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
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
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
Corn starch(CS)is a renewable,biodegradable polysaccharide valued for its film-forming ability,yet native CS films exhibit lowmechanical strength,highwater sensitivity,and limited thermal stability.This study improves...Corn starch(CS)is a renewable,biodegradable polysaccharide valued for its film-forming ability,yet native CS films exhibit lowmechanical strength,highwater sensitivity,and limited thermal stability.This study improves CS-based films by blending with poly(vinyl alcohol)(PVA)or glycerol(GLY)and using citric acid(CA)as a green,non-toxic cross-linker.Composite films were prepared by casting CS–PVA or CS-GLY with CA at 0%-0.20%(w/w of starch).The influence of CA on physicochemical,mechanical,optical,thermal,and water barrier properties was evaluated.CA crosslinking markedly enhanced the tensile strength,water resistance,and thermal stability of CS-PVA films while increasing transparency in CS–GLY films.At 0.20%CA,the composite achieved 34.99MPa tensile strength,reducedwater vapor permeability,andminimized water uptake.FTIR confirmed ester bond formation between CAand hydroxyl groups of CS,PVA,and GLY,whereas thermal analysis showed higher decomposition temperatures and lower weight loss in crosslinked films.Increasing CA levels also decreased opacity and improved light transmittance,indicating greater homogeneity and reduced crystallinity.This dual-polymer matrix combined with a natural crosslinking strategy provides a sustainable route to high-performance,biodegradable CS-based packaging materials.展开更多
By the suspended condensation reaction of poly(choloromethylthiirane)with o-tolidine and o- dianisidine respectively, two newmicrobeads chelating resins were synthesized by usingγ-Fe_2O_3 asmagnetic core. Their adsor...By the suspended condensation reaction of poly(choloromethylthiirane)with o-tolidine and o- dianisidine respectively, two newmicrobeads chelating resins were synthesized by usingγ-Fe_2O_3 asmagnetic core. Their adsorption properties for Hg(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Pb(Ⅱ), Au(Ⅲ), Pd(Ⅱ), Pt (Ⅳ)and Ag(Ⅰ)were investigated. Themicrobeads posses excellent adsorbability for Hg(Ⅱ) and noble metalions, and predominantly adsorbed Pd(Ⅱ)or Hg(Ⅱ)in the coexistence ofCu(Ⅱ), Zn(Ⅱ)and Mg(Ⅱ).展开更多
Dielectric elastomers(DEs)have drawn much attention owing to their application prospects in artificial muscles and soft robotics,it is still a big challenge to prepare DEs with high electromechanical performances.This...Dielectric elastomers(DEs)have drawn much attention owing to their application prospects in artificial muscles and soft robotics,it is still a big challenge to prepare DEs with high electromechanical performances.This work reports a highly stretchable poly(thioether)-b-polysiloxane-b-poly(thioether)triblock copolymer based homogenous DEs with high electromechanical properties.The triblock copolymer(PSiPGE)was synthesized through the ring-opening polymerization(ROP)of phenyl glycidyl ether(PGE)and carbonyl sulfide(COS)catalyzed by silicon alkoxides.The dipoles(benzene rings)on the side groups of PSiPGE improved the dipole polarizations and the phase separation structure of this triblock copolymer enhanced the interfacial polarizations between poly(thioether)and polysiloxane,and thus improving the dielectric constant(ε',up to 5.8).In addition,the PSiPGE exhibited low elastic modulus(Y,0.04 MPa),and thus possessed high electromechanical sensitivity(β,~145 MPa^(-1)) which is much higher than that of most homogenous DEs.This work provides a new strategy to construct homogenous DEs with excellent electromechanical performances,leading to a greater application aspect in the actuated devices.展开更多
A novel cross-linking process using two high molecular weight aromatic poly（thioether）s, which were synthesized by the reactions of 4,4＇-thiobisbenzenethiol with 4,4＇-difluorobenzophenone and 4,4＇-difluorodipheny...A novel cross-linking process using two high molecular weight aromatic poly（thioether）s, which were synthesized by the reactions of 4,4＇-thiobisbenzenethiol with 4,4＇-difluorobenzophenone and 4,4＇-difluorodiphenylsulfone, respectively, and commercially available lower molecular weight poly（p-phenylene sulfide） was investigated. These reactions were carried out in bulk by the addition of silver tetrafluroborate and α,α＇-dibromo-p-xylene at 190℃ over a period of 45 min. Furthermore, the same procedure could be modified to cross-link compression-molded films of these three polymers. The thermal and solubility behaviors of these polymers before and after cross-linking reactions, are presented.展开更多
