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
Two kinds of UV curable polyurethane acrylate oligomers （PUPA and PUCA） were synthesized via the addition reaction between isophorone diisocyanate （IPDI） and polyethylene glycol monoacrylate （PEA6） or polycaprol...Two kinds of UV curable polyurethane acrylate oligomers （PUPA and PUCA） were synthesized via the addition reaction between isophorone diisocyanate （IPDI） and polyethylene glycol monoacrylate （PEA6） or polycaprolactone modified hydroxyethyl acrylate （PCLA2）. The structures of PUPA and PUCA were characterized by Fourier transform infrared spectroscopy （FT-IR）, IH nuclear magnetic resonance （^H NMR）, gel permeation chromatography （GPC） and differential scanning calorimeter （DSC）, and the thermal stability and dynamic mechanical thermal properties of their cured films were measured by thermogravimetric analysis （TGA） and dynamic mechanical analysis （DMA）, respectively. The viscosity of the oligomers and mechanical properties of the cured films were also studied. The results show that both oligomers have narrow molecular weight distribution. The viscosity of PUPA is 2.310 Pa.s at 25 ℃, while that of PUCA is： up to 3.980 Pa-s. The UV cured PUPA and PUCA films have homogeneous phase structure, and the PUCA film shows higher glass transition temperature and storage modulus. Furthermore, the PUCA film possesses better mechanical properties than PUPA, while the latter shows better alkali resistance.展开更多
This paper describes the fabrication, characterization and properties of a novel hybrid poly（ethylene glycol） （PEG） based hydrogel via in situ polymerization. The hybrid hydrogel was fabricated by free-radical red...This paper describes the fabrication, characterization and properties of a novel hybrid poly（ethylene glycol） （PEG） based hydrogel via in situ polymerization. The hybrid hydrogel was fabricated by free-radical redox polymerization using ammonium persulfate （APS） and N, N, N/, NCtetramethylethylenediamine （TEMED） as initiators and N, NCmethylene bisacrylamide （BIS） as cross-linker at 60~C. To create a hybrid hydrogel, 0.2% （mass fraction） of MgA1 layered double hydroxide （LDH） was added to the aqueous solution by ultrasonic disper- sion. The physicochemical properties of hybrid hydrogel under vacuum freeze-drying processing were characterized by Fourier transform infrared （FTIR） spectroscopy, thermal gravimetric analysis （TGA） and scanning electron microscopy （SEM）, while swelling kinetics and gel content were calculated. Swelling degree in distilled water varied from 94%--125% with a gel mass fraction of 83%--91%. SEM images showed that the micron pore size of hydrogel could be adjusted within the range of several micrometers by changing the cross-linker mass fraction from 2% to 10% （based on glycol）. The results showed that the hybrid hydrogels exhibited excellent physicochemical behavior and might be a promising material for applications in tissue engineering and drug delivery.展开更多
Multiarm star block copolymers hyperbranched polyethylenimine-b-poly（2-hydroxyethyl methacrylate） （HPEI-b- PHEMA） with average 28 PHEMA arms have been prepared by atom transfer radical polymerization （ATRP） of H...Multiarm star block copolymers hyperbranched polyethylenimine-b-poly（2-hydroxyethyl methacrylate） （HPEI-b- PHEMA） with average 28 PHEMA arms have been prepared by atom transfer radical polymerization （ATRP） of HEMA in a mixed solvent of methanol and water using a core-first strategy. The hyperbranched macroinitiator employed was prepared on the basis of well-defined hyperbranched polyethylenimine with Mw/Mn of 1.04 by amidation with 2-bromo-isobutyryl bromide. The polymerization condition was optimized to prepare star copolymers with narrow dispersity, and the variables included the volume ratio of methanol to water, the molar ratio of initiating site to CuC1 and the molar ratio of [CuCl]：[CuBr2]. Under the optimized polymerization condition, the lowest Mw/Mn value of the obtained star copolymers was around 1.3. Kinetic analysis showed that an induction period existed in the polymerization of HEMA. After this induction period, a linear dependence of ln（[M]0/[M]t） on time was observed. The obtained HPEI-b-PHEMA could adsorb hydrophilic molecules. The comparison with the star copolymer with hydrophobic core and hydrophilic PHEMA shell verified that both the hydrophilic core and shell could host the hydrophilic vips, but the amidated HPEI core was more effective than the PHEMA shell.展开更多
The thermal behavior of thermotropic hydroxyethyl cellulose acetate (HECA)/polyethylene (PE) blends has been studied by DSC. It is found that the blends of HECA and PE are immiscible but the crystallization of PE is a...The thermal behavior of thermotropic hydroxyethyl cellulose acetate (HECA)/polyethylene (PE) blends has been studied by DSC. It is found that the blends of HECA and PE are immiscible but the crystallization of PE is affected by HECA chains in the blends with more than 50% HECA, which results in the subordinate crystallization of PE and the formation of imperfect structures in the PE crystals. The imperfection of PE crystals in the blends can be eliminated after annealing at 393K.展开更多
A new blend of poly(2-hydroxyethyl methacrylate) (PHEMA) with poly (ethylene glycol) (PEG) was prepared. The results from solid-state NMR indicate that the PHEMA/PEG(88:12, w/w) blend is miscible on a molecular level.
