Polymers that exhibit both biodegradability and chemical recyclability offer a promising solution to environmental pollution and resource scarcity. Poly(glycolic acid)(PGA) is a promising chemically recyclable polymer...Polymers that exhibit both biodegradability and chemical recyclability offer a promising solution to environmental pollution and resource scarcity. Poly(glycolic acid)(PGA) is a promising chemically recyclable polymer, characterized by its seawater degradability and high mechanical strength. In this study, aliphatic polycarbonates were synthesized through melt polycondensation and subsequently copolymerized with glycolide(GL) to produce chemically recyclable PGA based triblock copolymers with well-defined structures. The properties of these copolymers, including their thermal properties, crystallization behavior, and mechanical performance, can be effectively adjusted by modifying the structure and content of the middle block. Furthermore, an in-depth investigation reveals that the pyrolysis process involves ester exchange, radical, and back-biting reactions. In addition, the high-efficiency "Monomer↔Copolymer" chemical recycling loop has been established, achieving a remarkable yield exceeding 88% along with a purity greater than 99%.展开更多
Control crosslink network and chain connectivity are essential to develop shape memory polymers(SMPs)with high shape memory capabilities,adjustable response temperature,and satisfying mechanistical properties.In this ...Control crosslink network and chain connectivity are essential to develop shape memory polymers(SMPs)with high shape memory capabilities,adjustable response temperature,and satisfying mechanistical properties.In this study,novel poly(ε-caprolactone)(PCL)-poly(2-vinyl)ethylene glycol(PVEG)copolymers bearing multi-pendant vinyl groups is synthesized by branched-selective allylic etherification polymerization of vinylethylene carbonate(VEC)with linear and tetra-arm PCLs under a synergistic catalysis of palladium complex and boron reagent.Facile thiol-ene photo-click reaction of PCL-PVEG copolymers with multifunctional thiols can rapidly access a serious crosslinked SMPs with high shape memory performance.The thermal properties,mechanical properties and response temperature of the obtained SMPs are tunable by the variation of PCL prepolymers,vinyl contents and functionality of thiols.Moreover,high elastic modulus in the rubbery plateau region can be maintained effectively owing to high-density topological networks of the PCL materials.In addition,the utility of the present SMPs is further demonstrated by the post-functionalization via thiol-ene photo-click chemistry.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
A novel poly（styrene-co-acrylonitrile）-graft-polyethylene glycol （SAN-g-PEG） copolymer was synthesized as new solid-solid phase change materials （SSPCMs） by grafting PEG to the main chain of poly（styrene-co-acr...A novel poly（styrene-co-acrylonitrile）-graft-polyethylene glycol （SAN-g-PEG） copolymer was synthesized as new solid-solid phase change materials （SSPCMs） by grafting PEG to the main chain of poly（styrene-co-acrylonitrile）. The chemical structure of the SAN-g-PEG was confirmed by the Fourier transform infrared （FT-IR） and proton nuclear magnetic resonance （1H NMR） spectroscopy techniques. The thermal energy storage properties and the storage durability of the SAN-g-PEG were investigated by differential scanning calorimetry （DSC）. The SAN-g-PEG was endowed with the solid- solid phase transition temperatures within the range of 23-36 ℃ and the latent heat enthalpy ranged from 66.8 kJ/kg to 68.3 kJ/kg. Thermal cycling tests revealed that the SAN-g-PEG kept great heat storage durability after 1000 thermal cycles. The thermal stability was evaluated by a thermal gravity analysis （TGA）, and the initial decomposition temperature （Td） of SAN-g-PEG is 350 ℃, which proves that the SAN-g-PEG possessed good thermal stabilitv.展开更多
Poly (L-lactide)-poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. These copolymers presented special properties, such as ...Poly (L-lactide)-poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. These copolymers presented special properties, such as better miscibility between the two components, low crystallinity and better hydrophilicity, which can be modulated by adjusting the block lengths of the two components.展开更多
Novel Y-shaped block copolymers of poly（ethylene glycol） and poly（N-isopropylacrylamide）, PEG-b-（PNIPAM）2, were successfully synthesized through atom transfer radical polymerization （ATRP）. A difunctional macr...Novel Y-shaped block copolymers of poly（ethylene glycol） and poly（N-isopropylacrylamide）, PEG-b-（PNIPAM）2, were successfully synthesized through atom transfer radical polymerization （ATRP）. A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly（ethylene glycol） monomethyl ether （PEG）. The copolymers were obtained via the ATRP ofN-isopropylacrylamide （NIPAM） at 30℃ with CuCl/Me6TREN as a catalyst system and DMF/H2O （v/v = 3：1） mixture as solvent. The resulting copolymers were characterized by gel permeation chromatography （GPC） and ^1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions （PDI 〈 1.15）. Their phase transition temperatures and the corresponding enthalpy changes in aqueous solution were measured by differential scanning calorimetry （DSC）. As a result, the phase transition temperature of PEG45-b-（PNIPAM55）2 is higher than that of PNIPAM, however, the corresponding enthalpy change is much lower, indicating the significant influence of the macromolecular composition and architecture on the phase transition.展开更多
Supercritical carbon dioxide （scCO2） was used as a reaction medium in synthesizing amphiphilic graft copolymers composed of poly（styrene-co-maleic anhydride） （SMA） backbones and methoxyl poly（ethylene glycol） ...Supercritical carbon dioxide （scCO2） was used as a reaction medium in synthesizing amphiphilic graft copolymers composed of poly（styrene-co-maleic anhydride） （SMA） backbones and methoxyl poly（ethylene glycol） （MPEG） side chains via esterification. The synthesized copolymers were characterized by Fourier transform infrared spectroscopy （FTIR）, gel permeation chromatography （GPC）, IH-NMR, thermo-gravimetric analysis （TGA） and differential scanning calorimetric analysis （DSC）. The gelation phenomenon was suppressed effectively by tuning reaction conditions. The influences of scCO2 temperature and pressure on the conversion of anhydride were investigated. It was found that the highest conversion ratio occurred at 80~C under a constant pressure of 14 MPa or 26 MPa. With the increase of scCO2 pressure, the conversion ratio increased first, and then leveled off. The conversion ratio of anhydride could be controlled by regulating the reaction conditions. It was also revealed that using low molecular weight MPEG brought a high conversion ratio of anhydride.展开更多