The synthesis of a thioether inserted, core-shell structured polymer from the scaffold of hyperbranched polyglycerol (PG) was described. PG was first allyl functionalized, and in the presence of AlBN, the allyl groups...The synthesis of a thioether inserted, core-shell structured polymer from the scaffold of hyperbranched polyglycerol (PG) was described. PG was first allyl functionalized, and in the presence of AlBN, the allyl groups further underwent radical addition to thiol compounds, thus thiol functional polyethylene oxide monomether (MPEO) were grafted onto PG. Similarly, 2-mercaptoethylammonium chloride was introduced onto PG via thiol addition, and the residual amino groups were further quaternized with decyl bromide, leading to an amphiphilic core-shell structure polymer. (c) 2007 De Cheng Wan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
A well-dispersed metallic palladium catalyst modified by polymer-anchored thioether ligands was used for the hydrogenation of cyclopentadiene to cyclopentene with high activity and selectivity in ambient condition. Th...A well-dispersed metallic palladium catalyst modified by polymer-anchored thioether ligands was used for the hydrogenation of cyclopentadiene to cyclopentene with high activity and selectivity in ambient condition. The evidences to show the modification of catalytic properties by polymer anchored ligands were given.展开更多
Ethyl cellulose(EC),an important biomass-based material,has excellent film-forming properties.Nevertheless,the high interchain hydrogen bond interaction leads to a high glass transition temperature of EC,which makes i...Ethyl cellulose(EC),an important biomass-based material,has excellent film-forming properties.Nevertheless,the high interchain hydrogen bond interaction leads to a high glass transition temperature of EC,which makes it too brittle to be used widely.The hydroxyl group on EC can form a supramolecular system in the form of a non-covalent bond with an effective plasticizer.In this study,an important vegetable-oil-based derivative named dimer fatty acid was used to prepare a novel special plasticizer for EC.Dimer-fatty-acid-based thioether polyol(DATP)was synthesized and used to modify ethyl cellulose films.The supramolecular composite films of DATP and ethyl cellulose were designed using the newly-formed van der Waals force.The thermal stability,morphology,hydrophilicity,and mechanical properties of the composite films were all tested.Pure EC is fragile,and the addition of DATP makes the ethyl cellulose films more flexible.The elongation at the break of EC supramolecular films increased and the tensile strength decreased with the increasing DATP content.The elongation at the break of EC/DATP(60/40)and EC/DATP(50/50)was up to 40.3%and 43.4%,respectively.Noticeably,the thermal initial degradation temperature of the film with 10%DATP is higher than that of pure EC,which may be attributed to the formation of a better supramolecular system in this composite film.The application of bio-based material(EC)is environmentally friendly,and the novel DATP can be used as a special and effective plasticizer to prepare flexible EC films,making it more widely used in energy,chemical industry,materials,agriculture,medicine,and other fields.展开更多
Although the efficiency of poly(ethylene terephthalate)(PET)degradation has been successfully improved by depolymerase engineering,mostly by using Goodfellow-PET(gf-PET)as a substrate,efforts to degrade unpretreated P...Although the efficiency of poly(ethylene terephthalate)(PET)degradation has been successfully improved by depolymerase engineering,mostly by using Goodfellow-PET(gf-PET)as a substrate,efforts to degrade unpretreated PET materials with high crystallinity remain insufficient.Here,we endeavored to improve the degradation capability of a WCCG mutant of leaf-branch compost cutinase(LCC)on a unpretreated PET substrate(crystallinity>40%)by employing iterative saturation mutagenesis.Using this method,we developed a high-throughput screening strategy appropriate for unpretreated substrates.Through extensive screening of residues around the substrate-binding groove,two variants,WCCG-sup1 and WCCG-sup2,showed good depolymerization capabilities with both high-(42%)and low-crystallinity(9%)substrates.The WCCG-sup1 variant completely depolymerized a commercial unpretreated PET product in 36 h at 72℃.In addition to enzyme thermostability and catalytic efficiency,the adsorption of enzymes onto substrates plays an important role in PET degradation.This study provides valuable insights into the structure-function relationship of LCC.展开更多