This work aimed at effectively utilizing the chemically depolymerized waste poly（ethylene terephthalate）（PET） fibers into useful products for the textile industry.PET fibers were glycolytically degraded by excess ...This work aimed at effectively utilizing the chemically depolymerized waste poly（ethylene terephthalate）（PET） fibers into useful products for the textile industry.PET fibers were glycolytically degraded by excess ethylene glycol as depolymerizing agent and zinc acetate dihydrate as catalyst.The glycolysis product,bis（2-hydroxyethyl） terephthalate（BHET）,was purified through repeated crystallization to get an average yield above 80%.Then,BHET was nitrated,reduced,and azotized to get diazonium salt.Finally,the produced diazonium salt was coupled with 1-（4-sulfophenyl）-3-methyl-5-pyrazolone to get azo dyestuff.The structures of BHET and azo dyestuff were identified by FT1 R and ^1H NMR spectra and elemental analysis.Nylon filaments dyed by the synthesized azo dyestuff with the dye bath pH from 4.14 to 5.88 showed bright yellow color.The performances of the dyestuff were described with dye uptake,color fastness,K/S,L^＊,a^＊,b^＊.and △E^＊ values.展开更多
Dehydroabietyl polyethylene glycol glycidyl ether-grafted hydroxyethyl cellulose(HEC)polymer surfactant(DA(EO)5GE-g-HEC)was prepared using ring-opening polymerization with biobased rosin and hydroxyethyl cellulose as ...Dehydroabietyl polyethylene glycol glycidyl ether-grafted hydroxyethyl cellulose(HEC)polymer surfactant(DA(EO)5GE-g-HEC)was prepared using ring-opening polymerization with biobased rosin and hydroxyethyl cellulose as feedstocks.Dehydroabietyl polyethylene glycol glycidyl ether(DA(EO)5GE)was formed by condensation of dehydroabietyl alcohol polyoxyethylene ether(Rosin derivative:DA(EO)5H)and epichlorohydrin.The grafting degree of DA(EO)5GE-g-HEC was manipulated by adjusting the mass ratio of HEC and DA(EO)5GE and confirmed by EA.According to the formula,when m(HEC)/m(DA(EO)2GE)was 1:1~1:5,the grafting rate of DA(EO)5GE in DA(EO)5GE-g-HEC varied from 34.43%to 38.33%.The surface activity and foam properties of DA(EO)5GE-g-HEC aqueous solution were studied.The results showed that with the increase in grafting rate,the critical micellar concentration(CMC)in aqueous solution changed from 1.28 to 0.96 g/L.The results of the thermogravimetric analysis showed that the temperature range of the main stage of mass loss of DA(EO)5GE-g-HEC was 310°C~410°C,and the thermal decomposition processes of the samples with five mass ratios were similar.An oil in water emulsion was prepared by choosing cyclohexane as the oil phase and DA(EO)5GE-g-HEC as the emulsifier.The effect of DA(EO)5GE-g-HEC mass fraction on emulsion particle size and stability was analyzed.The results suggested that when the oil-water ratio was 8:2 with 0.4%emulsifier,the emulsion droplets were the smallest in terms of particle size and were the most stable.The rheological test results showed that the apparent viscosity decreased with the increase in shear rate and showed a typical elastic gel phenomenon.展开更多
A comparative study related to the preparation of poly(2-hydroxyethyl methacrylate) (pHEMA) through radical polymerization process in the presence of three different protective colloid substances, respectively poly(vi...A comparative study related to the preparation of poly(2-hydroxyethyl methacrylate) (pHEMA) through radical polymerization process in the presence of three different protective colloid substances, respectively poly(vinyl alcohol) (PVA), β-cyclodextrin, or poly(aspartic acid) (PAS), is presented. The dependence of the thermal behavior of the polymers as well as their morphological aspect, on the protective colloids used in synthesis was evidenced by polymers characterization. It is also demonstrated that the swelling capacity is dependent on the protective colloid variant present during the pHEMA preparation. This behavior induces as well interdependence on the ability to load bioactive compounds onto the polymeric matrices. The distribution of the indomethacin (INN), as model drug, into the pHEMA network was put into evidence by near infrared chemical imaging (NIR-CI), a non-destructive technique and with its correspondingly statistical analysis.展开更多
The copolymerization of 2-hydroxyethyl acrylate (HEA, M//1) and methyl methacrylate (MMA, M//2) in cyclohexanone was studied. The multiple experiments of solution copolymerization with low conversion were carried out...The copolymerization of 2-hydroxyethyl acrylate (HEA, M//1) and methyl methacrylate (MMA, M//2) in cyclohexanone was studied. The multiple experiments of solution copolymerization with low conversion were carried out at two sensitive composition feed points at 60, 80, 100, 120 and 140 degree C, respectively. The composition of the copolymers was analyzed by **1H-NMR. The reactivity ratios which were estimated by the Error-in-Variable Method (EVM) of Mayo-Lewis equation were found to be r//1 equals 0.328, r//2 equals 1.781 for 60 degree C; 0.375, 1.709 for 80 degree C; 0.406, 1.654 for 100 degree C; 0.439, 1.540 for 120 degree C and 0.455, 1.400 for 140 degree C, and the 95% joint confidence intervals of the reactivity ratios were also determined. According to r//1 and r//2, Arrhenius relations and the activity energy difference between the homo- and cross-propagation were calculated. (Author abstract) 12 Refs.展开更多
