Acta Biomaterialia
·
2022
·
IF 10.633
Fangjun Liu,Dun Wang,Miao Zhang,Liwei Ma,Cui-Yun Yu,Hua Wei
Synthesis of polyfluorene (PF) based theranostic amphiphilic copolymers with simultaneously high drug loading efficiency and tumor microenvironment-specific responsiveness for promoted intracellular drug release and enhanced cancer therapy has been rarely reported likely due to the lack of efficient synthetic approaches to integrate these desirable properties. In this work, we recorded the successful preparation of well-defined theranostic amphiliphilic bottlebrush copolymers composing of fluorescent backbone of PF and tunable enzyme-degradable side chains of polytyrosine (PTyr) and POEGMA by integrating Suzuki coupling , NCA ROP and ATRP techniques. Notably, the resulting copolymer, PF 25 - g -(PTyr 26 - b -(POEGMA 28 ) 2 (P 4 ) with two branched POEGMA brushes tethered to one PTyr termini for each unit could form steady unimolecular micelles with higher fluorescence quantum yield of 18.3% in aqueous and greater entrapment efficiency (EE) of 91.0% for DOX ascribed to the efficient π–π stacking interactions between PTyr blocks and drug molecules and the unique structure of branched hydrophilic brushes with a moderate chain length. DOX@P 4 micelles revealed visualization of intracellular trafficking and accelerated drug release due to the enzyme-triggered degradation of PTyr blocks with proteinase K and subsequent deshielding of POEGMA corona for micelle destruction. In vitro and In vivo animal study further verified the intensive therapeutic efficiency with attenuated systematic toxicity. Taken together, we provided a universal strategy toward multifunctional polymeric delivery vehicles based on conjugated PF and biocompatible and degradable polypeptide by integratied Suzuki coupling and NCA ROP, and identified the branched structure of hydrophilic brushes for better performance of bottlebrush copolymers-based micelles for drug delivery applications. Statement of significance Synthesis of polyfluorene (PF)-based theranostic amphiphilic copolymers with simultaneously high drug loading efficiency and tumor microenvironment-specific responsiveness for promoted intracellular drug release and enhanced cancer therapy has been rarely reported likely due to the lack of efficient synthetic approaches to integrate these desirable properties. We reported herein successful preparation of enzyme-responsive theranostic amphiliphilic bottlebrush copolymers with simultaneously high drug loading efficiency and tumor microenvironment-specific responsiveness for enhanced chemotherapy in vivo . This study therefore not only developed a universal strategy for the construction of multifunction polymeric vehicles based on the conjugated polymer of PF and degradable polypeptide by integrated Suzuki coupling and NCA ROP, but also emphasized the better stability of micelles endowed by the branched hydrophilic brushes than linear ones.
研究领域:
高分子化学
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生物医学工程
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癌症治疗
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产品关联
DOI
PubMed
高影响因子
Materials Today Physics
·
2021
·
IF 9.298
Feichong Yao,Wenhao Xie,Ming Yang,Hang Zhang,Hongbo Gu,Ai Du,Nithesh Naik,David P. Young,Jing Lin,Zhanhu Guo
With the purpose of ameliorating the electrical property, permittivity and magnetoresistance of polyaniline (PANI) nanofibers , three types of phenylenediamine (PDA), including o -PDA, m -PDA, and p -PDA, and different contents of PDA have been incorporated into the PANI polymer backbone by the interfacial copolymerization of aniline with PDA. The results demonstrate that different types and contents of PDAs could disclose the distinct effects on the chemical structures , crystalline structures, and morphologies for copolymers of aniline with PDA affirmed by Fourier transform infrared (FTIR) spectroscopy, solid-state 13 C nuclear magnetic resonance ( 13 C NMR), X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM). The molecular weight of all copolymers is reduced by several orders of magnitude relative to pure PANI nanofibers confirmed by gel permeation chromatography (GPC). The resistivity variations for the copolymers of aniline with different types of PDAs are well explained from the point view of their molecular structures based on the first-principle simulations (i.e. intrachain electrical conductivity) and degree of crystallinity gained from XRD (i.e. interchain electrical conductivity). A tunable room-temperature magnetoresistance (MR) and a controllable negative permittivity are discovered in the copolymers of aniline with different types and contents of PDAs. This work provides a new insight for the manipulation of electrical transport for PANI nanofibers and helps seek the new applications of conductive polymer .
