Poly(octamethylene citrate)(POC)is a promising bioelastomer material in the biomedical field.However,its thermosetting nature poses a significant challenge to processing and molding,especially manufacturing the POC-ba...Poly(octamethylene citrate)(POC)is a promising bioelastomer material in the biomedical field.However,its thermosetting nature poses a significant challenge to processing and molding,especially manufacturing the POC-based elastomer particles as potential,degradable and toughened fillers.Firstly,a Pickering emulsion with a pre-polymer(pre-POC)solution in dimethyl carbonate as a dispersed oil phase,a Pullulan(PUL)aqueous solution as a continuous water phase,and chitin nanocrystal(ChiNC)as a particle-type emulsifier was constructed.Secondly,the POC-based core/shell structured microspheres were prepared by spray-drying of the emulsions,and characterized by a scanning electron microscope and a transmission electron microscope.Finally,the POC-based core/shell structured microspheres were used as elastomer fillers to strengthen and toughen a chitosan film,resulting in 26%increase in the tensile strength and 45%increase in the strain at break;the POC-based core/shell structured microsphere as a double-layer drug release system was built in which the hydrophilic drug of tetracycline hydrochloride(TCH)was released from the outer layer and the hydrophobic drug of curcumin was released from the inner layer,roughly following the Ritger-Peppas model.展开更多
Dimethyl sulfoxide(DMSO)possessing strong solvency and high boiling point is a very important aprotic polar solvent in organic and polymer synthesis.Notably,it is also a useful synthon in organic chemistry.However,the...Dimethyl sulfoxide(DMSO)possessing strong solvency and high boiling point is a very important aprotic polar solvent in organic and polymer synthesis.Notably,it is also a useful synthon in organic chemistry.However,the direct incorporation of DMSO in polymer synthesis remains challenging.In this work,DMSO was successfully converted to nitrogen-containing heterocyclic polymers as a monomer via multicomponent polymerizations(MCPs)with dialdehydes and diamines in the presence of K_(2)S_(2)O_(8)/t-BuOK at 120℃in 6 h.A series of poly(phenylquinoline)s with high M_(w)values(up to 5.11×10^(4))were obtained in satisfactory yields(up to 82%),performing good solubility,good thermal and morphological stability as well as excellent film-forming ability.The thin films of poly(phenylquinoline)s exhibit high refractive index value in a wide wavelength range of 400–1700 nm.Thus,this work not only enriches the family of MCPs but also provides an efficient strategy for the conversion of DMSO into functional polymeric materials that are potentially applicable in diverse areas.展开更多
The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by...The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by sulfonation of ASIBS with acetyl sulfate.The hydrophilic ionic channels were generated for proton exchange membranes(PEMs)by ion aggregation of-SO_(3)H groups and microphase separation between hydrophobic polyisobutylene and hydrophilic sulfonated poly(α-methyl styrene)segments in S-ASIBS.The proton transport ability was improved while oxidative stability was decreased by increasing SP in S-ASIBS.The appropriate SP of about 12.7 mol%in S-ASIBS provides the available PEMs with high proton transport ability,low methanol permeability and good oxidative stability.The absence of active tertiary hydrogen atoms along S-ASIBS copolymer chains avoids their attack by peroxy radicals.The residual rates of weight(RW)and proton conductivity(Rσ)of S-ASIBS-12.7 membrane after oxidation treatment for 916 h were 84.3%and 88.1%respectively,near to those of commercial Nafion 117(RW=87.9%,Rσ=90.3%).The membrane electrode assembly(MEA)could be prepared by using various S-ASIBS as PEMs for direct methanol fuel cell.The single cell with S-ASIBS-12.7 MEA behaves high performance of open circuit voltage(OCV)of 548 mV and peak power density(Pmax)of 36.1 mW·cm^(-2),which is similar to those of Nafion 117(OCV=506 mV,P_(max)=35.6 mW·cm^(-2)).To the best of our knowledge,this is the first example of advanced S-ASIBS membrane with high proton conductivity,excellent fuel barrier property and remarkable oxidative stability for promising PEMs.展开更多
It is urgent to develop high-performance polyimide(PI)films that simultaneously exhibit high transparency,exceptional thermal stability,mechanical robustness,and low dielectric to fulfil the requirements of flexible d...It is urgent to develop high-performance polyimide(PI)films that simultaneously exhibit high transparency,exceptional thermal stability,mechanical robustness,and low dielectric to fulfil the requirements of flexible display technologies.Herein,a series of fluorinated polyimide films(FPIs)were fabricated by the condensation of 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione)(6FDA)and the fluorinated triphenylmethane diamine monomer(EDA,MEDA and DMEDA)with heat-crosslinkable tetrafluorostyrene side groups,which was incorporated by different numbers of methyl groups pendant in the ortho position of amino groups.Subsequently,the FPI films underwent heating to produce crosslinking FPIs(C-FPIs)through the self-crosslinking of double bonds in the tetrafluorostyrene.The transparency,solvent resistance,thermal stability,mechanical robustness and dielectric properties of FPI and C-FPI films can be tuned by the number of methyl groups and crosslinking,which were deeply investigated by virtue of molecular dynamics(MD)simulations and density functional theory(DFT).As a result,all the films exhibited exceptional optically colorless and transparent,with transmittance in the visible region of 450-700 nm exceeding 79.9%,and the cut-off wavelengths(λ_(off))were nearly 350 nm.The thermal decomposition temperatures at 5% weight loss(T_(d5%))for all samples exceeded 504℃.These films exhibited a wide range of tunable tensile strength(46.5-75.1 MPa).Significantly,they showed exceptional dielectric properties with the dielectric constant of 2.3-2.5 at full frequency(10^(7)-20 Hz).This study not only highlights the relationship between the polymer molecular structure and properties,but offer insights for balancing optical transparency,heat resistance and low dielectric constant in PI films.展开更多