The increasing deployment of electronics in everyday life has generated great concerns regarding the effective disposal of waste from these components.Here,we focused on a facile sustainable and economical strategy to...The increasing deployment of electronics in everyday life has generated great concerns regarding the effective disposal of waste from these components.Here,we focused on a facile sustainable and economical strategy to provide ideas for this issue.This strategy relied on using appropriate mechanical treatment and sodium lignosulfonate coating to improve the dispersion and interfacial compatibility of bamboo fibers in poly(lactic acid).By optimising the particle size and concentration of sodium lignosulphonate,high value-added and green composites were prepared using sectional pressurization with a venting procedure.The treated composite displayed an ultra-smooth surface(roughness of 0.592 nm),impressive transient properties(disintegration and degradation behaviour after 30 d),and outstanding ultraviolet(UV)shielding properties(100%).These properties hold the promise of being an excellent substrate for electronic devices,especially for high-precision processing,transient electronics,and UV damage prevention.The satisfactory interfacial compatibility of the composites was confirmed by detailed characterisation regarding the related physicochemical properties.This investigation offers a sustainable approach for producing high value-added green composites from biomass and biomass-derived materials.展开更多
Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to p...Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to prevent degradation and side reactions.In the contribution,histidine N-thiocarboxyanhydride(His-NTA)is directly synthesized in aqueous solution without protection.With the self-catalysis of the imidazole side group,the ring-closing reaction to form His-NTA does not require any activating reagent(e.g.,phosphorus tribromide),which is elucidated by density functional theory(DFT)calculations.His-NTA directly polymerizes into PHis bearing unprotected imidazole groups with designable molecular weights(4.2-7.7 kg/mol)and low dispersities(1.10-1.19).Kinetic experiments and Monte Carlo simulations reveal the elementary reactions and the relationship between the conversion of His-NTA and time during polymerization.Block copolymerization of His-NTA with sarcosine N-thiocarboxyanhydride(Sar-NTA)demonstrate versatile construction of functional polypept(o)ides.The triblock copoly(amino acid)PHis-b-PSar-b-PHis is capable to reversibly coordinate with transition metal ions(Fe^(2+),Co^(2+),Ni^(2+),Cu^(2+)and Zn^(2+))to form pH-sensitive hydrogels.展开更多
The rising prevalence of drug-resistant Gram-positive pathogens,particularly methicillin-resistant Staphy-lococcus aureus(MRSA)and vancomycin-resistant Enterococci(VRE),poses a substantial clinical challenge.Biofilm-a...The rising prevalence of drug-resistant Gram-positive pathogens,particularly methicillin-resistant Staphy-lococcus aureus(MRSA)and vancomycin-resistant Enterococci(VRE),poses a substantial clinical challenge.Biofilm-associated infections exacerbate this problem due to their inherent antibiotic resistance and complex structure.Current antibiotic treatments struggle to penetrate biofilms and eradicate persister cells,leading to prolonged antibiotic use and increased resistance.Host defense peptides(HDPs)have shown promise,but their clinical application is limited by factors such as enzymatic degradation and difficulty in largescale preparation.Synthetic HDP mimics,such as poly(2-oxazoline),have emerged as effective alter-natives.Herein,we found that the poly(2-oxazoline),Gly-POX_(20),demonstrated rapid and potent activity against clinically isolated multidrug-resistant Gram-positive strains.Gly-POX_(20) showed greater stability under physiological conditions compared to natural peptides,including resistance to protease degradation.Importantly,Gly-POX_(20) inhibited biofilm formation and eradicated mature biofilm and demonstrated superior in vivo therapeutic efficacy to vancomycin in a MRSA biofilm-associated mouse keratitis model,suggesting its potential as a novel antimicrobial agent against drug-resistant Gram-positive bacteria,especially biofilm-associated infections.展开更多
