Compatibilization is crucial for the blending of immiscible polymers to develop high-performance composites;however,traditional compatibilization by copolymers(pre-made or in-situ generation)suffers from weak interfac...Compatibilization is crucial for the blending of immiscible polymers to develop high-performance composites;however,traditional compatibilization by copolymers(pre-made or in-situ generation)suffers from weak interface anchoring,and inorganic particles have gained extensive attention recently owing to their large interfacial desorption energy,while their low affinity to bulk components is a drawback.In this study,an interfacial atom transfer radical polymerization(ATRP)technique was employed to grow polystyrene(PS)and poly(2-hydroxyethyl methacrylate)(PHEMA)simultaneously on different hemispheres of Br-functionalized SiO_(2) nanoparticles to stabilize a Pickering emulsion,whereby a brush-type Janus nanoparticle(SiO_(2)@JNP)was developed.The polymer brushes were well-characterized,and the Janus feature was validated by transmission electron microscope(TEM)observation of the sole hemisphere grafting of SiO_(2)-PS as a control sample.SiO_(2)@JNP was demonstrated to be an efficient compatibilizer for a PS/poly(methyl methacrylate)(PMMA)immiscible blend,and the droplet-matrix morphology was significantly refined.The mechanical strength and toughness of the blend were synchronously enhanced at a low content SiO_(2)@JNP optimized~0.9 wt%,with the tensile strength,elongation at break and impact strength increased by 17.7%,26.6%and 19.6%,respectively.This enhancement may be attributed to the entanglements between the grafted polymer brushes and individual components that improve the particle-bulk phase affinity and enforce interfacial adhesion.展开更多
Evolution and fractal character of the phase morphology of high impact polystyrene/poly（cis-butadiene） rubber （HIPS/PcBR） blends during melting and mixing were investigated using scanning electron microscopy （SEM...Evolution and fractal character of the phase morphology of high impact polystyrene/poly（cis-butadiene） rubber （HIPS/PcBR） blends during melting and mixing were investigated using scanning electron microscopy （SEM）. The characteristic length L was defined as the size of particles of the dispersed phase in blends. Different fractal dimensions, Df and Din, were introduced to study the distribution width of phase dimensions in the dimensionless region and the uniformity of the spatial distribution of particles, respectively. The results showed that the average characteristic length Lm and Df increase as the volume fraction of the dispersed phase increases, when the volume fraction of the dispersed phase is lower than 50%. In other words, the size of particles increases and their distribution in the dimensionless region becomes more uniform. Meanwhile, the uniformity of the spatial distribution becomes more perfect as the volume fraction increases. At a certain composition, Lm decreases in the initial stage of the mixing and levels off in the late stage. In the initial stage, Df becomes large rapidly with the process of blending, which means that the distribution of L in the dimensionless region becomes more uniform. Meanwhile, the spatial distribution tends to be ideal rapidly in the early stage and fluctuates in a definite range in the late stage of the mixing.展开更多
This paper focuses on the effects of the PSt content of polystyrene (PSt)-poly (dimethylsiloxane) (PDMS) interpenetrateing network (IPN) polymer membranes, on the pervaporation (PV) characteristics during the removal ...This paper focuses on the effects of the PSt content of polystyrene (PSt)-poly (dimethylsiloxane) (PDMS) interpenetrateing network (IPN) polymer membranes, on the pervaporation (PV) characteristics during the removal of benzene from an aqueous solution of dilute benzene. When an aqueous solution of 0.05wt% benzene was permeated through the PSt-PDMS IPN membranes, they showed high benzene/water selectivity. Both the permeability and the benzene/water selectivity of the membranes were enhanced with increasing PSt content in the PSt-PDMS IPN membrane. The physicochemical mechanism of permeation and separation through the PSt-PDMS IPN membranes during PV is also discussed. The best normalized permeation rate, separation factor for benzene selectivity, and PV separation index of the PSt-PDMS IPN membrane were 1.27 × 10-6 kgm (m2hr)-1, 3293, and 41821, respectively. These PV characteristics are discussed from the viewpoint of the chemical and physical structure of the PSt-PDMS IPN membranes.展开更多
The adsorption of linear poly(N-isopropylacrylamide) (PNIPAM) chains on surfactant-free polystyrene (PS) nanoparticles was used as a model system to study the hydrophobic adsorption of polymer on the surface, because ...The adsorption of linear poly(N-isopropylacrylamide) (PNIPAM) chains on surfactant-free polystyrene (PS) nanoparticles was used as a model system to study the hydrophobic adsorption of polymer on the surface, because the hydrophobility of PNIPAM can be continuously varied by a small temperature change. The adsorption was investigated by a combination of static and dynamic laser light scattering (LLS) measurements. In static LLS, the absolute excess scattered light intensity led to the amount of PNIPAM adsorbed on the surface. In dynamic LLS, the hydrodynamic thickness of the adsorbed PNIPAM layer was accurately measured. For a given particle concentration, the adsorption increases as the PNIPAM concentration and the incubation temperature increase. The average density of the adsorbed PNIPAM layer is reciprocally proportional to the number of the PNIPAM chains on the surface, revealing a simple scaling of the chain density distribution. The adsorption follows the Langmuir's isotherm. The enthalpy change estimated from the adsorption at 25 degrees C and 30 degrees C is slightly positive, indicating that the adsorption involves the coil-to-globule transition of the chains on the surface.展开更多