研究领域:
材料科学
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化学
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产品关联
DOI
高影响因子
International Journal of Electrochemical Science
·
2023
·
IF 1.5
Lanlan Shen,Zhiru Bai,Yu Jiang,Liying Li,Fengxing Jiang,Jingkun Xu,Huanhuan Qiu,Huixuan Liu,Rongri Tan
Based on quaterthiophenen, bisethyleneoxyl are appended to thiophene rings (2,5-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)thieno[3,2-b]thiophene, BED-TT) for modified monomer structure and obtain a lower onset potential as well as strong electron donor properties. Different molar ratio copolymers of BED-TT with 3,4-ethylenedioxythiophene (EDOT) was electrochemically synthesized, and the effects of changes in the amount of EDOT on the electrochemical and spectrochemistry properties of the copolymers were tracked. The resultant copolymer P(BED-TT- co -EDOT) was characterized via cyclic voltammetry, Raman, and spectroelecrochemistry. The study found that the amount of EDOT in the mixed system of BED-TT and EDOT can regulate the oxidation potential, electrochemical activity, and redox process of polymer films to a certain extent. The spectroelectrochemical results revealed that the copolymer P(BED-TT- co -EDOT) has a narrower optical band gap (1.63-1.67eV) and a richer electrochromic color (from pink purple, purple to gray blue, blue).
研究领域:
材料科学
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电化学
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分析化学
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产品关联
DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
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2023
·Vol. 141
·期 10
·e55051
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IF 3
Xiaoling Da,Zhaoyi Deng,Tong Wu,Ya Cao,Ming Xiang,Feng Yang
To study the effect of molecular structure on ethylene-vinyl alcohol copolymer (EVOH) thermal stability during processing, EVOH samples with different molecular weights and comonomer distributions were prepared by solubility fractionation from two different commercial materials, and then, the structure features of samples were characterized by 1 H-NMR, viscometry, differential scanning calorimetry, and, especially, successive self-nucleation and annealing. Their thermal stabilities were further analyzed by isothermal oxygen treatment and thermogravimetry. Attenuated total internal reflectance Fourier transform infrared spectroscopy and UV were used to obverse the structural changes in samples (the formation of chromogenic groups: CO and CC ). According to the results of isothermal oxygen treatment at 200°C, at the same ethylene content, low-molecular-weight samples have worse thermal stability, which were extremely easy to yellowing and form insoluble gel. To investigate the structure differences between the low-molecular-weight samples, it was found that long vinyl alcohol segments may not worsen the thermal stability in the conditions of the same ethylene content. But samples with a uniform distribution of ethylene segments and a certain length of ethylene segments will have better thermal stability, which makes it more difficult to form carbonyl even diketene conjugation structure.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF POLYMER ANALYSIS AND CHARACTERIZATION
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2023
·
IF 1.9
Xiaohong Hu,Weiwei Jin,Haitao Zhang,Qinyu Qing,Juan Pang
Visible-light-driven azobenzene had been reported by theoretical calculation, but could not be detected by any characterization method due to unstable cis structure. Herein, copolymerization was applied to solve the problem based on a time-dependent characteristic of macromolecular motion. Therefore, two copolymers, namely, MRAA-PEG20 copolymer and MRAA-NIPAM copolymer, were synthesized with a definite segment ratio. Both copolymers had photosensitive groups, which were confirmed by UV-vis spectra. Furthermore, copolymer concentration had a linear relationship with absorbance value at 425 nm. Firstly, blue light as an excitation source to induce the isomerization of copolymers. At the same time, repeated interval irradiation was used to evaluate the fatigue performance of the copolymer. Consequently, both copolymers could quickly transform to their cis isomers upon irradiation, which could be reversible recovered to their trans isomers in operable recovery time after removing irradiation. However, the MRAA-PEG20 copolymer had an obvious photobleaching phenomenon along with the circle index, which did not exist in the MRAA-NIPAM copolymer. Secondly, the effects of excitation light source on isomerization were investigated. It was found that blue light was the most efficient excitation source for both copolymers though other light could also induce trans-to-cis transition. Thirdly, the influence of light intensity and temperature was respectively studied. With increasing of light intensity, the absorbance ratio before and after irradiation monotonously decreased, the irradiation response time shortened and the recovery response time prolonged. Moreover, higher temperature resulted in a higher absorbance ratio, shorter irradiation response time, and shorter recovery response time. Finally, synthesized copolymers had characteristic of pH indicator with a critical point of pH 5.0.
