POLYMER
·
2022
·
IF 4.432
Jie Huan,Jing Li,Yinjia Lan,Sheng Wang,Xiaohong Li,Xiaoming Yang,Huanjun Lu,Yingfeng Tu
We present here the effect of oligo(ethylene glycol) (OEG) segmental length on properties of cyclic oligo(oligoethylene glycol terephthalate)s (COEGTs) and their corresponding polymer counterparts, poly(oligoethylene glycol terephthalate)s (POEGTs). COEGT monomers were synthesized from terephthaloyl chloride with corresponding diethylene glycol , triethylene glycol , and tetraethylene glycol under pseudo-high-dilution conditions. As those large ring cyclic monomers are hard to be polymerized via traditional ring-opening polymerization, a cascade polycondensation-coupling ring-opening polymerization method is utilized to obtain high molecular weight POEGTs. The cascade polymerization mechanism is confirmed by the kinetics study . The structures of COEGTs and POEGTs were well characterized and their properties were studied to reveal the structure-property relationship. With the increment of OEG length in repeating units, the chain flexibility of POEGT and COEGTs is enhanced. As a result, the melting temperatures of COEGTs and glass transition temperatures of POEGTs decrease. On the other hand, the thermal degradation temperature of POEGTs and COEGTs increases due to the enhanced ether fraction and reduced ring strain. Solid-state polymer electrolytes based on POEGTs was prepared by blending with lithium bis(trifluoromethanesulfonyl)imide. The measured ionic conductivity increased with the OEG length in POEGT repeating units. Our results revealed the effect of OEG length on the structure-property relationship in cyclic oligo(ether ester)s and copoly(ether ester)s, providing a facile way to tune their properties.
研究领域:
高分子化学
·
材料科学
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DOI
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2015
·Vol. 33
·期 8
·1150-1161
·
IF 1.835
Yuan Qiu-lin,Liu Wen-jun,Deng Yong,Ling Ying,Tang Hao-yu
A series of polypeptides bearing biphenyl mesogenic side-chains and oligo-ethylene-glycol (OEG) tails (PPLG
n
- g -BPOEG
m
, n = 26 and 63, m = 2, 3, and 7) has been synthesized via a 1,3-dipolar cycloaddition with quantitative grafting density. FTIR results revealed that the polypeptides adopted highly stable α -helix in the temperature range of 25–200 °C. DSC, POM and WAXS analysis revealed that PPLG
n
- g -BPOEG
m
( m ≤ 3) samples with short OEG tail length showed two main phase transitions including crystal to liquid crystalline (smectic C, SmC) phase transition and the melting transition of crystalline E-phase, while PPLG
n
- g -BPOEG 7 with longer OEG tail length ( m = 7) exhibited the melting transitions without the formation of liquid crystalline phase.
研究领域:
材料科学
·
生物化学
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产品关联
DOI
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2016
·Vol. 34
·期 12
·1436-1447
·
IF 1.811
Fu Xiao-hui,Ma Yi-nan,Sun Jing,Li Zhi-bo
A series of poly( L -glutamate)s grafted with oligo(ethylene glycol) (OEG) side-chains through the thioether linkages (PALG
n
- g -EG
x
, x = 2, 3 and 4) were prepared by ring-opening polymerization (ROP) of γ-allyl- L -glutamate N -carboxyanhydride (ALG-NCA) and thiol-ene photoaddition. The chemical structures and physical properties were characterized by 1 H-NMR, Fourier transform infrared (FTIR), circular dichroism (CD), etc . The PALG
n
-g-EG
x
samples with x = 3 and 4 displayed lower critical solution temperature (LCST) in water due to the presence of OEG units. The clouding point (CP) of polypeptides can be finely tuned by changing the side chain structures, molecular weights and sample concentrations. In addition, the thioether linkages in the side chains offer additional redox-responsive properties. The influence of both OEG units and thioether linkages on the LCST behavior was systematically investigated. This work provides an efficient way to prepare multi-stimuli responsive materials with highly tunable properties.
