In this study,a series of poly(ethylene succinate)-b-poly(butylene carbonate)(PES-b-PBC)multiblock copolymers were prepared through the chain-extension reaction of hydroxyl-terminated PES(PES-OH)and hydroxyl-terminate...In this study,a series of poly(ethylene succinate)-b-poly(butylene carbonate)(PES-b-PBC)multiblock copolymers were prepared through the chain-extension reaction of hydroxyl-terminated PES(PES-OH)and hydroxyl-terminated PBC(PBC-OH)prepolymers with 1,6-hexmethylene diisocyanate(HDI)as a chain extender.The effects of the prepolymer molecular weight and content on the structure and application properties of the PES-b-PBC copolymers were systematically investigated using various techniques.It was found that the compatibility of PES and PBC blocks in PES-b-PBC copolymers can be greatly enhanced by lowering the length of the prepolymers,and the amorphous phase of the PES and PBC chain segments in the PES-b-PBC copolymer would transform from immiscibility and partial miscibility to miscibility when the number-average molecular weight(M_(n))of the PES-OH and PBC-OH prepolymers is less than 2000 g/mol.Only the crystal structure of bare PES can be observed in the wide-angle X-ray diffraction(WAXD)spectrum of the PES-b-PBC copolymers,but their crystallinity degrees were found to decrease with increasing PBC fraction.The thermal behavior,crystallization performance,rheological properties,mechanical properties,and degradation properties of the PES-b-PBC multiblock copolymers can be easily modulated by altering the block length and composition of the prepolymers,offering potential applications in biodegradable materials.展开更多
Poly(ethylene succinate)(PES),a promising biodegradable polyester with cost advantages,suffers from inherently slow crystallization kinetics,which severely limits its processability and practical applications.To addre...Poly(ethylene succinate)(PES),a promising biodegradable polyester with cost advantages,suffers from inherently slow crystallization kinetics,which severely limits its processability and practical applications.To address this challenge,this study explored the use of commercially available,low-cost,and food-safe sugar alcohols,including Xylitol(Xy),D-sorbitol(DS),and D-mannitol(DM),as effective nucleating agents for PES.Remarkably,all three polyols significantly enhanced the nucleation and crystallization ability of PES,with DM exhibiting the most pronounced effect.DM increased the crystallization temperature by up to 23.9°C and accelerated the overall crystallization rate by more than 13-fold at only 0.5 wt%loading level.Through a combination of differential scanning calorimetry(DSC),polarized optical microscopy(POM),and wide-angle X-ray diffraction(WAXD)analyses,we revealed that DM promotes PES crystallization via a dual mechanism:epitaxial templating facilitated by excellent lattice matching,and enhanced chain adjustment through intermolecular hydrogen-bonding interactions.In contrast,Xy and DS primarily function through hydrogen-bonding interactions.This work not only identifies DM as a highly efficient,economical,and industrially viable nucleating agent for PES,but also provides fundamental insights into the role of the molecular structure and crystallization ability of nucleating agents in regulating polymer crystallization.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
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
In this study,composite films consisting of polylactic acid(PLA),ethyl cellulose(EC),and zein were prepared by solution casting method,and their performance and application in chilled fresh meat preservation were inve...In this study,composite films consisting of polylactic acid(PLA),ethyl cellulose(EC),and zein were prepared by solution casting method,and their performance and application in chilled fresh meat preservation were investigated.The results showed that the three materials had satisfactory compatibility in the composite film.Addition of EC and zein effectively improved the mechanical properties,thermodynamic properties,surface hydrophilicity,oxygen permeability,and degradation properties of PLA films.When the ratio of PLA to EC was 3:7,the tensile strength and elongation at break reached maximum values of 16.6 MPa and 30.5%,respectively.Moreover,under different conditions,the composite film exhibited better degradability than the PLA film.The composite film with a 3:7 ratio of PLA to EC had the best performance,with a degradation rate of 21.75%after 84 days.Chilled fresh meat wrapped with the composite film showed significantly improved antioxidant,antibacterial,and water-holding properties.展开更多
The membrane aeration biofilm reactor(MABR)represents an innovative approach to wastewater treatment,integrating gas separation membranes with biofilm process and demonstrating effectiveness in treating wastewater ric...The membrane aeration biofilm reactor(MABR)represents an innovative approach to wastewater treatment,integrating gas separation membranes with biofilm process and demonstrating effectiveness in treating wastewater rich in ammonia nitrogen.In this system,hollow fiber membranes are essential,serving as a substrate for biofilm attachment while facilitating oxygen transfer to microorganisms through aeration,hydrophobic microporous membranes are utilized in MABR applications.This study focuses on the use of poly-4-methyl-1-pentene(PMP)hollow fiber membranes,which exhibit superior oxygen permeation capabilities compared to traditional hydrophobic microporous membranes.To overcome the challenges posed by the hydrophobic nature and low bubble point of PMP microporous membranes,a hydrophilic modification was conducted using dopamine/poly(ethyleneimine)(DOPA/PEI)co-deposition to enhance microbial adhesion on the membrane surface.The composite membrane modified with DOPA/PEI exhibited an approximately 20%higher NH_(4)^(+)-N removal efficiency than the unmodified membrane.These findings suggest that the incorporation of DOPA/PEI significantly improves MABR performance,underscoring its potential for further research and development in membrane technology for MABR.展开更多
