promise for advanced engineering applications that demand fire safety,structural durability,and extended service life through self-repair.展开更多
Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardan...Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardant strategies often compromise their mechanical properties,hindering their practical applications.Herein,a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)-based comonomer(DDP)was used to synthesize flame-retardant poly(ethylene furandicarboxylate-co-phosphaphenanthrene)(PEFDn).The covalent integration of DDP confers intrinsic flame retardancy,avoiding the plasticization and migration issues associated with additive-type systems.Upon thermal decomposition,the DOPO-derived moieties release phosphoric acid and radical scavengers,promoting char formation and suppressing flame propagation.Furthermore,density functional theory(DFT)calculations combined with non-covalent interaction(NCI)analysis revealed that DOPO dimer molecules adopt a stable parallel-displaced π-π stacking configu ration,potentially facilitating microphase separation and enhancing the energy dissipation capability.PEFD_(10)achieves a UL-94 V-0 rating while simultaneously increasing impact toughness from 1.5 kJ/m^(2) to 14.7 kJ/m^(2).Im portantly,PEFDn maintained acceptable oxygen-barrier properties.PEFD10 also exhibited high transparency and UV-shielding performance.The combination of intrinsic flame safety,im pact-toughness resistance,UV shielding,and an oxygen barrier ensures reliable protection of electrical components and long-term operational stability.The integration of multiple critical properties within a single bio-based material represents a novel approach fo r enabling sustainable polymer solutions for high-pe rformance electrical applications.展开更多
Core-shell structured SiO2/poly（N-isopropylacrylamide） （SiO2/PNIPAM） microspheres were successfully fabricated through hydrolysis and condensation reaction of tertraethyl orthosilicate （TEOS） on the surface of P...Core-shell structured SiO2/poly（N-isopropylacrylamide） （SiO2/PNIPAM） microspheres were successfully fabricated through hydrolysis and condensation reaction of tertraethyl orthosilicate （TEOS） on the surface of PNIPAM template at 50 ~C. The PNIPAM template can be easily removed by water at room temperature so that SiO2 hollow microspheres were finally obtained. The transmission electron microscope and scanning electron microscope observations indicated that SiO2 hollow microspheres with an average diameter of 150 nm can be formed only if there are enough concentration of PNIPAM and TEOS, and the hy- drolysis time of TEOS. FTIR analysis showed that part of PNIPAM remained on the wall of SiO2 because of the strong interaction between PNIPAM and silica. This work provides a clean and efficient way to prepare hollow microspheres.展开更多
A series of novel aromatic poly ( amide imide)s containing phthalazinone moieties were prepared from 2-(4-aminophenyl)-4-[3-methyl-4-(4-aminophenoxy)-2,3-phthalazinone-1], a novel diamine 1 with four diimide-dicarboxy...A series of novel aromatic poly ( amide imide)s containing phthalazinone moieties were prepared from 2-(4-aminophenyl)-4-[3-methyl-4-(4-aminophenoxy)-2,3-phthalazinone-1], a novel diamine 1 with four diimide-dicarboxylic acids by Yamazaki phosphorylation method with the inherent viscosity of 0.36~0.65 dL/g. These polymers had high glass transition temperatures above 300C and they lost 10% weight between 426~475C in N2. The structure of diamine 1 and the polymers was confirmed by IR, 1H NMR and MS. The obtained polymers were readily soluble in polar solvents such as NMP, m-cresol etc. and easily cast into tough, flexible films. The X-ray indicated that they are all amorphous.展开更多
Two novel heterocyclic diamine monomers: 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)phenyl] (2H)phthalazin-1-one and 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)-3,5-dimethylphenyl](2H)phthalazin-1-one ...Two novel heterocyclic diamine monomers: 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)phenyl] (2H)phthalazin-1-one and 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)-3,5-dimethylphenyl](2H)phthalazin-1-one were successfully synthesized from readily available heterocyclic bisphenol-like monomers in two steps in high yield. A series of novel poly(aryl ether amide)s containing the phthalazinone moiety were successfully prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents.展开更多