研究领域:
高分子化学
·
材料科学
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产品关联
DOI
高影响因子
AUSTRALIAN JOURNAL OF CHEMISTRY
·
2015
·Vol. 69
·期 1
·112-118
·
IF 1.558
Yu Yang,Yan Wu,Ruirui Li,Ying Ling,Haoyu Tang
A series of random copolypeptides, i.e. poly(γ-propyl-l-glutamate)-graft-(oligo-ethylene-glycol)-random-poly(γ-benzyl-l-glutamate)s (PPLG-g-OEG3-ran-PBLG) with similar main chain lengths and various compositions of OEG and benzyl pendants were synthesized in three steps, including ring-opening polymerization of γ-chloropropyl-l-glutamic acid-based N-carboxyanhydride (CPLG-NCA) and γ-benzyl-l-glutamic acid-based N-carboxyanhydride (BLG-NCA), nucleophilic substitution in the presence of NaN3, and copper-mediated alkyne–azide 1,3-dipolar cycloaddition. 1H NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography results confirmed the molecular structures of the resulting copolypeptides and characterized their molar masses, molar mass distributions, and the OEG/benzyl compositions. Fourier transform infrared spectroscopy and circular dichroism analysis revealed that PPLG-g-OEG3-ran-PBLG samples adopted α-helical conformations both in aqueous solution and solid state. Variable-temperature UV-visible spectroscopy revealed that PPLG-g-OEG3-ran-PBLG samples with high OEG molar content (x ≥ 0.57) possessed lower critical solution temperature-type phase transitions in water. The cloud point temperature, in the range of 22–53°C, can be readily obtained by controlling the OEG/benzyl composition.
研究领域:
高分子化学
·
材料科学
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DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2014
·
IF 1.599
Yugang Huang,Weiang Luo,Guodong Ye
A new polypeptide-based copolymer brush composed of poly (γ-propargyl- L -glutamate)- block -poly (propylene oxide)- block -poly (γ-propargyl- L -glutamate) backbone (PPLG- b -PPO- b -PPLG) and oligo (ethylene glycol) (PEG) side-chain was synthesized by combination of N -carboxyanhydride ring-opening polymerization and click chemistry. Nearly 100% grafting efficiency was achieved by copper-catalyzed azide-alkyne Huisgen 1,3-dipolar cycloaddition (CuAAc) reaction. The α -helical conformation adopted by the grafted polypeptide blocks in water was relatively stable and showed a reversible change in a heating–cooling circle from 5 to 70 °C. It displayed weak stability against elevated temperature but still reversible changes in the presence of 0.47 M NaCl. The brushes were amphiphilic and could self-assemble into thermo-sensitive micelles in water. Big micelles could break into small micelles upon heating due to the improved solubility.
研究领域:
高分子化学
·
生物材料科学
✓ 已验证
产品关联
DOI
高影响因子
MACROMOLECULAR CHEMISTRY AND PHYSICS
·
2015
·Vol. 216
·期 23
·2270-2278
·
IF 2.616
Dan Liu,Qiulin Yuan,Ying Ling,Haoyu Tang
A series of polypeptides bearing various alkyl (i.e., propyl, hexyl, or octyl) spacers, biphenyl mesogens, and oligo-ethylene-glycol (OEG) tails (i.e., PPLG 26 -BPOEG m , PHLG 34 -BPOEG m , and POLG 32 -BPOEG m [ m = 3 or 7]) has been synthesized via 1,3-dipolar cycloaddition reactions with quantitative grafting densities. Fourier transform infrared results reveal that the polypeptides adopted an α -helical conformation in the solid-state. Differential scanning calorimetry (DSC) analysis reveals that the glass transition temperatures ( T g s) of the polypeptides with OEG 3 tails decrease with the increasing length of the alkyl spacers. For the samples containing alkyl spacers of the same length, T g significantly decreases with the increasing lengths of the OEG tails. Polarized optical microscope (POM) results reveal that all polypeptides exhibit strong birefringence at room temperature. Polypeptides with long alkyl spacers (i.e., hexyl or octyl) or OEG 7 tails show isotropic transitions, while PPLG 26 -BPOEG 3 show no clear point temperature before thermal decomposition. DSC, POM, and wide-angle X-ray scattering results collectively reveal that polypeptides with long alkyl spacers (i.e., hexyl or octyl) and OEG 3 tails undergo a reversible smectic E phase to isotropic phase transition, while polypeptides with OEG 7 tails undergo a reversible liquid crystalline phase to isotropic phase transition. The transition temperatures increase with the increasing length of alkyl spacers.