Poly(octamethylene citrate)(POC)is a promising bioelastomer material in the biomedical field.However,its thermosetting nature poses a significant challenge to processing and molding,especially manufacturing the POC-ba...Poly(octamethylene citrate)(POC)is a promising bioelastomer material in the biomedical field.However,its thermosetting nature poses a significant challenge to processing and molding,especially manufacturing the POC-based elastomer particles as potential,degradable and toughened fillers.Firstly,a Pickering emulsion with a pre-polymer(pre-POC)solution in dimethyl carbonate as a dispersed oil phase,a Pullulan(PUL)aqueous solution as a continuous water phase,and chitin nanocrystal(ChiNC)as a particle-type emulsifier was constructed.Secondly,the POC-based core/shell structured microspheres were prepared by spray-drying of the emulsions,and characterized by a scanning electron microscope and a transmission electron microscope.Finally,the POC-based core/shell structured microspheres were used as elastomer fillers to strengthen and toughen a chitosan film,resulting in 26%increase in the tensile strength and 45%increase in the strain at break;the POC-based core/shell structured microsphere as a double-layer drug release system was built in which the hydrophilic drug of tetracycline hydrochloride(TCH)was released from the outer layer and the hydrophobic drug of curcumin was released from the inner layer,roughly following the Ritger-Peppas model.展开更多
Dimethyl sulfoxide(DMSO)possessing strong solvency and high boiling point is a very important aprotic polar solvent in organic and polymer synthesis.Notably,it is also a useful synthon in organic chemistry.However,the...Dimethyl sulfoxide(DMSO)possessing strong solvency and high boiling point is a very important aprotic polar solvent in organic and polymer synthesis.Notably,it is also a useful synthon in organic chemistry.However,the direct incorporation of DMSO in polymer synthesis remains challenging.In this work,DMSO was successfully converted to nitrogen-containing heterocyclic polymers as a monomer via multicomponent polymerizations(MCPs)with dialdehydes and diamines in the presence of K_(2)S_(2)O_(8)/t-BuOK at 120℃in 6 h.A series of poly(phenylquinoline)s with high M_(w)values(up to 5.11×10^(4))were obtained in satisfactory yields(up to 82%),performing good solubility,good thermal and morphological stability as well as excellent film-forming ability.The thin films of poly(phenylquinoline)s exhibit high refractive index value in a wide wavelength range of 400–1700 nm.Thus,this work not only enriches the family of MCPs but also provides an efficient strategy for the conversion of DMSO into functional polymeric materials that are potentially applicable in diverse areas.展开更多
The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by...The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by sulfonation of ASIBS with acetyl sulfate.The hydrophilic ionic channels were generated for proton exchange membranes(PEMs)by ion aggregation of-SO_(3)H groups and microphase separation between hydrophobic polyisobutylene and hydrophilic sulfonated poly(α-methyl styrene)segments in S-ASIBS.The proton transport ability was improved while oxidative stability was decreased by increasing SP in S-ASIBS.The appropriate SP of about 12.7 mol%in S-ASIBS provides the available PEMs with high proton transport ability,low methanol permeability and good oxidative stability.The absence of active tertiary hydrogen atoms along S-ASIBS copolymer chains avoids their attack by peroxy radicals.The residual rates of weight(RW)and proton conductivity(Rσ)of S-ASIBS-12.7 membrane after oxidation treatment for 916 h were 84.3%and 88.1%respectively,near to those of commercial Nafion 117(RW=87.9%,Rσ=90.3%).The membrane electrode assembly(MEA)could be prepared by using various S-ASIBS as PEMs for direct methanol fuel cell.The single cell with S-ASIBS-12.7 MEA behaves high performance of open circuit voltage(OCV)of 548 mV and peak power density(Pmax)of 36.1 mW·cm^(-2),which is similar to those of Nafion 117(OCV=506 mV,P_(max)=35.6 mW·cm^(-2)).To the best of our knowledge,this is the first example of advanced S-ASIBS membrane with high proton conductivity,excellent fuel barrier property and remarkable oxidative stability for promising PEMs.展开更多
The synthesis of polyurethanes(PUs)from the reaction of low molecular weight poly(ethylene carbonate)diol(PECD)is rarely investigated.This work reports a novel PU with excellent mechanical properties from the solution...The synthesis of polyurethanes(PUs)from the reaction of low molecular weight poly(ethylene carbonate)diol(PECD)is rarely investigated.This work reports a novel PU with excellent mechanical properties from the solution polymerization of 4,4-diphenylmethane diisocyanate(MDI)with PECD that was derived from the copolymerization of carbon dioxide(CO_(2))and ethylene oxide(EO).The tensile strength,the elongation at break and 300%constant tensile strength of the PECD-PU were up to 66±2 MPa,880%±50%and 13 MPa,respectively,higher than the control PUs from the reaction of MDI with commercial polyethers or polyesters.The PECD-PU with high CO_(2) carbonate content exhibited good solvent resistance and chemical stability.Of importance,the mechanical properties and chemical resistance of PECD-PU were significantly enhanced with the increasing content of CO_(2),i.e.,the carbonate unit in PECD.This work provides comprehensive properties of PECD-derived PUs,indicating that PECD is a competitive precursor for the preparation of PU and has broad application prospects.展开更多