Lactide was synthesized using lactic acid and stannous octoate as raw material and catalyst, respectively. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was prepared by lactide and poly (ethylene glycol) (PEG) via...Lactide was synthesized using lactic acid and stannous octoate as raw material and catalyst, respectively. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was prepared by lactide and poly (ethylene glycol) (PEG) via ring-opening polymerization. The most appropriate technological conditions of synthesis of lactide were researched in the paper. The copolymers were measured by Infrared spectroscopy (IR) and <sup>1</sup>H nuclear magnetic resonance (<sup>1</sup>H NMR). The results proved that the lactide and PLA-PEG were synthesized successfully. Hydrophilic performance of the copolymer was measured by a water contact angle tester after prepared into a flat membrane. The water contact angle changed from 81.5? to 71.6?, which proved that the hydrophily of PLA-PEG was better than PLA.展开更多
By reacting alkynylthiacalix[4]arenes with polyethylene glycol azido compounds,a series of novel thiacalix[4]arene 1,2,3-triazole-polyethylene glycol netty polymers were conveniently prepared in good yields.Their stru...By reacting alkynylthiacalix[4]arenes with polyethylene glycol azido compounds,a series of novel thiacalix[4]arene 1,2,3-triazole-polyethylene glycol netty polymers were conveniently prepared in good yields.Their structures and morphologies were studied by ^1H NMR,IR.and elemental analysis and SEM images.On average,approximately 28-31 thiacalixarene units exist in each polymeric molecule.These novel polymers possess excellent adsorption ability for both cationic and anionic dyes.The saturation adsorption capacity for Congo red reached 1.3-1.4 mmol/g.They exhibit high and stable adsorption ability in the scope of pH 5-9,and maintain good properties in five cycles.展开更多
The behaviour of monolayers of copolymers of oxyethylene and oxypropylene (UH29 and UH68), polypropylene glycol (UHPPG)and their binary mixtures on air-water interface has been investigated carefully on compression-ex...The behaviour of monolayers of copolymers of oxyethylene and oxypropylene (UH29 and UH68), polypropylene glycol (UHPPG)and their binary mixtures on air-water interface has been investigated carefully on compression-expansion cycles. The first compression isotherm is approximately an equilibrium one. In the UHPPG-UH29 and UHPPG-UH68 systems, the calculated average π-a curves based on simple additivity of the two individual components coincide with the experimental results reasonably well. It is suggested that the two components are miscible and form near-ideal solution at the air-water interface. The compression-expansion cycle experiments shows some degree of hysteresis. The order of degree of hysteresis for individual components is UH68>UH29>UHPPG. The explanation for the hysteresis is proposed.展开更多
A novel kind of copolymer with ABA-type block structure was synthesized by anionic ring-opening polymerization of beta-butyrolactone (beta-BL) in the presence of a PEG-based dicarboxylates as macroinitiators which wer...A novel kind of copolymer with ABA-type block structure was synthesized by anionic ring-opening polymerization of beta-butyrolactone (beta-BL) in the presence of a PEG-based dicarboxylates as macroinitiators which were prepared by the esterification of aliphatic cyclic anhydride and poly(ethylene glycol) (PEG) oligomers (M-n = 2000, 4000 and 6000) and conversion of potassium dicarboxylates. The resultant copolymers as well as the intermediates were characterized by IR, H-1-NMR and GPC.展开更多
Diblock copolymer poly(ethylene glycol) methyl ether–polylactide (MePEG–PLA) micelles were prepared by dialysis against water. Indomethacin (IMC) as a model drug was entrapped into the micelles by dialysis method. T...Diblock copolymer poly(ethylene glycol) methyl ether–polylactide (MePEG–PLA) micelles were prepared by dialysis against water. Indomethacin (IMC) as a model drug was entrapped into the micelles by dialysis method. The critical micelle concentration (CMC) of the prepared micelles in distilled water investigated by fluorescence spectroscopy was 0.0051 mg/mL which is lower than that of common low molecular weight surfactants. The diameters of MePEGPLA micelles and IMC loaded MePEGPLA micelles in a number-averaged scale measured by dynamic light scattering were 52.4 and 53.7 nm respectively. The observation with transmission electron microscope and scanning electron microscope showed that the appearance of MePEGPLA micelles was in a spherical shape. The content of IMC incorporated in the core portion of the micelles was 18% (ω). The effects of the synthesis method of the copolymer on the polydispersity of the micelles and the yield of the micelles formation were discussed.展开更多
Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylen...Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate(P(EO2-co-EG4/5))are synthesized via atom transfer radical polymerization(ATRP).The successful synthesis and the narrow polydispersity index(PDI)of two copolymers are indicated by 1H nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)analyses.The transition behaviors of polymers in the aqueous solution are demonstrated by changes in turbidity and particle sizes.The transition behavior of P(EO2-co-EG4/5)is found to be milder than that of P(EO2-co-EO4/5).Moreover,the presence of hydrogen bonds without thermo-responsive properties established by hydroxyl groups in the end-side chain of P(EO_(2)-co-EG_(4/5))hinders the dehydration at the transition temperature(TT).Attenuated total reflection Fourier transform infrared spectrometry(ATR-FTIR)analysis along with contact angle measurements reveals that both P(EO_(2)-co-EO_(4/5))and P(EO_(2)-co-EG_(4/5))films undergo phase transitions from hydrophilicity to hydrophobicity above TT.By examining the swelling and collapse behaviors of the polymer films during phase transitions,it can be concluded that the end hydroxyl groups may establish hydrogen bonds with neighboring ether groups within the films,which remain intact throughout the phase transition process due to their strong bonding interactions.This leads to an increase in steric hindrance within swollen films thereby impeding dehydration processes and inducing hysteresis during phase transitions.展开更多
