Compared to subtractive manufacturing and casting,3D printing(additive manufacturing)offers advantages,such as the rapid production of complex structures,reduced material waste,and environmental friendliness.Direct in...Compared to subtractive manufacturing and casting,3D printing(additive manufacturing)offers advantages,such as the rapid production of complex structures,reduced material waste,and environmental friendliness.Direct ink writing(DIW)is one of the most popular 3D printing techniques owing to its ability to print multiple materials simultaneously and its high compatibility with printing inks.However,DIW presents significant challenges,particularly in the printing of high-performance polymers.The main challenges are as follows:1.The rigid structures and reaction kinetics of high-performance polymers make developing new inks difficult.2.The limited types of available high-performance polymers underscore the need for new DIW-suitable materials.3.Layer-by-layer stacking weakens interlayer bonding,affecting the mechanical properties of the printed product.4.The accuracy and speed of DIW printing are insufficient for large-scale manufacturing.After introducing the topic,the requirements for DIW printing inks are first reviewed,emphasizing the importance of thixotropic agents.Then,research progress regarding DIW printing of high-performance polymers is comprehensively reviewed according to the requirements of different polymer inks.Additionally,the applications of these materials across various fields are summarized.Finally,the challenges in DIW printing of high-performance polymers,along with corresponding solutions and future development prospects,are discussed in detail.展开更多
Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation...Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation reaction.The structures of PIKs are characterized by means of elemental analysis,FT-IR,~1H-NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structure.The general properties of PIKs are studied by DSC,TG and wide-angle X-ray diffraction,the solubility behavior is...展开更多
Impact-resistant structures designed to withstand forces and maintain integrity under loads require high compressive strength,energy absorption capacity,tensile strength,and stiffness.These structures typically featur...Impact-resistant structures designed to withstand forces and maintain integrity under loads require high compressive strength,energy absorption capacity,tensile strength,and stiffness.These structures typically feature complex geometries that are difficult to produce using traditional manufacturing methods.Additive manufacturing(AM)technology has revolutionized the fabrication of such structures by offering superior capabilities in complexity,customization,and material efficiency.High-performance polymers(HPPs)including polyamide(PA),polyetherimide(PEI),polyphenylene sulfide(PPS),polyaryletherketones(PAEKs),and polyimide(PI)and their composites have gained prominence for impact-resistant applications due to their exceptional mechanical properties and AM compatibility.This review examines recent advances in the AM of HPPs for achieving impact resistance.It focuses on three key areas:the relationship between process parameters and mechanical/energyabsorbing performance,the properties of HPPs and their composites,and the impact-resistant characteristics of novel structural architectures.Additionally,the study addresses the current challenges and future perspectives in developing 3D-printed impact-resistant structures.By synthesizing this information,the review establishes a foundation for future research in innovative AM designs and new material feedstocks for impact-resistant applications.展开更多
The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs).However,binary blends often suffer from suboptimal phase separation,which limits the effici...The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs).However,binary blends often suffer from suboptimal phase separation,which limits the efficiency of OSCs.Herein,two bridging polymer acceptors(PAs)—benzodithiophene-(2-ethylhexyl)oxy(BDT-C2C4)and benzodithiophene-octyloxy(BDT-C_(8))—are designed and synthesized by combining a benzodithiophene(BDT)unit as the donor moiety[poly({4,8-bis[5-(2-ethylhexyl)-4-fluorothiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}){5,8-bis[4-(2-butyloctyl)thiophen-2-yl]dithieno[3',2':3,4]},D18],and a 2,2′-((2Z,2′Z)-{[12,13-Bis(2-butyloctyl)-12,13-dihydro-3,9-dinonylthieno[2,3]thieno[3,2-b]pyrrolo[4,5-g]thieno[2,3-b]indole-2,10-diyl]bis(methanylylidene)}bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(Y6)derivative as the acceptor moiety.BDT-C2C4 and BDT-C_(8) are functionalized with(2-ethylhexyl)oxy and octyloxy side chains on the BDT unit,respectively.Both PAs show complementary absorption and cascaded energy levels with the donor D18 and the acceptor 2,2′-((2Z,2′Z)-{[12,13-bis(3-ethylheptyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″∶4′,5′]thieno[2′,3′∶4,5]pyrrolo[3,2-g]thieno[2′,3′∶4,5]thieno[3,2-b]indole-2,10-diyl]bis(meth⁃aneylylidene)}bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(N3),but BDT-C_(8) exhibits better compatibility with D18 and N3 compared to BDT-C2C4.When incorporated as a third component into the D18∶N3 blend,both PAs improve the active layer morphology.In particular,the D18∶N3∶BDT-C_(8) blend shows significantly optimized morphology,featuring reduced phase separation and a fibrous network structure.As a result,the device based on D18∶N3∶BDT-C_(8) achieves a power conversion efficiency of 18.18%,significantly higher than that of the device based on D18∶N3(ca.17.37%).This work presents a compatibilizer strategy for optimizing blend morphology towards high-performance ternary OSCs.展开更多