A hydrophilic/hydrophobic interpenetrating polymer network （IPN） of poly （vinyl alcohol） / polystyrene was prepared by conversion of the IPN of poly （vinyl acetate）/polystyrene. The hydrophilic/hydrophobic IPN w...A hydrophilic/hydrophobic interpenetrating polymer network （IPN） of poly （vinyl alcohol） / polystyrene was prepared by conversion of the IPN of poly （vinyl acetate）/polystyrene. The hydrophilic/hydrophobic IPN was characterized by FT-IR and DSC, and the swelling ratios of the IPN in different solvents were measured.展开更多
Dielectric elastomers(DEs)have drawn much attention owing to their application prospects in artificial muscles and soft robotics,it is still a big challenge to prepare DEs with high electromechanical performances.This...Dielectric elastomers(DEs)have drawn much attention owing to their application prospects in artificial muscles and soft robotics,it is still a big challenge to prepare DEs with high electromechanical performances.This work reports a highly stretchable poly(thioether)-b-polysiloxane-b-poly(thioether)triblock copolymer based homogenous DEs with high electromechanical properties.The triblock copolymer(PSiPGE)was synthesized through the ring-opening polymerization(ROP)of phenyl glycidyl ether(PGE)and carbonyl sulfide(COS)catalyzed by silicon alkoxides.The dipoles(benzene rings)on the side groups of PSiPGE improved the dipole polarizations and the phase separation structure of this triblock copolymer enhanced the interfacial polarizations between poly(thioether)and polysiloxane,and thus improving the dielectric constant(ε',up to 5.8).In addition,the PSiPGE exhibited low elastic modulus(Y,0.04 MPa),and thus possessed high electromechanical sensitivity(β,~145 MPa^(-1)) which is much higher than that of most homogenous DEs.This work provides a new strategy to construct homogenous DEs with excellent electromechanical performances,leading to a greater application aspect in the actuated devices.展开更多
New siloxane and sulfone containing poly（benzimidazole/sulfone/siloxane/amide） （PBSSA） has been prepared for the formation of hybrid membranes （PBSSA/PS-S/SiNPs） with sulfonated polystyrene （PS-S） and 0.1 wt%-...New siloxane and sulfone containing poly（benzimidazole/sulfone/siloxane/amide） （PBSSA） has been prepared for the formation of hybrid membranes （PBSSA/PS-S/SiNPs） with sulfonated polystyrene （PS-S） and 0.1 wt%-2 wt% silica nanoparticles （SiNPs）. Field emission scanning electron micrographs showed good dispersion of filler, formation of dense nanoporous honeycomb like structure and uniform ionic pathway in these hybrids. The porous membrane structure was responsible for the fine water retention capability and higher proton conductivity of the new hybrids. Increasing the amount of nanoparticles from 0.1 wt% to 2 wt% increased the tensile stress of acid doped PBSSA/PS-S/SiNPs nanocomposites from 65.7 MPa to 68.5 MPa. A relationship between nanofiller loading and thermal stability of the membranes was also experientially studied, as the glass transition temperature of phosphoric acid doped PBSSAJPS-S/SiNPs nanocomposites increased from 207℃ to 215 ℃. The membranes also had higher ion exchange capacity （IEC） around 2.01 mmol/g to 3.01 mmol/g. The novel membranes with high IEC value achieved high proton conductivity of 1.10-2.34 S/cm in a wide range of humidity values at 80 ~C which was higher than that of perfluorinated Nafion 117 membrane （1.1 × 10^-1 S/cm） at 80 ~C （94% RH）. A H2/O2 fuel cell using the PBSSA/PS-S/SiNP 2 （IEC 3.01 retool/g） showed better performance than that of Nation 117 at 40 ℃ and 30% RH.展开更多
The present paper covers the poly (ethylene oxide) macromer with vinyl benzyl terminal group (PEO-VB) prepared by deactivation of the alkoxide function of mono-functional 'living' PEO chains with vinyl benzyl ...The present paper covers the poly (ethylene oxide) macromer with vinyl benzyl terminal group (PEO-VB) prepared by deactivation of the alkoxide function of mono-functional 'living' PEO chains with vinyl benzyl chloride (VBC). The obtained macromers were subjected to careful purification and detailed characterization. A new kind of amphiphilic polystyrene-g-poly(ethylene oxide) (PS-g-PEO) with both mi-crophase separated and PEO side chains was synthesized from radical copolymerization of PEO-VB macromer with styrene monomer. An improved purification method, referred as 'selective dissolvation', was established for the isolation of graft copolymers from the grafting products, and the purity and yield of the purified copolymers were satisfactory. The well-defined structure of the purified copolymers was confirmed by IR, 1H NMR and GPC. The bulk composition of the graft copolymers was determined by a well-established first derivative UV spectrometry. Various experimental parameters controlling the copolymerization were also studied. The results indicate that the feed ratio of macromer to styrene (M/S) was the most important factor in determining the composition of the copolymers. Thus a series of PS-g-PEO with a wide range of bulk compositions were obtained simply by adjusting the value of M/S. As clearly indicated by transmission electron microscopy, this amphiphilic graft copolymers may readily form microphase separated structures.展开更多
The polyelectrolyte complex formed from the polyanion and polycation was studied by turbidimetry, static and electrophoretic light scattering, and elementary analysis. Sodium salts of polyacrylate （PA） and heparin ...The polyelectrolyte complex formed from the polyanion and polycation was studied by turbidimetry, static and electrophoretic light scattering, and elementary analysis. Sodium salts of polyacrylate （PA） and heparin （Hep） were chosen as the polyanion, and hydrochloric salts of poly（vinyl amine） （PVA） and chitosan （Chts） as the polycation. Although these vinyl polymers and polysaccharides have remarkably different backbone chemical structures and linear charge densities, all the four combinations PA-PVA, PA-Chts, Hep-PVA, and Hep-Chts provide almost stoichiometric polyelectrolyte complexes which are slightly charged owing to the adsorption of the excess polyelectrolyte component onto the neutral complex. The charges stabilize the complex colloids in aqueous solution of a non-stoichiometric mixture, and the aggregation number of the complex colloids increases with approaching to the stoichiometric mixing ratio. The mixing ratio dependence of the aggregation number for the four complexes is explained by the model proposed in the previous study.展开更多