Peripheral nerve injuries result in the rapid degeneration of distal nerve segments and immediate loss of motor and sensory functions;behavioral recovery is typically poor.We used a plasmalemmal fusogen,polyethylene g...Peripheral nerve injuries result in the rapid degeneration of distal nerve segments and immediate loss of motor and sensory functions;behavioral recovery is typically poor.We used a plasmalemmal fusogen,polyethylene glycol(PEG),to immediately fuse closely apposed open ends of severed proximal and distal axons in rat sciatic nerves.We have previously reported that sciatic nerve axons repaired by PEG-fusion do not undergo Wallerian degeneration,and PEG-fused animals exhibit rapid(within 2–6 weeks)and extensive locomotor recovery.Furthermore,our previous report showed that PEG-fusion of severed sciatic motor axons was non-specific,i.e.,spinal motoneurons in PEG-fused animals were found to project to appropriate as well as inappropriate target muscles.In this study,we examined the consequences of PEG-fusion for sensory axons of the sciatic nerve.Young adult male and female rats(Sprague–Dawley)received either a unilateral single cut or ablation injury to the sciatic nerve and subsequent repair with or without(Negative Control)the application of PEG.Compound action potentials recorded immediately after PEG-fusion repair confirmed conduction across the injury site.The success of PEG-fusion was confirmed through Sciatic Functional Index testing with PEG-fused animals showing improvement in locomotor function beginning at 35 days postoperatively.At 2–42 days postoperatively,we anterogradely labeled sensory afferents from the dorsal aspect of the hindpaw following bilateral intradermal injection of wheat germ agglutinin conjugated horseradish peroxidase.PEG-fusion repair reestablished axonal continuity.Compared to unoperated animals,labeled sensory afferents ipsilateral to the injury in PEG-fused animals were found in the appropriate area of the dorsal horn,as well as inappropriate mediolateral and rostrocaudal areas.Unexpectedly,despite having intact peripheral nerves,similar reorganizations of labeled sensory afferents were also observed contralateral to the injury and repair.This central reorganization may contribute to the improved behavioral recovery seen after PEG-fusion repair,supporting the use of this novel repair methodology over currently available treatments.展开更多
Herein,an external crosslinker facilitated the hypercrosslinking of ferrocene and a nitrogen heterocyclic compound(either melamine or imidazole)through a direct Friedel-Crafts reaction,which led to the formation of ni...Herein,an external crosslinker facilitated the hypercrosslinking of ferrocene and a nitrogen heterocyclic compound(either melamine or imidazole)through a direct Friedel-Crafts reaction,which led to the formation of nitrogen-containing hypercrosslinked fer-rocene polymer precursors(HCP-FCs).Subsequent carbonization of these precursors results in the production of iron-nitrogen-doped por-ous carbon absorbers(Fe-NPCs).The Fe-NPCs demonstrate a porous structure comprising aggregated nanotubes and nanospheres.The porosity of this structure can be modulated by adjusting the iron and nitrogen contents to optimize impedance matching.The uniform dis-tribution of Fe-N_(x)C,N dipoles,andα-Fe within the carbon matrix can be ensured by using hypercrosslinked ferrocenes in constructing porous carbon,providing the absorber with numerous polarization sites and a conductive network.The electromagnetic wave absorption performance of the specially designed Fe-NPC-M_(2)absorbers is satisfactory,revealing a minimum reflection loss of-55.3 dB at 2.5 mm and an effective absorption bandwidth of 6.00 GHz at 2.0 mm.By utilizing hypercrosslinked polymers(HCPs)as precursors,a novel method for developing highly efficient carbon-based absorbing agents is introduced in this research.展开更多
A poly(ethylene glycol) (PEG) based macroinitiator (MI) with terminal chloride atom at both ends was prepared by the reaction of PEG-400 with chloroacetyl chloride and used for the cationic polymerization of dodecyl v...A poly(ethylene glycol) (PEG) based macroinitiator (MI) with terminal chloride atom at both ends was prepared by the reaction of PEG-400 with chloroacetyl chloride and used for the cationic polymerization of dodecyl vinyl ether (DVE) yielding ABA type block copolymer. The block copolymer was then used as the surfactant for the emulsion polymerization of vinyl acetate and styrene in the presence of potassium persulfate as an initiator. The effects of new polymeric emulsifier on the physicochemical properties of obtained latexes were investigated depending on surfactant percentage in homopolymerizations.展开更多
Cholesteric liquid crystals(CLCs)exhibit unique helical superstructures that selectively reflect circularly polarized light,enabling them to dynamically respond to environmental changes with tunable structural colors....Cholesteric liquid crystals(CLCs)exhibit unique helical superstructures that selectively reflect circularly polarized light,enabling them to dynamically respond to environmental changes with tunable structural colors.This dynamic color-changing capability is crucial for applications that require adaptable optical properties,positioning CLCs as key materials in advanced photonic technologies.This review focuses on the mechanisms of dynamic color tuning in CLCs across various forms,including small molecules,cholesteric liquid crystal elastomers(CLCEs),and cholesteric liquid crystal networks(CLCNs),and emphasizes the distinct responsive coloration each structure provides.Key developments in photochromic mechanisms based on azobenzene,dithienylethene,and molecular motor switches,are discussed for their roles in enhancing the stability and tuning range of CLCs.We examine the color-changing behaviors of CLCEs under mechanical stimuli and CLCNs under swelling,highlighting the advantages of each form.Following this,applications of dynamic color-tuning CLCs in information encryption,adaptive camouflage,and smart sensing technologies are explored.The review concludes with an outlook on current challenges and future directions in CLC research,particularly in biomimetic systems and dynamic photonic devices,aiming to broaden their functional applications and impact.展开更多
