In this article, poly（2-hydroxyethylmethacrylate-co-acrylamide） hydrogels were synthesized by bulk free-radical copolymerization of 2-hydroxyethylmethacrylate （HEMA） and acrylamide （AAm） for soft contact lens（...In this article, poly（2-hydroxyethylmethacrylate-co-acrylamide） hydrogels were synthesized by bulk free-radical copolymerization of 2-hydroxyethylmethacrylate （HEMA） and acrylamide （AAm） for soft contact lens（SCL）-based ophthalmic drug delivery system. The copolymer was characterized with FT-IR and SEM, the swelling property of the hydrogels were studied by gravimetrical method, and chloramphenicol was used as a model drug to investigate drug release profile of the hydrogels. The results showed that poly（2-hydroxyethylmethacrylateco-acrylamide） hydrogels were transparent and useful SCL biomaterial, the water content increased as AAm content increase and pH decrease, and in the same way, hydrogel composition affected chloramphenicol release process too. Migration rate of chloramphenicol increased as the AAm content in the hydrogels increased in the first stage of diffusion process, whereas there was no significant difference thereafter.展开更多
A series of clay/poly（N-isopropylacrylamide-co-acrylamide） nanocomposite hydrogels （S-N-M gels） have been successfully prepared by in situ polymerization. The mechanical properties, swelling behavior of S-N-M gels...A series of clay/poly（N-isopropylacrylamide-co-acrylamide） nanocomposite hydrogels （S-N-M gels） have been successfully prepared by in situ polymerization. The mechanical properties, swelling behavior of S-N-M gels and the transparency changes during polymerization of S-N-M gels have been systematically investigated. Compared to traditional hydrogels, S-N-M gels show excellent tensile properties and their swelling ratio increases with increasing acrylamide （AAm） content. The results of stress relaxation indicate that the stress loss decreases with increasing AAm content. It was surprisingly found that the transparency during all S-N-M gel synthesis changes abruptly, and the changes become more abrupt with increasing N-isopropylacrylamide content. It was concluded that the fact may be related to the hydrophilicity of copolymers. The weaker the hydrophilicity of copolymer, the more apparent the transparency change during S-N-M gels polymerization. We believe the relationship between hydrophilicity of copolymer and transparency changes will help to design novel nanocomposite hydrogels.展开更多
Mesoporous polyethylene glycol-resorcinol and formaldehyde（PEG-RF） carbon xerogels were prepared by a new polymer blend method in which PEG-RF mixed organic xerogels were synthesized by blending thermally unstable p...Mesoporous polyethylene glycol-resorcinol and formaldehyde（PEG-RF） carbon xerogels were prepared by a new polymer blend method in which PEG-RF mixed organic xerogels were synthesized by blending thermally unstable polyethylene glycol with organic monomers, resorcinol and formaldehyde and then subjected to pyrolization at 1 000 ℃. The influences of mass ratio of PEG to the theoretical yield of RF xerogel, m（PEG）/m（RF） and the （relative） molecular mass of PEG on the pore structure and electric double layer capacitance（EDLC） performance of PEG-RF carbon xerogels were investigated. The results show that PEG under different conditions leads to the difference of phase separation structure of the polymer blend and thus the change of pore structure of PEG-RF carbon xerogels. Specific surface area and capacity of PEG-RF carbon xerogels in 30% H2SO4 solution can reach （755 m2/g） and 150 F/g, respectively. Their surface can be fully utilized to form electric double layer. However, the pore structure differences of PEG-RF carbon xerogels result in their different EDLC performances. The distributed capacitance effect increases with decreasing the pore size of PEG-RF carbon xerogels.展开更多
Graft copolymers of MMA （methyl methacrylate） with NRL （natural rubber latex） referred to as NR-g-PMMA have been prepared using CHP （cumene hydroperoxide）/TEPA （tetraetbylenepentamine） redox initiator. 1H NMR ...Graft copolymers of MMA （methyl methacrylate） with NRL （natural rubber latex） referred to as NR-g-PMMA have been prepared using CHP （cumene hydroperoxide）/TEPA （tetraetbylenepentamine） redox initiator. 1H NMR （proton nuclear magnetic resonance） and FTIR （Fourier transform infrared） analysis have confirmed the occurrence of graft copolymerisations of MMA onto NR that containing 30% and 50% of MMA monomer. The influence of coagulating agents such as formic acid, sulfuric acid and boiling water on the coagulation of NR-g-PMMA latices were investigated. These types of coagulating agent formed compact coagulum and the effect of NR-g-PMMA compounds on cure characteristics, physical properties and appearances were reported.展开更多