The polycondensation of the mixture of diamines 5,5-methylene bis(2-aminophenol) and 4,4-(hexafluoroisopropylidene)dianiline(molar ratio 0.8:0.2) with isophthaloyl dichloride was used to synthesize poly(amido-o-hydrox...The polycondensation of the mixture of diamines 5,5-methylene bis(2-aminophenol) and 4,4-(hexafluoroisopropylidene)dianiline(molar ratio 0.8:0.2) with isophthaloyl dichloride was used to synthesize poly(amido-o-hydroxy amide)(POA-F)-new heat resistant binder of the composites for microelectronics. The copolymer was fractionated, its hydrodynamic, optical, and conformational properties were researched, and molecular masses(ММ) of the fractions were defined. The polydispersity index was estimated. Based on experimental data, calculation of the size of a segment of Kuhn characterizing degree of an intramolecular orientation order and value of coefficients of the equation of Mark-Kuhn-Hauvink for viscometric and diffusion data were performed. It was demonstrated that introducing 20 mol % of the monomer with-CF3-groups does not lead to any changes in conformational properties of the macromolecules and does not change the degree of intramolecular orientational order(the Kuhn segment length). Optical characteristics of POA-F solutions are virtually similar to the corresponding values for POA prepared with the use of single amine-containing component-5,5-methylene bis(2-aminophenol). The received MM distribution for POA-F(prepolymer) provided the solubility of its films in alkaline solutions. The heat resistance(τ5 and τ10-temperatures corresponding to 5% and of 10% PBO-F mass loss of a polymer) of the powders and the films of PBO, PBO-F were determined. The electrophysical parameters-dielectric permittivity(ε) and dielectric loss tangent(tan δ) of the PBO-F films decreased down to 3.30 and 0.017, in comparison 3.40 and 0.025 for PBO respectively.展开更多
The feasibility of employing nanofiltration for the removal of chromium（VI） from wastewater was investigated. Poly （m-phenylene isophthalamide） （PMIA） was used to fabricate asymmetric nanofiltration membrane thr...The feasibility of employing nanofiltration for the removal of chromium（VI） from wastewater was investigated. Poly （m-phenylene isophthalamide） （PMIA） was used to fabricate asymmetric nanofiltration membrane through the phase-inversion technique. Scanning electron microscopy （SEM） and atomic force microscopy （AFM） were used to characterize the obtained membrane, and the both confirmed a much smoother surface which could reduce membrane fouling. The PMIA membrane showed different rejections to electrolytes in a sequence of Na2SO4 〉 MgSO4 〉 NaC1 〉 MgC12, which was similar to the sequence of the negatively charged nanofiltration membranes. Separation experiments on chromium（VI） solution were conducted at various operating conditions, such as feed concentration, applied pressure and pH. It is concluded that chromium（VI） could be effectively removed from chromiumcontaining wastewater by the PMIA nanofiltration membranes while maintaining their pollution resistance under alkaline condition.展开更多
Novel bio-based and biodegradable block copolymers were synthesized by "click" reaction between poly(L-lactide)(PLLA) and polyamide 4(PA4). Upon tuning the molar mass of PLLA block, the properties of copolym...Novel bio-based and biodegradable block copolymers were synthesized by "click" reaction between poly(L-lactide)(PLLA) and polyamide 4(PA4). Upon tuning the molar mass of PLLA block, the properties of copolymers and electrospun ultrafine fibers were investigated and compared with those of PLLA and PA4 blends. PLLA and PA4 were found incompatible and formed individual crystalline regions, along with reciprocal inhibition in crystallization. Electrospun fibers were highly hydrophobic, even if hydrophilic PA4 was the rich component. The crystallinity of either PLLA or PA4 decreased after electrospinning and PLLA-rich as-spun fibers were almost amorphous. Immersion tests proved that fibers of block copolymers were relatively homogeneous with micro-phase separation between PLLA and PA4. The fibrous structures of copolymers were different from those of the fibers electrospun from blends, for which sheath-core structure induced by macro-phase separation between homopolymers of PLLA and PA4 was confirmed by TEM, EDS, and XPS.展开更多