As a typical bioflavonoid,diosmetin is desirable in the field of natural medicine,healthy food,and cosmetics by anti-cancer,antibacterial,antioxidant,estrogen-like and anti-inflammatory activities,and it comes from a ...As a typical bioflavonoid,diosmetin is desirable in the field of natural medicine,healthy food,and cosmetics by anti-cancer,antibacterial,antioxidant,estrogen-like and anti-inflammatory activities,and it comes from a wide range of sources in traditional Chinese medicine like spider fragrance,spearmint and chrysanthemum,as well as in Citrus fruit.However,traditional analytical methods such as silica gel column chromatography face multiple challenges in the selective extraction of diosmetin from biological materials and traditional Chinese medicinal materials.Therefore,it is urgent to develop a new type of absorbent with high efficiency,recyclability and good specificity to diosmetin.In this investigation,a magnetic surface molecularly imprinted polymer(labeled as Diosmetin/SMIPs)was synthesized employing magnetic nanoparticles as the carrier and 4-vinylpyridinyl(4-VP)as the functional monomer by surface imprinting technology.The functional monomer was screened by the binding energy(△E)between functional monomers and template molecules via computational simulation.The Diosmetin/SMIPs had a high level of specific recognition and adsorption capability towards diosmetin with a 20.25 mg g^(-1) adsorption capacity and an imprinting factor(IF)of 2.28.Additionally,it demonstrated excellent regeneration performance with 8 adsorption/desorption cycles.In addition,91.20%-94.16% of spiked diosmetin was recovered from the lemon peel samples.The strategy of constructing Diosmetin/SMIPs based on computational simulation can effectively enhance the specific adsorption performance of diosmetin.Meanwhile,Diosmetin/SMIPs synthesized by imprinting polymerization showed excellent anti-interference and reusability,and realized efficient targeted extraction of diosmetin from lemon peel samples.The results of this investigation provide a promising adsorbent for selective enrichment of diosmetin from Citrus fruit and complicated materials.展开更多
In recent years,smart materials have emerged as a groundbreaking innovation in the field of water filtration,offering sustainable,efficient,and environmentally friendly solutions to address the growing global water cr...In recent years,smart materials have emerged as a groundbreaking innovation in the field of water filtration,offering sustainable,efficient,and environmentally friendly solutions to address the growing global water crisis.This review explores the latest advancements in the application of smart materials—including biomaterials,nanocomposites,and stimuli-responsive polymers—specifically for water treatment.It examines their effectiveness in detecting and removing various types of pollutants,including organic contaminants,heavy metals,and microbial infections,while adapting to dynamic environmental conditions such as fluctuations in temperature,pH,and pressure.The review highlights the remarkable versatility of these materials,emphasizing their multifunctionality,which allows them to address a wide range of water quality issues with high efficiency and low environmental impact.Moreover,it explores the potential of smart materials to overcome significant challenges in water purification,such as the need for real-time pollutant detection and targeted removal processes.The research also discusses the scalability and future development of these materials,considering their cost-effectiveness and potential for large-scale application.By aligning with the principles of sustainable development,smart materials represent a promising direction for ensuring global water security,offering both innovative solutions for current water pollution issues and long-term benefits for the environment and public health.展开更多
Methoxy poly(ethylene glycol)-poly(D,L-lactide) block copolymers (PEG-PLA) were prepared through ring-opening polymerization.The oil in water suspension method was used to prepare block copolymer micelles. The critica...Methoxy poly(ethylene glycol)-poly(D,L-lactide) block copolymers (PEG-PLA) were prepared through ring-opening polymerization.The oil in water suspension method was used to prepare block copolymer micelles. The critical micelle concentration (CMC) by fluorescence spectroscopy was 0.0056 mg·ml -1 . The physical state of the inner core region of micelles was characterized with 1HNMR. The size of indomethacin (IMC) loaded micelles measured by dynamic light scattering (DLS) showed narrow monodisperse size distribution and the average diameters were less than 50 nm. In addition, the nanoparticles with relatively high drug loading content (DLC) were obtained.展开更多
基金financially supported by the National Key R&D Program of China(No.2021YFB3801901)the Institutional Research Fund from Sichuan University(No.2020SCUNL205)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Higher Education Discipline Innovation Project(No.B20001)。
文摘Polymers that exhibit both biodegradability and chemical recyclability offer a promising solution to environmental pollution and resource scarcity. Poly(glycolic acid)(PGA) is a promising chemically recyclable polymer, characterized by its seawater degradability and high mechanical strength. In this study, aliphatic polycarbonates were synthesized through melt polycondensation and subsequently copolymerized with glycolide(GL) to produce chemically recyclable PGA based triblock copolymers with well-defined structures. The properties of these copolymers, including their thermal properties, crystallization behavior, and mechanical performance, can be effectively adjusted by modifying the structure and content of the middle block. Furthermore, an in-depth investigation reveals that the pyrolysis process involves ester exchange, radical, and back-biting reactions. In addition, the high-efficiency "Monomer↔Copolymer" chemical recycling loop has been established, achieving a remarkable yield exceeding 88% along with a purity greater than 99%.