研究领域:
材料科学
·
生物化学
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DOI
高影响因子
POLYMER
·
2020
·
IF 4.231
Ke Wang,Qi Liu,Guiyan Liu,Yongfei Zeng
The study of thermoresponsive homopolymers has attracted great attention due to their broad application value. Herein, a series of novel thermoresponsive homopolymers of poly[oligo(ethylene glycol) (acyloxy) methacrylate]s containing oligo(ethylene glycol) (OEG) units and substituent groups of ester have been designed and prepared by RAFT polymerization . The solution properties of these polymers have been investigated in detail, which indicate that most of them exhibit lower critical solution temperature (LCST) in water and upper critical solution temperature (UCST) in alcohols, and their LCST-type or UCST-type cloud point temperature ( T CP L or T CP U ) is closely related to the OEG units and ester groups. Furthermore, the parameters affecting the thermoresponse of these polymers including polymerization degree (DP) and concentration have also been investigated. The present work not only discovers a series of novel thermoresponsive polymers, but also has certain guiding significance on the understanding of molecular structure and thermoresponsive property relationships, which is useful for the design of new thermosensitive polymers.
研究领域:
高分子化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2015
·Vol. 6
·期 4
·2602-2610
·
IF 3.84
Yanna Zhao,Jing Zhao,Chunying Hao,Meihua Han,Mincan Wang,Yifei Guo,Xiangtao Wang
An amphiphilic dendron–drug conjugate was synthesized via oligoethylene glycol (OEG) dendrons coupled with anticancer drug doxorubicin (DOX). The amphiphilic conjugate OEG–DOX (GD) self-assembled into spherical nanoparticles in aqueous solution, with mean diameters of approximately 212.5 nm. As an effective drug carrier, DOX was entrapped into GD to form drug-loaded nanoparticles (GD/D) with high drug loading content (24%, wt%), due to the enhanced hydrophobic/aromatic interactions between the DOX moiety in GD and free DOX. Besides, GD nanoparticles exhibited thermo-induced collapse and aggregation, therefore, the temperature-dependent drug release profiles of DOX from GD/D nanoparticles were measured and the possible mechanism was proposed. Moreover, hemolytic activity of GD/D revealed the good blood compatibility, and the cytotoxicity of DOX in GD/D was enhanced significantly in vitro against HepG2 cells. Overall, amphiphilic conjugate GD was considered to be potentially feasible to overcome formulation challenges for drug delivery and to be used in clinic.
研究领域:
药剂学
·
生物材料
·
肿瘤学
✓ 已验证
DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2014
·Vol. 131
·期 21
·
IF 1.64
Yan Wu,Yong Deng,Qiulin Yuan,Ying Ling,Haoyu Tang
A series of thermoresponsive poly(γ-propyl- L -glutamate)-graft-(oligo ethylene glycol)s (PPLG-g-OEGs) with different main-chain and side-chain lengths have been synthesized via copper-mediated alkyne-azide 1,3-dipolar cycloaddition between poly(γ-azidopropyl- L -glutamate)s (PAPLG) and propargyl terminated oligo ethylene glycols (Pr-OEGs). Fourier transform infrared spectrometer analysis revealed that PAPLG 10 adopted 39.4% β-sheet, 47.4% α-helix, and 13.2% random coil while PAPLG with longer main-chain length (DP = 37 and 88) and PPLG-g-OEGs adopted exclusive α-helix in the solid state. Circular dichroism analysis revealed that PPLG-g-OEGs adopted α-helical conformations with helicities in the range of 50∼100%. The thermoresponsive behaviors of PPLG-g-OEGs in water have been studied by dynamic light scattering. The polymer concentration, main-/side-chain length, and helicity collectively affected their cloud point temperatures. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131 , 41022.