A series of new optically active poly（amide-imide）s were synthesized by direct polycondensation reaction of 4,4＇-diaminochalcone with several N-trimellitylimido-L-amino acids using a tosyl chloride （TsCl）, pyridi...A series of new optically active poly（amide-imide）s were synthesized by direct polycondensation reaction of 4,4＇-diaminochalcone with several N-trimellitylimido-L-amino acids using a tosyl chloride （TsCl）, pyridine （Py） and dimethylformamide （DMF） system as condensing agent. The resulting thermally stable poly（amide-imide）s were obtained in good to high yields and inherent viscosities ranging between 0.35 dL/g and 0.58 dL/g and were characterized with FTIR, IH-NMR, CHN, Ultraviolet, TGA and DTG techniques.展开更多
基金supported by the National Natural Science Foundation of China(21971177)the Natural Science Foundation of the Jiangsu Higher Education Institution of China(22KJA150004)+3 种基金the Suzhou Science and Technology Bureau(SZM2021008)the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutionsthe Jiangsu Key Laboratory of Advanced Functional Polymers Design and Application,Soochow University,Suzhou Medical and Industrial Cooperation Innovation Project(SZM2022011)the Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis and the Program of Innovative Research Team of Soochow University。
文摘Poly(ester amide)s(PEAs)represent promising biomaterials because of their well-balanced mechanical properties,biodegradability,and biocompatibility.However,practical applications of PEAs are still limited by challenges in functional versatility and environmental adaptability.Here,we present the first synthesis of periodic selenium-incorporated PEAs(Se-PEAs)via a rapid,catalyst-free selenol-yne click polymerization process.By harnessing the versatility of selenium,we achieved precise modulation of material properties.The resulting Se-PEAs demonstrated tunable mechanical behavior,spanning rigid plastics to elastomers,alongside exceptional thermal stability and high optical clarity.Programmable degradation profiles ensure long-term stability in physiological environments while facilitating rapid oxidative degradation at the end of the lifecycle.Surface selenoniumization further conferred robust antibacterial efficacy without compromising mechanical integrity.This multifunctionality positions Se-PEAs as transformative materials for biomedical implants,sustainable packaging,and high-refractiveindex optics.Our work advanced functional polymer design and underscored the potential of selenium chemistry in addressing global challenges in terms of plastic waste and ecological sustainability.
基金financially supported by the National Natural Science Foundation of China(Nos.22473105 and 22341302).
文摘This study uses all-atom molecular dynamics simulations to investigate the dislocation propagation, stress transmission, and mechanical properties in poly(p-phenylene terephthalamide) fibers under uniaxial tension. The results indicate that the dislocation propagates and the stress transfers not only along the fiber axis but also between adjacent molecular chains through hydrogen bonds, demonstrating their influence on the yield behavior. As the degree of polymerization increases, breakage of covalent bonds and interchain slippage contribute to the yield of fibers together. This work provides theoretical guidance for the design and manufacturing of high-performance fibers.
文摘Poly(m-phenylene isophthalamide)(PMIA),a key aromatic polyamide,is widely used for its outstanding mechanical strength,high thermal stability,and excellent insulation properties.However,different applications demand varying dielectric properties,so tailoring its dielectric per-formance is essential.PMIA was first synthesized in this study,followed by introducing pores and developing porous PMIA films and PMIA-based composites with reduced dielectric constants.Porous PMIA films were fabricated using the wet phase inversion process with N,N-dimethylac-etamide(DMAC)solvent and water as the non-solvent.The impact of casting solution composi-tion and coagulation bath temperature on pore structures was analyzed.A film produced with 18%PMIA and 5%LiCl in a 35℃coagulation bath achieved the lowest dielectric constant of 1.76 at 1 Hz,48%lower than the standard PMIA film,which had a tensile strength of 18.5 MPa and an initial degradation temperature of 320℃.