Compatibilization is crucial for the blending of immiscible polymers to develop high-performance composites;however,traditional compatibilization by copolymers(pre-made or in-situ generation)suffers from weak interfac...Compatibilization is crucial for the blending of immiscible polymers to develop high-performance composites;however,traditional compatibilization by copolymers(pre-made or in-situ generation)suffers from weak interface anchoring,and inorganic particles have gained extensive attention recently owing to their large interfacial desorption energy,while their low affinity to bulk components is a drawback.In this study,an interfacial atom transfer radical polymerization(ATRP)technique was employed to grow polystyrene(PS)and poly(2-hydroxyethyl methacrylate)(PHEMA)simultaneously on different hemispheres of Br-functionalized SiO_(2) nanoparticles to stabilize a Pickering emulsion,whereby a brush-type Janus nanoparticle(SiO_(2)@JNP)was developed.The polymer brushes were well-characterized,and the Janus feature was validated by transmission electron microscope(TEM)observation of the sole hemisphere grafting of SiO_(2)-PS as a control sample.SiO_(2)@JNP was demonstrated to be an efficient compatibilizer for a PS/poly(methyl methacrylate)(PMMA)immiscible blend,and the droplet-matrix morphology was significantly refined.The mechanical strength and toughness of the blend were synchronously enhanced at a low content SiO_(2)@JNP optimized~0.9 wt%,with the tensile strength,elongation at break and impact strength increased by 17.7%,26.6%and 19.6%,respectively.This enhancement may be attributed to the entanglements between the grafted polymer brushes and individual components that improve the particle-bulk phase affinity and enforce interfacial adhesion.展开更多
Poly(ethylene 2,5-furandicarboxylate)(PEF),a bioplastic synthesized via the polymerization of 2,5-furandicarboxylic acid(FDCA)with ethylene glycol,can be served as a substitute to petroleum-based polyethylene terephth...Poly(ethylene 2,5-furandicarboxylate)(PEF),a bioplastic synthesized via the polymerization of 2,5-furandicarboxylic acid(FDCA)with ethylene glycol,can be served as a substitute to petroleum-based polyethylene terephthalate(PET)due to its enhanced material properties.However,the fabrication of PEF with stable and desirable properties is still a challenge,largely due to the impurities in FDCA.In this study,a highly efficient purification strategy for FDCA was proposed,utilizing a dioxane/H_(2)O binary solvent system for effective crystallization.Furthermore,PEFs were synthesized from FDCA with varying impurity and the effects of these impurities were systematically characterized.The results revealed that impurities in FDCA could result in PEFs with relatively poor thermal properties.This study provides crucial insights for the impact of impurities on PEF properties and FDCA purification.展开更多
Electrocatalytic valorization of disused poly(ethylene terephthalate)(PET)plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading,but it faces challenge...Electrocatalytic valorization of disused poly(ethylene terephthalate)(PET)plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading,but it faces challenges in the development of efficient catalysts for PET-derived ethylene glycol(EG)electrooxidation.Herein,we proposed pyramid arrays on sheet Fe-doped NiO/FeNi_(3)(SPA-NiFeO_(x)/FeNi_(3))heterostructure,which is derived from the pyrolysis of MOF-on-MOF heterostructure growth triggered by graphene quantum dots(GQDs).Such SPA-NiFeO_(x)/FeNi_(3)exhibits superior catalytic performance on the electrooxidation of EG(EGOR)from PET hydrolysate,with a formic acid(FA)selectivity of 91.5%and a Faradaic efficiency of 92%.The ligand effect of GQDs in both the catalyst design and improved electrocatalytic performance was studied with combined spectroscopy analysis and theoretical calculations,which revealed that such spatially separated NiFeO_(x)and FeNi_(3)components by GQDs possess more active sites to anticipate in electrocatalytic EGOR,and the large sp2 domains in GQDs possess a strong electron-withdrawing ability to reduce the electron density of bonded Ni and Fe,resulting in high-valenced Ni^(δ+)/Fe^(δ+)in FeNi_(3)and Ni(2+δ)in NiO,respectively.Furthermore,the coordination number of Ni and Fe centers was lowered due to the steric effect of GQDs.Therefore,the adsorption of EG on Ni^(δ+)for cascade dehydrogenation and C–C bond cleavage led to adsorbed FA that transferred to adjacent Fe for desorption,which was promoted by the enrichment of OH−on nearby Ni^((2+δ))sites,along with optimized Gibbs free energy change in the multistep reaction pathway.This work provides an efficient multi-active-site catalyst for disused PET plastics valorization,thereby presenting a new approach to enhance the efficiency of PET plastics valorization reactions.展开更多
The dynamics of the drying process of polymer solutions are important for the development of coatings and films.In the present work,digital holographic microscopy(DHM)was performed to capture the drying dynamics of po...The dynamics of the drying process of polymer solutions are important for the development of coatings and films.In the present work,digital holographic microscopy(DHM)was performed to capture the drying dynamics of poly(ethylene oxide)(PEO)droplets using a gold nanoparticle tracer,where the heterogeneous flow field in different regions was illustrated.This demonstrates that the gold nanoparticles at either the center or the edge regions of the droplet exhibit anisotropic kinematic behavior.At early stage,Marangoni backflow causes gold nanoparticles to move towards the edge firstly,and the circles back towards the droplet center after arriving the contact line with a sudden increase in z axis for 10.4μm,indicating the scale of the upward-moving microscopic flow vortices.This phenomenon does not occur in water droplets in the absence of polymers.The gold nanoparticles underwent Brownian-like motion at the center of the PEO droplet or water droplet owing to the low perturbation of the flow field.At the late stage of pinning of the PEO droplets,the motion showed multiple reverses in the direction of the gold nanoparticles,indicating the complexity of the flow field.This study enhances the understanding of the drying dynamics of polymer solution droplets and offers valuable insights into the fabrication of surface materials.展开更多