In order to investigate the rules on formation of zeolite during crystallization of titanium silicalite zeolite (TS-1) the X-ray diffractometry and Foulier transform infra-red spectrometry were applied to track the pr...In order to investigate the rules on formation of zeolite during crystallization of titanium silicalite zeolite (TS-1) the X-ray diffractometry and Foulier transform infra-red spectrometry were applied to track the process of crystallization of titanium silicalite zeolite. The research results revealed that at the initial stage of crystallization the interactions between silica gel and titania gel in the polymer blend could gradually lead to the formation of tiny crystal nuclei with complicated structure that could slowly grow up to form molecular sieves. Quite different from the conventional zeolites that use the acid sites as the catalytically active centers, the oxidative reactivity of the titanium silicalite zeolite was not proportional to its crystallinity and is associated with the oxidative centers of titanium contained in the zeolite.展开更多
Constructing high strength pH sensitive supramolecular polymer hydrogel remains very challenging due to the unavoidable network swelling caused by ionization of acid or basic groups at a specified pH.In this work,we p...Constructing high strength pH sensitive supramolecular polymer hydrogel remains very challenging due to the unavoidable network swelling caused by ionization of acid or basic groups at a specified pH.In this work,we proposed a simple and very convenient approach to fabricate high strength pH responsive supramolecular polymer(SP) hydrogels by one-pot copolymerization of N-acryloyl glycinamide(NAGA) and 2-vinyl-4,6-diamino-1,3,5-triazine(VDT),two feature hydrogen bonding monomers.In these PNAGA-PVDT SP hydrogels obtained,the hydrogen bonding of NAGA was shown to play a dominant role in reinforcing strength,while the hydrogen bonding of diaminotriazine served as a pH sensitive moiety.At pH 3,the mechanical properties of PNAGA-PVDT hydrogels decreased to a different extent due to the breakup of hydrogen bonding;in contrast,the hydrogel resumed the original strength while pH was raised to 7.4 because of reconstruction of hydrogen bonding.Over the selected pH range,the PNAGA-PVDT hydrogels exhibited up to 1.25 MPa tensile strength,845% breaking strain,69 kPa Young's modulus and 21 MPa compressive strength.This novel high strength pH-responsive SP hydrogels may find applications in biomedical and industrial fields.展开更多
A series of ABA triblock copolymers of poly(?-(2-methoxy ethoxy)esteryl-glutamate)-block-poly(ethylene glycol)-blockpoly(?-(2-methoxy ethoxy)esteryl-glutamate) with poly(ethylene glycol) as middle hydrophilic B block ...A series of ABA triblock copolymers of poly(?-(2-methoxy ethoxy)esteryl-glutamate)-block-poly(ethylene glycol)-blockpoly(?-(2-methoxy ethoxy)esteryl-glutamate) with poly(ethylene glycol) as middle hydrophilic B block and oligo(ethylene glycol)-functionalized polyglutamate(poly-L-EG2Glu) as terminal A blocks were prepared via ring-opening polymerization of EG2 Glu N-carboxyanhydride(NCA). The resulting P(EG2Glu)-b-PEG-b-P(EG2Glu) triblocks can spontaneously form hydrogels in water. The intermolecular hydrogen bonding interactions between polypeptides blocks were responsible for the formation of gel network structure. These hydrogels displayed shear-thinning and rapid recovery properties, which endowed them potential application as injectable drug delivery system. The mechanical strength of hydrogels can be modulated by copolymer composition, molecular weight and concentrations. Also, it was found that the hydrogels' strength decreased with temperature due to dehydration of polypeptide segments. Atomic force microscopy and scanning electron microscopy images revealed that these hydrogels were formed through micelle packing mechanism. Circular dichroism and Fourier transform infrared spectroscopy characterizations suggested the poly-L-EG2 Glu block adopted mixed conformation. A preliminary assessment of drug release in vitro demonstrated the hydrogels can offer a sustained release of doxorubicin(DOX) and the release rate could be controlled by varying chemical composition.展开更多
Quasi-solid state dye-sensitized solar cells based on chemically crosslinking with backbone polymers of poly(vinylpyridine-co-acrylonitrile) (P(VP-co-AN)) or poly(vinylimidazole-co-acrylonitrile) (P(VIM-co- AN)) and d...Quasi-solid state dye-sensitized solar cells based on chemically crosslinking with backbone polymers of poly(vinylpyridine-co-acrylonitrile) (P(VP-co-AN)) or poly(vinylimidazole-co-acrylonitrile) (P(VIM-co- AN)) and diiodide compounds of I(CH2)6I or I(CH2CH2O)nCH2CH2I solidified EC/PC/KI/I2 gel electrolytes have been fabricated. The ionic conductivities and apparent diffusion coefficients of I3? of the electro- lytes and cell performances have been investigated. Providing chemically crosslinking points, pyridine or imidazole from the backbone polymers benefited the open circuit voltage and fill factor of the cells. Consequently, the overall energy conversion efficiencies of the quasi-solid DSSCs improved over 10% even near 20% from that of the liquid electrolyte before solidification. Besides, the employing of crosslinker I(CH2CH2O)nCH2CH2I showed higher electrolytic and cell characters than that of I(CH2)6I.展开更多