基金financially supported by the National Natural Science Foundation of China(No.22171182)Sichuan Tianfu Emei Plan.
文摘Control crosslink network and chain connectivity are essential to develop shape memory polymers(SMPs)with high shape memory capabilities,adjustable response temperature,and satisfying mechanistical properties.In this study,novel poly(ε-caprolactone)(PCL)-poly(2-vinyl)ethylene glycol(PVEG)copolymers bearing multi-pendant vinyl groups is synthesized by branched-selective allylic etherification polymerization of vinylethylene carbonate(VEC)with linear and tetra-arm PCLs under a synergistic catalysis of palladium complex and boron reagent.Facile thiol-ene photo-click reaction of PCL-PVEG copolymers with multifunctional thiols can rapidly access a serious crosslinked SMPs with high shape memory performance.The thermal properties,mechanical properties and response temperature of the obtained SMPs are tunable by the variation of PCL prepolymers,vinyl contents and functionality of thiols.Moreover,high elastic modulus in the rubbery plateau region can be maintained effectively owing to high-density topological networks of the PCL materials.In addition,the utility of the present SMPs is further demonstrated by the post-functionalization via thiol-ene photo-click chemistry.
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Financial support of this work is provided by National Natural Science Foundation of China(No.51373027)Education Department of General Item of China(No.LR2012017)
文摘A novel poly（styrene-co-acrylonitrile）-graft-polyethylene glycol （SAN-g-PEG） copolymer was synthesized as new solid-solid phase change materials （SSPCMs） by grafting PEG to the main chain of poly（styrene-co-acrylonitrile）. The chemical structure of the SAN-g-PEG was confirmed by the Fourier transform infrared （FT-IR） and proton nuclear magnetic resonance （1H NMR） spectroscopy techniques. The thermal energy storage properties and the storage durability of the SAN-g-PEG were investigated by differential scanning calorimetry （DSC）. The SAN-g-PEG was endowed with the solid- solid phase transition temperatures within the range of 23-36 ℃ and the latent heat enthalpy ranged from 66.8 kJ/kg to 68.3 kJ/kg. Thermal cycling tests revealed that the SAN-g-PEG kept great heat storage durability after 1000 thermal cycles. The thermal stability was evaluated by a thermal gravity analysis （TGA）, and the initial decomposition temperature （Td） of SAN-g-PEG is 350 ℃, which proves that the SAN-g-PEG possessed good thermal stabilitv.
基金The authors are Indebted to the National Basic Science Rescarch and Development Grants(973)(No.1999054306).
文摘Poly (L-lactide)-poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. These copolymers presented special properties, such as better miscibility between the two components, low crystallinity and better hydrophilicity, which can be modulated by adjusting the block lengths of the two components.
基金support from the National Natural Science Foundation of China(No. 20134020)the Visiting Scholar Project of Shandong Province of China(No.20081001)the Science Research Fund of Shandong Jiaotong University of China(No.Z200802)
文摘Novel Y-shaped block copolymers of poly（ethylene glycol） and poly（N-isopropylacrylamide）, PEG-b-（PNIPAM）2, were successfully synthesized through atom transfer radical polymerization （ATRP）. A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly（ethylene glycol） monomethyl ether （PEG）. The copolymers were obtained via the ATRP ofN-isopropylacrylamide （NIPAM） at 30℃ with CuCl/Me6TREN as a catalyst system and DMF/H2O （v/v = 3：1） mixture as solvent. The resulting copolymers were characterized by gel permeation chromatography （GPC） and ^1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions （PDI 〈 1.15）. Their phase transition temperatures and the corresponding enthalpy changes in aqueous solution were measured by differential scanning calorimetry （DSC）. As a result, the phase transition temperature of PEG45-b-（PNIPAM55）2 is higher than that of PNIPAM, however, the corresponding enthalpy change is much lower, indicating the significant influence of the macromolecular composition and architecture on the phase transition.