Dimethyl carbonate(DMC)is an important chemical raw material extensively used in organic synthesis,lithium-ion battery electrolytes,etc.The primary method for industrial synthesis of DMC involves transesterification b...Dimethyl carbonate(DMC)is an important chemical raw material extensively used in organic synthesis,lithium-ion battery electrolytes,etc.The primary method for industrial synthesis of DMC involves transesterification between ethylene carbonate and MeOH but faces issues with difficult catalyst separation and low catalytic activity.Based on the synergistic catalytic activity of cation and anion,this study develops poly(ionic liquid)s of[N_(X)PIL][PHO]and[N_(3)PIL][Y]with varying alkaline sites and alkalinity levels.This is accomplished by constructing functional polymer monomers containing free radical polymerization sites and nitrogencontaining alkaline groups,and by polymerizing them with suitable crosslinking monomers in a specific ratio before exchanging the resulting polymers with different anions.Results show that doping with nitrogen-containing alkaline groups leads to enhanced basic functional sites while appropriate anions provide intensified alkalinity levels.The[N_(3)PIL][PHO]obtained exhibits superior catalytic activity in transesterification synthesis of DMC,with a yield of 91.43%and selectivity of 99.96%at a reaction time of 2 h.The study also investigates the impact of poly(ionic liquid)cationic structure and anion types,as well as their interactions,on catalytic performance.The findings reveal that the catalytic activity of poly(ionic liquid)is restricted by the interactions between cation and anion.Based on these findings,a possible reaction mechanism was proposed,providing theoretical support for the high-efficiency production of DMC.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
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
Although amide-and hydrazide-based nucleating agents have been extensively used to enhance the crystallization performance of poly(lactic acid)(PLA),structurally similar nucleating agents exhibit significant differenc...Although amide-and hydrazide-based nucleating agents have been extensively used to enhance the crystallization performance of poly(lactic acid)(PLA),structurally similar nucleating agents exhibit significant differences in their crystallization-promoting efficiency,and the underlying mechanism remains unclear.In this study,a series of nucleating agents,including N,N-diphenylterephthalamide(DPTA),N,N,N-triphenyl-1,3,5-benzenetricarboxamide(TPTA),N,N-diphenyl terephthalohydrazide(DBTA),and N,N,N-tribenzoyl-1,3,5-benzenetricarbohydrazide(TBTA),were designed and synthesized to investigate the differences in their effects on the crystallization performance of PLA.Density functional theory(DFT)and molecular dynamics(MD)simulations showed that DBTA had a smaller electrostatic potential difference(66.2 kcal/mol).During the cooling process,DBTA could stably form more intermolecular hydrogen bonds with PLA and exhibit a higher interaction energy,thus theoretically enabling more efficient promotion of PLA crystallization.Further differential scanning calorimetry(DSC)results revealed that at a 0.5wt%loading of DBTA,the crystallization peak temperature of the PLA-DBTA composite reached 118.1℃during cooling,whereas no distinct crystallization peak was observed for pure PLA under identical conditions.The crystallinity of the composite was significantly increased to 58.4%compared to 14.6%of pure PLA.Moreover,under isothermal crystallization at 130℃,DBTA reduced the half-crystallization time of PLA to 2.9min,while the half-crystallization time for pure PLA was 27.4 min.Time-resolved Fourier transform infrared spectroscopy(FTIR)results also confirmed that DBTA promoted the formation of gt conformational isomers of PLA during the crystallization process.This study elucidates the mechanism behind the performance differences between structurally similar nucleating agents in regulating PLA crystallization from the perspective of molecular electrostatic potential and hydrogen bonding interactions,providing a theoretical basis for the molecular design of efficient nucleating agents.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
Ocean-degradable polyesters incorporating hydrophilic and rapidly degradable glycolide(GL)units into the polymer chain are the most promising for addressing marine plastic pollution,however,it is challenging to obtain...Ocean-degradable polyesters incorporating hydrophilic and rapidly degradable glycolide(GL)units into the polymer chain are the most promising for addressing marine plastic pollution,however,it is challenging to obtain high-molecular-weight copolymers with narrow molecular weight distributions.Herein,we prepared a novel biodegradable material,poly(butylene succinate-co-glycolide)(PBSGL),through ring-opening copolymerization using glycolide,succinic anhydride,and 1,4-butanediol as raw materials,providing a new solution strategy for marine pollution.GL could be polymerized according to the pre-designed composition by 1H-nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)results,indicating controlled polymerization with the synthesized PBSGLs having a weight-average molecular weight of up to 12.30×10^(4) g/mol and a narrow molecular weight distribution(1.33–1.65).Differential scanning calorimeter(DSC)and thermogravimetric analysis(TGA)results showed that T_(g) of PBSGLs increased from−32.5°C to−26.5°C with the increase of GL content from 0%to 40%,while T_(m)(>76°C)was much lower than T_(d,5%)(>314°C),which indicated that PBSGLs had good thermal stability and expanded the processing window and application range of the original poly(butylene succinate)(PBS)materials.Under simulated difficult conditions,PBSGL copolyesters could degrade faster with increasing GL content,where PBSGL40 degraded by 22.6%in 12 days,showing good biodegradability.Currently,most biodegradable polyesters with good performance slowly degrade in seawater.In a 30-day artificial seawater degradation test,the amorphous PBSGL40 copolyester showed a about 15-fold(2.33%weight loss)improvement in degradation ability compared to pure PBS,demonstrating rapid seawater degradation capability.展开更多
基金financially supported by the Science and Technology Projects of Changji Prefecture(No.2023112258)Shihezi Coal Chemical Industry Common Technology Research Institute Project(No.MGJY0104)the Program for Young Innovative Talents of Shihezi University(No.CXFZ202302).