Polysubstituted cyclopropanes were efficiently prepared with poly（ethylene glycol）（PEG） as soluble support. The reaction of PEG-supported pyridinium ylide with arylidenemalononitrile（R=CN） or ethyl arylidenecyan...Polysubstituted cyclopropanes were efficiently prepared with poly（ethylene glycol）（PEG） as soluble support. The reaction of PEG-supported pyridinium ylide with arylidenemalononitrile（R=CN） or ethyl arylidenecyanoa-cetate（R=COOEt） in the presence of triethylamine（TEA） afforded PEG-supported cyclopropanecarboxylates, which were cleaved by 1% KCN/EtOH to obtain polysubstituted cyclopropanes with exclusive trans-selectivity and good yields.展开更多
A facile and green approach has been developed for fabricating well-dispersed palladium nanoparticles(Pd NPs)supported on the surface of poly(N-vinylpyrrolidone)(PVP)-stabilized polystyrene(PS)microspheres.The strateg...A facile and green approach has been developed for fabricating well-dispersed palladium nanoparticles(Pd NPs)supported on the surface of poly(N-vinylpyrrolidone)(PVP)-stabilized polystyrene(PS)microspheres.The strategy harnesses the reducing ability of PVP and the affinity between PVP and Pd NPs to achieve in situ surface-assisted growth of small noble metal NPs on the PS microspheres,without involving any additional stabilizer or reducing agent.The stabilizer-free formation contributes to the superior availability and accessibility of active sites for catalysis.The resulting PS/Pd composite particles have demonstrated excellent catalytic performance in the probe reaction of 4-nitrophenol reduction.As far as we know,this approach has been the first straightforward in situ deposition of Pd NPs on the PS microspheres,obviating surface treatment and the use of an exogenous reducing agent or a stabilizer.Furthermore,it is extendable to the fabrication of other composite systems,PS/Ag composite particles for example.展开更多
The clinical application of Chuanminshen violaceum polysaccharides(CVP),a natural immunomodulator with intrinsic antioxidant activity,is constrained by rapid systemic clearance,limited tissue specificity,and short-liv...The clinical application of Chuanminshen violaceum polysaccharides(CVP),a natural immunomodulator with intrinsic antioxidant activity,is constrained by rapid systemic clearance,limited tissue specificity,and short-lived bioactivity.To address these limitations,a multifunctional biomimetic nanoplatform incorporating erythrocyte membrane camouflage,mannose-mediated active targeting,and squalene-stabilized Pickering emulsion technology was developed.CVP-loaded poly(lactic-co-glycolic acid)(PLGA)nanoparticles(CVPP)were fabricated via solvent evaporation,coated with erythrocyte membranes,and subsequently functionalized with mannose to obtain CVPP@M-M.This dual modification enabled selective recognition by macrophage and dendritic cell(DC)mannose receptors,while the erythrocyte membrane imparted prolonged systemic circulation.Subsequent emulsification for the first time with squalene yielded CVPP@M-M-PPAS,a Pickering emulsion designed for enhanced lymph node delivery.In vitro,CVPP@M-M-PPAS significantly promoted macrophage activation,as evidenced by elevated CD80+/CD86+expression,compared with free CVP.In vivo,intramuscular co-administration with ovalbumin(OVA)antigen induced pronounced DC maturation and T cell polarization in the spleen.This formulation also elicited robust and sustained production of antigen-specific IgG,accompanied by increased upregulation of pro-inflammatory cytokines interleukin-6(IL-6)and interferon-γ(IFN-γ).In vivo imaging demonstrated prolonged lymph node retention(>336 h)with a near-linear fluorescence decay profile,confirming controlled release kinetics.By integrating stealth properties,receptor-specific targeting,and emulsion-enabled lymphatic trafficking,this nanoplatform effectively circumvents the pharmacokinetic and biodistributional barriers of plant-derived polysaccharides,enabling durable humoral and cellular immune responses.This strategy offers a generalizable framework for translating natural immunomodulators into clinically viable nanotherapeutics.展开更多
Highly ordered honeycomb-patterned polystyrene (PS)/poly(ethylene glycol) (PEG) films were prepared by a water-assisted method using an improved setup, which facilitated the formation of films with higher regularity, ...Highly ordered honeycomb-patterned polystyrene (PS)/poly(ethylene glycol) (PEG) films were prepared by a water-assisted method using an improved setup, which facilitated the formation of films with higher regularity, better reproducibility, and larger area of honeycomb structures. Surface aggregation of hydrophilic PEG and adsorption of bovine serum albumin (BSA) on the honeycomb-patterned films were investigated. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) were used to observe the surface morphologies of the films before and after being rinsed with water. As confirmed by the FESEM images and the AFM phase images, PEG was enriched in the pores and could be gradually removed by water. The adsorption of fluorescence-labeled BSA on the films was studied in visual form using laser scanning confocal microscopy. Results clearly demonstrated that the protein-resistant PEG was selectively enriched in the pores. This water-assisted method may be a latent tool to prepare honeycomb-patterned biofunctional surfaces.展开更多