A series of homo and copolymers of styrene (ST) and 2-hydroxyethyl methacrylate (HEMA) in three different media (bulk, tetrahydrofuran, and benzene) have been investigated by free radical polymerization method. The sa...A series of homo and copolymers of styrene (ST) and 2-hydroxyethyl methacrylate (HEMA) in three different media (bulk, tetrahydrofuran, and benzene) have been investigated by free radical polymerization method. The samples obtained from the synthesis were characterized by Fourier Transform-Infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (<sup>1</sup>H NMR), atomic force microscopy (AFM), and differential scanning calorimetry (DSC). The results show that the synthesis of the polymers is more feasible under neat conditions rather than solvent directed reaction. Moreover, the DSC data shows that the polystyrene obtained is amorphous in nature and therefore displayed only a glass transition signal rather than crystallization and melting peaks. In addition, this study indicates that homolopolymerization of styrene via free radical polymerization tends to be preferable in less polar solvents like THF than in non-polar solvents like benzene. Benzene might destabilize the formation of the reactive radicals leading to the formation of the products. In summary, the homolpolymerization of styrene is more feasible than the homopolymerization 2-hydroxyethyl methacrylate under the experimental setup used. Styrene is more reactive than 2-hydroxyethyl methacrylate than free radical polymerization reaction due in part of the generation of the benzylic radical intermediate which is more stable leading to the formation of products than alkyl radical which are less stable. Furthermore, polymerization of styrene under neat conditions is preferable in solvent-assisted environments. The choice of solvent for the synthesis of these polymers is crucial and therefore the selection of solvent that leads to the formation of a more stable reaction intermediate is more favorable. It is worth noting that the structure of the proposed copolymer consists of a highly polar and hydrophilic monomer, 2-hydroxyethyl methacrylate and a highly non-polar and hydrophobic monomer, styrene. These functionalities constitute an amphiphilic copolymer with diverse characteristics. A plausible explanation underlying our observations is that the reaction conditions employed in the synthesis of these copolymers might not be the right route required under free radical polymerization.展开更多
Polyfluoroarenes represent an essential group of compounds in the fields of medical and material chemistry.It is still a challenge to synthesize alkylated polyfluoroarenes.Herein,a Ni-catalyzed reductive alkylation of...Polyfluoroarenes represent an essential group of compounds in the fields of medical and material chemistry.It is still a challenge to synthesize alkylated polyfluoroarenes.Herein,a Ni-catalyzed reductive alkylation of polyfluoroarenes with alkyl halides under mild conditions is reported.Polyfluoroarenes(3~6 F)can reacted smoothly with a diverse range of alkyl halides,such as primary,secondary,and tertiary alkyl iodides.The efficient formation of C(sp2)—C(sp3)can be achieved through the combination of Ni catalysis and(Bpin)2/K2CO3 as terminal reductant.展开更多
Poly(butylene succinate-co-furandicarboxylate)(PBSF)and poly(butylene adipateco-furandicarboxylate)(PBAF)are novel furandicarboxylic acid-based biodegradable copolyesters with great potential to replace fossil-derived...Poly(butylene succinate-co-furandicarboxylate)(PBSF)and poly(butylene adipateco-furandicarboxylate)(PBAF)are novel furandicarboxylic acid-based biodegradable copolyesters with great potential to replace fossil-derived terephthalic acid-based copolyesters such as poly(butylene succinate-co-terephthalate)(PBST)and poly(butylene adipate-co-terephthalate)(PBAT).In this study,quantum chemistry techniques after molecular dynamics simulations are employed to investigate the degradationmechanism of PBSF and PBAF catalyzed by Candida antarctica lipase B(CALB).Computational analysis indicates that the catalytic reaction follows a four-step mechanism resembling the ping-pong bibi mechanism,with the initial two steps being acylation reactions and the subsequent two being hydrolysis reactions.Notably,the first step of the hydrolysis is identified as the rate-determining step.Moreover,by introducing single-point mutations to expand the substrate entrance tunnel,the catalytic distance of the first acylation step decreases.Additionally,energy barrier of the rate-determining step is decreased in the PBSF system by site-directed mutations on key residues increasing hydrophobicity of the enzyme’s active site.This study unprecedently show the substrate binding pocket and hydrophobicity of the enzyme’s active site have the potential to be engineered to enhance the degradation of copolyesters catalyzed by CALB.展开更多
Although the efficiency of poly(ethylene terephthalate)(PET)degradation has been successfully improved by depolymerase engineering,mostly by using Goodfellow-PET(gf-PET)as a substrate,efforts to degrade unpretreated P...Although the efficiency of poly(ethylene terephthalate)(PET)degradation has been successfully improved by depolymerase engineering,mostly by using Goodfellow-PET(gf-PET)as a substrate,efforts to degrade unpretreated PET materials with high crystallinity remain insufficient.Here,we endeavored to improve the degradation capability of a WCCG mutant of leaf-branch compost cutinase(LCC)on a unpretreated PET substrate(crystallinity>40%)by employing iterative saturation mutagenesis.Using this method,we developed a high-throughput screening strategy appropriate for unpretreated substrates.Through extensive screening of residues around the substrate-binding groove,two variants,WCCG-sup1 and WCCG-sup2,showed good depolymerization capabilities with both high-(42%)and low-crystallinity(9%)substrates.The WCCG-sup1 variant completely depolymerized a commercial unpretreated PET product in 36 h at 72℃.In addition to enzyme thermostability and catalytic efficiency,the adsorption of enzymes onto substrates plays an important role in PET degradation.This study provides valuable insights into the structure-function relationship of LCC.展开更多