The increasing deployment of electronics in everyday life has generated great concerns regarding the effective disposal of waste from these components.Here,we focused on a facile sustainable and economical strategy to...The increasing deployment of electronics in everyday life has generated great concerns regarding the effective disposal of waste from these components.Here,we focused on a facile sustainable and economical strategy to provide ideas for this issue.This strategy relied on using appropriate mechanical treatment and sodium lignosulfonate coating to improve the dispersion and interfacial compatibility of bamboo fibers in poly(lactic acid).By optimising the particle size and concentration of sodium lignosulphonate,high value-added and green composites were prepared using sectional pressurization with a venting procedure.The treated composite displayed an ultra-smooth surface(roughness of 0.592 nm),impressive transient properties(disintegration and degradation behaviour after 30 d),and outstanding ultraviolet(UV)shielding properties(100%).These properties hold the promise of being an excellent substrate for electronic devices,especially for high-precision processing,transient electronics,and UV damage prevention.The satisfactory interfacial compatibility of the composites was confirmed by detailed characterisation regarding the related physicochemical properties.This investigation offers a sustainable approach for producing high value-added green composites from biomass and biomass-derived materials.展开更多
Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to p...Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to prevent degradation and side reactions.In the contribution,histidine N-thiocarboxyanhydride(His-NTA)is directly synthesized in aqueous solution without protection.With the self-catalysis of the imidazole side group,the ring-closing reaction to form His-NTA does not require any activating reagent(e.g.,phosphorus tribromide),which is elucidated by density functional theory(DFT)calculations.His-NTA directly polymerizes into PHis bearing unprotected imidazole groups with designable molecular weights(4.2-7.7 kg/mol)and low dispersities(1.10-1.19).Kinetic experiments and Monte Carlo simulations reveal the elementary reactions and the relationship between the conversion of His-NTA and time during polymerization.Block copolymerization of His-NTA with sarcosine N-thiocarboxyanhydride(Sar-NTA)demonstrate versatile construction of functional polypept(o)ides.The triblock copoly(amino acid)PHis-b-PSar-b-PHis is capable to reversibly coordinate with transition metal ions(Fe^(2+),Co^(2+),Ni^(2+),Cu^(2+)and Zn^(2+))to form pH-sensitive hydrogels.展开更多
The rising prevalence of drug-resistant Gram-positive pathogens,particularly methicillin-resistant Staphy-lococcus aureus(MRSA)and vancomycin-resistant Enterococci(VRE),poses a substantial clinical challenge.Biofilm-a...The rising prevalence of drug-resistant Gram-positive pathogens,particularly methicillin-resistant Staphy-lococcus aureus(MRSA)and vancomycin-resistant Enterococci(VRE),poses a substantial clinical challenge.Biofilm-associated infections exacerbate this problem due to their inherent antibiotic resistance and complex structure.Current antibiotic treatments struggle to penetrate biofilms and eradicate persister cells,leading to prolonged antibiotic use and increased resistance.Host defense peptides(HDPs)have shown promise,but their clinical application is limited by factors such as enzymatic degradation and difficulty in largescale preparation.Synthetic HDP mimics,such as poly(2-oxazoline),have emerged as effective alter-natives.Herein,we found that the poly(2-oxazoline),Gly-POX_(20),demonstrated rapid and potent activity against clinically isolated multidrug-resistant Gram-positive strains.Gly-POX_(20) showed greater stability under physiological conditions compared to natural peptides,including resistance to protease degradation.Importantly,Gly-POX_(20) inhibited biofilm formation and eradicated mature biofilm and demonstrated superior in vivo therapeutic efficacy to vancomycin in a MRSA biofilm-associated mouse keratitis model,suggesting its potential as a novel antimicrobial agent against drug-resistant Gram-positive bacteria,especially biofilm-associated infections.展开更多