Commercial-level sodium metal batteries require electrolytes with high ionic mobility and excellent thermo-mechanical and electrochemical stability.Conventional flammable liquid electrolytes,prone to dendrite growth a...Commercial-level sodium metal batteries require electrolytes with high ionic mobility and excellent thermo-mechanical and electrochemical stability.Conventional flammable liquid electrolytes,prone to dendrite growth and unstable interfacial reactions,rarely perform beyond coin-cell demonstrations.To address these shortcomings,a multifunctional composite quasi-solid polymer electrolyte(QSPE)that incorporates boron nitride(BN)as an engineered filler in a highly conductive polymer blend system has been developed.The optimized formation(15BN QSPE)delivers a room-temperature ionic conductivity of 2.15 m S cm^(-1)and a sodium-ion transference number of 0.80.Molecular dynamics simulations elucidate the coordination environment and show improved transport in the presence of BN.BN is chemically active and bifunctional:boron acts as an electron acceptor,interacting with solvents and macromolecules,while nitrogen coordinates with sodium ions,tailoring the solvation environment and transport pathways to promote efficient ion migration.The 15BN QSPE is self-extinguishing,resists oxidative thermal degradation,and enables stable cycling in symmetric sodium cells for>1400 h at0.5 m A cm^(-2).A Prussian blue full cell achieves>1500 stable cycles at 1C with -99% Coulombic efficiency in coin-cell configuration.A two-layer pouch cell with dual 15BN QSPE layers delivers 600 stable cycles at 0.125C and withstands rigorous mechanical abuse.These results position 15BN QSPE as a scalable,highperformance electrolyte offering enhanced safety and efficiency for next-generation sodium metal batteries.展开更多
Polymer matrix composites with high dielectric constants and low dielectric losses are in high demand for flexible electronics.However,simultaneously satisfying these requirements poses a significant scientific challe...Polymer matrix composites with high dielectric constants and low dielectric losses are in high demand for flexible electronics.However,simultaneously satisfying these requirements poses a significant scientific challenge owing to the intrinsic trade-off relationship.Herein,we utilized the in situ controllable reduction of graphene oxide(GO)within a poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene)(P(VDF-Tr FE-CFE))matrix to regulate the dielectric properties.The as-obtained composite exhibited a high relative dielectric constant of 1415coupled with a low loss tangent of 0.380 at 100 Hz.Experimental and theoretical studies indicate that the increased degree of electron conjugation and conductivity of the reduced GO(RGO)are responsible for the high-k.The constrained reduction degree of GO,combined with its homogeneous dispersion in the polymer matrix,effectively suppresses long-range charge carrier migration,thereby minimizing dielectric loss.This novel strategy could be successfully applied to both organic and aqueous systems.Furthermore,a high-performance flexible capacitive proximity sensor was exemplified by the optimization of both the dielectric layer and electrode pattern,exhibiting excellent sensitivity and stability.The fundamental mechanisms elucidated in this study provide crucial design principles for developing dielectric PMCs with tailored properties,thereby opening new avenues for advanced flexible electronic applications.展开更多
CONSPECTUS:Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable,high-performance,polymeric materials.Although lignin is a highly available and low-cost source of natural aromatics,it is...CONSPECTUS:Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable,high-performance,polymeric materials.Although lignin is a highly available and low-cost source of natural aromatics,it is commonly burned for heat or disposed of as waste.The use of lignin for new materials introduces both challenges and opportunities with respect to incumbent petrochemical-based compounds.These considerations are derived from two fundamental aspects of lignin:its recalcitrant/heterogeneous nature and aromatic methoxy substituents.展开更多
Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O...Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O)]·DMA}n(1)and{[Cd(hfdp)(ndc)(H_(2)O)]·DMA}_(n)(2),respectively(DMA=N,N‑dimethylacetamide).Single‑crystal X‑ray diffraction analyses showed that both complexes 1 and 2 contain similar structures.Topological analysis indicates that complexes 1 and 2 have a{44·62}planar structure.In addition,both complexes reveal good thermal stability and fluorescence sensing performance.They exhibited good sensitivity and selectivity towards 2,4,6‑trinitrophenol(TNP)by fluorescent quenching.The limits of detection of 1 and 2 for TNP were 0.107 and 0.327μmol·L^(-1),respectively.CCDC:2475515,1;2475516,2.展开更多
Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the...Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the blood is crucial for the treatment of liver diseases.Hemoperfusion,which relies on adsorbents to efficiently adsorb toxins,is a widely applied procedure for the removal of blood toxins.To broaden and improve the range and performance of hemoperfusion adsorbents,we synthesized cationic hyper crosslinked polymers(HCPs)with strong affinity for bilirubin.This material exhibited outstanding adsorption performance,with a maximum adsorption capacity of 934 mg/g and a removal efficiency of 96%.Further investigation confirmed their excellent selectivity,reusability,and biocompatibility.These findings expand the potential applications of HCPs and provide insight into strategies for constructing promising hemoperfusion adsorbent materials.展开更多
Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need fo...Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.展开更多
Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2...Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2)O(1)was synthesized as a 2D structure using Coas the metal source,methanol‑water(4∶6,V/V)as the solvent,and specific concentrations of 2,5‑furandicarboxylic acid(H_(2)FDCA)and 1,3,5‑triimidazole benzene(L).Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of[Co(HL)2(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(2).Using Cu(Ⅱ)as the metal source,methanol/water(9∶1,V/V)as the solvent,and specific concentrations of L and H2FDCA,the 1D chain structure of[Cu(L)(FDCA)(H_(2)O)]·2H_(2)O(3)was synthesized.Upon increasing the concentrations of L and H2FDCA,and switching the solvent to pure water,the 1D chain structure of[Cu(HL)_(2)(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(4)was obtained.This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs.In addition,the solid‑state photoluminescence of CPs 1‑4 at room temperature was studied,and their morphological changes were observed via scanning electron microscopy.Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand,facilitating ligand‑metal ion coordination.CCDC:2403934,1;2403935,2;2403936,3;2403938,4.展开更多
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polym...To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.展开更多
Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid an...Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid antibiotic removal.However,their low concentrations limit mass transfer efficiency,resulting in suboptimal performance.Adsorption is crucial for enhancing photocatalytic efficiency.In this study,a series of binary heterojunction catalysts(x%BWO@STHP)were synthesized,consisting of Bi_(2)WO_(6)(BWO)grafted with sulfonated triptycene-based hypercrosslinked polymer(STHP).The high specific surface area of STHP,combined withπ-πconjugation and ionic interactions with antibiotics,significantly enhances adsorption capacity.This facilitates effective contact between low-concentration pollutants in aqueous solutions and the active sites of the catalyst.The formation of a Z-scheme heterojunction between BWO and STHP facilitates photogenerated charge separation,and further significantly improves photocatalytic degradation performance.Specifically,the 20%BWO@STHP catalyst achieved rapid adsorption equilibrium for oxytetracycline(OTC),doxycycline(DOX),and tetracycline(TC)within 2 min and completely degraded them after 15 min of irradiation.Compared to pristine BWO,the photocatalytic reaction rate constants are significantly increased,being 9.69 times higher for OTC and 13.45 times higher for DOX.The catalyst exhibits excellent reusability and holds promising potential for practical applications.展开更多
Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated fo...Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.展开更多
Pure organic room-temperature phosphorescent(RTP)polymers possess good processability and flexibility over small molecular crystals.However,most of RTP polymers reported so far are based on non-conjugated polymers,and...Pure organic room-temperature phosphorescent(RTP)polymers possess good processability and flexibility over small molecular crystals.However,most of RTP polymers reported so far are based on non-conjugated polymers,and achieving efficient phosphorescent emission in RTP conjugated polymers(CPs)remains a significant challenge.Herein,we developed two RTP CPs(P(PSe ZPh-p-Ph)and P(PSe ZPh-m-Ph))by linking the phenoselenazine units with the para-and meta-phenylene units,respectively,to form the conjugated main chains.The phenylene linker with different lingking mode manipulates the effictiveπ-conjugation of the polymer backbones.Comparing with the para-linked P(PSe ZPh-pPh),meta-linked P(PSe ZPh-m-Ph)exhibit the decreased effectiveπ-conjugation and the enhanced contribution of selenium atoms to the frontier orbitals,leading to the larger spin-orbit coupling(SOC)constants and the accelerated phosphorescence radiative decay process.The P(PSe ZPhm-Ph)achieves a phosphorescence quantum yield of 21.4%in doped polystyrene films,which is among the highest efficiencies reported to date for pure organic RTP CPs.These CPs are applied to construct phosphorescent film sensors for oxygen detection with the high quenching constants(K_(sv))up to 14.80 kPa^(-1)and low detection of limit of 0.84 ppm,demostrating the potential for application in oxygen film sensors.展开更多
Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cat...Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cationic ring-opening polymerization.The ratio of blocks,the order of their attachment to the core,and arm length were varied.Conformation of synthesized stars was determined by methods of molecular hydrodynamics and optics.It has been shown that star-shaped molecules were characterized by high intramolecular density,and the arm folding increased with their lengthening.The influence of the structure of block copolymers and their molar mass on the critical micelle concentration has been established.Complexes of synthesized star-shaped block copolymers with curcumin were obtained and the efficient binding of curcumin to polymer molecules was demonstrated.The behavior of the aqueous solutions of the prepared polymer stars and their complexes with curcumin was investigated by light scattering and turbidimetry methods.The influence of the structure and molar mass of star polymers on their thermoresponsiveness and the phase separation temperatures in aqueous solutions was analyzed.A slight increase in the phase separation temperature was found on passage from polymer solutions to solutions of polymer complexes with hydrophobic curcumin.展开更多
Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we dev...Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we develop a constitutive model that explicitly couples the solvent concentration,structural relaxation,and mechanical response.This framework is built on a multiplicative decomposition of deformation and an Eyring-type flow rule,with structural evolution described by an effective temperature.A generalized shift factor is introduced to quantify how the solvent concentration and effective temperature jointly affect the relaxation time,thereby integrating physical aging and plasticization.The model is subsequently applied to methacrylate(MA)-based copolymer networks immersed in phosphate-buffered saline for up to nine months.Simulations accurately capture key experimental features,including the strong softening of highly swellable networks,the partial recovery due to aging,and the mitigating role of hydrophobic crosslinking in reducing solvent uptake.While the current single-mode description cannot reproduce the full relaxation spectrum,it establishes an efficient framework for predicting the long-term mechanical performance under coupled environmental and mechanical loading.This study provides a constitutive description of solvent-swollen glassy polymers,offering mechanistic insight into the interplay between plasticization and aging.Beyond biomedical MA networks,this framework establishes a foundation for predicting the long-term performance of polymer glasses under coupled aqueous environmental and mechanical loading.展开更多
Organic room-temperature phosphorescence(RTP)materials are promising for bioimaging applications due to their tunable structures,excellent biocompatibility,and long-lived luminescence.However,the development of highly...Organic room-temperature phosphorescence(RTP)materials are promising for bioimaging applications due to their tunable structures,excellent biocompatibility,and long-lived luminescence.However,the development of highly efficient organic RTP materials for aqueous systems remains challenging,as the organic phosphorescence is prone to being quenched by the dissolved oxygen in water.Herein,heteroaromatic carboxylic acids serve as ligand vips to construct a series of host-vip composites with nontoxic,dense EDTA-M(M=Ca,Mg,and Al)coordination polymer in water.These composites exhibit ultra-long pure RTP of vip molecules with phosphorescence quantum yield up to 53%,and lifetime up to 589.7 ms,due to the synergistic effect of dual-network structure:a coordinatively cross-linked network of EDTA-M,and a non-covalent bonded network formed by ligands and water molecules.The phosphorescence intensity is more than three times that of the composite with a single coordination network.Notably,the dual-network configuration can form a rigid and dense structure and block the intrusion of external H_(2)O and O_(2) molecules to avoid phosphorescence quenching in water.As a result,the RTP of the composites remains unchanged after 1 month in water.Furthermore,the nanoparticles fabricated from composites and anionic surfactants can be successfully applied in in vivo imaging of mice for the stable RTP in water.This work provides a novel strategy for the development of high-performance RTP materials in aqueous systems.展开更多
Near-infrared(NIR)light-responsive shape memory polymers(SMPs)show great promise for biomedical applications,but conventional photothermal agents suffer from high cost,complex preparation,or poor biocompatibility,whil...Near-infrared(NIR)light-responsive shape memory polymers(SMPs)show great promise for biomedical applications,but conventional photothermal agents suffer from high cost,complex preparation,or poor biocompatibility,while lignin-based alternatives exhibit insufficient photothermal conversion efficiency.Herein,we developed a novel strategy to enhance photothermal performance of lignin through sequential demethylation modification and Fe^(3+)complexation for constructing NIR light responsive SMPs.Dealkaline lignin(DL)was first demethylated using iodocyclohexane to produce demethylated lignin(DDL)with increased catechol content,which was then incorporated into polycaprolactone-based polyurethane synthesis followed by Fe^(3+)complexation.Results showed that DDL-Fe^(3+)complexes have significantly enhanced photothermal conversion performance,and the resulting PU-DDL+Fe^(3+)polyurethane with 0.5 wt%DDL content demonstrated a temperature increases of 39.8℃under 0.33 W·cm-2808 nm NIR irradiation.This excellent photothermal performance enables the shape-fixed PU-DDL+Fe^(3+)polyurethane to rapidly recover to its initial shape under NIR light irradiation.Additionally,PU-DDL+Fe^(3+)polyurethane exhibits good mechanical properties and biocompatibility,demonstrating significant biomedical application potential.展开更多
基金supported by National Key Research and Development Program of China(Grant No.2022YFB3809000)Major Science and Technology Project of Gansu Province(Grant No.23ZDGA011)+1 种基金National Natural Science Foundation of China(Grant No.22275199,52105224)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB04701022021).
文摘Compared to subtractive manufacturing and casting,3D printing(additive manufacturing)offers advantages,such as the rapid production of complex structures,reduced material waste,and environmental friendliness.Direct ink writing(DIW)is one of the most popular 3D printing techniques owing to its ability to print multiple materials simultaneously and its high compatibility with printing inks.However,DIW presents significant challenges,particularly in the printing of high-performance polymers.The main challenges are as follows:1.The rigid structures and reaction kinetics of high-performance polymers make developing new inks difficult.2.The limited types of available high-performance polymers underscore the need for new DIW-suitable materials.3.Layer-by-layer stacking weakens interlayer bonding,affecting the mechanical properties of the printed product.4.The accuracy and speed of DIW printing are insufficient for large-scale manufacturing.After introducing the topic,the requirements for DIW printing inks are first reviewed,emphasizing the importance of thixotropic agents.Then,research progress regarding DIW printing of high-performance polymers is comprehensively reviewed according to the requirements of different polymer inks.Additionally,the applications of these materials across various fields are summarized.Finally,the challenges in DIW printing of high-performance polymers,along with corresponding solutions and future development prospects,are discussed in detail.