Narrowly distributed polystyrene-g-p(N-isopropylacrylamide) (PSt-g-PNIPAM) was prepared by atom transfer radical polymerization (ATRP) of N-isopropylacrylamide using the brominated polystyrene as macroinitiator and Cu...Narrowly distributed polystyrene-g-p(N-isopropylacrylamide) (PSt-g-PNIPAM) was prepared by atom transfer radical polymerization (ATRP) of N-isopropylacrylamide using the brominated polystyrene as macroinitiator and CuCl combined with hexamethyltriethylenetetramine as catalyst. Fourier transform infrared (FT-IR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy confirmed the structure of PSt-g-PNIPAM. The gel permeation chromatography (GPC) showed that the graft copoly- mer had a single distribution peak with molecular weight, Mn (g/mol) of 19815 g/mol (using polystyrene as the standard). Differential scanning calorimetry (DSC) revealed that due to both effects of hydro- phobic isopropyl groups and hydrogen bonds in the amide group, the glass transition temperature (Tg) of PSt-g-PNIPAM enhanced 16.0 ℃ compared to the Tg of the polystyrene.展开更多
Herein,manganese(Mn)‑doped poly(1,5‑diaminonaphthalene)(PN)electrode material(Mn@PN)was synthesized via chemical oxidative polymerization.The material′s distinctive vesicular architecture enables rapid ion transport ...Herein,manganese(Mn)‑doped poly(1,5‑diaminonaphthalene)(PN)electrode material(Mn@PN)was synthesized via chemical oxidative polymerization.The material′s distinctive vesicular architecture enables rapid ion transport while maintaining the structural stability of the electrode under continuous charge‑discharge cycles.Electrochemical characterization under a three‑electrode system revealed exceptional rate capability:Mn@PN delivered an ultrahigh specific capacitance of 10318 F·g^(-1) at a low current density of 3 A·g^(-1) and retained 9415 F·g^(-1)(91.2%retention compared to the value at 3 A·g^(-1))even at an ultrahigh current density of 50 A·g^(-1).Moreover,the material exhibited 97.4%capacitance retention after 9000 cycles at 30 A·g^(-1),corresponding with a low capacitance decay rate of 0.003‰per cycle,significantly outperforming conventional conductive polymers like polyaniline(PANI).An asymmetric supercapacitor assembled with Mn@PN as the positive electrode(Mn@PN||AC)achieved an energy density of 328 Wh·kg^(-1) at 15 A·g^(-1) and retained 80.7%of its initial specific capacitance after 4000 cycles at 20 A·g^(-1).展开更多
Mucopolysaccharidoses(MPS)are a group of rare inborn errors of metabolism caused by defective lysosomal enzymes which prevent cells from degrading and recycling certain carbohydrates and fats,resulting in the storage ...Mucopolysaccharidoses(MPS)are a group of rare inborn errors of metabolism caused by defective lysosomal enzymes which prevent cells from degrading and recycling certain carbohydrates and fats,resulting in the storage of glycosaminoglycans in cells throughout the body.This leads to multisystem abnormalities involving bone,connective tissues,brain,blood,spinal cord,skin,and other tissues.展开更多
In this study,a series of poly(ethylene succinate)-b-poly(butylene carbonate)(PES-b-PBC)multiblock copolymers were prepared through the chain-extension reaction of hydroxyl-terminated PES(PES-OH)and hydroxyl-terminate...In this study,a series of poly(ethylene succinate)-b-poly(butylene carbonate)(PES-b-PBC)multiblock copolymers were prepared through the chain-extension reaction of hydroxyl-terminated PES(PES-OH)and hydroxyl-terminated PBC(PBC-OH)prepolymers with 1,6-hexmethylene diisocyanate(HDI)as a chain extender.The effects of the prepolymer molecular weight and content on the structure and application properties of the PES-b-PBC copolymers were systematically investigated using various techniques.It was found that the compatibility of PES and PBC blocks in PES-b-PBC copolymers can be greatly enhanced by lowering the length of the prepolymers,and the amorphous phase of the PES and PBC chain segments in the PES-b-PBC copolymer would transform from immiscibility and partial miscibility to miscibility when the number-average molecular weight(M_(n))of the PES-OH and PBC-OH prepolymers is less than 2000 g/mol.Only the crystal structure of bare PES can be observed in the wide-angle X-ray diffraction(WAXD)spectrum of the PES-b-PBC copolymers,but their crystallinity degrees were found to decrease with increasing PBC fraction.The thermal behavior,crystallization performance,rheological properties,mechanical properties,and degradation properties of the PES-b-PBC multiblock copolymers can be easily modulated by altering the block length and composition of the prepolymers,offering potential applications in biodegradable materials.展开更多
Various hydrophilic poly(ethylene-co-vinyl alcohol)(EVOH)were used herein to precisely control the structure and hydrodynamic properties of polysulfone(PSF)membranes.Particularly,to prepare pristine PSF and PSF/EVOH b...Various hydrophilic poly(ethylene-co-vinyl alcohol)(EVOH)were used herein to precisely control the structure and hydrodynamic properties of polysulfone(PSF)membranes.Particularly,to prepare pristine PSF and PSF/EVOH blends with increasing vinyl alcohol(VOH:73%,68%,56%),the non-solvent-induced phase separation(NIPS)technique was used.Polyethylene glycol was used as a compatibilizer and as a porogen in N,Ndimethylacetamide.Rheological and ultrasonic separation kinetic measurements were also carried out to develop an ultrafiltration membrane mechanism.The extracted membrane properties and filtration capabilities were systematically compared to the proposed mechanism.Accordingly,the addition of EVOH led to an increase in the rheology of the dopes.The resulting membranes exhibited a microporous structure,while the finger-like structures became more evident with increasing VOH content.The PSF/EVOH behavior was changed from immediate to delayed segregation due to a change in the hydrodynamic kinetics.Interestingly,the PSF/EVOH32 membranes showed high hydrophilicity and achieved a pure water permeability of 264 L·m^(–2)·h^(–1)·bar^(–1),which was higher than that of pure PSF membranes(171 L·m^(–2)·h^(–1)·bar^(–1)).In addition,PSF/EVOH32 rejected bovine serum albumin at a high rate(>90%)and achieved a significant restoration of permeability.Finally,from the thermodynamic and hydrodynamic results,valuable insights into the selection of hydrophilic copolymers were provided to tailor the membrane structure while improving both the permeability and antifouling performance.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22172028,21903015,and 22403017)Natural Science Foundation of Fujian Province of China(No.2022J05041)。