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Project(2007168303) supported by Guangdong-Hong Kong Technology Cooperation Funding
文摘Two kinds of UV curable polyurethane acrylate oligomers （PUPA and PUCA） were synthesized via the addition reaction between isophorone diisocyanate （IPDI） and polyethylene glycol monoacrylate （PEA6） or polycaprolactone modified hydroxyethyl acrylate （PCLA2）. The structures of PUPA and PUCA were characterized by Fourier transform infrared spectroscopy （FT-IR）, IH nuclear magnetic resonance （^H NMR）, gel permeation chromatography （GPC） and differential scanning calorimeter （DSC）, and the thermal stability and dynamic mechanical thermal properties of their cured films were measured by thermogravimetric analysis （TGA） and dynamic mechanical analysis （DMA）, respectively. The viscosity of the oligomers and mechanical properties of the cured films were also studied. The results show that both oligomers have narrow molecular weight distribution. The viscosity of PUPA is 2.310 Pa.s at 25 ℃, while that of PUCA is： up to 3.980 Pa-s. The UV cured PUPA and PUCA films have homogeneous phase structure, and the PUCA film shows higher glass transition temperature and storage modulus. Furthermore, the PUCA film possesses better mechanical properties than PUPA, while the latter shows better alkali resistance.
基金the National Natural Science Foundation of China(No.31000427)the China Postdoctoral Science Foundation(No.20100481214)the Fundamental Research Funds for the Central Universities of China(Nos.2012QN052 and 2012TD013)
文摘This paper describes the fabrication, characterization and properties of a novel hybrid poly（ethylene glycol） （PEG） based hydrogel via in situ polymerization. The hybrid hydrogel was fabricated by free-radical redox polymerization using ammonium persulfate （APS） and N, N, N/, NCtetramethylethylenediamine （TEMED） as initiators and N, NCmethylene bisacrylamide （BIS） as cross-linker at 60~C. To create a hybrid hydrogel, 0.2% （mass fraction） of MgA1 layered double hydroxide （LDH） was added to the aqueous solution by ultrasonic disper- sion. The physicochemical properties of hybrid hydrogel under vacuum freeze-drying processing were characterized by Fourier transform infrared （FTIR） spectroscopy, thermal gravimetric analysis （TGA） and scanning electron microscopy （SEM）, while swelling kinetics and gel content were calculated. Swelling degree in distilled water varied from 94%--125% with a gel mass fraction of 83%--91%. SEM images showed that the micron pore size of hydrogel could be adjusted within the range of several micrometers by changing the cross-linker mass fraction from 2% to 10% （based on glycol）. The results showed that the hybrid hydrogels exhibited excellent physicochemical behavior and might be a promising material for applications in tissue engineering and drug delivery.
基金financially supported by the Program for New Century Excellent Talents in Universitiesthe National Natural Science Foundation of China (Nos. 21074088, 31201426)
文摘Multiarm star block copolymers hyperbranched polyethylenimine-b-poly（2-hydroxyethyl methacrylate） （HPEI-b- PHEMA） with average 28 PHEMA arms have been prepared by atom transfer radical polymerization （ATRP） of HEMA in a mixed solvent of methanol and water using a core-first strategy. The hyperbranched macroinitiator employed was prepared on the basis of well-defined hyperbranched polyethylenimine with Mw/Mn of 1.04 by amidation with 2-bromo-isobutyryl bromide. The polymerization condition was optimized to prepare star copolymers with narrow dispersity, and the variables included the volume ratio of methanol to water, the molar ratio of initiating site to CuC1 and the molar ratio of [CuCl]：[CuBr2]. Under the optimized polymerization condition, the lowest Mw/Mn value of the obtained star copolymers was around 1.3. Kinetic analysis showed that an induction period existed in the polymerization of HEMA. After this induction period, a linear dependence of ln（[M]0/[M]t） on time was observed. The obtained HPEI-b-PHEMA could adsorb hydrophilic molecules. The comparison with the star copolymer with hydrophobic core and hydrophilic PHEMA shell verified that both the hydrophilic core and shell could host the hydrophilic vips, but the amidated HPEI core was more effective than the PHEMA shell.
文摘The thermal behavior of thermotropic hydroxyethyl cellulose acetate (HECA)/polyethylene (PE) blends has been studied by DSC. It is found that the blends of HECA and PE are immiscible but the crystallization of PE is affected by HECA chains in the blends with more than 50% HECA, which results in the subordinate crystallization of PE and the formation of imperfect structures in the PE crystals. The imperfection of PE crystals in the blends can be eliminated after annealing at 393K.