Compatibilization is crucial for the blending of immiscible polymers to develop high-performance composites;however,traditional compatibilization by copolymers(pre-made or in-situ generation)suffers from weak interfac...Compatibilization is crucial for the blending of immiscible polymers to develop high-performance composites;however,traditional compatibilization by copolymers(pre-made or in-situ generation)suffers from weak interface anchoring,and inorganic particles have gained extensive attention recently owing to their large interfacial desorption energy,while their low affinity to bulk components is a drawback.In this study,an interfacial atom transfer radical polymerization(ATRP)technique was employed to grow polystyrene(PS)and poly(2-hydroxyethyl methacrylate)(PHEMA)simultaneously on different hemispheres of Br-functionalized SiO_(2) nanoparticles to stabilize a Pickering emulsion,whereby a brush-type Janus nanoparticle(SiO_(2)@JNP)was developed.The polymer brushes were well-characterized,and the Janus feature was validated by transmission electron microscope(TEM)observation of the sole hemisphere grafting of SiO_(2)-PS as a control sample.SiO_(2)@JNP was demonstrated to be an efficient compatibilizer for a PS/poly(methyl methacrylate)(PMMA)immiscible blend,and the droplet-matrix morphology was significantly refined.The mechanical strength and toughness of the blend were synchronously enhanced at a low content SiO_(2)@JNP optimized~0.9 wt%,with the tensile strength,elongation at break and impact strength increased by 17.7%,26.6%and 19.6%,respectively.This enhancement may be attributed to the entanglements between the grafted polymer brushes and individual components that improve the particle-bulk phase affinity and enforce interfacial adhesion.展开更多
The membrane aeration biofilm reactor(MABR)represents an innovative approach to wastewater treatment,integrating gas separation membranes with biofilm process and demonstrating effectiveness in treating wastewater ric...The membrane aeration biofilm reactor(MABR)represents an innovative approach to wastewater treatment,integrating gas separation membranes with biofilm process and demonstrating effectiveness in treating wastewater rich in ammonia nitrogen.In this system,hollow fiber membranes are essential,serving as a substrate for biofilm attachment while facilitating oxygen transfer to microorganisms through aeration,hydrophobic microporous membranes are utilized in MABR applications.This study focuses on the use of poly-4-methyl-1-pentene(PMP)hollow fiber membranes,which exhibit superior oxygen permeation capabilities compared to traditional hydrophobic microporous membranes.To overcome the challenges posed by the hydrophobic nature and low bubble point of PMP microporous membranes,a hydrophilic modification was conducted using dopamine/poly(ethyleneimine)(DOPA/PEI)co-deposition to enhance microbial adhesion on the membrane surface.The composite membrane modified with DOPA/PEI exhibited an approximately 20%higher NH_(4)^(+)-N removal efficiency than the unmodified membrane.These findings suggest that the incorporation of DOPA/PEI significantly improves MABR performance,underscoring its potential for further research and development in membrane technology for MABR.展开更多
Polybutylacrylate (PBA)/poly(methyl methacrylate) (PMMA) core-shell elastic particles (CSEP), whose rubbery core diameter ranged from 0.08 μm to 1.38μm, were synthesized by using conventional emulsion polymerization...Polybutylacrylate (PBA)/poly(methyl methacrylate) (PMMA) core-shell elastic particles (CSEP), whose rubbery core diameter ranged from 0.08 μm to 1.38μm, were synthesized by using conventional emulsion polymerization, multi-step emulsion polymerization, and soapless polymerization. Allyl methacylate (ALMA) and ethylene glycol dimethacrylate (EGDMA) were selected as crosslinking reagents for core polymerization. Methacrylic acid (MAA) was used as functional co-monomer with methyl methacrylate as shell component. The content of vinyl groups in PBA rubbery core increased with the amount of crosslinking reagents. The core-shell ratio affected great on the morphology of the complex particles. Furthermore, the amounts of carboxyl on the surface of core-shell particles, copolymerized with acrylic acid, were determined by potentiometric titration. Results showed that methylacrylic acid was distributed mostly on the surface of particles.展开更多
Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical p...Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical polymerization of ethyl 2-bromoacrylate. The obtained comblike polymers were characterized by GPC and 1H NMR.展开更多
Polylactide(PLA),methyl methacrylate-butadiene-styrene copolymer(MBS),and poly(propylene carbonate)polyurethane(PPCU)were blended and subjected to blown film process.The rheological,mechanical,morphological,thermal,an...Polylactide(PLA),methyl methacrylate-butadiene-styrene copolymer(MBS),and poly(propylene carbonate)polyurethane(PPCU)were blended and subjected to blown film process.The rheological,mechanical,morphological,thermal,and crystalline properties of the PLA/MBS/PPCU ternary blends and the mechanical properties of the resulting films were studied.Results of mechanical test showed that PPCU and MBS could synergistically toughen PLA.The impact strength of 50/10/40 PLA/MBS/PPCU blend(74.7 k J/m^2)was about 7.5 times higher than that of the neat PLA(10.8 k J/m^2),and the elongation at break of 50/10/40 PLA/MBS/PPCU blend(276.5%)was higher by about 45 times that of PLA(6.2%).The tear strength of PLA/MBS/PPCU films was 20 k N/m higher than that of PLA,and the elongation at break(MD/TD)of 50/10/40 PLA/MBS/PPCU films was 271.1%/222.3%,whereas that of PLA was only 2.7%/3.0%.POM observations displayed that the density of spherulite nucleation increased and the size of crystalline particles decreased with the addition of MBS.With increasing PPCU content from 5%to 20%,the density of spherulite nucleation increased and the size of crystalline particles decreased continuously,but the nucleation density of spherulites was slightly lowered with increasing PPCU content from 30%to 40%.The PLA/MBS/PPCU films exhibited excellent mechanical properties,which expanded the application range of these biodegradable films.展开更多
DNA methylation,one of the most important epigenetic phenomena,plays a vital role in tuning gene expression during plant development as well as in response to environmental stimuli.In the present study,a methylation-s...DNA methylation,one of the most important epigenetic phenomena,plays a vital role in tuning gene expression during plant development as well as in response to environmental stimuli.In the present study,a methylation-sensitive amplified polymorphism（MSAP） analysis was performed to profile DNA methylation changes in two contrasting rice genotypes under salt stress.Consistent with visibly different phenotypes in response to salt stress,epigenetic markers classified as stable inter-cultivar DNA methylation differences were determined between salt-tolerant FL478 and salt-sensitive IR29.In addition,most tissue-specific DNA methylation loci were conserved,while many of the growth stage-dependent DNA methylation loci were dynamic between the two genotypes.Strikingly,salt stress induced a decrease in DNA methylation specifically in roots at the seedling stage that was more profound in IR29 than in the FL478.This result may indicate that demethylation of genes is an active epigenetic response to salt stress in roots at the seedling stage,and helps to further elucidate the implications of DNA methylation in crop growth and development.展开更多