基金supported by the National Natural Science Foundation of China(22479022)the Natural Science Foundation of Liaoning Province(2020-MS-021)。
文摘Aqueous zinc metal batteries(ZMBs)are vital to potable electronics and electric energy infrastructures because of their high energy conversion efficiency,high energy density,and environmental friendliness.However,rampant zinc dendrite growth and side reactions on the Zn anode seriously impede the practical application of ZMBs.In this work,morpholine-crosslinked polyacrylamide hydrogel electrolytes(ploy(acrylamide),6m-PAM)are successfully developed to simultaneously regulate solvation shell to suppress side reactions and homogenize Zn^(2+)ion migration for dendrite-free ZMBs.Notably,the 6m-PAM electrolyte exhibits excellent mechanical strength of 50.6 kPa,high Zn^(2+)ion conductivity of 52 mS cm^(-1)at room temperature,and fast self-healing ability,providing stable and adaptable electrolyte-anode interfaces.Experimental and theoretical calculation results reveal that Zn^(2+)-N(morpholine)coordination interaction effectively reshapes the primary solvation shell of Zn^(2+),suppressing the activity of free water and Zn dendrites.As a result,the 6m-PAM electrolyte endows symmetric zinc cells with a long-term cycling life of 2000 h at 7.5 mA cm^(-2).Notably,Zn/Polyaniline(PANI)batteries equipped with 6m-PAM electrolytes also exhibit a high capacity of 124 mA h g^(-1)at 1 A g^(-1)and a long cycling life of 4000 times with a high-capacity retention of 98.3%,This functional crosslinked hydrogel electrolyte paves a new way to construct durable dendrite-free ZMBs.
基金the National Natural Science Foundation of China(Nos.22150410339,W2432012,22301233 and 22171218)the Ministry of Science and Technology China(No.wgxz2022188)。
文摘α-Chiral amides are common in pharmaceuticals,agrochemicals,natural products,and peptides,prompting the need for new synthetic methods.Here,we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesizeα-chiral amides from benzyl ammonium salts and isocyanates.The key to success is using a chiral 2,2-bipyridine ligand(-)-Ph-SBpy,enabling high yield(up to 95%)and enantiomeric ratio(up to 98:2 er)under mild conditions.Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate,enhancing selectivity and efficiency.The synthetic utility is showcased through transformations of the enantioenriched amides,and the mechanism and enantioselectivity are supported by experimental and computational studies.
文摘Herein,manganese(Mn)‑doped poly(1,5‑diaminonaphthalene)(PN)electrode material(Mn@PN)was synthesized via chemical oxidative polymerization.The material′s distinctive vesicular architecture enables rapid ion transport while maintaining the structural stability of the electrode under continuous charge‑discharge cycles.Electrochemical characterization under a three‑electrode system revealed exceptional rate capability:Mn@PN delivered an ultrahigh specific capacitance of 10318 F·g^(-1) at a low current density of 3 A·g^(-1) and retained 9415 F·g^(-1)(91.2%retention compared to the value at 3 A·g^(-1))even at an ultrahigh current density of 50 A·g^(-1).Moreover,the material exhibited 97.4%capacitance retention after 9000 cycles at 30 A·g^(-1),corresponding with a low capacitance decay rate of 0.003‰per cycle,significantly outperforming conventional conductive polymers like polyaniline(PANI).An asymmetric supercapacitor assembled with Mn@PN as the positive electrode(Mn@PN||AC)achieved an energy density of 328 Wh·kg^(-1) at 15 A·g^(-1) and retained 80.7%of its initial specific capacitance after 4000 cycles at 20 A·g^(-1).
基金supported by the Science Foundation of High-Level Talents of Wuyi University(Nos.2019AL017,2021AL002).