文摘Compatibilization is crucial for the blending of immiscible polymers to develop high-performance composites;however,traditional compatibilization by copolymers(pre-made or in-situ generation)suffers from weak interface anchoring,and inorganic particles have gained extensive attention recently owing to their large interfacial desorption energy,while their low affinity to bulk components is a drawback.In this study,an interfacial atom transfer radical polymerization(ATRP)technique was employed to grow polystyrene(PS)and poly(2-hydroxyethyl methacrylate)(PHEMA)simultaneously on different hemispheres of Br-functionalized SiO_(2) nanoparticles to stabilize a Pickering emulsion,whereby a brush-type Janus nanoparticle(SiO_(2)@JNP)was developed.The polymer brushes were well-characterized,and the Janus feature was validated by transmission electron microscope(TEM)observation of the sole hemisphere grafting of SiO_(2)-PS as a control sample.SiO_(2)@JNP was demonstrated to be an efficient compatibilizer for a PS/poly(methyl methacrylate)(PMMA)immiscible blend,and the droplet-matrix morphology was significantly refined.The mechanical strength and toughness of the blend were synchronously enhanced at a low content SiO_(2)@JNP optimized~0.9 wt%,with the tensile strength,elongation at break and impact strength increased by 17.7%,26.6%and 19.6%,respectively.This enhancement may be attributed to the entanglements between the grafted polymer brushes and individual components that improve the particle-bulk phase affinity and enforce interfacial adhesion.
基金This work was supported by the National Natural Science Foundation of China (No. 50390090).
文摘Evolution and fractal character of the phase morphology of high impact polystyrene/poly（cis-butadiene） rubber （HIPS/PcBR） blends during melting and mixing were investigated using scanning electron microscopy （SEM）. The characteristic length L was defined as the size of particles of the dispersed phase in blends. Different fractal dimensions, Df and Din, were introduced to study the distribution width of phase dimensions in the dimensionless region and the uniformity of the spatial distribution of particles, respectively. The results showed that the average characteristic length Lm and Df increase as the volume fraction of the dispersed phase increases, when the volume fraction of the dispersed phase is lower than 50%. In other words, the size of particles increases and their distribution in the dimensionless region becomes more uniform. Meanwhile, the uniformity of the spatial distribution becomes more perfect as the volume fraction increases. At a certain composition, Lm decreases in the initial stage of the mixing and levels off in the late stage. In the initial stage, Df becomes large rapidly with the process of blending, which means that the distribution of L in the dimensionless region becomes more uniform. Meanwhile, the spatial distribution tends to be ideal rapidly in the early stage and fluctuates in a definite range in the late stage of the mixing.
文摘This paper focuses on the effects of the PSt content of polystyrene (PSt)-poly (dimethylsiloxane) (PDMS) interpenetrateing network (IPN) polymer membranes, on the pervaporation (PV) characteristics during the removal of benzene from an aqueous solution of dilute benzene. When an aqueous solution of 0.05wt% benzene was permeated through the PSt-PDMS IPN membranes, they showed high benzene/water selectivity. Both the permeability and the benzene/water selectivity of the membranes were enhanced with increasing PSt content in the PSt-PDMS IPN membrane. The physicochemical mechanism of permeation and separation through the PSt-PDMS IPN membranes during PV is also discussed. The best normalized permeation rate, separation factor for benzene selectivity, and PV separation index of the PSt-PDMS IPN membrane were 1.27 × 10-6 kgm (m2hr)-1, 3293, and 41821, respectively. These PV characteristics are discussed from the viewpoint of the chemical and physical structure of the PSt-PDMS IPN membranes.
文摘The adsorption of linear poly(N-isopropylacrylamide) (PNIPAM) chains on surfactant-free polystyrene (PS) nanoparticles was used as a model system to study the hydrophobic adsorption of polymer on the surface, because the hydrophobility of PNIPAM can be continuously varied by a small temperature change. The adsorption was investigated by a combination of static and dynamic laser light scattering (LLS) measurements. In static LLS, the absolute excess scattered light intensity led to the amount of PNIPAM adsorbed on the surface. In dynamic LLS, the hydrodynamic thickness of the adsorbed PNIPAM layer was accurately measured. For a given particle concentration, the adsorption increases as the PNIPAM concentration and the incubation temperature increase. The average density of the adsorbed PNIPAM layer is reciprocally proportional to the number of the PNIPAM chains on the surface, revealing a simple scaling of the chain density distribution. The adsorption follows the Langmuir's isotherm. The enthalpy change estimated from the adsorption at 25 degrees C and 30 degrees C is slightly positive, indicating that the adsorption involves the coil-to-globule transition of the chains on the surface.