Prosthetic joint infection(PJI)is the most serious complication following total joint arthroplasty,this being because it is associated with,among other things,high morbidity and low quality of life,is difficult to pre...Prosthetic joint infection(PJI)is the most serious complication following total joint arthroplasty,this being because it is associated with,among other things,high morbidity and low quality of life,is difficult to prevent,and is very challenging to treat/manage.The many shortcomings of antibiotic-loaded poly(methyl methacrylate)(PMMA)bone cement(ALBC)as an agent for preventing and treating/managing PJI are well-known.One is that microorganisms responsible for most PJI cases,such as methicillin-resistant S.aureus,have developed or are developing resistance to gentamicin sulfate,which is the antibiotic in the vast majority of approved ALBC brands.This has led to many research efforts to develop cements that do not contain gentamicin(or,for that matter,any antibiotic)but demonstrate excellent antimicrobial efficacy.There is a sizeable body of literature on these socalled“antibiotic-free antimicrobial”PMMA bone cements(AFAMBCs).The present work is a comprehensive and critical review of this body.In addition to summaries of key trends in results of characterization studies of AFAMBCs,the attractive features and shortcomings of the literature are highlighted.Shortcomings provide motivation for future work,with some ideas being formulation of a new generation of AFAMBCs by,example,adding a nanostructured material and/or an extract from a natural product to the powder and/or liquid of the basis cement,respectively.展开更多
The adsorption of Methyl Violet （MV） cationic dye from aqueous solution was carried out by using crosslinked poly （acrylic acid-coacrylamide）/attapulgite （Poly（AA-co-AM）/ATP） composite as adsorbent. The factor...The adsorption of Methyl Violet （MV） cationic dye from aqueous solution was carried out by using crosslinked poly （acrylic acid-coacrylamide）/attapulgite （Poly（AA-co-AM）/ATP） composite as adsorbent. The factors influencing adsorption capacity of the composite such as pH, concentration of the dye, temperature, contact time, adsorbent dosage, ionic strength and surfactant were systematically investigated. The equilibrium data fitted very well to the Langmuir isotherm and the maximum adsorption capacity reached 1194 mg/g at 30℃. The thermodynamic parameters including △G0, △H0 and △S0 for the adsorption processes of MV on the composite were also calculated, and the negative △H0 and △G0 confirmed that the adsorption process was exothermicand spontaneous. The kinetic studies showed that the adsorption process was consistent with the pseudo second-order kinetic model and the desorption studies revealed that the regeneration of the composite adsorbent can be easily achieved.展开更多
Membrane fouling is one of the most important challenges faced in membrane ultrafiltration operations. The copolymers of polysulfone-graft-methyl acrylate were synthesized by homogeneous photo-initiated graft copolyme...Membrane fouling is one of the most important challenges faced in membrane ultrafiltration operations. The copolymers of polysulfone-graft-methyl acrylate were synthesized by homogeneous photo-initiated graft copolymerization. The variables affecting the degree of grafting, such as the time of UV （Ultraviolet-visible） irradiation and the concentrations of the methyl acrylate and photoinitiator, were investigated. The graft copolymer membranes were prepared by the phase inversion method. The chemical and morphological changes were characterized by attenuated total reflection-Fourier transform infrared spectroscopy （ATR/FT-IR）, scanning electron microscopy, and water contact angles measurements. Results revealed that methyl acrylate groups were present on the membranes and the graft degree of methyl acrylate had remarkable effect on the performance of membranes. Pure water contact angle on the membrane surface decreases with the increase of methyl acrylate graft degree, which indicated that the hydrophilicity of graft copolymer membranes was improved. The permeation fluxes of pure water and bovine serum albumin solution were measured to evaluate the antifouling property of graft copolymer membranes, the results of which have shown an enhancement of antifouling property for graft copolymer membranes.展开更多
Poly(L-lactic acid)(PLLA)-based composites exhibit wide applications in many fields.However,most of hydrophilic fillers usually accelerate the hydrolytic degradation of PLLA,which is unfavorable for the prolonging of ...Poly(L-lactic acid)(PLLA)-based composites exhibit wide applications in many fields.However,most of hydrophilic fillers usually accelerate the hydrolytic degradation of PLLA,which is unfavorable for the prolonging of the service life of the articles.In this work,a small quantity of poly(methyl methacrylate)(PMMA)(2 wt%-10 wt%)was incorporated into the PLLA/carbon nanotubes(CNTs)composites.The effects of PMMA content on the dispersion of CNTs as well as the microstructure and hydrolytic degradation behaviors of the composites were systematically investigated.The results showed that PMMA promoted the dispersion of CNTs in the composites.Amorphous PLLA was obtained in all the composites.Largely enhanced hydrolytic degradation resistance was achieved by incorporating PMMA,especially at relatively high PMMA content.Incorporating 10 wt%PMMA led to a dramatic decrease in the hydrolytic degradation rate from 0.19%/h of the PLLA/CNT composite sample to 0.059%/h of the PLLA/PMMA-10/CNT composite sample.The microstructure evolution of the composites was also detected,and the results showed that no crystallization occurred in the PLLA matrix.Further results based on the interfacial tension calculation showed that the enhanced hydrolytic degradation resistance of the PLLA matrix was mainly attributed to the relatively strong interfacial affinity between PMMA and CNTs,which prevented the occurrence of hydrolytic degradation at the interface between PLLA and CNTs.This work provides an alternative method for tailoring the hydrolytic degradation ability of the PLLA-based composites.展开更多
Aggregation process of isotactic poly（methyl methacrylate） （i-PMMA） has been studied extensively for many years, and considerable progress has been made in both experimental and theoretical studies. They are, howe...Aggregation process of isotactic poly（methyl methacrylate） （i-PMMA） has been studied extensively for many years, and considerable progress has been made in both experimental and theoretical studies. They are, however, seldom sustained by real-space observations of the underlying morphology. In this paper, the aggregation process of i-PMMA in concentrated acetone solutions and the fractal structure of the resulting three-dimensional clusters were characterized on the basis of real-space AFM observations of their two-dimensional projection. It was found that spherical multiple-chain particles formed upon collapse and aggregation of the involving chains as a whole during quenching the solution to room temperature. By keeping the solution at room temperature, the initially formed particles stick together upon contact to form larger particles through reassembling very slowly. The succeeding collision of the enlarged spherical particles leads to the formation of small clusters. These newly formed small clusters grow when they meet with other clusters or single Brownian particles. This leads to the formation of large clusters with fractal dimension of 1.95 ± 0.05, which suggest a reaction-limited cluster aggregation of i-PMMA in a concentrated acetone solution. This is in accordance with the conclusion obtained by light scattering measurements.展开更多