文摘In this study,a series of poly(ethylene succinate)-b-poly(butylene carbonate)(PES-b-PBC)multiblock copolymers were prepared through the chain-extension reaction of hydroxyl-terminated PES(PES-OH)and hydroxyl-terminated PBC(PBC-OH)prepolymers with 1,6-hexmethylene diisocyanate(HDI)as a chain extender.The effects of the prepolymer molecular weight and content on the structure and application properties of the PES-b-PBC copolymers were systematically investigated using various techniques.It was found that the compatibility of PES and PBC blocks in PES-b-PBC copolymers can be greatly enhanced by lowering the length of the prepolymers,and the amorphous phase of the PES and PBC chain segments in the PES-b-PBC copolymer would transform from immiscibility and partial miscibility to miscibility when the number-average molecular weight(M_(n))of the PES-OH and PBC-OH prepolymers is less than 2000 g/mol.Only the crystal structure of bare PES can be observed in the wide-angle X-ray diffraction(WAXD)spectrum of the PES-b-PBC copolymers,but their crystallinity degrees were found to decrease with increasing PBC fraction.The thermal behavior,crystallization performance,rheological properties,mechanical properties,and degradation properties of the PES-b-PBC multiblock copolymers can be easily modulated by altering the block length and composition of the prepolymers,offering potential applications in biodegradable materials.
基金financially supported by the National Natural Science Foundation of China(Nos.22173116 and 22473113)the Science Foundation of China University of Petroleum,Beijing(No.2462025YJRC032)for providing financial support.
文摘Poly(ethylene succinate)(PES),a promising biodegradable polyester with cost advantages,suffers from inherently slow crystallization kinetics,which severely limits its processability and practical applications.To address this challenge,this study explored the use of commercially available,low-cost,and food-safe sugar alcohols,including Xylitol(Xy),D-sorbitol(DS),and D-mannitol(DM),as effective nucleating agents for PES.Remarkably,all three polyols significantly enhanced the nucleation and crystallization ability of PES,with DM exhibiting the most pronounced effect.DM increased the crystallization temperature by up to 23.9°C and accelerated the overall crystallization rate by more than 13-fold at only 0.5 wt%loading level.Through a combination of differential scanning calorimetry(DSC),polarized optical microscopy(POM),and wide-angle X-ray diffraction(WAXD)analyses,we revealed that DM promotes PES crystallization via a dual mechanism:epitaxial templating facilitated by excellent lattice matching,and enhanced chain adjustment through intermolecular hydrogen-bonding interactions.In contrast,Xy and DS primarily function through hydrogen-bonding interactions.This work not only identifies DM as a highly efficient,economical,and industrially viable nucleating agent for PES,but also provides fundamental insights into the role of the molecular structure and crystallization ability of nucleating agents in regulating polymer crystallization.
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.
文摘In this study,composite films consisting of polylactic acid(PLA),ethyl cellulose(EC),and zein were prepared by solution casting method,and their performance and application in chilled fresh meat preservation were investigated.The results showed that the three materials had satisfactory compatibility in the composite film.Addition of EC and zein effectively improved the mechanical properties,thermodynamic properties,surface hydrophilicity,oxygen permeability,and degradation properties of PLA films.When the ratio of PLA to EC was 3:7,the tensile strength and elongation at break reached maximum values of 16.6 MPa and 30.5%,respectively.Moreover,under different conditions,the composite film exhibited better degradability than the PLA film.The composite film with a 3:7 ratio of PLA to EC had the best performance,with a degradation rate of 21.75%after 84 days.Chilled fresh meat wrapped with the composite film showed significantly improved antioxidant,antibacterial,and water-holding properties.
基金supported by the National Key Research and Development Program of China(2023YFB3810502)the National Natural Science Foundation of China(22078146)the Key Research and Development program of Anhui Province(2023h11020004).
文摘The membrane aeration biofilm reactor(MABR)represents an innovative approach to wastewater treatment,integrating gas separation membranes with biofilm process and demonstrating effectiveness in treating wastewater rich in ammonia nitrogen.In this system,hollow fiber membranes are essential,serving as a substrate for biofilm attachment while facilitating oxygen transfer to microorganisms through aeration,hydrophobic microporous membranes are utilized in MABR applications.This study focuses on the use of poly-4-methyl-1-pentene(PMP)hollow fiber membranes,which exhibit superior oxygen permeation capabilities compared to traditional hydrophobic microporous membranes.To overcome the challenges posed by the hydrophobic nature and low bubble point of PMP microporous membranes,a hydrophilic modification was conducted using dopamine/poly(ethyleneimine)(DOPA/PEI)co-deposition to enhance microbial adhesion on the membrane surface.The composite membrane modified with DOPA/PEI exhibited an approximately 20%higher NH_(4)^(+)-N removal efficiency than the unmodified membrane.These findings suggest that the incorporation of DOPA/PEI significantly improves MABR performance,underscoring its potential for further research and development in membrane technology for MABR.