基金supported by the National Natural Science Foundation of China(No.20474015)the Scientific Research Fund of Hunan Provincial Education Department(No.04A029).
文摘A hydrophilic/hydrophobic interpenetrating polymer network （IPN） of poly （vinyl alcohol） / polystyrene was prepared by conversion of the IPN of poly （vinyl acetate）/polystyrene. The hydrophilic/hydrophobic IPN was characterized by FT-IR and DSC, and the swelling ratios of the IPN in different solvents were measured.
基金National Natural Science Foundation of China(Nos.51973190 and 21774108)Zhejiang Provincial Department of Science and Technology(No.2020R52006)for financial supports。
文摘Dielectric elastomers(DEs)have drawn much attention owing to their application prospects in artificial muscles and soft robotics,it is still a big challenge to prepare DEs with high electromechanical performances.This work reports a highly stretchable poly(thioether)-b-polysiloxane-b-poly(thioether)triblock copolymer based homogenous DEs with high electromechanical properties.The triblock copolymer(PSiPGE)was synthesized through the ring-opening polymerization(ROP)of phenyl glycidyl ether(PGE)and carbonyl sulfide(COS)catalyzed by silicon alkoxides.The dipoles(benzene rings)on the side groups of PSiPGE improved the dipole polarizations and the phase separation structure of this triblock copolymer enhanced the interfacial polarizations between poly(thioether)and polysiloxane,and thus improving the dielectric constant(ε',up to 5.8).In addition,the PSiPGE exhibited low elastic modulus(Y,0.04 MPa),and thus possessed high electromechanical sensitivity(β,~145 MPa^(-1)) which is much higher than that of most homogenous DEs.This work provides a new strategy to construct homogenous DEs with excellent electromechanical performances,leading to a greater application aspect in the actuated devices.
文摘New siloxane and sulfone containing poly（benzimidazole/sulfone/siloxane/amide） （PBSSA） has been prepared for the formation of hybrid membranes （PBSSA/PS-S/SiNPs） with sulfonated polystyrene （PS-S） and 0.1 wt%-2 wt% silica nanoparticles （SiNPs）. Field emission scanning electron micrographs showed good dispersion of filler, formation of dense nanoporous honeycomb like structure and uniform ionic pathway in these hybrids. The porous membrane structure was responsible for the fine water retention capability and higher proton conductivity of the new hybrids. Increasing the amount of nanoparticles from 0.1 wt% to 2 wt% increased the tensile stress of acid doped PBSSA/PS-S/SiNPs nanocomposites from 65.7 MPa to 68.5 MPa. A relationship between nanofiller loading and thermal stability of the membranes was also experientially studied, as the glass transition temperature of phosphoric acid doped PBSSAJPS-S/SiNPs nanocomposites increased from 207℃ to 215 ℃. The membranes also had higher ion exchange capacity （IEC） around 2.01 mmol/g to 3.01 mmol/g. The novel membranes with high IEC value achieved high proton conductivity of 1.10-2.34 S/cm in a wide range of humidity values at 80 ~C which was higher than that of perfluorinated Nafion 117 membrane （1.1 × 10^-1 S/cm） at 80 ~C （94% RH）. A H2/O2 fuel cell using the PBSSA/PS-S/SiNP 2 （IEC 3.01 retool/g） showed better performance than that of Nation 117 at 40 ℃ and 30% RH.
基金Supported by the National Natural Science Foundation of China The State Education Commission of China
文摘The present paper covers the poly (ethylene oxide) macromer with vinyl benzyl terminal group (PEO-VB) prepared by deactivation of the alkoxide function of mono-functional 'living' PEO chains with vinyl benzyl chloride (VBC). The obtained macromers were subjected to careful purification and detailed characterization. A new kind of amphiphilic polystyrene-g-poly(ethylene oxide) (PS-g-PEO) with both mi-crophase separated and PEO side chains was synthesized from radical copolymerization of PEO-VB macromer with styrene monomer. An improved purification method, referred as 'selective dissolvation', was established for the isolation of graft copolymers from the grafting products, and the purity and yield of the purified copolymers were satisfactory. The well-defined structure of the purified copolymers was confirmed by IR, 1H NMR and GPC. The bulk composition of the graft copolymers was determined by a well-established first derivative UV spectrometry. Various experimental parameters controlling the copolymerization were also studied. The results indicate that the feed ratio of macromer to styrene (M/S) was the most important factor in determining the composition of the copolymers. Thus a series of PS-g-PEO with a wide range of bulk compositions were obtained simply by adjusting the value of M/S. As clearly indicated by transmission electron microscopy, this amphiphilic graft copolymers may readily form microphase separated structures.
基金supported by the a Grant-in-Aid for Scientific Research (No. 23350055) from the Japan Society for the Promotion of Science
文摘The polyelectrolyte complex formed from the polyanion and polycation was studied by turbidimetry, static and electrophoretic light scattering, and elementary analysis. Sodium salts of polyacrylate （PA） and heparin （Hep） were chosen as the polyanion, and hydrochloric salts of poly（vinyl amine） （PVA） and chitosan （Chts） as the polycation. Although these vinyl polymers and polysaccharides have remarkably different backbone chemical structures and linear charge densities, all the four combinations PA-PVA, PA-Chts, Hep-PVA, and Hep-Chts provide almost stoichiometric polyelectrolyte complexes which are slightly charged owing to the adsorption of the excess polyelectrolyte component onto the neutral complex. The charges stabilize the complex colloids in aqueous solution of a non-stoichiometric mixture, and the aggregation number of the complex colloids increases with approaching to the stoichiometric mixing ratio. The mixing ratio dependence of the aggregation number for the four complexes is explained by the model proposed in the previous study.