Poly （ethyleneglycol monomethylether） methacrylate （PEGMM）was synthesized by means of the reaction of methacrylyl chloride with sodium monomethylpolyethyleneglycoxide and was characterized by FTIR,;H-NMR,and ultra...Poly （ethyleneglycol monomethylether） methacrylate （PEGMM）was synthesized by means of the reaction of methacrylyl chloride with sodium monomethylpolyethyleneglycoxide and was characterized by FTIR,;H-NMR,and ultraviolet spectrometries. A series of poly （vinyl alcohol）-graft-PEGMM （PVA-g-PEGMM ）and methyl methacrylate-PEGMM copolymer （PMMA-PEGMM） were prepared and tested for antithrombogenicity in vitro. The results indicate that the antithrombogenicity of the copolymers basically increases with the increasing of the DP of polyoxyethylene （POE） chain and tends to a plateau after the DP around 114,i.e. the long chain structure of POE is favourable to the antithrombogenicityof its copolymers ;moreover, the extent of the improvement ofantithrombogenicity also relates to the PEGMM content of the copolymers and the kind of the matrix that the POE chains are located on. These results are consistent with the anticipation of the hypothesis of maintaining proteins normal conformations for blood compatible bioraaterials.展开更多
An exfoliated layered double hydroxides/poly（methyl methacrylate） （LDHs/PMMA） nanocomposite was prepared by in situ solution polymerization of methyl methacrylate （MMA） in the presence of 4-vinylbenzenesulfonate...An exfoliated layered double hydroxides/poly（methyl methacrylate） （LDHs/PMMA） nanocomposite was prepared by in situ solution polymerization of methyl methacrylate （MMA） in the presence of 4-vinylbenzenesulfonate intercalated LDHs（MgAl-VBS LDHs）. MgAl-VBS LDHs was prepared by the ion exchange method, and the structure and composition of the MgAl-VBS LDHs were determined by X-ray diffraction （XRD）, infrared spectroscopy and elemental analysis. XRD and transmission electron microscopy （TEM） were employed to examine the structure of LDHs/PMMA nanocomposite. It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix. The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.展开更多
Investigation of the relationships of phenotypic and epigenetic variations might he a good way to dissect the genetic or molecular basis of phenotypic variation and plasticity in plants, Castor bean （Ricinus cornraun...Investigation of the relationships of phenotypic and epigenetic variations might he a good way to dissect the genetic or molecular basis of phenotypic variation and plasticity in plants, Castor bean （Ricinus cornraunis L）, an important non-edible oilseed crop, is a mono-species genus plant in the family Euphorbiaceae. Since it displays rich phenotypic variations with low genetic diversity, castor bean is a good model to investigate the molecular basis of phenotypic and epigenetic variations. Cytosine DNA methylation represents a major molecular mechanism of epigenetic occurrence. In this study, epigenetic diversity of sixty landrace accessions collected worldwide was investigated using the methylation- sensitive amplification polymorphism （MSAP） technique, Results showed that the epigenetic diversity （based on the polymorphism of DNA methylated loci） exhibited a medium variation （Ne = 1.395, He = 0.242, I = 0.366） at the population level though the variation was great, ranging from 3,80% to 3431% among accessions. Both population structure analysis and the phylogenetic construction （using the neighbor-joining criteria） revealed that the two main clades were identified, but they did not display a distinct geographic structure, After inspecting the location of polymorphic methylated loci on genome we identified that the polymorphic methylated loci occur widely in nuclear and organelle genomes. This study provides new data to understand phenotypic and epigenetic variations in castor bean,展开更多
In this study, commercial biaxially oriented polypropylene （BOPP）, polyvinyl chlo- ride （PVC） and poly （methyl methacrylate） （PMMA） films were treated with nitrogen plasma over different exposure times in a Py...In this study, commercial biaxially oriented polypropylene （BOPP）, polyvinyl chlo- ride （PVC） and poly （methyl methacrylate） （PMMA） films were treated with nitrogen plasma over different exposure times in a Pyrex tube surrounded by a DC variable magnetic field. The chemi- cal changes that appeared on the surface of the samples were investigated using Fourier transform infrared （FT4R） spectroscopy and attenuated total reflectance Fourier transform infrared （ATR- FTIR） spectroscopy after treatment for 2 min, 4 min and 6 rain in a nitrogen plasma chamber. Effects of the plasma treatment on the surface topographies and contact angles of the untreated and plasma treated films were also analyzed by atomic force microscopy （AFM） and a contact angle measuring system. The results show that the plasma treated films become more hydrophilic with an enhanced wettability due to the formation of some new polar groups on the surface of the treated films. Moreover, at higher exposure times, the total surface energy in all treated films increased while a reduction in contact angle occurred. The behavior of surface roughness in each sample was completely different at higher exposure times.展开更多
Cross-linked poly（diallyldimethylammonium chloride） and its derivative copolymers were synthesized and used as phase transfer catalyst in the nucleophilic substitution reaction especially halogen exchange reactions....Cross-linked poly（diallyldimethylammonium chloride） and its derivative copolymers were synthesized and used as phase transfer catalyst in the nucleophilic substitution reaction especially halogen exchange reactions.In addition,the effect of hydrophilic-hydrophobic character of the polymers in the nucleophilic reactions was investigated.展开更多
文摘Poly(octamethylene citrate)(POC)is a promising bioelastomer material in the biomedical field.However,its thermosetting nature poses a significant challenge to processing and molding,especially manufacturing the POC-based elastomer particles as potential,degradable and toughened fillers.Firstly,a Pickering emulsion with a pre-polymer(pre-POC)solution in dimethyl carbonate as a dispersed oil phase,a Pullulan(PUL)aqueous solution as a continuous water phase,and chitin nanocrystal(ChiNC)as a particle-type emulsifier was constructed.Secondly,the POC-based core/shell structured microspheres were prepared by spray-drying of the emulsions,and characterized by a scanning electron microscope and a transmission electron microscope.Finally,the POC-based core/shell structured microspheres were used as elastomer fillers to strengthen and toughen a chitosan film,resulting in 26%increase in the tensile strength and 45%increase in the strain at break;the POC-based core/shell structured microsphere as a double-layer drug release system was built in which the hydrophilic drug of tetracycline hydrochloride(TCH)was released from the outer layer and the hydrophobic drug of curcumin was released from the inner layer,roughly following the Ritger-Peppas model.
