Co-reporter:Na-er Guang;Shou-xin Liu 刘守信;Xuan Li;Lei Tian
Chinese Journal of Polymer Science 2016 Volume 34( Issue 8) pp:965-980
Publication Date(Web):2016 August
DOI:10.1007/s10118-016-1817-1
A double thermoresponsive ABC-type triblock copolymer (poly(ethyleneglycol)-block-poly(2-(2-methoxyethoxy) ethyl methacrylate)-block-poly(2-(2-methoxy ethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methyl ether methacrylate, PEG-b-PMEO2MA-b-P(MEO2MA-co-OEGMA)) was designed and synthesized by reversible additionfragmentation chain transfer polymerization (RAFT). The ABC-type triblock copolymer endowed a thermal-induced two-step phase transition at 29 and 39 °C, corresponding to the thermosensitive properties of PMEO2MA and P(MEO2MA-co-OEGMA) segments, respectively. The two-step self-assembly of copolymer solutions was studied by UV transmittance measurement, dynamic light scattering (DLS), transmission electron microscopy (TEM) and so on. The triblock copolymers showed the distinct thermosensitive behavior with respect to transition temperatures, aggregate type and size, which was correlated to the degree of polymerization of thermosensitive blocks and the molar fraction of OEGMA in the P(MEO2MA-co-OEGMA) segments. In addition, micelles could further aggregate to form the hydrogel by the self-associate of PEG chains under the abduction of the concentration and temperature. The transition from sol to gel was investigated by a test tube inverting method and dynamic rheological measurement.
Co-reporter:S. Liu;X. Li;N. Guang;L. Tian;H. Mao;W. Ning
Journal of Polymer Research 2016 Volume 23( Issue 7) pp:
Publication Date(Web):2016 July
DOI:10.1007/s10965-016-1036-z
A series of well-defined novel amphiphilic temperature-responsive graft copolymers containing PCL analogues P(αClεCL-co-εCL) as the hydrophobic backbone, and the hydrophilic side-chain PEG analogues P(MEO2MA-co-OEGMA), designated as P(αClεCL-co-εCL)-g-P(MEO2MA-co-OEGMA) have been prepared via a combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). The composition and structure of these copolymers were characterized by 1H NMR and GPC analyses. The self-assembly behaviors of these amphiphilic graft copolymers were investigated by UV transmittance, a fluorescence probe method, dynamic light scattering (DLS) and transmission electron microscopy (TEM) analyses. The results showed that the graft copolymers exhibited the good solubility in water, and was given the low critical temperature (LCST) at 35(±1) °C, which closed to human physiological temperature. The critical micelle concentrations (CMC) of P(αClεCL-co-εCL)-g-P(MEO2MA-co-OEGMA) in aqueous solution were investigated to be 2.0 × 10−3, 9.1 × 10−4 and 1.5 × 10−3 mg·mL−1, respectively. The copolymer could self-assemble into sphere-like aggregates in aqueous solution with diverse sizes when changing the environmental temperature. The vial inversion test demonstrated that the graft copolymers could trigger the sol-gel transition which also depended on the temperature.
Co-reporter:Weijuan Sheng;Teng Liu;Qinqin Wang;Xuan Li;Naer Guang
Polymer International 2015 Volume 64( Issue 10) pp:1415-1424
Publication Date(Web):
DOI:10.1002/pi.4934
Abstract
A novel temperature responsive copolymer, poly[2-(2-methoxyethoxy)ethyl methacrylate-co-oligo(ethylene glycol)methacrylate-co-N-hydroxymethyl acrylamide] [P(MEO2MA-co-OEGMA-co-HMAM)], was synthesized by atom transfer radical polymerization. pH responsive poly(methacrylic acid) (PMAA) was synthesized by reversible addition-fragmentation chain transfer polymerization. After the hydroxyl groups on P(MEO2MA-co-OEGMA-co-HMAM) were transformed into azide groups and the carboxyl groups on PMAA were transformed into alkyne groups respectively, a novel temperature and pH responsive hydrogel was fabricated by click chemistry between the azide-P(MEO2MA-co-OEGMA-co-HMAM) and alkyne-PMAA in the presence of CuSO4 and sodium ascorbate in aqueous solution. The rheological kinetics of gel formation demonstrated that gelation had commenced within 5 min at 25 °C, since then the storage modulus (G′) was higher than the loss modulus (G″). SEM images of hydrogel morphology and the swelling ratios of hydrogel at different temperatures and pH proved that the formed hydrogel had temperature and pH sensitivities. Bovine serum albumin was used as a model to evaluate the sustained release of the hydrogel; the results indicated that the hydrogel was a promising candidate for controlling protein drug delivery. © 2015 Society of Chemical Industry
Co-reporter:Lijuan Peng;Teng Liu;Yanan Han;Xuan Li
Journal of Polymer Research 2015 Volume 22( Issue 7) pp:
Publication Date(Web):2015 July
DOI:10.1007/s10965-015-0772-9