基金This work was financially supported by the National Natural Science Foundation of China(No.15076017).
文摘Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation reaction.The structures of PIKs are characterized by means of elemental analysis,FT-IR,~1H-NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structure.The general properties of PIKs are studied by DSC,TG and wide-angle X-ray diffraction,the solubility behavior is...
基金supported by National Key Research and Development Program of China(Grant No.2023YFB4603500).
文摘Impact-resistant structures designed to withstand forces and maintain integrity under loads require high compressive strength,energy absorption capacity,tensile strength,and stiffness.These structures typically feature complex geometries that are difficult to produce using traditional manufacturing methods.Additive manufacturing(AM)technology has revolutionized the fabrication of such structures by offering superior capabilities in complexity,customization,and material efficiency.High-performance polymers(HPPs)including polyamide(PA),polyetherimide(PEI),polyphenylene sulfide(PPS),polyaryletherketones(PAEKs),and polyimide(PI)and their composites have gained prominence for impact-resistant applications due to their exceptional mechanical properties and AM compatibility.This review examines recent advances in the AM of HPPs for achieving impact resistance.It focuses on three key areas:the relationship between process parameters and mechanical/energyabsorbing performance,the properties of HPPs and their composites,and the impact-resistant characteristics of novel structural architectures.Additionally,the study addresses the current challenges and future perspectives in developing 3D-printed impact-resistant structures.By synthesizing this information,the review establishes a foundation for future research in innovative AM designs and new material feedstocks for impact-resistant applications.
文摘The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs).However,binary blends often suffer from suboptimal phase separation,which limits the efficiency of OSCs.Herein,two bridging polymer acceptors(PAs)—benzodithiophene-(2-ethylhexyl)oxy(BDT-C2C4)and benzodithiophene-octyloxy(BDT-C_(8))—are designed and synthesized by combining a benzodithiophene(BDT)unit as the donor moiety[poly({4,8-bis[5-(2-ethylhexyl)-4-fluorothiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}){5,8-bis[4-(2-butyloctyl)thiophen-2-yl]dithieno[3',2':3,4]},D18],and a 2,2′-((2Z,2′Z)-{[12,13-Bis(2-butyloctyl)-12,13-dihydro-3,9-dinonylthieno[2,3]thieno[3,2-b]pyrrolo[4,5-g]thieno[2,3-b]indole-2,10-diyl]bis(methanylylidene)}bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(Y6)derivative as the acceptor moiety.BDT-C2C4 and BDT-C_(8) are functionalized with(2-ethylhexyl)oxy and octyloxy side chains on the BDT unit,respectively.Both PAs show complementary absorption and cascaded energy levels with the donor D18 and the acceptor 2,2′-((2Z,2′Z)-{[12,13-bis(3-ethylheptyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″∶4′,5′]thieno[2′,3′∶4,5]pyrrolo[3,2-g]thieno[2′,3′∶4,5]thieno[3,2-b]indole-2,10-diyl]bis(meth⁃aneylylidene)}bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(N3),but BDT-C_(8) exhibits better compatibility with D18 and N3 compared to BDT-C2C4.When incorporated as a third component into the D18∶N3 blend,both PAs improve the active layer morphology.In particular,the D18∶N3∶BDT-C_(8) blend shows significantly optimized morphology,featuring reduced phase separation and a fibrous network structure.As a result,the device based on D18∶N3∶BDT-C_(8) achieves a power conversion efficiency of 18.18%,significantly higher than that of the device based on D18∶N3(ca.17.37%).This work presents a compatibilizer strategy for optimizing blend morphology towards high-performance ternary OSCs.