文摘Polymer-electrolyte-based solid-state Li metal batteries with high-voltage Ni-rich cathodes are promising energy storage technologies owing to their favorable security and high energy densities.However,operating in wide temperature range and at high voltage is a tough challenge for them.Herein,F/N donating fluorinated-amide-based plasticizers regulated polymer electrolyte capable of enabling high-voltage Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)batteries with excellent performance in wide temperature range is developed.F/N donating fluorinated-amide-based plasticizers significantly improve ionic conductivity(1.52 mS/cm at 30℃),enhance oxidation stability(5.0 V vs.Li^(+)/Li)and fabricate robust LiF/Li_(3)N-rich electrode-electrolyte interphases,which significantly improve the interface stability of Li metal anode and NCM811 cathode.The designed polymer electrolyte is nonflammable and has excellent dimensional stability at 200℃.Capitalizing on these advantageous attributes,the Li||NCM811 cells show excellent cycle stability and rate capability from−20℃ to 60℃ at high voltages(∼4.6 V),and under high-loading full cell condition,which display impressive capacity retention of 84.4%after 1000 cycles and ultrahigh capacity of 154.8 mAh/g at 10 C.This work provides a rational design strategy of polymer electrolytes for wide-temperature high-energy solid-state Li metal batteries.
基金supported by the National Natural Science Foundation of China(52433012)the National Key R&D Program of China(2024YFF1500300)the China Postdoctoral Science Foundation(2023M741201,2024T170286)。
文摘Conductive polymers have recently drawn tremendous attention due to their promising applications in electronic and energy-related devices.While p-type conductive polymers such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)have achieved commercialization,the development of stable,high-performance n-type polymers has lagged.Recently,the discovery of n-type polymer poly(benzodifurandione)(PBFDO)has greatly promoted the development and application of n-type conductive polymers.However,the synthesis process involves cumbersome post-processing,which greatly increases the cost and difficulty of mass production.Herein,a novel synthesis method for PBFDO has been developed,which was promoted by the combination of solvent dimethyl sulfoxide(DMSO)and acetic anhydride(Ac_(2)O).This method exploits the oxidative capability of DMSO,activated by Ac_(2)O,which can promote the keto-enol tautomerism of 3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione(BFDO)and induce the rapid polymerization.The resulting PBFDO ink exhibits a high electronic conductivity of more than 2000 S cm^(-1)and excellent ambient stability.Significantly,the additives and by-products remain in a liquid state during the polymerization process and possess low boiling points,allowing for the production of pure PBFDO films through straightforward heating and drying.Furthermore,this approach holds considerable promise for in situ polymerization,as functional conductive films can be prepared by merely combining the monomers with the DMSO/Ac_(2)O mixture and applying heat.This efficient,purification-free strategy represents a significant step toward the industrial application of the highperformance n-type conductive polymer PBFDO.
基金the financial support from the National Natural Science Foundation of China (No. 52072390)the National High-Level Talents Special Support Program (Leading Talent of Technological Innovation)+2 种基金the China Postdoctoral Science Foundation (No. 2023M743648)the Young Scientists Fund of the National Natural Science Foundation of China (No. 52302330)the support from the Shanghai Emperor of Cleaning Hi-Tech Co.,LTD
文摘In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still faced with defects such as low intrinsic ionic conductivity,a narrow electrochemical window,and poor thermal stability.A crosslinking and fluorination molecular design strategy toward PDOL is proposed to tackle the issues above.The amorphous crosslinked structure effectively improves ionic conductivity by inhibiting long-chain crystallization.Especially,the antioxidant–CF_(3)groups,stable crosslinked structure,and reduced terminal hydroxyl groups significantly enhance the electrochemical oxidation stability with a superb high-voltage window of 4.7 V.In addition,the designed electrolyte also exhibits obviously improved thermal stability with no deformation at 120°C for 5 min.Furthermore,the semi-solid NCM811||Li batteries exhibit a favourable capacity retention of 88.8%after 150 cycles at 0.5 C.Even assembled with NCM622 cathode working at 4.5 V,the semi-solid batteries can still show a satisfactory capacity retention of 85.3%after 100 cycles at 0.5 C.Also,a 0.1 Ah NCM811||Li pouch cell with active materials loading of 9 mg/cm2 demonstrates satisfactory cycling stability and working ability,which shows promising practical application prospects.