文摘Poly(octamethylene citrate)(POC)is a promising bioelastomer material in the biomedical field.However,its thermosetting nature poses a significant challenge to processing and molding,especially manufacturing the POC-based elastomer particles as potential,degradable and toughened fillers.Firstly,a Pickering emulsion with a pre-polymer(pre-POC)solution in dimethyl carbonate as a dispersed oil phase,a Pullulan(PUL)aqueous solution as a continuous water phase,and chitin nanocrystal(ChiNC)as a particle-type emulsifier was constructed.Secondly,the POC-based core/shell structured microspheres were prepared by spray-drying of the emulsions,and characterized by a scanning electron microscope and a transmission electron microscope.Finally,the POC-based core/shell structured microspheres were used as elastomer fillers to strengthen and toughen a chitosan film,resulting in 26%increase in the tensile strength and 45%increase in the strain at break;the POC-based core/shell structured microsphere as a double-layer drug release system was built in which the hydrophilic drug of tetracycline hydrochloride(TCH)was released from the outer layer and the hydrophobic drug of curcumin was released from the inner layer,roughly following the Ritger-Peppas model.
基金supported by the Scientific Research Start-up Fund Project of Anhui Polytechnic University for Introducing Talents(No.2022YQQ081)Natural Science Research Project of the Anhui Educational Committee(No.2024AH050133)the National Natural Science Foundation of China(No.22101088)。
文摘Dimethyl sulfoxide(DMSO)possessing strong solvency and high boiling point is a very important aprotic polar solvent in organic and polymer synthesis.Notably,it is also a useful synthon in organic chemistry.However,the direct incorporation of DMSO in polymer synthesis remains challenging.In this work,DMSO was successfully converted to nitrogen-containing heterocyclic polymers as a monomer via multicomponent polymerizations(MCPs)with dialdehydes and diamines in the presence of K_(2)S_(2)O_(8)/t-BuOK at 120℃in 6 h.A series of poly(phenylquinoline)s with high M_(w)values(up to 5.11×10^(4))were obtained in satisfactory yields(up to 82%),performing good solubility,good thermal and morphological stability as well as excellent film-forming ability.The thin films of poly(phenylquinoline)s exhibit high refractive index value in a wide wavelength range of 400–1700 nm.Thus,this work not only enriches the family of MCPs but also provides an efficient strategy for the conversion of DMSO into functional polymeric materials that are potentially applicable in diverse areas.
基金financially supported by the National Natural Science Foundation of China (No. 21774006)
文摘The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by sulfonation of ASIBS with acetyl sulfate.The hydrophilic ionic channels were generated for proton exchange membranes(PEMs)by ion aggregation of-SO_(3)H groups and microphase separation between hydrophobic polyisobutylene and hydrophilic sulfonated poly(α-methyl styrene)segments in S-ASIBS.The proton transport ability was improved while oxidative stability was decreased by increasing SP in S-ASIBS.The appropriate SP of about 12.7 mol%in S-ASIBS provides the available PEMs with high proton transport ability,low methanol permeability and good oxidative stability.The absence of active tertiary hydrogen atoms along S-ASIBS copolymer chains avoids their attack by peroxy radicals.The residual rates of weight(RW)and proton conductivity(Rσ)of S-ASIBS-12.7 membrane after oxidation treatment for 916 h were 84.3%and 88.1%respectively,near to those of commercial Nafion 117(RW=87.9%,Rσ=90.3%).The membrane electrode assembly(MEA)could be prepared by using various S-ASIBS as PEMs for direct methanol fuel cell.The single cell with S-ASIBS-12.7 MEA behaves high performance of open circuit voltage(OCV)of 548 mV and peak power density(Pmax)of 36.1 mW·cm^(-2),which is similar to those of Nafion 117(OCV=506 mV,P_(max)=35.6 mW·cm^(-2)).To the best of our knowledge,this is the first example of advanced S-ASIBS membrane with high proton conductivity,excellent fuel barrier property and remarkable oxidative stability for promising PEMs.
基金financially supported by the Maoming Science and Technology Bureau(No.2022DZXHT007)。
文摘The synthesis of polyurethanes(PUs)from the reaction of low molecular weight poly(ethylene carbonate)diol(PECD)is rarely investigated.This work reports a novel PU with excellent mechanical properties from the solution polymerization of 4,4-diphenylmethane diisocyanate(MDI)with PECD that was derived from the copolymerization of carbon dioxide(CO_(2))and ethylene oxide(EO).The tensile strength,the elongation at break and 300%constant tensile strength of the PECD-PU were up to 66±2 MPa,880%±50%and 13 MPa,respectively,higher than the control PUs from the reaction of MDI with commercial polyethers or polyesters.The PECD-PU with high CO_(2) carbonate content exhibited good solvent resistance and chemical stability.Of importance,the mechanical properties and chemical resistance of PECD-PU were significantly enhanced with the increasing content of CO_(2),i.e.,the carbonate unit in PECD.This work provides comprehensive properties of PECD-derived PUs,indicating that PECD is a competitive precursor for the preparation of PU and has broad application prospects.
基金financially supported by the National Natural Science Foundation of China(Nos.22172028,21903015,and 22403017)Natural Science Foundation of Fujian Province of China(No.2022J05041)。
文摘Compatibilization is crucial for the blending of immiscible polymers to develop high-performance composites;however,traditional compatibilization by copolymers(pre-made or in-situ generation)suffers from weak interface anchoring,and inorganic particles have gained extensive attention recently owing to their large interfacial desorption energy,while their low affinity to bulk components is a drawback.In this study,an interfacial atom transfer radical polymerization(ATRP)technique was employed to grow polystyrene(PS)and poly(2-hydroxyethyl methacrylate)(PHEMA)simultaneously on different hemispheres of Br-functionalized SiO_(2) nanoparticles to stabilize a Pickering emulsion,whereby a brush-type Janus nanoparticle(SiO_(2)@JNP)was developed.The polymer brushes were well-characterized,and the Janus feature was validated by transmission electron microscope(TEM)observation of the sole hemisphere grafting of SiO_(2)-PS as a control sample.SiO_(2)@JNP was demonstrated to be an efficient compatibilizer for a PS/poly(methyl methacrylate)(PMMA)immiscible blend,and the droplet-matrix morphology was significantly refined.The mechanical strength and toughness of the blend were synchronously enhanced at a low content SiO_(2)@JNP optimized~0.9 wt%,with the tensile strength,elongation at break and impact strength increased by 17.7%,26.6%and 19.6%,respectively.This enhancement may be attributed to the entanglements between the grafted polymer brushes and individual components that improve the particle-bulk phase affinity and enforce interfacial adhesion.