基金a seed grant from IIT Delhi(SGNF148)supported by the JST-ERATO Yamauchi Materials SpaceTectonics Project(JPMJER2003)+2 种基金the ARC Australian Laureate Fellowship(FL230100095)the UQ-Yonsei International Joint Research Projectthe support from JSPS Postdoctoral Fellowships for Research in Japan。
文摘Commercial-level sodium metal batteries require electrolytes with high ionic mobility and excellent thermo-mechanical and electrochemical stability.Conventional flammable liquid electrolytes,prone to dendrite growth and unstable interfacial reactions,rarely perform beyond coin-cell demonstrations.To address these shortcomings,a multifunctional composite quasi-solid polymer electrolyte(QSPE)that incorporates boron nitride(BN)as an engineered filler in a highly conductive polymer blend system has been developed.The optimized formation(15BN QSPE)delivers a room-temperature ionic conductivity of 2.15 m S cm^(-1)and a sodium-ion transference number of 0.80.Molecular dynamics simulations elucidate the coordination environment and show improved transport in the presence of BN.BN is chemically active and bifunctional:boron acts as an electron acceptor,interacting with solvents and macromolecules,while nitrogen coordinates with sodium ions,tailoring the solvation environment and transport pathways to promote efficient ion migration.The 15BN QSPE is self-extinguishing,resists oxidative thermal degradation,and enables stable cycling in symmetric sodium cells for>1400 h at0.5 m A cm^(-2).A Prussian blue full cell achieves>1500 stable cycles at 1C with -99% Coulombic efficiency in coin-cell configuration.A two-layer pouch cell with dual 15BN QSPE layers delivers 600 stable cycles at 0.125C and withstands rigorous mechanical abuse.These results position 15BN QSPE as a scalable,highperformance electrolyte offering enhanced safety and efficiency for next-generation sodium metal batteries.
基金financially supported by the Innovation and Technology Commission of the Hong Kong SAR Government(No.MRP/020/21)Hong Kong Polytechnic University(No.847A)+1 种基金RI-Wear Seed Fund of Poly U(1-CD8J)Start-up Fund of Poly U(1-BD49)。
文摘Polymer matrix composites with high dielectric constants and low dielectric losses are in high demand for flexible electronics.However,simultaneously satisfying these requirements poses a significant scientific challenge owing to the intrinsic trade-off relationship.Herein,we utilized the in situ controllable reduction of graphene oxide(GO)within a poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene)(P(VDF-Tr FE-CFE))matrix to regulate the dielectric properties.The as-obtained composite exhibited a high relative dielectric constant of 1415coupled with a low loss tangent of 0.380 at 100 Hz.Experimental and theoretical studies indicate that the increased degree of electron conjugation and conductivity of the reduced GO(RGO)are responsible for the high-k.The constrained reduction degree of GO,combined with its homogeneous dispersion in the polymer matrix,effectively suppresses long-range charge carrier migration,thereby minimizing dielectric loss.This novel strategy could be successfully applied to both organic and aqueous systems.Furthermore,a high-performance flexible capacitive proximity sensor was exemplified by the optimization of both the dielectric layer and electrode pattern,exhibiting excellent sensitivity and stability.The fundamental mechanisms elucidated in this study provide crucial design principles for developing dielectric PMCs with tailored properties,thereby opening new avenues for advanced flexible electronic applications.
基金the Army Research Office under Cooperative Agreement Number W911NF-22-2-0257the National Science Foundation(NSF)Growing Convergence Research program(NSF GCR CMMI 1934887)in Materials Life Cycle Management for financial support during the writing of this manuscript.
文摘CONSPECTUS:Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable,high-performance,polymeric materials.Although lignin is a highly available and low-cost source of natural aromatics,it is commonly burned for heat or disposed of as waste.The use of lignin for new materials introduces both challenges and opportunities with respect to incumbent petrochemical-based compounds.These considerations are derived from two fundamental aspects of lignin:its recalcitrant/heterogeneous nature and aromatic methoxy substituents.
文摘Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O)]·DMA}n(1)and{[Cd(hfdp)(ndc)(H_(2)O)]·DMA}_(n)(2),respectively(DMA=N,N‑dimethylacetamide).Single‑crystal X‑ray diffraction analyses showed that both complexes 1 and 2 contain similar structures.Topological analysis indicates that complexes 1 and 2 have a{44·62}planar structure.In addition,both complexes reveal good thermal stability and fluorescence sensing performance.They exhibited good sensitivity and selectivity towards 2,4,6‑trinitrophenol(TNP)by fluorescent quenching.The limits of detection of 1 and 2 for TNP were 0.107 and 0.327μmol·L^(-1),respectively.CCDC:2475515,1;2475516,2.
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
基金financially supported by the International Cooperation Program of the Ministry of Science and Technology of Hubei Province(No.2023EHA069)Shenzhen Science and Technology Program(No.JCYJ20230807143702005)the National Foreign Experts Program(No.G2022027015L)。
文摘Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the blood is crucial for the treatment of liver diseases.Hemoperfusion,which relies on adsorbents to efficiently adsorb toxins,is a widely applied procedure for the removal of blood toxins.To broaden and improve the range and performance of hemoperfusion adsorbents,we synthesized cationic hyper crosslinked polymers(HCPs)with strong affinity for bilirubin.This material exhibited outstanding adsorption performance,with a maximum adsorption capacity of 934 mg/g and a removal efficiency of 96%.Further investigation confirmed their excellent selectivity,reusability,and biocompatibility.These findings expand the potential applications of HCPs and provide insight into strategies for constructing promising hemoperfusion adsorbent materials.
基金supported by the National Natural Science Foundation of China(Nos.22322107,22101169 and 22071144)by Shanghai Scientific and Technological Committee(No.22010500300).
文摘Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.