基金financially supported by the Jiangsu Forestry Science and Technology Innovation and Promotion Project(No.LYKJ-Nanjing[2022]02)the Jiangsu Agricultural Science and Technology Innovation Fund(No.CX(23)3090)。
文摘Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this study,a novel p H/glutathione dual-responsive pesticide delivery system was constructed through the synthesis of disulfide-bridged hollow mesoporous organosilica nanospheres(HMONs)via the St??ber method,followed by poly(acrylic acid)(PAA)coating through distillation-precipitation polymerization to form HMONs@PAA nanocomposites.The resulting abamectin-loaded system(Abamectin-HMONs@PAA)demonstrated a 12.73% pesticide loading capacity and significantly improved photostability,retaining twice as much active ingredient as free abamectin after 250 h of UV irradiation(36 W).Release studies revealed p H-and glutathione-dependent characteristics,with cumulative releases in acidic conditions exceeding those in neutral and alkaline environments by 18.66% and 40.98%,respectively,and a 14.2% increase in glutathione-containing solution(0.2 mmol·L^(-1) in 70% ethanol)after 97 h.Bioassays showed superior performance against Plutella xylostella,with a 13.33% reduction in survival rate compared to conventional suspension at equivalent dosage(40 mg·L^(-1)),while maintaining efficacy after extensive rainfall simulation(20 events over 10 days).This study provides a promising approach for developing environmentally responsive nanopesticides with enhanced durability and controlled-release properties,offering significant potential for sustainable crop protection.
基金the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(No.2023C01072)the Institute of Zhejiang University-Quzhou for their financial support。
文摘Poly(phenylene oxide)(PPO)exhibits excellent dielectric properties,making it an ideal substrate for high-frequency,high-speed copper-clad laminates.The phenolic hydroxyl group at the end of PPO plays a key role in its reactivity.Accurately quantifying the phenolic hydroxyl content in PPO is essential but challenging.In this study,we proposed a method for measuring the phenolic hydroxyl content of PPO using differential UV absorption spectroscopy.In alkaline solutions,the phenolic hydroxyl in PPO completely ionizes to form phenoxide ions,leading to a significant increase in UV absorbance at approximately 250 and 300 nm.Notably,the differential UV absorbance at approximately 300 nm was directly proportional to the phenolic hydroxyl concentration.Using 2,6-dimethylphenol as a standard,a calibration curve was established to relate the phenolic hydroxyl concentration to differential UV absorbance at approximately 300 nm,providing a precise and straightforward method for phenolic hydroxyl quantification in PPO with distinct advantages over conventional techniques.
文摘Although poly(urethane-urea)elastomers(PUEs)possess excellent mechanical properties and durability,their inherent flammability and inability to self-repair after damage significantly limits their applications in high-end fields.To address this challenge,this study employs a supramolecular chemistry approach by simultaneously incorporating multiple hydrogen bonds as dynamic cross-linking points and a phosphorus-nitrogen synergistic flame-retardant structure into the poly(urethane-urea)network.The multiple hydrogen bonds endow the material with efficient intrinsic self-healing capability,while the phosphorus-nitrogen flame retardant ensures outstanding thermal stability and flame resistance,leading to the successful synthesis of a high-performance multifunctional poly(urethane-urea)elastomer.Experimental results demonstrated that when the content of the flame retardant diethyl(2-((2-aminoethyl)amino)ethyl)phosphoramidate(DEPTA)was 10 wt%,the resulting PUE/10%DEPTA achieved a V-0 rating in the vertical burning test,with a limiting oxygen index(LOI)of 30%.Concurrently,the elastomer maintained good toughness,exhibiting a tensile strength of 27.3 MPa,an elongation at break of 601%,and a self-healing efficiency of up to 94.46%.This breakthrough shows significant promise for advanced engineering applications that demand fire safety,structural durability,and extended service life through self-repair.