基金supported by the National Natural Science Foundation of China(22378338,U22A20421)the Project for Science and Technology Plan of Fujian Province of China(2024H4007)。
文摘Poly(ethylene 2,5-furandicarboxylate)(PEF),a bioplastic synthesized via the polymerization of 2,5-furandicarboxylic acid(FDCA)with ethylene glycol,can be served as a substitute to petroleum-based polyethylene terephthalate(PET)due to its enhanced material properties.However,the fabrication of PEF with stable and desirable properties is still a challenge,largely due to the impurities in FDCA.In this study,a highly efficient purification strategy for FDCA was proposed,utilizing a dioxane/H_(2)O binary solvent system for effective crystallization.Furthermore,PEFs were synthesized from FDCA with varying impurity and the effects of these impurities were systematically characterized.The results revealed that impurities in FDCA could result in PEFs with relatively poor thermal properties.This study provides crucial insights for the impact of impurities on PEF properties and FDCA purification.
基金support from the National Natural Science Foundation of China(Grant No.22102140the Natural Science Foundation of Jiangsu Province(Grant No.BK20211602)+1 种基金the Qing Lan Project of Yangzhou Universitythe Postgraduate Research&Practice Innovation Program of Jiangsu Province(Yangzhou University,Grant No.SJCX23_1911).
文摘Electrocatalytic valorization of disused poly(ethylene terephthalate)(PET)plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading,but it faces challenges in the development of efficient catalysts for PET-derived ethylene glycol(EG)electrooxidation.Herein,we proposed pyramid arrays on sheet Fe-doped NiO/FeNi_(3)(SPA-NiFeO_(x)/FeNi_(3))heterostructure,which is derived from the pyrolysis of MOF-on-MOF heterostructure growth triggered by graphene quantum dots(GQDs).Such SPA-NiFeO_(x)/FeNi_(3)exhibits superior catalytic performance on the electrooxidation of EG(EGOR)from PET hydrolysate,with a formic acid(FA)selectivity of 91.5%and a Faradaic efficiency of 92%.The ligand effect of GQDs in both the catalyst design and improved electrocatalytic performance was studied with combined spectroscopy analysis and theoretical calculations,which revealed that such spatially separated NiFeO_(x)and FeNi_(3)components by GQDs possess more active sites to anticipate in electrocatalytic EGOR,and the large sp2 domains in GQDs possess a strong electron-withdrawing ability to reduce the electron density of bonded Ni and Fe,resulting in high-valenced Ni^(δ+)/Fe^(δ+)in FeNi_(3)and Ni(2+δ)in NiO,respectively.Furthermore,the coordination number of Ni and Fe centers was lowered due to the steric effect of GQDs.Therefore,the adsorption of EG on Ni^(δ+)for cascade dehydrogenation and C–C bond cleavage led to adsorbed FA that transferred to adjacent Fe for desorption,which was promoted by the enrichment of OH−on nearby Ni^((2+δ))sites,along with optimized Gibbs free energy change in the multistep reaction pathway.This work provides an efficient multi-active-site catalyst for disused PET plastics valorization,thereby presenting a new approach to enhance the efficiency of PET plastics valorization reactions.
基金supported by the Key-Area Research and Development Program of Guangdong Province(No.2023B0101200006)Guangdong Basic and Applied Basic Research Foundation(No.2024A1515011926)+1 种基金Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates,Guangzhou 510640,China(South China University of Technology)(No.2023B1212060003)State Key Laboratory of Applied Microbiology Southern China(No.SKLAM008-2022)。
文摘The dynamics of the drying process of polymer solutions are important for the development of coatings and films.In the present work,digital holographic microscopy(DHM)was performed to capture the drying dynamics of poly(ethylene oxide)(PEO)droplets using a gold nanoparticle tracer,where the heterogeneous flow field in different regions was illustrated.This demonstrates that the gold nanoparticles at either the center or the edge regions of the droplet exhibit anisotropic kinematic behavior.At early stage,Marangoni backflow causes gold nanoparticles to move towards the edge firstly,and the circles back towards the droplet center after arriving the contact line with a sudden increase in z axis for 10.4μm,indicating the scale of the upward-moving microscopic flow vortices.This phenomenon does not occur in water droplets in the absence of polymers.The gold nanoparticles underwent Brownian-like motion at the center of the PEO droplet or water droplet owing to the low perturbation of the flow field.At the late stage of pinning of the PEO droplets,the motion showed multiple reverses in the direction of the gold nanoparticles,indicating the complexity of the flow field.This study enhances the understanding of the drying dynamics of polymer solution droplets and offers valuable insights into the fabrication of surface materials.