Objectives:Monitoring of Cancer Antigen 125(CA125)during ovarian cancer(OC)maintenance treatment with poly(ADP-ribose)polymerase inhibitors(PARPis)may be insufficient when using Gynecologic Cancer Intergroup(GCIG)bioc...Objectives:Monitoring of Cancer Antigen 125(CA125)during ovarian cancer(OC)maintenance treatment with poly(ADP-ribose)polymerase inhibitors(PARPis)may be insufficient when using Gynecologic Cancer Intergroup(GCIG)biochemical progression criteria.This study aimed to evaluate the usefulness of CA125 monitoring in detecting OC recurrence during PARPis maintenance treatment.Methods:This multicenter retrospective cohort study included patients with primary OC who achieved complete or partial response after first-line platinum-based chemotherapy followed by PARPis maintenance treatment.Progressionwas defined using Response EvaluationCriteria in Solid Tumors(RECIST)and GCIG biochemical criteria.New biochemical progression definitions,based on CA125 nadir determined using receiver operating characteristic(ROC)curve analysis,were proposed.Concordance between radiological and biochemical progression was assessed.Results:Of 142 patients,progression was detected in 54(38.03%)and 29(20.42%)using RECIST and GCIG criteria,respectively.The sensitivity,specificity,positive predictive value(PPV),and negative predictive value(NPV)of the GCIG criteria were 53.70%[95%confidence interval(CI):39.61%–67.38%],100.00%[95%CI:95.91%–100.00%],100.00%[95%CI:88.10%–100.00%]and 77.88%[95%CI:72.54%–82.43%],respectively.A cut-off of 1.59×nadir achieved 88.90%sensitivity and 87.20%specificity[Area Under Curve(AUC):91.10%,95%CI:84.70%–97.40%]with a false positive rate(FPR)of 12.67%.Defining biochemical progression as an increase in CA125 of≥3×nadir achieved sensitivity,specificity,PPV,NPV,and FPR of 79.63%[95%CI:66.47%–89.37%],98.86%[95%CI:93.83%–99.97%],97.73%[95%CI:85.91%–99.67%],88.78%[95%CI:82.35%–93.06%],and 1.14%,respectively.Diagnostic accuracy was higher using the≥3×nadir criterion compared with GCIG definition(91.55%vs.82.39%).Conclusion:GCIG biochemical progression criteria during PARPis maintenance treatment after first-line chemotherapymissed 46.3%of progressing patients.Anewcriterion—CA125≥3×nadir—improves sensitivity and NPV,while maintaining high specificity,offering a simple and practical approach for clinical implementation.展开更多
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 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.
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.
基金supported through RIIM Competition funding from the Indonesia Endowment Fund for Education Agency,Ministry of Finance of the Republic of Indonesia and National Research and Innovation Agency of Indonesia according to the contract number:61/IV/KS/5/2023 and 2131/UN6.3.1/PT.00/2023.
文摘Corn starch(CS)is a renewable,biodegradable polysaccharide valued for its film-forming ability,yet native CS films exhibit lowmechanical strength,highwater sensitivity,and limited thermal stability.This study improves CS-based films by blending with poly(vinyl alcohol)(PVA)or glycerol(GLY)and using citric acid(CA)as a green,non-toxic cross-linker.Composite films were prepared by casting CS–PVA or CS-GLY with CA at 0%-0.20%(w/w of starch).The influence of CA on physicochemical,mechanical,optical,thermal,and water barrier properties was evaluated.CA crosslinking markedly enhanced the tensile strength,water resistance,and thermal stability of CS-PVA films while increasing transparency in CS–GLY films.At 0.20%CA,the composite achieved 34.99MPa tensile strength,reducedwater vapor permeability,andminimized water uptake.FTIR confirmed ester bond formation between CAand hydroxyl groups of CS,PVA,and GLY,whereas thermal analysis showed higher decomposition temperatures and lower weight loss in crosslinked films.Increasing CA levels also decreased opacity and improved light transmittance,indicating greater homogeneity and reduced crystallinity.This dual-polymer matrix combined with a natural crosslinking strategy provides a sustainable route to high-performance,biodegradable CS-based packaging materials.