基金financially supported by the 973 Program of China(No.2009CB623402)the Fundamental Research Funds for the Central Universities(MOE Engineering Research Center of Membrane and Water Treatment Technology, Grant no.KYJD09011)+1 种基金the 863 Program of China(No.2009AA062902)Zhejiang Provincial Sci & Tech Plan of China(No.2010C31028)
文摘Supercritical carbon dioxide （scCO2） was used as a reaction medium in synthesizing amphiphilic graft copolymers composed of poly（styrene-co-maleic anhydride） （SMA） backbones and methoxyl poly（ethylene glycol） （MPEG） side chains via esterification. The synthesized copolymers were characterized by Fourier transform infrared spectroscopy （FTIR）, gel permeation chromatography （GPC）, IH-NMR, thermo-gravimetric analysis （TGA） and differential scanning calorimetric analysis （DSC）. The gelation phenomenon was suppressed effectively by tuning reaction conditions. The influences of scCO2 temperature and pressure on the conversion of anhydride were investigated. It was found that the highest conversion ratio occurred at 80~C under a constant pressure of 14 MPa or 26 MPa. With the increase of scCO2 pressure, the conversion ratio increased first, and then leveled off. The conversion ratio of anhydride could be controlled by regulating the reaction conditions. It was also revealed that using low molecular weight MPEG brought a high conversion ratio of anhydride.
文摘Lactide was synthesized using lactic acid and stannous octoate as raw material and catalyst, respectively. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was prepared by lactide and poly (ethylene glycol) (PEG) via ring-opening polymerization. The most appropriate technological conditions of synthesis of lactide were researched in the paper. The copolymers were measured by Infrared spectroscopy (IR) and <sup>1</sup>H nuclear magnetic resonance (<sup>1</sup>H NMR). The results proved that the lactide and PLA-PEG were synthesized successfully. Hydrophilic performance of the copolymer was measured by a water contact angle tester after prepared into a flat membrane. The water contact angle changed from 81.5? to 71.6?, which proved that the hydrophily of PLA-PEG was better than PLA.
基金Financial support from the National Natural Science Foundation of China(No:21406036)Fujian Natural Science Foundation of China(No.2014J01034)+1 种基金Project of Fujian provincial department of education(Nos.JA11044,JA10056,JB13011)the Program for Innovative Research Team in Science and Technology in Fujian Province University were greatly acknowledged
文摘By reacting alkynylthiacalix[4]arenes with polyethylene glycol azido compounds,a series of novel thiacalix[4]arene 1,2,3-triazole-polyethylene glycol netty polymers were conveniently prepared in good yields.Their structures and morphologies were studied by ^1H NMR,IR.and elemental analysis and SEM images.On average,approximately 28-31 thiacalixarene units exist in each polymeric molecule.These novel polymers possess excellent adsorption ability for both cationic and anionic dyes.The saturation adsorption capacity for Congo red reached 1.3-1.4 mmol/g.They exhibit high and stable adsorption ability in the scope of pH 5-9,and maintain good properties in five cycles.
文摘The behaviour of monolayers of copolymers of oxyethylene and oxypropylene (UH29 and UH68), polypropylene glycol (UHPPG)and their binary mixtures on air-water interface has been investigated carefully on compression-expansion cycles. The first compression isotherm is approximately an equilibrium one. In the UHPPG-UH29 and UHPPG-UH68 systems, the calculated average π-a curves based on simple additivity of the two individual components coincide with the experimental results reasonably well. It is suggested that the two components are miscible and form near-ideal solution at the air-water interface. The compression-expansion cycle experiments shows some degree of hysteresis. The order of degree of hysteresis for individual components is UH68>UH29>UHPPG. The explanation for the hysteresis is proposed.
文摘A novel kind of copolymer with ABA-type block structure was synthesized by anionic ring-opening polymerization of beta-butyrolactone (beta-BL) in the presence of a PEG-based dicarboxylates as macroinitiators which were prepared by the esterification of aliphatic cyclic anhydride and poly(ethylene glycol) (PEG) oligomers (M-n = 2000, 4000 and 6000) and conversion of potassium dicarboxylates. The resultant copolymers as well as the intermediates were characterized by IR, H-1-NMR and GPC.
基金National Natural Science Foundation of China (No.29836130)
文摘Diblock copolymer poly(ethylene glycol) methyl ether–polylactide (MePEG–PLA) micelles were prepared by dialysis against water. Indomethacin (IMC) as a model drug was entrapped into the micelles by dialysis method. The critical micelle concentration (CMC) of the prepared micelles in distilled water investigated by fluorescence spectroscopy was 0.0051 mg/mL which is lower than that of common low molecular weight surfactants. The diameters of MePEGPLA micelles and IMC loaded MePEGPLA micelles in a number-averaged scale measured by dynamic light scattering were 52.4 and 53.7 nm respectively. The observation with transmission electron microscope and scanning electron microscope showed that the appearance of MePEGPLA micelles was in a spherical shape. The content of IMC incorporated in the core portion of the micelles was 18% (ω). The effects of the synthesis method of the copolymer on the polydispersity of the micelles and the yield of the micelles formation were discussed.