文摘A new blend of poly(2-hydroxyethyl methacrylate) (PHEMA) with poly (ethylene glycol) (PEG) was prepared. The results from solid-state NMR indicate that the PHEMA/PEG(88:12, w/w) blend is miscible on a molecular level.
基金financially supported by the National High-tech R&D Program of China(863 Program,No.2012AA030313)the Open Project Program of Key Laboratory of Eco-Textiles(Jiangnan University),Ministry of Education,China(No.KLET1115)+1 种基金the Fundamental Research Funds for the Central Universities(No. JUSRP11201)the Cooperative Innovation Fund-Prospective Project of Jiangsu Province,China(No.BY2012060)
文摘This work aimed at effectively utilizing the chemically depolymerized waste poly（ethylene terephthalate）（PET） fibers into useful products for the textile industry.PET fibers were glycolytically degraded by excess ethylene glycol as depolymerizing agent and zinc acetate dihydrate as catalyst.The glycolysis product,bis（2-hydroxyethyl） terephthalate（BHET）,was purified through repeated crystallization to get an average yield above 80%.Then,BHET was nitrated,reduced,and azotized to get diazonium salt.Finally,the produced diazonium salt was coupled with 1-（4-sulfophenyl）-3-methyl-5-pyrazolone to get azo dyestuff.The structures of BHET and azo dyestuff were identified by FT1 R and ^1H NMR spectra and elemental analysis.Nylon filaments dyed by the synthesized azo dyestuff with the dye bath pH from 4.14 to 5.88 showed bright yellow color.The performances of the dyestuff were described with dye uptake,color fastness,K/S,L^＊,a^＊,b^＊.and △E^＊ values.
基金supported by the National Natural Science Foundation of China(31901257 and 32071706)School-Level Research Projects of the Yancheng Institute of Technology(xjr2019008).
文摘Dehydroabietyl polyethylene glycol glycidyl ether-grafted hydroxyethyl cellulose(HEC)polymer surfactant(DA(EO)5GE-g-HEC)was prepared using ring-opening polymerization with biobased rosin and hydroxyethyl cellulose as feedstocks.Dehydroabietyl polyethylene glycol glycidyl ether(DA(EO)5GE)was formed by condensation of dehydroabietyl alcohol polyoxyethylene ether(Rosin derivative:DA(EO)5H)and epichlorohydrin.The grafting degree of DA(EO)5GE-g-HEC was manipulated by adjusting the mass ratio of HEC and DA(EO)5GE and confirmed by EA.According to the formula,when m(HEC)/m(DA(EO)2GE)was 1:1~1:5,the grafting rate of DA(EO)5GE in DA(EO)5GE-g-HEC varied from 34.43%to 38.33%.The surface activity and foam properties of DA(EO)5GE-g-HEC aqueous solution were studied.The results showed that with the increase in grafting rate,the critical micellar concentration(CMC)in aqueous solution changed from 1.28 to 0.96 g/L.The results of the thermogravimetric analysis showed that the temperature range of the main stage of mass loss of DA(EO)5GE-g-HEC was 310°C~410°C,and the thermal decomposition processes of the samples with five mass ratios were similar.An oil in water emulsion was prepared by choosing cyclohexane as the oil phase and DA(EO)5GE-g-HEC as the emulsifier.The effect of DA(EO)5GE-g-HEC mass fraction on emulsion particle size and stability was analyzed.The results suggested that when the oil-water ratio was 8:2 with 0.4%emulsifier,the emulsion droplets were the smallest in terms of particle size and were the most stable.The rheological test results showed that the apparent viscosity decreased with the increase in shear rate and showed a typical elastic gel phenomenon.
文摘A comparative study related to the preparation of poly(2-hydroxyethyl methacrylate) (pHEMA) through radical polymerization process in the presence of three different protective colloid substances, respectively poly(vinyl alcohol) (PVA), β-cyclodextrin, or poly(aspartic acid) (PAS), is presented. The dependence of the thermal behavior of the polymers as well as their morphological aspect, on the protective colloids used in synthesis was evidenced by polymers characterization. It is also demonstrated that the swelling capacity is dependent on the protective colloid variant present during the pHEMA preparation. This behavior induces as well interdependence on the ability to load bioactive compounds onto the polymeric matrices. The distribution of the indomethacin (INN), as model drug, into the pHEMA network was put into evidence by near infrared chemical imaging (NIR-CI), a non-destructive technique and with its correspondingly statistical analysis.