基金supported by the National Natural Science Foundation of China(Grant No.22278077,22408209 and 22108040)National Key Research and Development Program of China(Grant No.2022YFB4101800)+2 种基金Key Program of Qingyuan Innovation Laboratory(Grant No.00221004)Research Program of Qingyuan Innovation Laboratory(Grant No.00523006)Natural Science Foundation of Fujian Province(Grant No.2022J02019,2024J011550).
文摘Dimethyl carbonate(DMC)is an important chemical raw material extensively used in organic synthesis,lithium-ion battery electrolytes,etc.The primary method for industrial synthesis of DMC involves transesterification between ethylene carbonate and MeOH but faces issues with difficult catalyst separation and low catalytic activity.Based on the synergistic catalytic activity of cation and anion,this study develops poly(ionic liquid)s of[N_(X)PIL][PHO]and[N_(3)PIL][Y]with varying alkaline sites and alkalinity levels.This is accomplished by constructing functional polymer monomers containing free radical polymerization sites and nitrogencontaining alkaline groups,and by polymerizing them with suitable crosslinking monomers in a specific ratio before exchanging the resulting polymers with different anions.Results show that doping with nitrogen-containing alkaline groups leads to enhanced basic functional sites while appropriate anions provide intensified alkalinity levels.The[N_(3)PIL][PHO]obtained exhibits superior catalytic activity in transesterification synthesis of DMC,with a yield of 91.43%and selectivity of 99.96%at a reaction time of 2 h.The study also investigates the impact of poly(ionic liquid)cationic structure and anion types,as well as their interactions,on catalytic performance.The findings reveal that the catalytic activity of poly(ionic liquid)is restricted by the interactions between cation and anion.Based on these findings,a possible reaction mechanism was proposed,providing theoretical support for the high-efficiency production of DMC.
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supported by the Project of the National Science Foundation of China(Nos.52173033,51773044 and 51603047)Foshan Science and Technology Innovation Project(No.FS0AA-KJ919-4402-0145)。
文摘Although amide-and hydrazide-based nucleating agents have been extensively used to enhance the crystallization performance of poly(lactic acid)(PLA),structurally similar nucleating agents exhibit significant differences in their crystallization-promoting efficiency,and the underlying mechanism remains unclear.In this study,a series of nucleating agents,including N,N-diphenylterephthalamide(DPTA),N,N,N-triphenyl-1,3,5-benzenetricarboxamide(TPTA),N,N-diphenyl terephthalohydrazide(DBTA),and N,N,N-tribenzoyl-1,3,5-benzenetricarbohydrazide(TBTA),were designed and synthesized to investigate the differences in their effects on the crystallization performance of PLA.Density functional theory(DFT)and molecular dynamics(MD)simulations showed that DBTA had a smaller electrostatic potential difference(66.2 kcal/mol).During the cooling process,DBTA could stably form more intermolecular hydrogen bonds with PLA and exhibit a higher interaction energy,thus theoretically enabling more efficient promotion of PLA crystallization.Further differential scanning calorimetry(DSC)results revealed that at a 0.5wt%loading of DBTA,the crystallization peak temperature of the PLA-DBTA composite reached 118.1℃during cooling,whereas no distinct crystallization peak was observed for pure PLA under identical conditions.The crystallinity of the composite was significantly increased to 58.4%compared to 14.6%of pure PLA.Moreover,under isothermal crystallization at 130℃,DBTA reduced the half-crystallization time of PLA to 2.9min,while the half-crystallization time for pure PLA was 27.4 min.Time-resolved Fourier transform infrared spectroscopy(FTIR)results also confirmed that DBTA promoted the formation of gt conformational isomers of PLA during the crystallization process.This study elucidates the mechanism behind the performance differences between structurally similar nucleating agents in regulating PLA crystallization from the perspective of molecular electrostatic potential and hydrogen bonding interactions,providing a theoretical basis for the molecular design of efficient nucleating agents.
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financially supported by the National Natural Science Foundation of China (No. 52203012)Shanghai Rising-Star Program (No. 23QC1400900).
文摘Ocean-degradable polyesters incorporating hydrophilic and rapidly degradable glycolide(GL)units into the polymer chain are the most promising for addressing marine plastic pollution,however,it is challenging to obtain high-molecular-weight copolymers with narrow molecular weight distributions.Herein,we prepared a novel biodegradable material,poly(butylene succinate-co-glycolide)(PBSGL),through ring-opening copolymerization using glycolide,succinic anhydride,and 1,4-butanediol as raw materials,providing a new solution strategy for marine pollution.GL could be polymerized according to the pre-designed composition by 1H-nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)results,indicating controlled polymerization with the synthesized PBSGLs having a weight-average molecular weight of up to 12.30×10^(4) g/mol and a narrow molecular weight distribution(1.33–1.65).Differential scanning calorimeter(DSC)and thermogravimetric analysis(TGA)results showed that T_(g) of PBSGLs increased from−32.5°C to−26.5°C with the increase of GL content from 0%to 40%,while T_(m)(>76°C)was much lower than T_(d,5%)(>314°C),which indicated that PBSGLs had good thermal stability and expanded the processing window and application range of the original poly(butylene succinate)(PBS)materials.Under simulated difficult conditions,PBSGL copolyesters could degrade faster with increasing GL content,where PBSGL40 degraded by 22.6%in 12 days,showing good biodegradability.Currently,most biodegradable polyesters with good performance slowly degrade in seawater.In a 30-day artificial seawater degradation test,the amorphous PBSGL40 copolyester showed a about 15-fold(2.33%weight loss)improvement in degradation ability compared to pure PBS,demonstrating rapid seawater degradation capability.