基金Fujian External Cooperation project of Natural Science Foundation,China(No.2022I0042)。
文摘Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate(P(EO2-co-EG4/5))are synthesized via atom transfer radical polymerization(ATRP).The successful synthesis and the narrow polydispersity index(PDI)of two copolymers are indicated by 1H nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)analyses.The transition behaviors of polymers in the aqueous solution are demonstrated by changes in turbidity and particle sizes.The transition behavior of P(EO2-co-EG4/5)is found to be milder than that of P(EO2-co-EO4/5).Moreover,the presence of hydrogen bonds without thermo-responsive properties established by hydroxyl groups in the end-side chain of P(EO_(2)-co-EG_(4/5))hinders the dehydration at the transition temperature(TT).Attenuated total reflection Fourier transform infrared spectrometry(ATR-FTIR)analysis along with contact angle measurements reveals that both P(EO_(2)-co-EO_(4/5))and P(EO_(2)-co-EG_(4/5))films undergo phase transitions from hydrophilicity to hydrophobicity above TT.By examining the swelling and collapse behaviors of the polymer films during phase transitions,it can be concluded that the end hydroxyl groups may establish hydrogen bonds with neighboring ether groups within the films,which remain intact throughout the phase transition process due to their strong bonding interactions.This leads to an increase in steric hindrance within swollen films thereby impeding dehydration processes and inducing hysteresis during phase transitions.
基金supported by the Department of Defense AFIRMⅢW81XWH-20-2-0029 grant subcontractLone Star Paralysis gift,UT POC19-1774-13 grant+1 种基金Neuraptive Therapeutics Inc.26-7724-56 grantNational Institutes of Health R01-NS128086(all to GDB)。
文摘Peripheral nerve injuries result in the rapid degeneration of distal nerve segments and immediate loss of motor and sensory functions;behavioral recovery is typically poor.We used a plasmalemmal fusogen,polyethylene glycol(PEG),to immediately fuse closely apposed open ends of severed proximal and distal axons in rat sciatic nerves.We have previously reported that sciatic nerve axons repaired by PEG-fusion do not undergo Wallerian degeneration,and PEG-fused animals exhibit rapid(within 2–6 weeks)and extensive locomotor recovery.Furthermore,our previous report showed that PEG-fusion of severed sciatic motor axons was non-specific,i.e.,spinal motoneurons in PEG-fused animals were found to project to appropriate as well as inappropriate target muscles.In this study,we examined the consequences of PEG-fusion for sensory axons of the sciatic nerve.Young adult male and female rats(Sprague–Dawley)received either a unilateral single cut or ablation injury to the sciatic nerve and subsequent repair with or without(Negative Control)the application of PEG.Compound action potentials recorded immediately after PEG-fusion repair confirmed conduction across the injury site.The success of PEG-fusion was confirmed through Sciatic Functional Index testing with PEG-fused animals showing improvement in locomotor function beginning at 35 days postoperatively.At 2–42 days postoperatively,we anterogradely labeled sensory afferents from the dorsal aspect of the hindpaw following bilateral intradermal injection of wheat germ agglutinin conjugated horseradish peroxidase.PEG-fusion repair reestablished axonal continuity.Compared to unoperated animals,labeled sensory afferents ipsilateral to the injury in PEG-fused animals were found in the appropriate area of the dorsal horn,as well as inappropriate mediolateral and rostrocaudal areas.Unexpectedly,despite having intact peripheral nerves,similar reorganizations of labeled sensory afferents were also observed contralateral to the injury and repair.This central reorganization may contribute to the improved behavioral recovery seen after PEG-fusion repair,supporting the use of this novel repair methodology over currently available treatments.
基金supported by the National Natural Science Foundation of China(No.51803041)the University and Local Integration Development Project of Yantai,China(No.2022 XDRHXMXK08).
文摘Herein,an external crosslinker facilitated the hypercrosslinking of ferrocene and a nitrogen heterocyclic compound(either melamine or imidazole)through a direct Friedel-Crafts reaction,which led to the formation of nitrogen-containing hypercrosslinked fer-rocene polymer precursors(HCP-FCs).Subsequent carbonization of these precursors results in the production of iron-nitrogen-doped por-ous carbon absorbers(Fe-NPCs).The Fe-NPCs demonstrate a porous structure comprising aggregated nanotubes and nanospheres.The porosity of this structure can be modulated by adjusting the iron and nitrogen contents to optimize impedance matching.The uniform dis-tribution of Fe-N_(x)C,N dipoles,andα-Fe within the carbon matrix can be ensured by using hypercrosslinked ferrocenes in constructing porous carbon,providing the absorber with numerous polarization sites and a conductive network.The electromagnetic wave absorption performance of the specially designed Fe-NPC-M_(2)absorbers is satisfactory,revealing a minimum reflection loss of-55.3 dB at 2.5 mm and an effective absorption bandwidth of 6.00 GHz at 2.0 mm.By utilizing hypercrosslinked polymers(HCPs)as precursors,a novel method for developing highly efficient carbon-based absorbing agents is introduced in this research.
基金This work were supported by the Turkish Scientific and Technological Research Council(TUBITAK)(Project Number:108T722)Scientific Research Projects Coordination Center of Yildiz Technical University(Project Number:2012-01-02-KAP04).
文摘A poly(ethylene glycol) (PEG) based macroinitiator (MI) with terminal chloride atom at both ends was prepared by the reaction of PEG-400 with chloroacetyl chloride and used for the cationic polymerization of dodecyl vinyl ether (DVE) yielding ABA type block copolymer. The block copolymer was then used as the surfactant for the emulsion polymerization of vinyl acetate and styrene in the presence of potassium persulfate as an initiator. The effects of new polymeric emulsifier on the physicochemical properties of obtained latexes were investigated depending on surfactant percentage in homopolymerizations.