基金Funded by Natural Science Foundation of Hubei Province (NO.2000J022)
文摘By the suspended condensation reaction of poly(choloromethylthiirane)with o-tolidine and o- dianisidine respectively, two newmicrobeads chelating resins were synthesized by usingγ-Fe_2O_3 asmagnetic core. Their adsorption properties for Hg(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Pb(Ⅱ), Au(Ⅲ), Pd(Ⅱ), Pt (Ⅳ)and Ag(Ⅰ)were investigated. Themicrobeads posses excellent adsorbability for Hg(Ⅱ) and noble metalions, and predominantly adsorbed Pd(Ⅱ)or Hg(Ⅱ)in the coexistence ofCu(Ⅱ), Zn(Ⅱ)and Mg(Ⅱ).
基金National Natural Science Foundation of China(Nos.51973190 and 21774108)Zhejiang Provincial Department of Science and Technology(No.2020R52006)for financial supports。
文摘Dielectric elastomers(DEs)have drawn much attention owing to their application prospects in artificial muscles and soft robotics,it is still a big challenge to prepare DEs with high electromechanical performances.This work reports a highly stretchable poly(thioether)-b-polysiloxane-b-poly(thioether)triblock copolymer based homogenous DEs with high electromechanical properties.The triblock copolymer(PSiPGE)was synthesized through the ring-opening polymerization(ROP)of phenyl glycidyl ether(PGE)and carbonyl sulfide(COS)catalyzed by silicon alkoxides.The dipoles(benzene rings)on the side groups of PSiPGE improved the dipole polarizations and the phase separation structure of this triblock copolymer enhanced the interfacial polarizations between poly(thioether)and polysiloxane,and thus improving the dielectric constant(ε',up to 5.8).In addition,the PSiPGE exhibited low elastic modulus(Y,0.04 MPa),and thus possessed high electromechanical sensitivity(β,~145 MPa^(-1)) which is much higher than that of most homogenous DEs.This work provides a new strategy to construct homogenous DEs with excellent electromechanical performances,leading to a greater application aspect in the actuated devices.
文摘A novel cross-linking process using two high molecular weight aromatic poly（thioether）s, which were synthesized by the reactions of 4,4＇-thiobisbenzenethiol with 4,4＇-difluorobenzophenone and 4,4＇-difluorodiphenylsulfone, respectively, and commercially available lower molecular weight poly（p-phenylene sulfide） was investigated. These reactions were carried out in bulk by the addition of silver tetrafluroborate and α,α＇-dibromo-p-xylene at 190℃ over a period of 45 min. Furthermore, the same procedure could be modified to cross-link compression-molded films of these three polymers. The thermal and solubility behaviors of these polymers before and after cross-linking reactions, are presented.
文摘The synthesis of a thioether inserted, core-shell structured polymer from the scaffold of hyperbranched polyglycerol (PG) was described. PG was first allyl functionalized, and in the presence of AlBN, the allyl groups further underwent radical addition to thiol compounds, thus thiol functional polyethylene oxide monomether (MPEO) were grafted onto PG. Similarly, 2-mercaptoethylammonium chloride was introduced onto PG via thiol addition, and the residual amino groups were further quaternized with decyl bromide, leading to an amphiphilic core-shell structure polymer. (c) 2007 De Cheng Wan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
文摘A well-dispersed metallic palladium catalyst modified by polymer-anchored thioether ligands was used for the hydrogenation of cyclopentadiene to cyclopentene with high activity and selectivity in ambient condition. The evidences to show the modification of catalytic properties by polymer anchored ligands were given.
基金supported by Jiangsu Province Biomass Energy and Materials Laboratory,China(Grant No.JSBEM-S-202007).