文摘The copolymerization of 2-hydroxyethyl acrylate (HEA, M//1) and methyl methacrylate (MMA, M//2) in cyclohexanone was studied. The multiple experiments of solution copolymerization with low conversion were carried out at two sensitive composition feed points at 60, 80, 100, 120 and 140 degree C, respectively. The composition of the copolymers was analyzed by **1H-NMR. The reactivity ratios which were estimated by the Error-in-Variable Method (EVM) of Mayo-Lewis equation were found to be r//1 equals 0.328, r//2 equals 1.781 for 60 degree C; 0.375, 1.709 for 80 degree C; 0.406, 1.654 for 100 degree C; 0.439, 1.540 for 120 degree C and 0.455, 1.400 for 140 degree C, and the 95% joint confidence intervals of the reactivity ratios were also determined. According to r//1 and r//2, Arrhenius relations and the activity energy difference between the homo- and cross-propagation were calculated. (Author abstract) 12 Refs.
基金supported by the National Natural Science Foundation of China(Nos.31971741 and 31760195)the Yunnan Fundamental Research Projects(Nos.2018FB066 and 202001AT070141)the Yunnan Agricultural Basic Research Special Projects(No.202101BD070001-086).
文摘The increasing deployment of electronics in everyday life has generated great concerns regarding the effective disposal of waste from these components.Here,we focused on a facile sustainable and economical strategy to provide ideas for this issue.This strategy relied on using appropriate mechanical treatment and sodium lignosulfonate coating to improve the dispersion and interfacial compatibility of bamboo fibers in poly(lactic acid).By optimising the particle size and concentration of sodium lignosulphonate,high value-added and green composites were prepared using sectional pressurization with a venting procedure.The treated composite displayed an ultra-smooth surface(roughness of 0.592 nm),impressive transient properties(disintegration and degradation behaviour after 30 d),and outstanding ultraviolet(UV)shielding properties(100%).These properties hold the promise of being an excellent substrate for electronic devices,especially for high-precision processing,transient electronics,and UV damage prevention.The satisfactory interfacial compatibility of the composites was confirmed by detailed characterisation regarding the related physicochemical properties.This investigation offers a sustainable approach for producing high value-added green composites from biomass and biomass-derived materials.
基金financially supported by the National Natural Science Foundation of China(Nos.22271252 and 22201105)。
文摘Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to prevent degradation and side reactions.In the contribution,histidine N-thiocarboxyanhydride(His-NTA)is directly synthesized in aqueous solution without protection.With the self-catalysis of the imidazole side group,the ring-closing reaction to form His-NTA does not require any activating reagent(e.g.,phosphorus tribromide),which is elucidated by density functional theory(DFT)calculations.His-NTA directly polymerizes into PHis bearing unprotected imidazole groups with designable molecular weights(4.2-7.7 kg/mol)and low dispersities(1.10-1.19).Kinetic experiments and Monte Carlo simulations reveal the elementary reactions and the relationship between the conversion of His-NTA and time during polymerization.Block copolymerization of His-NTA with sarcosine N-thiocarboxyanhydride(Sar-NTA)demonstrate versatile construction of functional polypept(o)ides.The triblock copoly(amino acid)PHis-b-PSar-b-PHis is capable to reversibly coordinate with transition metal ions(Fe^(2+),Co^(2+),Ni^(2+),Cu^(2+)and Zn^(2+))to form pH-sensitive hydrogels.
基金financially supported by the National Key Research and Development Program of China(no.2022YFC2303100)National Natural Science Foundation of China(nos.T2325010,22305082,52203162,and 22075078)+1 种基金Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism(Shanghai Municipal Education Commission),the Fundamental Research Funds for the Central Universities(nos.JKVD1241029 and JKD01241701)Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry(Changchun Institute of Applied Chemistry,Chinese Academy of Sciences),the Open Project of Engineering Research Center of Dairy Quality and Safety Control Technology(Ministry of Education,no.R202201).
文摘The rising prevalence of drug-resistant Gram-positive pathogens,particularly methicillin-resistant Staphy-lococcus aureus(MRSA)and vancomycin-resistant Enterococci(VRE),poses a substantial clinical challenge.Biofilm-associated infections exacerbate this problem due to their inherent antibiotic resistance and complex structure.Current antibiotic treatments struggle to penetrate biofilms and eradicate persister cells,leading to prolonged antibiotic use and increased resistance.Host defense peptides(HDPs)have shown promise,but their clinical application is limited by factors such as enzymatic degradation and difficulty in largescale preparation.Synthetic HDP mimics,such as poly(2-oxazoline),have emerged as effective alter-natives.Herein,we found that the poly(2-oxazoline),Gly-POX_(20),demonstrated rapid and potent activity against clinically isolated multidrug-resistant Gram-positive strains.Gly-POX_(20) showed greater stability under physiological conditions compared to natural peptides,including resistance to protease degradation.Importantly,Gly-POX_(20) inhibited biofilm formation and eradicated mature biofilm and demonstrated superior in vivo therapeutic efficacy to vancomycin in a MRSA biofilm-associated mouse keratitis model,suggesting its potential as a novel antimicrobial agent against drug-resistant Gram-positive bacteria,especially biofilm-associated infections.