基金financially supported by the National Natural Science Foundation of China(Nos.52233001,51927805,and 52173110)the Innovation Program of Shanghai Municipal Education Commission(No.2023ZKZD07)the Shanghai Rising-Star Program(No.22QA1401200)。
文摘Cholesteric liquid crystals(CLCs)exhibit unique helical superstructures that selectively reflect circularly polarized light,enabling them to dynamically respond to environmental changes with tunable structural colors.This dynamic color-changing capability is crucial for applications that require adaptable optical properties,positioning CLCs as key materials in advanced photonic technologies.This review focuses on the mechanisms of dynamic color tuning in CLCs across various forms,including small molecules,cholesteric liquid crystal elastomers(CLCEs),and cholesteric liquid crystal networks(CLCNs),and emphasizes the distinct responsive coloration each structure provides.Key developments in photochromic mechanisms based on azobenzene,dithienylethene,and molecular motor switches,are discussed for their roles in enhancing the stability and tuning range of CLCs.We examine the color-changing behaviors of CLCEs under mechanical stimuli and CLCNs under swelling,highlighting the advantages of each form.Following this,applications of dynamic color-tuning CLCs in information encryption,adaptive camouflage,and smart sensing technologies are explored.The review concludes with an outlook on current challenges and future directions in CLC research,particularly in biomimetic systems and dynamic photonic devices,aiming to broaden their functional applications and impact.
基金supported by the National Natural Science Foundation of China(Nos.32301259,32101228,32271527 and 32371536)the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(Nos.2022C02023 and 2023C02015)+1 种基金the Research Foundation of Talented Scholars of Zhejiang A&F University(No.2021LFR058)the Dean-ship of Scientific Research at Northern Border University,Arar,KSA for funding this research work through the project number“NBU-FPEJ-2024-177-01”.
文摘As a typical bioflavonoid,diosmetin is desirable in the field of natural medicine,healthy food,and cosmetics by anti-cancer,antibacterial,antioxidant,estrogen-like and anti-inflammatory activities,and it comes from a wide range of sources in traditional Chinese medicine like spider fragrance,spearmint and chrysanthemum,as well as in Citrus fruit.However,traditional analytical methods such as silica gel column chromatography face multiple challenges in the selective extraction of diosmetin from biological materials and traditional Chinese medicinal materials.Therefore,it is urgent to develop a new type of absorbent with high efficiency,recyclability and good specificity to diosmetin.In this investigation,a magnetic surface molecularly imprinted polymer(labeled as Diosmetin/SMIPs)was synthesized employing magnetic nanoparticles as the carrier and 4-vinylpyridinyl(4-VP)as the functional monomer by surface imprinting technology.The functional monomer was screened by the binding energy(△E)between functional monomers and template molecules via computational simulation.The Diosmetin/SMIPs had a high level of specific recognition and adsorption capability towards diosmetin with a 20.25 mg g^(-1) adsorption capacity and an imprinting factor(IF)of 2.28.Additionally,it demonstrated excellent regeneration performance with 8 adsorption/desorption cycles.In addition,91.20%-94.16% of spiked diosmetin was recovered from the lemon peel samples.The strategy of constructing Diosmetin/SMIPs based on computational simulation can effectively enhance the specific adsorption performance of diosmetin.Meanwhile,Diosmetin/SMIPs synthesized by imprinting polymerization showed excellent anti-interference and reusability,and realized efficient targeted extraction of diosmetin from lemon peel samples.The results of this investigation provide a promising adsorbent for selective enrichment of diosmetin from Citrus fruit and complicated materials.
文摘In recent years,smart materials have emerged as a groundbreaking innovation in the field of water filtration,offering sustainable,efficient,and environmentally friendly solutions to address the growing global water crisis.This review explores the latest advancements in the application of smart materials—including biomaterials,nanocomposites,and stimuli-responsive polymers—specifically for water treatment.It examines their effectiveness in detecting and removing various types of pollutants,including organic contaminants,heavy metals,and microbial infections,while adapting to dynamic environmental conditions such as fluctuations in temperature,pH,and pressure.The review highlights the remarkable versatility of these materials,emphasizing their multifunctionality,which allows them to address a wide range of water quality issues with high efficiency and low environmental impact.Moreover,it explores the potential of smart materials to overcome significant challenges in water purification,such as the need for real-time pollutant detection and targeted removal processes.The research also discusses the scalability and future development of these materials,considering their cost-effectiveness and potential for large-scale application.By aligning with the principles of sustainable development,smart materials represent a promising direction for ensuring global water security,offering both innovative solutions for current water pollution issues and long-term benefits for the environment and public health.
文摘Methoxy poly(ethylene glycol)-poly(D,L-lactide) block copolymers (PEG-PLA) were prepared through ring-opening polymerization.The oil in water suspension method was used to prepare block copolymer micelles. The critical micelle concentration (CMC) by fluorescence spectroscopy was 0.0056 mg·ml -1 . The physical state of the inner core region of micelles was characterized with 1HNMR. The size of indomethacin (IMC) loaded micelles measured by dynamic light scattering (DLS) showed narrow monodisperse size distribution and the average diameters were less than 50 nm. In addition, the nanoparticles with relatively high drug loading content (DLC) were obtained.