A well-defined temperature responsive ABA triblock copolymer, poly(2-(2-methoxyethoxy) ethyl methacrylate-co-N-hydroxymethyl acrylamide)-b- poly(ethylene glycol)-b-poly (2-(2-methoxyethoxy) ethyl methacrylate-co-N- hydroxymethyl acrylamide) [P(MEO2MA-co-HMAM)-b-PEG-b-P(MEO2MA-co- HMAM)], was synthesized by atom transfer radical polymerization (ATRP). The synthesized triblock copolymer was characterized by 1H nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectroscopy and Gel Permeation Chromatography (GPC). The aqueous solution phase behaviors of the triblock copolymers were investigated by UV transmittance measurements, surface tension measurement, laser particle size and viscosity analysis. The micellization of temperature responsive triblock copolymer was investigated by fluorescence probe technique, dynamic light scattering (DLS) and transmission electron microscopy (TEM). The results showed that the molecular weight of the poly(ethylene glycol) (PEG), the N-hydroxymethylacrylamide (HMAM) content, and the degree of polymerization (DP) of the P(MEO2MA-co- HMAM) block for the synthesized triblock copolymers could all affect the lower critical solution temperature (LCST) of the triblock copolymer aqueous solution. The higher the molecular weight of the PEG and the HMAM content for a given triblock copolymer are, the higher the LCST of its aqueous solution. The higher the DP of the P(MEO2MA-co-HMAM) block is, the lower the LCST of the copolymer aqueous solution. Sol–gel transition temperature (Tsol-gel) for the triblock copolymer determined by vial inversion test further indicated that it is dependent on the molecular weights of the PEG, the DP of the P(MEO2MA-co-HMAM) blocks and the concentration of the copolymer aqueous solution. Copolymer hydrogels loaded with bovine serum albumin (BSA) were used for the release study. The results revealed that 1) the hydrogels had sustained release for the BSA, 2) the release rate for the BSA is dependent of the length of the PEG chain, and 3) the longer the PEG chain is, the faster the release rate of the hydrogel for the BSA.
Co-reporter:Wei-Na Yu;Shou-Xin Liu;Hong-Mei Wang;Rong Tian
Journal of Polymer Research 2012 Volume 19( Issue 11) pp:
Publication Date(Web):2012 November
DOI:10.1007/s10965-012-9989-z
Temperature-responsive P(NIPAM-co-HMAM)-b-PEO-b-P(NIPAM-co-HMAM) triblock copolymers were synthesized by an atomic transfer radical polymerization (ATRP) method without freeze–pump–thaw cycles. The composition, structure, and molecular weight of the synthesized block copolymer were characterized by 1 H NMR and GPC. The phase transitions induced by temperature for different copolymers in dilute aqueous solutions have been studied using transmittance measurements, laser particle size measurements, viscosity analysis, and surface tension measurement, which showed that the HMAM content and the PEO (or PEG) chain length in the synthesized triblock copolymer affects the copolymer’s lower critical solution temperature (LCST). The micellization behavior of each temperature-responsive triblock copolymer was investigated by fluorescence probe measurements and transmission electron microscopy (TEM), which showed that the triblock copolymers form stable micelles above the LCST. The introduction of the HMAM component and the formation of micelles represent the first steps in the development of an injectable gel that forms in situ through chemical and physical crosslinking.
Co-reporter:Shouxin Liu;Xia Liu;Fang Li;Yu Fang;Yijuan Wang;Juan Yu
Journal of Applied Polymer Science 2008 Volume 109( Issue 6) pp:4036-4042
Publication Date(Web):
DOI:10.1002/app.28602
Abstract
Several different composition temperature- and pH-sensitive poly(acrylic acid-g-N-isopropylacrylamide) (P(AA-g-NIPAM)) graft copolymers were synthesized by free-radical copolymerization utilizing macromonomer technique. The phase behavior and conformation change of P(AA-g-NIPAM) in aqueous solutions were investigated by UV–vis transmittance measurements, fluorescence probe, and fluorescence quenching techniques. The results demonstrate that the P(AA-g-NIPAM) copolymers have temperature- and pH-sensitivities, and these different composition graft copolymers have different lower critical solution temperature (LCST) and critical phase transition pH values. The LCST of graft copolymer decreases with increasing PNIPAM content, and the critical phase transition pH value increases with increasing Poly(N-isopropylacrylamide) (PNIPAM) content. At room temperature (20°C), different composition of P(AA-g-NIPAM) graft copolymers in dilute aqueous solutions (0.001 wt %) have a loose conformation, and there is no hydrophobic microdomain formation within researching pH range (pH 3 ∼ 10). In addition, for the P(AA-g-NIPAM) aqueous solutions, transition from coil to globular is an incomplete reversible process in heating and cooling cycles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008