文摘Ethyl cellulose(EC),an important biomass-based material,has excellent film-forming properties.Nevertheless,the high interchain hydrogen bond interaction leads to a high glass transition temperature of EC,which makes it too brittle to be used widely.The hydroxyl group on EC can form a supramolecular system in the form of a non-covalent bond with an effective plasticizer.In this study,an important vegetable-oil-based derivative named dimer fatty acid was used to prepare a novel special plasticizer for EC.Dimer-fatty-acid-based thioether polyol(DATP)was synthesized and used to modify ethyl cellulose films.The supramolecular composite films of DATP and ethyl cellulose were designed using the newly-formed van der Waals force.The thermal stability,morphology,hydrophilicity,and mechanical properties of the composite films were all tested.Pure EC is fragile,and the addition of DATP makes the ethyl cellulose films more flexible.The elongation at the break of EC supramolecular films increased and the tensile strength decreased with the increasing DATP content.The elongation at the break of EC/DATP(60/40)and EC/DATP(50/50)was up to 40.3%and 43.4%,respectively.Noticeably,the thermal initial degradation temperature of the film with 10%DATP is higher than that of pure EC,which may be attributed to the formation of a better supramolecular system in this composite film.The application of bio-based material(EC)is environmentally friendly,and the novel DATP can be used as a special and effective plasticizer to prepare flexible EC films,making it more widely used in energy,chemical industry,materials,agriculture,medicine,and other fields.
文摘Although the efficiency of poly(ethylene terephthalate)(PET)degradation has been successfully improved by depolymerase engineering,mostly by using Goodfellow-PET(gf-PET)as a substrate,efforts to degrade unpretreated PET materials with high crystallinity remain insufficient.Here,we endeavored to improve the degradation capability of a WCCG mutant of leaf-branch compost cutinase(LCC)on a unpretreated PET substrate(crystallinity>40%)by employing iterative saturation mutagenesis.Using this method,we developed a high-throughput screening strategy appropriate for unpretreated substrates.Through extensive screening of residues around the substrate-binding groove,two variants,WCCG-sup1 and WCCG-sup2,showed good depolymerization capabilities with both high-(42%)and low-crystallinity(9%)substrates.The WCCG-sup1 variant completely depolymerized a commercial unpretreated PET product in 36 h at 72℃.In addition to enzyme thermostability and catalytic efficiency,the adsorption of enzymes onto substrates plays an important role in PET degradation.This study provides valuable insights into the structure-function relationship of LCC.
基金supported by the National Natural Science Foundation of China(Nos.31971741 and 31760195)the Yunnan Fundamental Research Projects(Nos.2018FB066 and 202001AT070141)the Yunnan Agricultural Basic Research Special Projects(No.202101BD070001-086).
文摘The increasing deployment of electronics in everyday life has generated great concerns regarding the effective disposal of waste from these components.Here,we focused on a facile sustainable and economical strategy to provide ideas for this issue.This strategy relied on using appropriate mechanical treatment and sodium lignosulfonate coating to improve the dispersion and interfacial compatibility of bamboo fibers in poly(lactic acid).By optimising the particle size and concentration of sodium lignosulphonate,high value-added and green composites were prepared using sectional pressurization with a venting procedure.The treated composite displayed an ultra-smooth surface(roughness of 0.592 nm),impressive transient properties(disintegration and degradation behaviour after 30 d),and outstanding ultraviolet(UV)shielding properties(100%).These properties hold the promise of being an excellent substrate for electronic devices,especially for high-precision processing,transient electronics,and UV damage prevention.The satisfactory interfacial compatibility of the composites was confirmed by detailed characterisation regarding the related physicochemical properties.This investigation offers a sustainable approach for producing high value-added green composites from biomass and biomass-derived materials.
基金financially supported by the National Natural Science Foundation of China(Nos.22271252 and 22201105)。
文摘Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to prevent degradation and side reactions.In the contribution,histidine N-thiocarboxyanhydride(His-NTA)is directly synthesized in aqueous solution without protection.With the self-catalysis of the imidazole side group,the ring-closing reaction to form His-NTA does not require any activating reagent(e.g.,phosphorus tribromide),which is elucidated by density functional theory(DFT)calculations.His-NTA directly polymerizes into PHis bearing unprotected imidazole groups with designable molecular weights(4.2-7.7 kg/mol)and low dispersities(1.10-1.19).Kinetic experiments and Monte Carlo simulations reveal the elementary reactions and the relationship between the conversion of His-NTA and time during polymerization.Block copolymerization of His-NTA with sarcosine N-thiocarboxyanhydride(Sar-NTA)demonstrate versatile construction of functional polypept(o)ides.The triblock copoly(amino acid)PHis-b-PSar-b-PHis is capable to reversibly coordinate with transition metal ions(Fe^(2+),Co^(2+),Ni^(2+),Cu^(2+)and Zn^(2+))to form pH-sensitive hydrogels.