Many pH-and temperature-responsive polymers have been designed for preparing hydrogel.In the present study,in order to decrease the pH sensitivity of reported poly(amidoamine)-poly(ethyleneglycol)-poly(amidoamine)(PAA...Many pH-and temperature-responsive polymers have been designed for preparing hydrogel.In the present study,in order to decrease the pH sensitivity of reported poly(amidoamine)-poly(ethyleneglycol)-poly(amidoamine)(PAA1580-PEG4600-PAA1580),we designed and synthesized poly(amidoamine)-poly(ethyleneglycol)-poly(amidoamine)(PAA-PEG-PAA)with shorter length of PAA chain by decreasing reaction temperature for preparing PAA-PEG-PAA hydrogel solution containing doxorubicin(DOX).The PAA-PEG-PAA was synthesized via the Michael-addition polymerization.The characteristic of PAA-PEG-PAA was evaluated.The PAA-PEG-PAA hydrogel solution was prepared and investigated.DOX-loaded PAA-PEG-PAA hydrogel solution was prepared,and its in vitro DOX release and in vitro anti-tumor activity were evaluated.Our results indicated that the viscosity of PAA-PEG-PAA hydrogel solution was concentration-and temperature-dependent.The sol-gel transition temperature of PAA-PEG-PAA hydrogel solution(12%,w/w)ranged from 35 to 29℃,and its pH ranged from 6.0 to 7.4.The released DOX from DOX-loaded PAA-PEG-PAA hydrogel showed sustained release characteristics.The in vitro anti-tumor activity of DOX-loaded PAA-PEG-PAA hydrogel was confirmed in B16 F10 cell line.Considering the acidic tumor microenvironment,this DOX-loaded PAA-PEG-PAA hydrogel solution would be easy in situ administration for intra-tumor injection or para-tumor injection forming hydrogel at body temperature.We suggested that this DOX-loaded PAA-PEG-PAAhydrogel solution,if containing photothermal conversion agents,would have a potential further use for photothermal therapy.展开更多
基金Supported by the Natural Science Foundation of Guangdong Province （5300978） and Zhongkai University of Agriculture and Engineering （G2360221）.
文摘In this article, poly（2-hydroxyethylmethacrylate-co-acrylamide） hydrogels were synthesized by bulk free-radical copolymerization of 2-hydroxyethylmethacrylate （HEMA） and acrylamide （AAm） for soft contact lens（SCL）-based ophthalmic drug delivery system. The copolymer was characterized with FT-IR and SEM, the swelling property of the hydrogels were studied by gravimetrical method, and chloramphenicol was used as a model drug to investigate drug release profile of the hydrogels. The results showed that poly（2-hydroxyethylmethacrylateco-acrylamide） hydrogels were transparent and useful SCL biomaterial, the water content increased as AAm content increase and pH decrease, and in the same way, hydrogel composition affected chloramphenicol release process too. Migration rate of chloramphenicol increased as the AAm content in the hydrogels increased in the first stage of diffusion process, whereas there was no significant difference thereafter.
基金the National Natural Science Foundation of China （Project No.50473002）,and the Cultivation Fund of the Key Scientific and Technical Innovation Project, Ministry of Education of China （No.704021）. the National High-tech 863 Project （2002AA302616）, and the Shanghai Nano Special Projects （0452nm006, 05nm05005）.
文摘A series of clay/poly（N-isopropylacrylamide-co-acrylamide） nanocomposite hydrogels （S-N-M gels） have been successfully prepared by in situ polymerization. The mechanical properties, swelling behavior of S-N-M gels and the transparency changes during polymerization of S-N-M gels have been systematically investigated. Compared to traditional hydrogels, S-N-M gels show excellent tensile properties and their swelling ratio increases with increasing acrylamide （AAm） content. The results of stress relaxation indicate that the stress loss decreases with increasing AAm content. It was surprisingly found that the transparency during all S-N-M gel synthesis changes abruptly, and the changes become more abrupt with increasing N-isopropylacrylamide content. It was concluded that the fact may be related to the hydrophilicity of copolymers. The weaker the hydrophilicity of copolymer, the more apparent the transparency change during S-N-M gels polymerization. We believe the relationship between hydrophilicity of copolymer and transparency changes will help to design novel nanocomposite hydrogels.