研究领域:
材料科学
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高分子化学
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产品关联
DOI
高影响因子
Journal of Physical Chemistry C
·
2023
·
IF 3.7
Ting Qu,Xue Hu,Ying Ou,Jie Wang,Fuqiang Hu,Jing Ni,Fan Cheng,Chunli Gong,Hai Liu
Robust metallic doped semiconducting networks of precise organization, over large scales and small dimensionality, hold great application potential in the basis of photocatalytic materials. Herein, a facile method to fabricate robust Au@TiO2 hierarchical nanoporous network films is reported, which is templated by thermally stable poly(4-vinylpyridine)-block-poly{11-[4-(4-butylphenylazo)phenoxy]undecyl methacrylate} (P4VP-b-PMA(11C)Az) liquid crystalline (LC) block copolymers (BCPs). A P4VP100-b-PMA(11C)Az15 thin film can self-assemble to form ∼50 nm orderly packed PMA(11C)Az periodic spheres in the P4VP matrix via a solvent-annealing process. When these spherical P4VP100-b-PMA(11C)Az15 films with different thicknesses were exposed to the sol–gel titania precursors alcohol solutions with titanium(IV) isopropoxide (TIPT) and titanium tetrachloride (TiCl4; mass ratio, 3:1), titania was well-formed in the P4VP phase during the calcination process. After a further deposition–precipitation (DP) process, ∼10 nm Au nanoparticles were homogeneously doped in robust TiO2 nanoporous network films. The photocatalytic performance of the obtained robust Au@TiO2 films was studied in detail. It displays significantly enhanced visible light photocatalytic activity. The enhancement mechanism was ascribed to the injection of hot electrons of photoexcited Au nanoparticles to robust porous TiO2 films, which was confirmed by 420 nm Xe laser-induced fast photodegradation of rhodamine B.
研究领域:
材料科学
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化学工程
·
纳米技术
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Xinyu Zhang,Chunhui Zhang,Zhenglun Lin,Xinsheng Luo,Jingtao Xu,XiaoXiang Cheng,Daoji Wu,Congwei Luo,Feiyong Chen
Reverse osmosis (RO) membrane technology encounters challenges such as membrane biofouling and oxidation during practical use, which significantly hinders its further development and application. To improve the chlorine and biofouling resistance of RO membrane, we suggest a method that modifies the mass ratios of zwitterionic and quaternary ammonium copolymers in the mussel-inspired coating layer. This method successfully controls the hydrophilicity and positive charge of the membrane surface, enhancing its overall performance. The plate counting results indicate that the bacterial killing efficiency of the blended modified TFC membrane (50:50) against E. coli and S. aureus is ≥98 %. Thanks to the combined effects of the anti-adhesion zwitterionic copolymer and the antibacterial quaternary ammonium copolymer, the blended modified TFC membrane (50:50) demonstrates superior anti-biofouling performance in dynamic biofouling tests. Furthermore, the desalination performance of the blending modified TFC membrane (50:50) remains stable after long-term exposure to 60,000 ppm·h of active chlorine, while the desalination performance of the pristine TFC membrane significantly declines. In conclusion, our advancements in chlorine-tolerant and anti-biofouling RO membranes could enhance the reliability of RO technology.
研究领域:
材料科学
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环境工程
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF PHYSICAL CHEMISTRY B
·
2016
·
IF 3.187
Yihuang Chen,Tiansheng Gan,Chunfeng Ma,Linge Wang,Guangzhao Zhang
Crystallization of polymer chains confined on a surface greatly influences surface properties. We have grafted comb-like copolymer, consisting of poly(2-hydroxyethyl methacrylate) (PHEMA) backbone and semicrystalline poly(ε-caprolactone) (PCL) side chains, on silicon surface and investigated the crystallization of such confined PCL chains upon solvent evaporation by using atomic force microscopy (AFM), grazing incidence wide-angle X-ray scattering (GI-WAXS), and polarized optical microscope (POM). Our studies reveal that the PCL chains align and form “flat-on” lamellae at a low PCL chain density. As the chain density increases, the comb-like polymer (PHEMA-g-PCL) chains undergo pancake-to-mushroom-to-brush transition, and the lamellae turn from “flat-on” to “edge-on” in orientation. Further increasing PCL chain density leads the “edge-on” lamellae to change from a quasi-two-dimensional (quasi-2D) to quasi-three-dimensional (quasi-3D). Because of the confinements of polymer chains, we can observe the evolution of spherulites at different stages during the mushroom-to-brush transition of PHEMA-g-PCL chains. The confinements also result in knobbly substructures in the edge-on lamellae.
研究领域:
材料科学
·
高分子化学
✓ 已验证
DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2017
·Vol. 134
·期 26
·
IF 1.86
Fangqiao Zhao,Xiaoma Fei,Wei Wei,Weitao Ye,Jing Luo,Yaxin Chen,Ye Zhu,Xiaoya Liu
Toughening of epoxy resin by block copolymers containing an epoxy-philic block and an epoxy-phobic block is usually costly because of their complex preparation procedure. In this work, a novel, random epoxy-amphiphilic copolymer (PHGEL), which combines an “epoxy-philic” component and an “epoxy-phobic” component, has been synthesized and evaluated as a potential toughening agent for a diglycidyl ether of bisphenol A–based epoxy thermoset (EP). The curing behavior of the EP/PHGEL system has been investigated, and the results show that the hydroxyl group on the PHGEL chain can slightly activate the curing reaction. The mechanical testing shows that the toughness of the epoxy resin is improved by 294% when 4 wt % of PHGEL is added. Simultaneously, the tensile strength, elongation at break, and glass-transition temperature are also improved. In addition, the thermogravimetric analysis shows that PHGEL has no obvious effect on the thermal stability of the epoxy thermosets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44863.