基金financially supported by the National Key Research and Development Program of China(no.2022YFC2303100)National Natural Science Foundation of China(nos.T2325010,22305082,52203162,and 22075078)+1 种基金Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism(Shanghai Municipal Education Commission),the Fundamental Research Funds for the Central Universities(nos.JKVD1241029 and JKD01241701)Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry(Changchun Institute of Applied Chemistry,Chinese Academy of Sciences),the Open Project of Engineering Research Center of Dairy Quality and Safety Control Technology(Ministry of Education,no.R202201).
文摘The rising prevalence of drug-resistant Gram-positive pathogens,particularly methicillin-resistant Staphy-lococcus aureus(MRSA)and vancomycin-resistant Enterococci(VRE),poses a substantial clinical challenge.Biofilm-associated infections exacerbate this problem due to their inherent antibiotic resistance and complex structure.Current antibiotic treatments struggle to penetrate biofilms and eradicate persister cells,leading to prolonged antibiotic use and increased resistance.Host defense peptides(HDPs)have shown promise,but their clinical application is limited by factors such as enzymatic degradation and difficulty in largescale preparation.Synthetic HDP mimics,such as poly(2-oxazoline),have emerged as effective alter-natives.Herein,we found that the poly(2-oxazoline),Gly-POX_(20),demonstrated rapid and potent activity against clinically isolated multidrug-resistant Gram-positive strains.Gly-POX_(20) showed greater stability under physiological conditions compared to natural peptides,including resistance to protease degradation.Importantly,Gly-POX_(20) inhibited biofilm formation and eradicated mature biofilm and demonstrated superior in vivo therapeutic efficacy to vancomycin in a MRSA biofilm-associated mouse keratitis model,suggesting its potential as a novel antimicrobial agent against drug-resistant Gram-positive bacteria,especially biofilm-associated infections.
文摘Objectives:Monitoring of Cancer Antigen 125(CA125)during ovarian cancer(OC)maintenance treatment with poly(ADP-ribose)polymerase inhibitors(PARPis)may be insufficient when using Gynecologic Cancer Intergroup(GCIG)biochemical progression criteria.This study aimed to evaluate the usefulness of CA125 monitoring in detecting OC recurrence during PARPis maintenance treatment.Methods:This multicenter retrospective cohort study included patients with primary OC who achieved complete or partial response after first-line platinum-based chemotherapy followed by PARPis maintenance treatment.Progressionwas defined using Response EvaluationCriteria in Solid Tumors(RECIST)and GCIG biochemical criteria.New biochemical progression definitions,based on CA125 nadir determined using receiver operating characteristic(ROC)curve analysis,were proposed.Concordance between radiological and biochemical progression was assessed.Results:Of 142 patients,progression was detected in 54(38.03%)and 29(20.42%)using RECIST and GCIG criteria,respectively.The sensitivity,specificity,positive predictive value(PPV),and negative predictive value(NPV)of the GCIG criteria were 53.70%[95%confidence interval(CI):39.61%–67.38%],100.00%[95%CI:95.91%–100.00%],100.00%[95%CI:88.10%–100.00%]and 77.88%[95%CI:72.54%–82.43%],respectively.A cut-off of 1.59×nadir achieved 88.90%sensitivity and 87.20%specificity[Area Under Curve(AUC):91.10%,95%CI:84.70%–97.40%]with a false positive rate(FPR)of 12.67%.Defining biochemical progression as an increase in CA125 of≥3×nadir achieved sensitivity,specificity,PPV,NPV,and FPR of 79.63%[95%CI:66.47%–89.37%],98.86%[95%CI:93.83%–99.97%],97.73%[95%CI:85.91%–99.67%],88.78%[95%CI:82.35%–93.06%],and 1.14%,respectively.Diagnostic accuracy was higher using the≥3×nadir criterion compared with GCIG definition(91.55%vs.82.39%).Conclusion:GCIG biochemical progression criteria during PARPis maintenance treatment after first-line chemotherapymissed 46.3%of progressing patients.Anewcriterion—CA125≥3×nadir—improves sensitivity and NPV,while maintaining high specificity,offering a simple and practical approach for clinical implementation.