基金supported by the Scientific Research Start-up Fund Project of Anhui Polytechnic University for Introducing Talents(No.2022YQQ081)Natural Science Research Project of the Anhui Educational Committee(No.2024AH050133)the National Natural Science Foundation of China(No.22101088)。
文摘Dimethyl sulfoxide(DMSO)possessing strong solvency and high boiling point is a very important aprotic polar solvent in organic and polymer synthesis.Notably,it is also a useful synthon in organic chemistry.However,the direct incorporation of DMSO in polymer synthesis remains challenging.In this work,DMSO was successfully converted to nitrogen-containing heterocyclic polymers as a monomer via multicomponent polymerizations(MCPs)with dialdehydes and diamines in the presence of K_(2)S_(2)O_(8)/t-BuOK at 120℃in 6 h.A series of poly(phenylquinoline)s with high M_(w)values(up to 5.11×10^(4))were obtained in satisfactory yields(up to 82%),performing good solubility,good thermal and morphological stability as well as excellent film-forming ability.The thin films of poly(phenylquinoline)s exhibit high refractive index value in a wide wavelength range of 400–1700 nm.Thus,this work not only enriches the family of MCPs but also provides an efficient strategy for the conversion of DMSO into functional polymeric materials that are potentially applicable in diverse areas.
基金financially supported by the National Natural Science Foundation of China (No. 21774006)
文摘The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by sulfonation of ASIBS with acetyl sulfate.The hydrophilic ionic channels were generated for proton exchange membranes(PEMs)by ion aggregation of-SO_(3)H groups and microphase separation between hydrophobic polyisobutylene and hydrophilic sulfonated poly(α-methyl styrene)segments in S-ASIBS.The proton transport ability was improved while oxidative stability was decreased by increasing SP in S-ASIBS.The appropriate SP of about 12.7 mol%in S-ASIBS provides the available PEMs with high proton transport ability,low methanol permeability and good oxidative stability.The absence of active tertiary hydrogen atoms along S-ASIBS copolymer chains avoids their attack by peroxy radicals.The residual rates of weight(RW)and proton conductivity(Rσ)of S-ASIBS-12.7 membrane after oxidation treatment for 916 h were 84.3%and 88.1%respectively,near to those of commercial Nafion 117(RW=87.9%,Rσ=90.3%).The membrane electrode assembly(MEA)could be prepared by using various S-ASIBS as PEMs for direct methanol fuel cell.The single cell with S-ASIBS-12.7 MEA behaves high performance of open circuit voltage(OCV)of 548 mV and peak power density(Pmax)of 36.1 mW·cm^(-2),which is similar to those of Nafion 117(OCV=506 mV,P_(max)=35.6 mW·cm^(-2)).To the best of our knowledge,this is the first example of advanced S-ASIBS membrane with high proton conductivity,excellent fuel barrier property and remarkable oxidative stability for promising PEMs.
基金financially supported by the Natural Science Foundation of Shandong Province(Nos.ZR2021ME055,ZR2022QB170 and ZR2022MB034)the Foundation(No.GZKF202128)of State Key Laboratory of Biobased Material and Green Papermaking,Qilu University of Technology,Shandong Academy of Sciencesthe Development Program Project of Young Innovation Team of Institutions of Higher Learning in Shandong Province.
文摘It is urgent to develop high-performance polyimide(PI)films that simultaneously exhibit high transparency,exceptional thermal stability,mechanical robustness,and low dielectric to fulfil the requirements of flexible display technologies.Herein,a series of fluorinated polyimide films(FPIs)were fabricated by the condensation of 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione)(6FDA)and the fluorinated triphenylmethane diamine monomer(EDA,MEDA and DMEDA)with heat-crosslinkable tetrafluorostyrene side groups,which was incorporated by different numbers of methyl groups pendant in the ortho position of amino groups.Subsequently,the FPI films underwent heating to produce crosslinking FPIs(C-FPIs)through the self-crosslinking of double bonds in the tetrafluorostyrene.The transparency,solvent resistance,thermal stability,mechanical robustness and dielectric properties of FPI and C-FPI films can be tuned by the number of methyl groups and crosslinking,which were deeply investigated by virtue of molecular dynamics(MD)simulations and density functional theory(DFT).As a result,all the films exhibited exceptional optically colorless and transparent,with transmittance in the visible region of 450-700 nm exceeding 79.9%,and the cut-off wavelengths(λ_(off))were nearly 350 nm.The thermal decomposition temperatures at 5% weight loss(T_(d5%))for all samples exceeded 504℃.These films exhibited a wide range of tunable tensile strength(46.5-75.1 MPa).Significantly,they showed exceptional dielectric properties with the dielectric constant of 2.3-2.5 at full frequency(10^(7)-20 Hz).This study not only highlights the relationship between the polymer molecular structure and properties,but offer insights for balancing optical transparency,heat resistance and low dielectric constant in PI films.