基金financially supported by the National Key Research and Development Program of China(No.2021YFB3700300)the National Natural Science Foundation of China(Nos.52573017 and U21B2093)+1 种基金Key Research and Development Program of Ningbo(No.2022Z200)the Zhejiang Provincial Natural Science Foundation(No.LY23E030005)。
文摘Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardant strategies often compromise their mechanical properties,hindering their practical applications.Herein,a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)-based comonomer(DDP)was used to synthesize flame-retardant poly(ethylene furandicarboxylate-co-phosphaphenanthrene)(PEFDn).The covalent integration of DDP confers intrinsic flame retardancy,avoiding the plasticization and migration issues associated with additive-type systems.Upon thermal decomposition,the DOPO-derived moieties release phosphoric acid and radical scavengers,promoting char formation and suppressing flame propagation.Furthermore,density functional theory(DFT)calculations combined with non-covalent interaction(NCI)analysis revealed that DOPO dimer molecules adopt a stable parallel-displaced π-π stacking configu ration,potentially facilitating microphase separation and enhancing the energy dissipation capability.PEFD_(10)achieves a UL-94 V-0 rating while simultaneously increasing impact toughness from 1.5 kJ/m^(2) to 14.7 kJ/m^(2).Im portantly,PEFDn maintained acceptable oxygen-barrier properties.PEFD10 also exhibited high transparency and UV-shielding performance.The combination of intrinsic flame safety,im pact-toughness resistance,UV shielding,and an oxygen barrier ensures reliable protection of electrical components and long-term operational stability.The integration of multiple critical properties within a single bio-based material represents a novel approach fo r enabling sustainable polymer solutions for high-pe rformance electrical applications.
文摘Core-shell structured SiO2/poly（N-isopropylacrylamide） （SiO2/PNIPAM） microspheres were successfully fabricated through hydrolysis and condensation reaction of tertraethyl orthosilicate （TEOS） on the surface of PNIPAM template at 50 ~C. The PNIPAM template can be easily removed by water at room temperature so that SiO2 hollow microspheres were finally obtained. The transmission electron microscope and scanning electron microscope observations indicated that SiO2 hollow microspheres with an average diameter of 150 nm can be formed only if there are enough concentration of PNIPAM and TEOS, and the hy- drolysis time of TEOS. FTIR analysis showed that part of PNIPAM remained on the wall of SiO2 because of the strong interaction between PNIPAM and silica. This work provides a clean and efficient way to prepare hollow microspheres.
文摘A series of novel aromatic poly ( amide imide)s containing phthalazinone moieties were prepared from 2-(4-aminophenyl)-4-[3-methyl-4-(4-aminophenoxy)-2,3-phthalazinone-1], a novel diamine 1 with four diimide-dicarboxylic acids by Yamazaki phosphorylation method with the inherent viscosity of 0.36~0.65 dL/g. These polymers had high glass transition temperatures above 300C and they lost 10% weight between 426~475C in N2. The structure of diamine 1 and the polymers was confirmed by IR, 1H NMR and MS. The obtained polymers were readily soluble in polar solvents such as NMP, m-cresol etc. and easily cast into tough, flexible films. The X-ray indicated that they are all amorphous.
文摘Two novel heterocyclic diamine monomers: 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)phenyl] (2H)phthalazin-1-one and 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)-3,5-dimethylphenyl](2H)phthalazin-1-one were successfully synthesized from readily available heterocyclic bisphenol-like monomers in two steps in high yield. A series of novel poly(aryl ether amide)s containing the phthalazinone moiety were successfully prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents.
基金Funded by the Ministry of Education and Science of the Russian Federation(No.10.7608.2017/8.9).