文摘Mesoporous polyethylene glycol-resorcinol and formaldehyde（PEG-RF） carbon xerogels were prepared by a new polymer blend method in which PEG-RF mixed organic xerogels were synthesized by blending thermally unstable polyethylene glycol with organic monomers, resorcinol and formaldehyde and then subjected to pyrolization at 1 000 ℃. The influences of mass ratio of PEG to the theoretical yield of RF xerogel, m（PEG）/m（RF） and the （relative） molecular mass of PEG on the pore structure and electric double layer capacitance（EDLC） performance of PEG-RF carbon xerogels were investigated. The results show that PEG under different conditions leads to the difference of phase separation structure of the polymer blend and thus the change of pore structure of PEG-RF carbon xerogels. Specific surface area and capacity of PEG-RF carbon xerogels in 30% H2SO4 solution can reach （755 m2/g） and 150 F/g, respectively. Their surface can be fully utilized to form electric double layer. However, the pore structure differences of PEG-RF carbon xerogels result in their different EDLC performances. The distributed capacitance effect increases with decreasing the pore size of PEG-RF carbon xerogels.
文摘Graft copolymers of MMA （methyl methacrylate） with NRL （natural rubber latex） referred to as NR-g-PMMA have been prepared using CHP （cumene hydroperoxide）/TEPA （tetraetbylenepentamine） redox initiator. 1H NMR （proton nuclear magnetic resonance） and FTIR （Fourier transform infrared） analysis have confirmed the occurrence of graft copolymerisations of MMA onto NR that containing 30% and 50% of MMA monomer. The influence of coagulating agents such as formic acid, sulfuric acid and boiling water on the coagulation of NR-g-PMMA latices were investigated. These types of coagulating agent formed compact coagulum and the effect of NR-g-PMMA compounds on cure characteristics, physical properties and appearances were reported.
基金supported by the NationalScience Foundation of China(2006CB202508)wewould like to extend our heartfelt thanks to the RIPP’s labo-ratories engaging in XRD and FT-IR analyses for theirenergetical support and warm assistance provided to thisresearch work.
文摘In order to investigate the rules on formation of zeolite during crystallization of titanium silicalite zeolite (TS-1) the X-ray diffractometry and Foulier transform infra-red spectrometry were applied to track the process of crystallization of titanium silicalite zeolite. The research results revealed that at the initial stage of crystallization the interactions between silica gel and titania gel in the polymer blend could gradually lead to the formation of tiny crystal nuclei with complicated structure that could slowly grow up to form molecular sieves. Quite different from the conventional zeolites that use the acid sites as the catalytically active centers, the oxidative reactivity of the titanium silicalite zeolite was not proportional to its crystallinity and is associated with the oxidative centers of titanium contained in the zeolite.
基金supported by the National Natural Science Foundation of China(Grant No.51325305)National Key Research and Development Program(GrantNo.2016YFC1101301)Tianjin Municipal Natural Science Foundation(Grant Nos.13ZCZDSY00900,15JCZDJC38000)
文摘Constructing high strength pH sensitive supramolecular polymer hydrogel remains very challenging due to the unavoidable network swelling caused by ionization of acid or basic groups at a specified pH.In this work,we proposed a simple and very convenient approach to fabricate high strength pH responsive supramolecular polymer(SP) hydrogels by one-pot copolymerization of N-acryloyl glycinamide(NAGA) and 2-vinyl-4,6-diamino-1,3,5-triazine(VDT),two feature hydrogen bonding monomers.In these PNAGA-PVDT SP hydrogels obtained,the hydrogen bonding of NAGA was shown to play a dominant role in reinforcing strength,while the hydrogen bonding of diaminotriazine served as a pH sensitive moiety.At pH 3,the mechanical properties of PNAGA-PVDT hydrogels decreased to a different extent due to the breakup of hydrogen bonding;in contrast,the hydrogel resumed the original strength while pH was raised to 7.4 because of reconstruction of hydrogen bonding.Over the selected pH range,the PNAGA-PVDT hydrogels exhibited up to 1.25 MPa tensile strength,845% breaking strain,69 kPa Young's modulus and 21 MPa compressive strength.This novel high strength pH-responsive SP hydrogels may find applications in biomedical and industrial fields.