文摘A series of homo and copolymers of styrene (ST) and 2-hydroxyethyl methacrylate (HEMA) in three different media (bulk, tetrahydrofuran, and benzene) have been investigated by free radical polymerization method. The samples obtained from the synthesis were characterized by Fourier Transform-Infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (<sup>1</sup>H NMR), atomic force microscopy (AFM), and differential scanning calorimetry (DSC). The results show that the synthesis of the polymers is more feasible under neat conditions rather than solvent directed reaction. Moreover, the DSC data shows that the polystyrene obtained is amorphous in nature and therefore displayed only a glass transition signal rather than crystallization and melting peaks. In addition, this study indicates that homolopolymerization of styrene via free radical polymerization tends to be preferable in less polar solvents like THF than in non-polar solvents like benzene. Benzene might destabilize the formation of the reactive radicals leading to the formation of the products. In summary, the homolpolymerization of styrene is more feasible than the homopolymerization 2-hydroxyethyl methacrylate under the experimental setup used. Styrene is more reactive than 2-hydroxyethyl methacrylate than free radical polymerization reaction due in part of the generation of the benzylic radical intermediate which is more stable leading to the formation of products than alkyl radical which are less stable. Furthermore, polymerization of styrene under neat conditions is preferable in solvent-assisted environments. The choice of solvent for the synthesis of these polymers is crucial and therefore the selection of solvent that leads to the formation of a more stable reaction intermediate is more favorable. It is worth noting that the structure of the proposed copolymer consists of a highly polar and hydrophilic monomer, 2-hydroxyethyl methacrylate and a highly non-polar and hydrophobic monomer, styrene. These functionalities constitute an amphiphilic copolymer with diverse characteristics. A plausible explanation underlying our observations is that the reaction conditions employed in the synthesis of these copolymers might not be the right route required under free radical polymerization.
文摘Polyfluoroarenes represent an essential group of compounds in the fields of medical and material chemistry.It is still a challenge to synthesize alkylated polyfluoroarenes.Herein,a Ni-catalyzed reductive alkylation of polyfluoroarenes with alkyl halides under mild conditions is reported.Polyfluoroarenes(3~6 F)can reacted smoothly with a diverse range of alkyl halides,such as primary,secondary,and tertiary alkyl iodides.The efficient formation of C(sp2)—C(sp3)can be achieved through the combination of Ni catalysis and(Bpin)2/K2CO3 as terminal reductant.
基金supported by the Joint Funds of the National Natural Science Foundation of China(No.U21A20320)the National Natural Science Foundation of China(No.22106102)was also sponsored by the special fund of State Environmental Protection Key Laboratory of Environmental Health Impact Assessment of Emerging Contaminants(No.SEPKLEHIAEC-202203).
文摘Poly(butylene succinate-co-furandicarboxylate)(PBSF)and poly(butylene adipateco-furandicarboxylate)(PBAF)are novel furandicarboxylic acid-based biodegradable copolyesters with great potential to replace fossil-derived terephthalic acid-based copolyesters such as poly(butylene succinate-co-terephthalate)(PBST)and poly(butylene adipate-co-terephthalate)(PBAT).In this study,quantum chemistry techniques after molecular dynamics simulations are employed to investigate the degradationmechanism of PBSF and PBAF catalyzed by Candida antarctica lipase B(CALB).Computational analysis indicates that the catalytic reaction follows a four-step mechanism resembling the ping-pong bibi mechanism,with the initial two steps being acylation reactions and the subsequent two being hydrolysis reactions.Notably,the first step of the hydrolysis is identified as the rate-determining step.Moreover,by introducing single-point mutations to expand the substrate entrance tunnel,the catalytic distance of the first acylation step decreases.Additionally,energy barrier of the rate-determining step is decreased in the PBSF system by site-directed mutations on key residues increasing hydrophobicity of the enzyme’s active site.This study unprecedently show the substrate binding pocket and hydrophobicity of the enzyme’s active site have the potential to be engineered to enhance the degradation of copolyesters catalyzed by CALB.
文摘Although the efficiency of poly(ethylene terephthalate)(PET)degradation has been successfully improved by depolymerase engineering,mostly by using Goodfellow-PET(gf-PET)as a substrate,efforts to degrade unpretreated PET materials with high crystallinity remain insufficient.Here,we endeavored to improve the degradation capability of a WCCG mutant of leaf-branch compost cutinase(LCC)on a unpretreated PET substrate(crystallinity>40%)by employing iterative saturation mutagenesis.Using this method,we developed a high-throughput screening strategy appropriate for unpretreated substrates.Through extensive screening of residues around the substrate-binding groove,two variants,WCCG-sup1 and WCCG-sup2,showed good depolymerization capabilities with both high-(42%)and low-crystallinity(9%)substrates.The WCCG-sup1 variant completely depolymerized a commercial unpretreated PET product in 36 h at 72℃.In addition to enzyme thermostability and catalytic efficiency,the adsorption of enzymes onto substrates plays an important role in PET degradation.This study provides valuable insights into the structure-function relationship of LCC.