研究领域:
高分子化学
·
生物材料
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2014
·Vol. 4
·期 97
·54268-54281
·
IF 3.708
Yinwen Li,Huilong Guo,Jian Zheng,Jianqun Gan,Yan Zhang,Xiaoxiao Guan,Kun Wu,Mangeng Lu
Novel macromolecular star polymers with triazole and cyclodextrin (CD) segments as branch points and poly(oligo(ethylene glycol)methacrylate) (POEGMAs) as dense hydrophilic branches were synthesized via a combination of azide–alkyne click chemistry and atom transfer radical polymerization (ATRP). Firstly, a tetrafunctional linking agent (PETP) was prepared by the reaction of pentaerythritol (PE) and propargyl bromide, and then a four arm β-CD terminated star polymer (PE-CD) was obtained through the click chemistry reaction. Finally, thermally-responsive star polymers (PE-CD–POEGMAs) with PE as the central core, triazole and CD segments as branch points, and POEGMAs as side branches were synthesized by the ATRP of MEO2MA and OEGMA using PE-CD terminated with bromines as macroinitiators. A study on the thermoresponsivity and morphology of PE-CD–POEGMAs indicated that polymeric nano-aggregates existed as multimolecular micelles and behaved with tunable thermosensitivity, which were driven by the strong hydrophobic–hydrophilic interactions in the inner core and outer shell. The encapsulation capacities towards multi-guest molecules were investigated and the results indicated that water soluble guests could be encapsulated by PE-CD–POEGMAs, and the guest encapsulation capacities were derived from the special star molecular structure properties of PE-CD–POEGMAs and the synergistic encapsulation phenomenon of different guest molecules. This unique amphiphilic star polymer illustrated the potential applications in supramolecular science, drug delivery and other nanotechnology applications.
研究领域:
高分子化学
·
纳米技术
·
药物递送
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
·
2015
·Vol. 54
·期 10
·1348-1356
·
IF 3.113
Mengxiang Zhu,Yanzhi Xu,Chenglong Ge,Ying Ling,Haoyu Tang
A series of OEGylated poly(γ-benzyl- l -glutamate) with different oligo-ethylene-glycol side-chain length, molecular weight (MW = 8.4 × 10 3 to 13.5 × 10 4 ) and narrow molecular weight distribution (PDI = 1.12–1.19) can be readily prepared from triethylamine initiated ring-opening polymerization of OEGylated γ-benzyl- l -glutamic acid based N -carboxyanhydride. FTIR analysis revealed that the polymers adopted α-helical conformation in the solid-state. While they showed poor solubility in water, they exhibited a reversible upper critical solution temperature (UCST)-type phase behavior in various alcoholic organic solvents (i.e., methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, and isopropanol). Variable-temperature UV–vis analysis revealed that the UCST-type transition temperatures ( T pt s) of the resulting polymers were highly dependent on the type of solvent, polymer concentration, side- and main-chain length. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54 , 1348-1356
研究领域:
高分子化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
POLYMER
·
2015
·
IF 3.562
Xue Jiang,Chun Feng,Guolin Lu,Xiaoyu Huang
A homopolymer strategy was developed to synthesize temperature and pH/CO 2 stimulus-responsive homopolymers. A new class of acrylamide monomers bearing oligo(ethylene glycol) unit and N,N -diethylaminoethyl group were designed and prepared through Aza-Michael addition reaction followed by amidation with acryloyl chloride using amino group as a linkage to connect oligo(ethylene glycol), N,N -diethylaminoethyl, and polymerizable double bond groups together. Subsequently, the corresponding homopolymers containing oligo(ethylene glycol) unit and N,N -diethylaminoethyl group in each repeated unit were prepared via RAFT polymerization with controlled molecular weights and relatively narrow molecular weight distributions . The lower critical solution temperature (LCST) of homopolymer was examined to be influenced by molecular weight, salt concentration, and pH value of aqueous solution. The LCSTs of homopolymers could be tuned in a wide temperature window by changing pH value of aqueous solution and it increased with the decrease of pH value. Particularly, CO 2 gas as a unique pH stimulus can also reversibly adjust the solubility of homopolymer without the addition of acids or bases.
研究领域:
高分子化学
·
智能材料
·
药物递送
·
生物医用材料
·
刺激响应材料
✓ 已验证
DOI
高影响因子