文摘The polycondensation of the mixture of diamines 5,5-methylene bis(2-aminophenol) and 4,4-(hexafluoroisopropylidene)dianiline(molar ratio 0.8:0.2) with isophthaloyl dichloride was used to synthesize poly(amido-o-hydroxy amide)(POA-F)-new heat resistant binder of the composites for microelectronics. The copolymer was fractionated, its hydrodynamic, optical, and conformational properties were researched, and molecular masses(ММ) of the fractions were defined. The polydispersity index was estimated. Based on experimental data, calculation of the size of a segment of Kuhn characterizing degree of an intramolecular orientation order and value of coefficients of the equation of Mark-Kuhn-Hauvink for viscometric and diffusion data were performed. It was demonstrated that introducing 20 mol % of the monomer with-CF3-groups does not lead to any changes in conformational properties of the macromolecules and does not change the degree of intramolecular orientational order(the Kuhn segment length). Optical characteristics of POA-F solutions are virtually similar to the corresponding values for POA prepared with the use of single amine-containing component-5,5-methylene bis(2-aminophenol). The received MM distribution for POA-F(prepolymer) provided the solubility of its films in alkaline solutions. The heat resistance(τ5 and τ10-temperatures corresponding to 5% and of 10% PBO-F mass loss of a polymer) of the powders and the films of PBO, PBO-F were determined. The electrophysical parameters-dielectric permittivity(ε) and dielectric loss tangent(tan δ) of the PBO-F films decreased down to 3.30 and 0.017, in comparison 3.40 and 0.025 for PBO respectively.
基金supported by the High Technology Research and Development Program (863) of China(No. 2007AA06Z339)the National Key Technologies R&D Program of China (No. 2006BAD01B02-02,2006BAJ08B00)
文摘The feasibility of employing nanofiltration for the removal of chromium（VI） from wastewater was investigated. Poly （m-phenylene isophthalamide） （PMIA） was used to fabricate asymmetric nanofiltration membrane through the phase-inversion technique. Scanning electron microscopy （SEM） and atomic force microscopy （AFM） were used to characterize the obtained membrane, and the both confirmed a much smoother surface which could reduce membrane fouling. The PMIA membrane showed different rejections to electrolytes in a sequence of Na2SO4 〉 MgSO4 〉 NaC1 〉 MgC12, which was similar to the sequence of the negatively charged nanofiltration membranes. Separation experiments on chromium（VI） solution were conducted at various operating conditions, such as feed concentration, applied pressure and pH. It is concluded that chromium（VI） could be effectively removed from chromiumcontaining wastewater by the PMIA nanofiltration membranes while maintaining their pollution resistance under alkaline condition.
基金financially supported by the National Key Research and Development Program of China (Nos. 2017YFB0309301 and 2017YFB0309302)the Natural Science Foundation of Shanghai, China (No. 17ZR1407200)
文摘Novel bio-based and biodegradable block copolymers were synthesized by "click" reaction between poly(L-lactide)(PLLA) and polyamide 4(PA4). Upon tuning the molar mass of PLLA block, the properties of copolymers and electrospun ultrafine fibers were investigated and compared with those of PLLA and PA4 blends. PLLA and PA4 were found incompatible and formed individual crystalline regions, along with reciprocal inhibition in crystallization. Electrospun fibers were highly hydrophobic, even if hydrophilic PA4 was the rich component. The crystallinity of either PLLA or PA4 decreased after electrospinning and PLLA-rich as-spun fibers were almost amorphous. Immersion tests proved that fibers of block copolymers were relatively homogeneous with micro-phase separation between PLLA and PA4. The fibrous structures of copolymers were different from those of the fibers electrospun from blends, for which sheath-core structure induced by macro-phase separation between homopolymers of PLLA and PA4 was confirmed by TEM, EDS, and XPS.
文摘A series of new optically active poly（amide-imide）s were synthesized by direct polycondensation reaction of 4,4＇-diaminochalcone with several N-trimellitylimido-L-amino acids using a tosyl chloride （TsCl）, pyridine （Py） and dimethylformamide （DMF） system as condensing agent. The resulting thermally stable poly（amide-imide）s were obtained in good to high yields and inherent viscosities ranging between 0.35 dL/g and 0.58 dL/g and were characterized with FTIR, IH-NMR, CHN, Ultraviolet, TGA and DTG techniques.