文摘Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2)O(1)was synthesized as a 2D structure using Coas the metal source,methanol‑water(4∶6,V/V)as the solvent,and specific concentrations of 2,5‑furandicarboxylic acid(H_(2)FDCA)and 1,3,5‑triimidazole benzene(L).Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of[Co(HL)2(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(2).Using Cu(Ⅱ)as the metal source,methanol/water(9∶1,V/V)as the solvent,and specific concentrations of L and H2FDCA,the 1D chain structure of[Cu(L)(FDCA)(H_(2)O)]·2H_(2)O(3)was synthesized.Upon increasing the concentrations of L and H2FDCA,and switching the solvent to pure water,the 1D chain structure of[Cu(HL)_(2)(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(4)was obtained.This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs.In addition,the solid‑state photoluminescence of CPs 1‑4 at room temperature was studied,and their morphological changes were observed via scanning electron microscopy.Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand,facilitating ligand‑metal ion coordination.CCDC:2403934,1;2403935,2;2403936,3;2403938,4.
基金the support from the Jiangsu Provincial Senior Talent Program (Dengfeng,Jiangsu University)the support from the National Key R&D Program of China (No.2024YFB3612600)+3 种基金the National Natural Science Foundation of China (Nos.22275098,62288102)Basic Research Program of Jiangsu (No.BK20243057)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (No.NY222097)the National Natural Science Foundation of China (No.62205035)。
文摘To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
基金the financial support provided by the National Natural Science Foundation of China(22478267,22438009,U24A20535)Basic Research Program of Jiangsu province(BK20243002)+1 种基金Prospective Application Research Project of Suzhou(SYC2022042)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid antibiotic removal.However,their low concentrations limit mass transfer efficiency,resulting in suboptimal performance.Adsorption is crucial for enhancing photocatalytic efficiency.In this study,a series of binary heterojunction catalysts(x%BWO@STHP)were synthesized,consisting of Bi_(2)WO_(6)(BWO)grafted with sulfonated triptycene-based hypercrosslinked polymer(STHP).The high specific surface area of STHP,combined withπ-πconjugation and ionic interactions with antibiotics,significantly enhances adsorption capacity.This facilitates effective contact between low-concentration pollutants in aqueous solutions and the active sites of the catalyst.The formation of a Z-scheme heterojunction between BWO and STHP facilitates photogenerated charge separation,and further significantly improves photocatalytic degradation performance.Specifically,the 20%BWO@STHP catalyst achieved rapid adsorption equilibrium for oxytetracycline(OTC),doxycycline(DOX),and tetracycline(TC)within 2 min and completely degraded them after 15 min of irradiation.Compared to pristine BWO,the photocatalytic reaction rate constants are significantly increased,being 9.69 times higher for OTC and 13.45 times higher for DOX.The catalyst exhibits excellent reusability and holds promising potential for practical applications.
基金supported by the National Natural Science Foundation of China (Nos.22064020,22364022,and 22174125)the Applied Basic Research Foundation of Yunnan Province (Nos.202101AT070101 and 202201AT070029)。
文摘Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.
基金supported by the National Natural Science Foundation of China(Nos.22275182,22075272,51973211,51833009,21674111 and 52261135541)the Ministry of Science and Technology of the People’s Republic of China(the National Key R&D Program of China,No.2022YFB4200400)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0520102)。
文摘Pure organic room-temperature phosphorescent(RTP)polymers possess good processability and flexibility over small molecular crystals.However,most of RTP polymers reported so far are based on non-conjugated polymers,and achieving efficient phosphorescent emission in RTP conjugated polymers(CPs)remains a significant challenge.Herein,we developed two RTP CPs(P(PSe ZPh-p-Ph)and P(PSe ZPh-m-Ph))by linking the phenoselenazine units with the para-and meta-phenylene units,respectively,to form the conjugated main chains.The phenylene linker with different lingking mode manipulates the effictiveπ-conjugation of the polymer backbones.Comparing with the para-linked P(PSe ZPh-pPh),meta-linked P(PSe ZPh-m-Ph)exhibit the decreased effectiveπ-conjugation and the enhanced contribution of selenium atoms to the frontier orbitals,leading to the larger spin-orbit coupling(SOC)constants and the accelerated phosphorescence radiative decay process.The P(PSe ZPhm-Ph)achieves a phosphorescence quantum yield of 21.4%in doped polystyrene films,which is among the highest efficiencies reported to date for pure organic RTP CPs.These CPs are applied to construct phosphorescent film sensors for oxygen detection with the high quenching constants(K_(sv))up to 14.80 kPa^(-1)and low detection of limit of 0.84 ppm,demostrating the potential for application in oxygen film sensors.