基金financially supported by the National Natural Science Foundation of China for Distinguished Young Scholar(51225306)the CAS-CSIRO Cooperative Research Program(GJHZ1408)
文摘A series of ABA triblock copolymers of poly(?-(2-methoxy ethoxy)esteryl-glutamate)-block-poly(ethylene glycol)-blockpoly(?-(2-methoxy ethoxy)esteryl-glutamate) with poly(ethylene glycol) as middle hydrophilic B block and oligo(ethylene glycol)-functionalized polyglutamate(poly-L-EG2Glu) as terminal A blocks were prepared via ring-opening polymerization of EG2 Glu N-carboxyanhydride(NCA). The resulting P(EG2Glu)-b-PEG-b-P(EG2Glu) triblocks can spontaneously form hydrogels in water. The intermolecular hydrogen bonding interactions between polypeptides blocks were responsible for the formation of gel network structure. These hydrogels displayed shear-thinning and rapid recovery properties, which endowed them potential application as injectable drug delivery system. The mechanical strength of hydrogels can be modulated by copolymer composition, molecular weight and concentrations. Also, it was found that the hydrogels' strength decreased with temperature due to dehydration of polypeptide segments. Atomic force microscopy and scanning electron microscopy images revealed that these hydrogels were formed through micelle packing mechanism. Circular dichroism and Fourier transform infrared spectroscopy characterizations suggested the poly-L-EG2 Glu block adopted mixed conformation. A preliminary assessment of drug release in vitro demonstrated the hydrogels can offer a sustained release of doxorubicin(DOX) and the release rate could be controlled by varying chemical composition.
基金Supported by the National Research Fund for Fundamental Key Project (Grant No. 2006CB202605)the National Natural Science Foundation of China (Grant Nos. 50221201 and 50473055)
文摘Quasi-solid state dye-sensitized solar cells based on chemically crosslinking with backbone polymers of poly(vinylpyridine-co-acrylonitrile) (P(VP-co-AN)) or poly(vinylimidazole-co-acrylonitrile) (P(VIM-co- AN)) and diiodide compounds of I(CH2)6I or I(CH2CH2O)nCH2CH2I solidified EC/PC/KI/I2 gel electrolytes have been fabricated. The ionic conductivities and apparent diffusion coefficients of I3? of the electro- lytes and cell performances have been investigated. Providing chemically crosslinking points, pyridine or imidazole from the backbone polymers benefited the open circuit voltage and fill factor of the cells. Consequently, the overall energy conversion efficiencies of the quasi-solid DSSCs improved over 10% even near 20% from that of the liquid electrolyte before solidification. Besides, the employing of crosslinker I(CH2CH2O)nCH2CH2I showed higher electrolytic and cell characters than that of I(CH2)6I.
基金The National Key Research and Development Program of China(Grant No.2017YFA0205600)the National Natural Science Foundation of China(Grant No.81773646)the Innovation Team of the Ministry of Education(Grant No.BMU2017TD003)
文摘Many pH-and temperature-responsive polymers have been designed for preparing hydrogel.In the present study,in order to decrease the pH sensitivity of reported poly(amidoamine)-poly(ethyleneglycol)-poly(amidoamine)(PAA1580-PEG4600-PAA1580),we designed and synthesized poly(amidoamine)-poly(ethyleneglycol)-poly(amidoamine)(PAA-PEG-PAA)with shorter length of PAA chain by decreasing reaction temperature for preparing PAA-PEG-PAA hydrogel solution containing doxorubicin(DOX).The PAA-PEG-PAA was synthesized via the Michael-addition polymerization.The characteristic of PAA-PEG-PAA was evaluated.The PAA-PEG-PAA hydrogel solution was prepared and investigated.DOX-loaded PAA-PEG-PAA hydrogel solution was prepared,and its in vitro DOX release and in vitro anti-tumor activity were evaluated.Our results indicated that the viscosity of PAA-PEG-PAA hydrogel solution was concentration-and temperature-dependent.The sol-gel transition temperature of PAA-PEG-PAA hydrogel solution(12%,w/w)ranged from 35 to 29℃,and its pH ranged from 6.0 to 7.4.The released DOX from DOX-loaded PAA-PEG-PAA hydrogel showed sustained release characteristics.The in vitro anti-tumor activity of DOX-loaded PAA-PEG-PAA hydrogel was confirmed in B16 F10 cell line.Considering the acidic tumor microenvironment,this DOX-loaded PAA-PEG-PAA hydrogel solution would be easy in situ administration for intra-tumor injection or para-tumor injection forming hydrogel at body temperature.We suggested that this DOX-loaded PAA-PEG-PAAhydrogel solution,if containing photothermal conversion agents,would have a potential further use for photothermal therapy.