基金financially supported by the National Natural Science Foundation of China(Nos.22172028,21903015,and 22403017)Natural Science Foundation of Fujian Province of China(No.2022J05041)。
文摘Compatibilization is crucial for the blending of immiscible polymers to develop high-performance composites;however,traditional compatibilization by copolymers(pre-made or in-situ generation)suffers from weak interface anchoring,and inorganic particles have gained extensive attention recently owing to their large interfacial desorption energy,while their low affinity to bulk components is a drawback.In this study,an interfacial atom transfer radical polymerization(ATRP)technique was employed to grow polystyrene(PS)and poly(2-hydroxyethyl methacrylate)(PHEMA)simultaneously on different hemispheres of Br-functionalized SiO_(2) nanoparticles to stabilize a Pickering emulsion,whereby a brush-type Janus nanoparticle(SiO_(2)@JNP)was developed.The polymer brushes were well-characterized,and the Janus feature was validated by transmission electron microscope(TEM)observation of the sole hemisphere grafting of SiO_(2)-PS as a control sample.SiO_(2)@JNP was demonstrated to be an efficient compatibilizer for a PS/poly(methyl methacrylate)(PMMA)immiscible blend,and the droplet-matrix morphology was significantly refined.The mechanical strength and toughness of the blend were synchronously enhanced at a low content SiO_(2)@JNP optimized~0.9 wt%,with the tensile strength,elongation at break and impact strength increased by 17.7%,26.6%and 19.6%,respectively.This enhancement may be attributed to the entanglements between the grafted polymer brushes and individual components that improve the particle-bulk phase affinity and enforce interfacial adhesion.
基金supported by the National Key Research and Development Program of China(2023YFB3810502)the National Natural Science Foundation of China(22078146)the Key Research and Development program of Anhui Province(2023h11020004).
文摘The membrane aeration biofilm reactor(MABR)represents an innovative approach to wastewater treatment,integrating gas separation membranes with biofilm process and demonstrating effectiveness in treating wastewater rich in ammonia nitrogen.In this system,hollow fiber membranes are essential,serving as a substrate for biofilm attachment while facilitating oxygen transfer to microorganisms through aeration,hydrophobic microporous membranes are utilized in MABR applications.This study focuses on the use of poly-4-methyl-1-pentene(PMP)hollow fiber membranes,which exhibit superior oxygen permeation capabilities compared to traditional hydrophobic microporous membranes.To overcome the challenges posed by the hydrophobic nature and low bubble point of PMP microporous membranes,a hydrophilic modification was conducted using dopamine/poly(ethyleneimine)(DOPA/PEI)co-deposition to enhance microbial adhesion on the membrane surface.The composite membrane modified with DOPA/PEI exhibited an approximately 20%higher NH_(4)^(+)-N removal efficiency than the unmodified membrane.These findings suggest that the incorporation of DOPA/PEI significantly improves MABR performance,underscoring its potential for further research and development in membrane technology for MABR.
文摘Polybutylacrylate (PBA)/poly(methyl methacrylate) (PMMA) core-shell elastic particles (CSEP), whose rubbery core diameter ranged from 0.08 μm to 1.38μm, were synthesized by using conventional emulsion polymerization, multi-step emulsion polymerization, and soapless polymerization. Allyl methacylate (ALMA) and ethylene glycol dimethacrylate (EGDMA) were selected as crosslinking reagents for core polymerization. Methacrylic acid (MAA) was used as functional co-monomer with methyl methacrylate as shell component. The content of vinyl groups in PBA rubbery core increased with the amount of crosslinking reagents. The core-shell ratio affected great on the morphology of the complex particles. Furthermore, the amounts of carboxyl on the surface of core-shell particles, copolymerized with acrylic acid, were determined by potentiometric titration. Results showed that methylacrylic acid was distributed mostly on the surface of particles.
文摘Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical polymerization of ethyl 2-bromoacrylate. The obtained comblike polymers were characterized by GPC and 1H NMR.
基金financially supported by the National Science Foundation of Zhejiang Province of China (No. LQY19B040001)the fund of Science and Technology Bureau of Jilin Province of China (No. 20170204012SF)+1 种基金the Program of Changchun Science and Technology Bureau (No. 16CX23)National Key Research and Development Program of China (No. 2016YFC0501402-5)
文摘Polylactide(PLA),methyl methacrylate-butadiene-styrene copolymer(MBS),and poly(propylene carbonate)polyurethane(PPCU)were blended and subjected to blown film process.The rheological,mechanical,morphological,thermal,and crystalline properties of the PLA/MBS/PPCU ternary blends and the mechanical properties of the resulting films were studied.Results of mechanical test showed that PPCU and MBS could synergistically toughen PLA.The impact strength of 50/10/40 PLA/MBS/PPCU blend(74.7 k J/m^2)was about 7.5 times higher than that of the neat PLA(10.8 k J/m^2),and the elongation at break of 50/10/40 PLA/MBS/PPCU blend(276.5%)was higher by about 45 times that of PLA(6.2%).The tear strength of PLA/MBS/PPCU films was 20 k N/m higher than that of PLA,and the elongation at break(MD/TD)of 50/10/40 PLA/MBS/PPCU films was 271.1%/222.3%,whereas that of PLA was only 2.7%/3.0%.POM observations displayed that the density of spherulite nucleation increased and the size of crystalline particles decreased with the addition of MBS.With increasing PPCU content from 5%to 20%,the density of spherulite nucleation increased and the size of crystalline particles decreased continuously,but the nucleation density of spherulites was slightly lowered with increasing PPCU content from 30%to 40%.The PLA/MBS/PPCU films exhibited excellent mechanical properties,which expanded the application range of these biodegradable films.