基金Supported by the National High Technology Research and Development Program of China(No.2009AA03Z420)the Natural Science Foundation of Hubei Province of China(Nos.2007ABA031,2008CDA078)
文摘Polysubstituted cyclopropanes were efficiently prepared with poly（ethylene glycol）（PEG） as soluble support. The reaction of PEG-supported pyridinium ylide with arylidenemalononitrile（R=CN） or ethyl arylidenecyanoa-cetate（R=COOEt） in the presence of triethylamine（TEA） afforded PEG-supported cyclopropanecarboxylates, which were cleaved by 1% KCN/EtOH to obtain polysubstituted cyclopropanes with exclusive trans-selectivity and good yields.
基金National Natural Science Foundation of China(no.21204030)the MOE&the SAFEA for the 111 Project(B13025)for financial support.
文摘A facile and green approach has been developed for fabricating well-dispersed palladium nanoparticles(Pd NPs)supported on the surface of poly(N-vinylpyrrolidone)(PVP)-stabilized polystyrene(PS)microspheres.The strategy harnesses the reducing ability of PVP and the affinity between PVP and Pd NPs to achieve in situ surface-assisted growth of small noble metal NPs on the PS microspheres,without involving any additional stabilizer or reducing agent.The stabilizer-free formation contributes to the superior availability and accessibility of active sites for catalysis.The resulting PS/Pd composite particles have demonstrated excellent catalytic performance in the probe reaction of 4-nitrophenol reduction.As far as we know,this approach has been the first straightforward in situ deposition of Pd NPs on the PS microspheres,obviating surface treatment and the use of an exogenous reducing agent or a stabilizer.Furthermore,it is extendable to the fabrication of other composite systems,PS/Ag composite particles for example.
基金supported by the Natural Science Foundation of Sichuan(No.2024NSFJQ0005)in part by the Scientific and Technological Innovation Team for Qinghai-Tibetan Plateau Research in Southwest Minzu University(No.2024CXTD15).
文摘The clinical application of Chuanminshen violaceum polysaccharides(CVP),a natural immunomodulator with intrinsic antioxidant activity,is constrained by rapid systemic clearance,limited tissue specificity,and short-lived bioactivity.To address these limitations,a multifunctional biomimetic nanoplatform incorporating erythrocyte membrane camouflage,mannose-mediated active targeting,and squalene-stabilized Pickering emulsion technology was developed.CVP-loaded poly(lactic-co-glycolic acid)(PLGA)nanoparticles(CVPP)were fabricated via solvent evaporation,coated with erythrocyte membranes,and subsequently functionalized with mannose to obtain CVPP@M-M.This dual modification enabled selective recognition by macrophage and dendritic cell(DC)mannose receptors,while the erythrocyte membrane imparted prolonged systemic circulation.Subsequent emulsification for the first time with squalene yielded CVPP@M-M-PPAS,a Pickering emulsion designed for enhanced lymph node delivery.In vitro,CVPP@M-M-PPAS significantly promoted macrophage activation,as evidenced by elevated CD80+/CD86+expression,compared with free CVP.In vivo,intramuscular co-administration with ovalbumin(OVA)antigen induced pronounced DC maturation and T cell polarization in the spleen.This formulation also elicited robust and sustained production of antigen-specific IgG,accompanied by increased upregulation of pro-inflammatory cytokines interleukin-6(IL-6)and interferon-γ(IFN-γ).In vivo imaging demonstrated prolonged lymph node retention(>336 h)with a near-linear fluorescence decay profile,confirming controlled release kinetics.By integrating stealth properties,receptor-specific targeting,and emulsion-enabled lymphatic trafficking,this nanoplatform effectively circumvents the pharmacokinetic and biodistributional barriers of plant-derived polysaccharides,enabling durable humoral and cellular immune responses.This strategy offers a generalizable framework for translating natural immunomodulators into clinically viable nanotherapeutics.
基金Supported by the National Natural Science Foundation of China (Grant No. 50803053)the National Natural Science Foundation of China for Distinguished Young Scholars (Grant No. 50625309)+1 种基金the National Postdoctoral Science Foundation of China (Grant Nos. 20070421172 & 20081466)the National Undergradu-ate Innovative Test Program
文摘Highly ordered honeycomb-patterned polystyrene (PS)/poly(ethylene glycol) (PEG) films were prepared by a water-assisted method using an improved setup, which facilitated the formation of films with higher regularity, better reproducibility, and larger area of honeycomb structures. Surface aggregation of hydrophilic PEG and adsorption of bovine serum albumin (BSA) on the honeycomb-patterned films were investigated. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) were used to observe the surface morphologies of the films before and after being rinsed with water. As confirmed by the FESEM images and the AFM phase images, PEG was enriched in the pores and could be gradually removed by water. The adsorption of fluorescence-labeled BSA on the films was studied in visual form using laser scanning confocal microscopy. Results clearly demonstrated that the protein-resistant PEG was selectively enriched in the pores. This water-assisted method may be a latent tool to prepare honeycomb-patterned biofunctional surfaces.