研究领域:
材料科学
·
高分子化学
✓ 已验证
DOI
高影响因子
POLYMER DEGRADATION AND STABILITY
·
2019
·
IF 3.78
Piotr Rychter,Kamila Lewicka,Małgorzata Pastusiak,Marian Domański,Piotr Dobrzyński
Nowadays, researchers in the field of agrochemicals are trying to find effective methods to limit the excessive usage of pesticides and protect the environment. One of the most popular and promising techniques is the immobilization of pesticides using environment-friendly polymers. In the conducted research, it was demonstrated that the family of lactide/glycolide copolymers are unsuitable for this purpose due to very slow degradation in the soil. We examined influence of relatively small content of PEG blocks in newly synthesized poly( l -lactide-co-glycolide)-poly(ethylene glycol)–poly( l -lactide-co-glycolide) (PLGA–PEG–PLGA) on the degradation in soil, in activated sludge and usefulness of this terpolymers as a biodegraded carrier for the controlled release of two commonly used herbicides (Metazachlor and Pendimethalin). Presence of even small amount of PEG block in the terpolymer chain increases slightly the hydrophilicity of the polymeric chain, thereby increasing its susceptibility to hydrolytic and unexpectedly strongly to enzymatic degradation in soil environment. The amorphism of used as a carriers PLGA-PEG-PLGA terpolymers and the lack of the phenomenon of increasing the degree of crystallinity during degradation allow to achieve uniform progress of degradation, and thus is obtained a relatively constantly release of tested herbicides. In this way, it is possible to determine the optimal profile of degradation of polymer in soil and proper rate of diffusion and leaching of active agents which allows the release of herbicides in optimal and effective doses within 3–4 months of its application.
研究领域:
农业科学
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高分子化学
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环境科学
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2022
·
IF 8.025
Wenjian Huang,Xin Wen,Jin Zhou,Xuzhen Zhang
Poly (L-lactic acid) (PLLA) based copolymers modified with δ -valerolactone (DVL) through random copolymerization (PVLA-R) and block copolymerization (PVLA-B) with various DVL content were prepared to investigate their degradation regulation and mechanism. Chemical structure , thermal properties , hydrophilicity , crystallization as well as the crystal defects of the obtained copolymers were respectively confirmed. Degradation regulation of both PVLA-R and PVLA-B, such molecular weight and pH value changes of PLLA based copolymers were investigated via vitro degradation method. In order to further explore the degradation principle of the two copolymers , their degradation residues at different stages were systematically studied. The addition and increasing content of DVL disturbs the regularity of original PLLA molecular structure, resulting in accelerating degradation of copolymers . Compared with amorphous region, the crystalline region of both two copolymers has better corrosion resistance , which could be confirmed by increased melting point and crystallinity of both PVLA-R and PVLA-B degradation residues. PVLA-B copolymers show relatively superior degradation resistance mainly due to their higher molecular weight , crystallinity and hydrophobic index than PVLA-R copolymers.
研究领域:
材料科学
·
生物医学工程
✓ 已验证
DOI
高影响因子
Separations
·
2024
·Vol. 11
·期 11
·327
·
IF 2.5
Yifeng Li,Jingyue Chen,Xiwei Tan,Han Lou,Hongbo Gu
Hexavalent chromium, one of the heavy metal pollutants in water, harms the ecological environment and human health. In this work, an aniline-p-phenylenediamine copolymer has been prepared by chemical oxidative polymerization to remove the hexavalent chromium (Cr(VI)) from wastewater. The results show that when the initial Cr(VI) concentration is 1.5 mg·L−1, the removal percentage (RP%) of Cr(VI) could reach 94.84% after 180 s of treatment. The RP% of Cr(VI) increases with the dosage of copolymers and decreases with an increase in the initial Cr(VI) concentration. Additionally, the RP% of Cr(VI) removal reaches a maximum of 97.70% with a pH value of 1.0. The Cr(VI) removal kinetics of the copolymers follows a pseudo-first-order chemical reaction model. The X-ray photoelectron spectroscopy (XPS) results demonstrate that the Cr(VI) removal mechanism by the aniline-p-phenylenediamine copolymer is a redox reaction. The positive value of ΔH° and negative value of ΔG° affirm that the Cr(VI) removal process by aniline-p-phenylenediamine copolymer is endothermic, thermodynamically achievable, and spontaneous.
研究领域:
环境科学
·
材料科学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）