基金supported by the grants from the Central Public-interest Scientific Institution Basal Research Fund of ChinaThe National High Technology Research and Development Program of China(863 Program,No. 2007AA10Z191)
文摘DNA methylation,one of the most important epigenetic phenomena,plays a vital role in tuning gene expression during plant development as well as in response to environmental stimuli.In the present study,a methylation-sensitive amplified polymorphism（MSAP） analysis was performed to profile DNA methylation changes in two contrasting rice genotypes under salt stress.Consistent with visibly different phenotypes in response to salt stress,epigenetic markers classified as stable inter-cultivar DNA methylation differences were determined between salt-tolerant FL478 and salt-sensitive IR29.In addition,most tissue-specific DNA methylation loci were conserved,while many of the growth stage-dependent DNA methylation loci were dynamic between the two genotypes.Strikingly,salt stress induced a decrease in DNA methylation specifically in roots at the seedling stage that was more profound in IR29 than in the FL478.This result may indicate that demethylation of genes is an active epigenetic response to salt stress in roots at the seedling stage,and helps to further elucidate the implications of DNA methylation in crop growth and development.
文摘Prosthetic joint infection(PJI)is the most serious complication following total joint arthroplasty,this being because it is associated with,among other things,high morbidity and low quality of life,is difficult to prevent,and is very challenging to treat/manage.The many shortcomings of antibiotic-loaded poly(methyl methacrylate)(PMMA)bone cement(ALBC)as an agent for preventing and treating/managing PJI are well-known.One is that microorganisms responsible for most PJI cases,such as methicillin-resistant S.aureus,have developed or are developing resistance to gentamicin sulfate,which is the antibiotic in the vast majority of approved ALBC brands.This has led to many research efforts to develop cements that do not contain gentamicin(or,for that matter,any antibiotic)but demonstrate excellent antimicrobial efficacy.There is a sizeable body of literature on these socalled“antibiotic-free antimicrobial”PMMA bone cements(AFAMBCs).The present work is a comprehensive and critical review of this body.In addition to summaries of key trends in results of characterization studies of AFAMBCs,the attractive features and shortcomings of the literature are highlighted.Shortcomings provide motivation for future work,with some ideas being formulation of a new generation of AFAMBCs by,example,adding a nanostructured material and/or an extract from a natural product to the powder and/or liquid of the basis cement,respectively.
基金supported by the Western Action Project of Chinese Academy of Science (No.KGCX2-YW-501)the Taihu Project of Jiangsu Provincial Science and Technology Office (No.BS2007118,BE2008087)the Key Laboratory of Resources and Environment Chemistry of West China,Hexi University(No.XZ0606)
文摘The adsorption of Methyl Violet （MV） cationic dye from aqueous solution was carried out by using crosslinked poly （acrylic acid-coacrylamide）/attapulgite （Poly（AA-co-AM）/ATP） composite as adsorbent. The factors influencing adsorption capacity of the composite such as pH, concentration of the dye, temperature, contact time, adsorbent dosage, ionic strength and surfactant were systematically investigated. The equilibrium data fitted very well to the Langmuir isotherm and the maximum adsorption capacity reached 1194 mg/g at 30℃. The thermodynamic parameters including △G0, △H0 and △S0 for the adsorption processes of MV on the composite were also calculated, and the negative △H0 and △G0 confirmed that the adsorption process was exothermicand spontaneous. The kinetic studies showed that the adsorption process was consistent with the pseudo second-order kinetic model and the desorption studies revealed that the regeneration of the composite adsorbent can be easily achieved.
文摘Membrane fouling is one of the most important challenges faced in membrane ultrafiltration operations. The copolymers of polysulfone-graft-methyl acrylate were synthesized by homogeneous photo-initiated graft copolymerization. The variables affecting the degree of grafting, such as the time of UV （Ultraviolet-visible） irradiation and the concentrations of the methyl acrylate and photoinitiator, were investigated. The graft copolymer membranes were prepared by the phase inversion method. The chemical and morphological changes were characterized by attenuated total reflection-Fourier transform infrared spectroscopy （ATR/FT-IR）, scanning electron microscopy, and water contact angles measurements. Results revealed that methyl acrylate groups were present on the membranes and the graft degree of methyl acrylate had remarkable effect on the performance of membranes. Pure water contact angle on the membrane surface decreases with the increase of methyl acrylate graft degree, which indicated that the hydrophilicity of graft copolymer membranes was improved. The permeation fluxes of pure water and bovine serum albumin solution were measured to evaluate the antifouling property of graft copolymer membranes, the results of which have shown an enhancement of antifouling property for graft copolymer membranes.
基金financially supported by the National Natural Science Foundation of China (No. 51473137)the International Science and Technology Cooperation Project of Sichuan Province (No. 2017HH0066)+1 种基金the International Science and Technology Cooperation Project of Chengdu (No. 2016-GH0200097-HZ)the Fundamental Research Funds for the Central Universities (2682019JQ04)
文摘Poly(L-lactic acid)(PLLA)-based composites exhibit wide applications in many fields.However,most of hydrophilic fillers usually accelerate the hydrolytic degradation of PLLA,which is unfavorable for the prolonging of the service life of the articles.In this work,a small quantity of poly(methyl methacrylate)(PMMA)(2 wt%-10 wt%)was incorporated into the PLLA/carbon nanotubes(CNTs)composites.The effects of PMMA content on the dispersion of CNTs as well as the microstructure and hydrolytic degradation behaviors of the composites were systematically investigated.The results showed that PMMA promoted the dispersion of CNTs in the composites.Amorphous PLLA was obtained in all the composites.Largely enhanced hydrolytic degradation resistance was achieved by incorporating PMMA,especially at relatively high PMMA content.Incorporating 10 wt%PMMA led to a dramatic decrease in the hydrolytic degradation rate from 0.19%/h of the PLLA/CNT composite sample to 0.059%/h of the PLLA/PMMA-10/CNT composite sample.The microstructure evolution of the composites was also detected,and the results showed that no crystallization occurred in the PLLA matrix.Further results based on the interfacial tension calculation showed that the enhanced hydrolytic degradation resistance of the PLLA matrix was mainly attributed to the relatively strong interfacial affinity between PMMA and CNTs,which prevented the occurrence of hydrolytic degradation at the interface between PLLA and CNTs.This work provides an alternative method for tailoring the hydrolytic degradation ability of the PLLA-based composites.