文摘Narrowly distributed polystyrene-g-p(N-isopropylacrylamide) (PSt-g-PNIPAM) was prepared by atom transfer radical polymerization (ATRP) of N-isopropylacrylamide using the brominated polystyrene as macroinitiator and CuCl combined with hexamethyltriethylenetetramine as catalyst. Fourier transform infrared (FT-IR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy confirmed the structure of PSt-g-PNIPAM. The gel permeation chromatography (GPC) showed that the graft copoly- mer had a single distribution peak with molecular weight, Mn (g/mol) of 19815 g/mol (using polystyrene as the standard). Differential scanning calorimetry (DSC) revealed that due to both effects of hydro- phobic isopropyl groups and hydrogen bonds in the amide group, the glass transition temperature (Tg) of PSt-g-PNIPAM enhanced 16.0 ℃ compared to the Tg of the polystyrene.
文摘Herein,manganese(Mn)‑doped poly(1,5‑diaminonaphthalene)(PN)electrode material(Mn@PN)was synthesized via chemical oxidative polymerization.The material′s distinctive vesicular architecture enables rapid ion transport while maintaining the structural stability of the electrode under continuous charge‑discharge cycles.Electrochemical characterization under a three‑electrode system revealed exceptional rate capability:Mn@PN delivered an ultrahigh specific capacitance of 10318 F·g^(-1) at a low current density of 3 A·g^(-1) and retained 9415 F·g^(-1)(91.2%retention compared to the value at 3 A·g^(-1))even at an ultrahigh current density of 50 A·g^(-1).Moreover,the material exhibited 97.4%capacitance retention after 9000 cycles at 30 A·g^(-1),corresponding with a low capacitance decay rate of 0.003‰per cycle,significantly outperforming conventional conductive polymers like polyaniline(PANI).An asymmetric supercapacitor assembled with Mn@PN as the positive electrode(Mn@PN||AC)achieved an energy density of 328 Wh·kg^(-1) at 15 A·g^(-1) and retained 80.7%of its initial specific capacitance after 4000 cycles at 20 A·g^(-1).
文摘Mucopolysaccharidoses(MPS)are a group of rare inborn errors of metabolism caused by defective lysosomal enzymes which prevent cells from degrading and recycling certain carbohydrates and fats,resulting in the storage of glycosaminoglycans in cells throughout the body.This leads to multisystem abnormalities involving bone,connective tissues,brain,blood,spinal cord,skin,and other tissues.
基金financially supported by the Science and Technology Projects of Changji Prefecture(No.2023112258)Shihezi Coal Chemical Industry Common Technology Research Institute Project(No.MGJY0104)the Program for Young Innovative Talents of Shihezi University(No.CXFZ202302).
文摘In this study,a series of poly(ethylene succinate)-b-poly(butylene carbonate)(PES-b-PBC)multiblock copolymers were prepared through the chain-extension reaction of hydroxyl-terminated PES(PES-OH)and hydroxyl-terminated PBC(PBC-OH)prepolymers with 1,6-hexmethylene diisocyanate(HDI)as a chain extender.The effects of the prepolymer molecular weight and content on the structure and application properties of the PES-b-PBC copolymers were systematically investigated using various techniques.It was found that the compatibility of PES and PBC blocks in PES-b-PBC copolymers can be greatly enhanced by lowering the length of the prepolymers,and the amorphous phase of the PES and PBC chain segments in the PES-b-PBC copolymer would transform from immiscibility and partial miscibility to miscibility when the number-average molecular weight(M_(n))of the PES-OH and PBC-OH prepolymers is less than 2000 g/mol.Only the crystal structure of bare PES can be observed in the wide-angle X-ray diffraction(WAXD)spectrum of the PES-b-PBC copolymers,but their crystallinity degrees were found to decrease with increasing PBC fraction.The thermal behavior,crystallization performance,rheological properties,mechanical properties,and degradation properties of the PES-b-PBC multiblock copolymers can be easily modulated by altering the block length and composition of the prepolymers,offering potential applications in biodegradable materials.
基金This work was financially supported by the National Natural Science Foundation of China(Grant Nos.22278318 and 21878230).
文摘Various hydrophilic poly(ethylene-co-vinyl alcohol)(EVOH)were used herein to precisely control the structure and hydrodynamic properties of polysulfone(PSF)membranes.Particularly,to prepare pristine PSF and PSF/EVOH blends with increasing vinyl alcohol(VOH:73%,68%,56%),the non-solvent-induced phase separation(NIPS)technique was used.Polyethylene glycol was used as a compatibilizer and as a porogen in N,Ndimethylacetamide.Rheological and ultrasonic separation kinetic measurements were also carried out to develop an ultrafiltration membrane mechanism.The extracted membrane properties and filtration capabilities were systematically compared to the proposed mechanism.Accordingly,the addition of EVOH led to an increase in the rheology of the dopes.The resulting membranes exhibited a microporous structure,while the finger-like structures became more evident with increasing VOH content.The PSF/EVOH behavior was changed from immediate to delayed segregation due to a change in the hydrodynamic kinetics.Interestingly,the PSF/EVOH32 membranes showed high hydrophilicity and achieved a pure water permeability of 264 L·m^(–2)·h^(–1)·bar^(–1),which was higher than that of pure PSF membranes(171 L·m^(–2)·h^(–1)·bar^(–1)).In addition,PSF/EVOH32 rejected bovine serum albumin at a high rate(>90%)and achieved a significant restoration of permeability.Finally,from the thermodynamic and hydrodynamic results,valuable insights into the selection of hydrophilic copolymers were provided to tailor the membrane structure while improving both the permeability and antifouling performance.