基金financially supported by the Russian Science Foundation(No.23-13-00205)。
文摘Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cationic ring-opening polymerization.The ratio of blocks,the order of their attachment to the core,and arm length were varied.Conformation of synthesized stars was determined by methods of molecular hydrodynamics and optics.It has been shown that star-shaped molecules were characterized by high intramolecular density,and the arm folding increased with their lengthening.The influence of the structure of block copolymers and their molar mass on the critical micelle concentration has been established.Complexes of synthesized star-shaped block copolymers with curcumin were obtained and the efficient binding of curcumin to polymer molecules was demonstrated.The behavior of the aqueous solutions of the prepared polymer stars and their complexes with curcumin was investigated by light scattering and turbidimetry methods.The influence of the structure and molar mass of star polymers on their thermoresponsiveness and the phase separation temperatures in aqueous solutions was analyzed.A slight increase in the phase separation temperature was found on passage from polymer solutions to solutions of polymer complexes with hydrophobic curcumin.
基金the funding support from the Smart Medicine and Engineering Interdisciplinary Innovation Project of Ningbo University(No.ZHYG003)。
文摘Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we develop a constitutive model that explicitly couples the solvent concentration,structural relaxation,and mechanical response.This framework is built on a multiplicative decomposition of deformation and an Eyring-type flow rule,with structural evolution described by an effective temperature.A generalized shift factor is introduced to quantify how the solvent concentration and effective temperature jointly affect the relaxation time,thereby integrating physical aging and plasticization.The model is subsequently applied to methacrylate(MA)-based copolymer networks immersed in phosphate-buffered saline for up to nine months.Simulations accurately capture key experimental features,including the strong softening of highly swellable networks,the partial recovery due to aging,and the mitigating role of hydrophobic crosslinking in reducing solvent uptake.While the current single-mode description cannot reproduce the full relaxation spectrum,it establishes an efficient framework for predicting the long-term mechanical performance under coupled environmental and mechanical loading.This study provides a constitutive description of solvent-swollen glassy polymers,offering mechanistic insight into the interplay between plasticization and aging.Beyond biomedical MA networks,this framework establishes a foundation for predicting the long-term performance of polymer glasses under coupled aqueous environmental and mechanical loading.
基金supported by the Startup Funds for Introduced Talents of Wuyi University(YJ202304)the National Natural Science Foundation of China(22375044).
文摘Organic room-temperature phosphorescence(RTP)materials are promising for bioimaging applications due to their tunable structures,excellent biocompatibility,and long-lived luminescence.However,the development of highly efficient organic RTP materials for aqueous systems remains challenging,as the organic phosphorescence is prone to being quenched by the dissolved oxygen in water.Herein,heteroaromatic carboxylic acids serve as ligand vips to construct a series of host-vip composites with nontoxic,dense EDTA-M(M=Ca,Mg,and Al)coordination polymer in water.These composites exhibit ultra-long pure RTP of vip molecules with phosphorescence quantum yield up to 53%,and lifetime up to 589.7 ms,due to the synergistic effect of dual-network structure:a coordinatively cross-linked network of EDTA-M,and a non-covalent bonded network formed by ligands and water molecules.The phosphorescence intensity is more than three times that of the composite with a single coordination network.Notably,the dual-network configuration can form a rigid and dense structure and block the intrusion of external H_(2)O and O_(2) molecules to avoid phosphorescence quenching in water.As a result,the RTP of the composites remains unchanged after 1 month in water.Furthermore,the nanoparticles fabricated from composites and anionic surfactants can be successfully applied in in vivo imaging of mice for the stable RTP in water.This work provides a novel strategy for the development of high-performance RTP materials in aqueous systems.
基金supported by the National Natural Science Foundation of China(Nos.51603005,52403186 and 52573150)Fujian Provincial Natural Science Foundation of China(No.2024J011447)+1 种基金Natural Science Foundation of Xiamen,China(No.3502Z20227305)the Postdoctoral Fellowship Program of CPSF(No.GZC20240095)。
文摘Near-infrared(NIR)light-responsive shape memory polymers(SMPs)show great promise for biomedical applications,but conventional photothermal agents suffer from high cost,complex preparation,or poor biocompatibility,while lignin-based alternatives exhibit insufficient photothermal conversion efficiency.Herein,we developed a novel strategy to enhance photothermal performance of lignin through sequential demethylation modification and Fe^(3+)complexation for constructing NIR light responsive SMPs.Dealkaline lignin(DL)was first demethylated using iodocyclohexane to produce demethylated lignin(DDL)with increased catechol content,which was then incorporated into polycaprolactone-based polyurethane synthesis followed by Fe^(3+)complexation.Results showed that DDL-Fe^(3+)complexes have significantly enhanced photothermal conversion performance,and the resulting PU-DDL+Fe^(3+)polyurethane with 0.5 wt%DDL content demonstrated a temperature increases of 39.8℃under 0.33 W·cm-2808 nm NIR irradiation.This excellent photothermal performance enables the shape-fixed PU-DDL+Fe^(3+)polyurethane to rapidly recover to its initial shape under NIR light irradiation.Additionally,PU-DDL+Fe^(3+)polyurethane exhibits good mechanical properties and biocompatibility,demonstrating significant biomedical application potential.