基金This work was supported by the National Natural Science Foundations of China.
文摘Aggregation process of isotactic poly（methyl methacrylate） （i-PMMA） has been studied extensively for many years, and considerable progress has been made in both experimental and theoretical studies. They are, however, seldom sustained by real-space observations of the underlying morphology. In this paper, the aggregation process of i-PMMA in concentrated acetone solutions and the fractal structure of the resulting three-dimensional clusters were characterized on the basis of real-space AFM observations of their two-dimensional projection. It was found that spherical multiple-chain particles formed upon collapse and aggregation of the involving chains as a whole during quenching the solution to room temperature. By keeping the solution at room temperature, the initially formed particles stick together upon contact to form larger particles through reassembling very slowly. The succeeding collision of the enlarged spherical particles leads to the formation of small clusters. These newly formed small clusters grow when they meet with other clusters or single Brownian particles. This leads to the formation of large clusters with fractal dimension of 1.95 ± 0.05, which suggest a reaction-limited cluster aggregation of i-PMMA in a concentrated acetone solution. This is in accordance with the conclusion obtained by light scattering measurements.
文摘Poly （ethyleneglycol monomethylether） methacrylate （PEGMM）was synthesized by means of the reaction of methacrylyl chloride with sodium monomethylpolyethyleneglycoxide and was characterized by FTIR,;H-NMR,and ultraviolet spectrometries. A series of poly （vinyl alcohol）-graft-PEGMM （PVA-g-PEGMM ）and methyl methacrylate-PEGMM copolymer （PMMA-PEGMM） were prepared and tested for antithrombogenicity in vitro. The results indicate that the antithrombogenicity of the copolymers basically increases with the increasing of the DP of polyoxyethylene （POE） chain and tends to a plateau after the DP around 114,i.e. the long chain structure of POE is favourable to the antithrombogenicityof its copolymers ;moreover, the extent of the improvement ofantithrombogenicity also relates to the PEGMM content of the copolymers and the kind of the matrix that the POE chains are located on. These results are consistent with the anticipation of the hypothesis of maintaining proteins normal conformations for blood compatible bioraaterials.
基金This work was supported by the Zhejiang Grant Science and Technology Program(No.2005C11039).
文摘An exfoliated layered double hydroxides/poly（methyl methacrylate） （LDHs/PMMA） nanocomposite was prepared by in situ solution polymerization of methyl methacrylate （MMA） in the presence of 4-vinylbenzenesulfonate intercalated LDHs（MgAl-VBS LDHs）. MgAl-VBS LDHs was prepared by the ion exchange method, and the structure and composition of the MgAl-VBS LDHs were determined by X-ray diffraction （XRD）, infrared spectroscopy and elemental analysis. XRD and transmission electron microscopy （TEM） were employed to examine the structure of LDHs/PMMA nanocomposite. It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix. The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.
基金jointly supported by Chinese National Key Technology R & D Program (2015BAD15B02)National Natural Science Foundation of China (31661143002 and 31501034)
文摘Investigation of the relationships of phenotypic and epigenetic variations might he a good way to dissect the genetic or molecular basis of phenotypic variation and plasticity in plants, Castor bean （Ricinus cornraunis L）, an important non-edible oilseed crop, is a mono-species genus plant in the family Euphorbiaceae. Since it displays rich phenotypic variations with low genetic diversity, castor bean is a good model to investigate the molecular basis of phenotypic and epigenetic variations. Cytosine DNA methylation represents a major molecular mechanism of epigenetic occurrence. In this study, epigenetic diversity of sixty landrace accessions collected worldwide was investigated using the methylation- sensitive amplification polymorphism （MSAP） technique, Results showed that the epigenetic diversity （based on the polymorphism of DNA methylated loci） exhibited a medium variation （Ne = 1.395, He = 0.242, I = 0.366） at the population level though the variation was great, ranging from 3,80% to 3431% among accessions. Both population structure analysis and the phylogenetic construction （using the neighbor-joining criteria） revealed that the two main clades were identified, but they did not display a distinct geographic structure, After inspecting the location of polymorphic methylated loci on genome we identified that the polymorphic methylated loci occur widely in nuclear and organelle genomes. This study provides new data to understand phenotypic and epigenetic variations in castor bean,
文摘In this study, commercial biaxially oriented polypropylene （BOPP）, polyvinyl chlo- ride （PVC） and poly （methyl methacrylate） （PMMA） films were treated with nitrogen plasma over different exposure times in a Pyrex tube surrounded by a DC variable magnetic field. The chemi- cal changes that appeared on the surface of the samples were investigated using Fourier transform infrared （FT4R） spectroscopy and attenuated total reflectance Fourier transform infrared （ATR- FTIR） spectroscopy after treatment for 2 min, 4 min and 6 rain in a nitrogen plasma chamber. Effects of the plasma treatment on the surface topographies and contact angles of the untreated and plasma treated films were also analyzed by atomic force microscopy （AFM） and a contact angle measuring system. The results show that the plasma treated films become more hydrophilic with an enhanced wettability due to the formation of some new polar groups on the surface of the treated films. Moreover, at higher exposure times, the total surface energy in all treated films increased while a reduction in contact angle occurred. The behavior of surface roughness in each sample was completely different at higher exposure times.
文摘Cross-linked poly（diallyldimethylammonium chloride） and its derivative copolymers were synthesized and used as phase transfer catalyst in the nucleophilic substitution reaction especially halogen exchange reactions.In addition,the effect of hydrophilic-hydrophobic character of the polymers in the nucleophilic reactions was investigated.
