Polymer Chemistry
·
2024
·
IF 4.1
Quan Yan,Bailiang Xue,Tonghe Zhang,Wenliang Wang,Xinping Li,Xiaojun Shen,Lulu Ning,Xianzhi Meng,Wei Zhao
The star–star coupling is often regarded as an undesirable side reaction in in the synthesis of star polymers. To mitigate this issue, strategies such as operating at low temperatures, maintaining low monomer concentrations, and limiting monomer conversion are typically employed, albeit at the cost of reduced synthetic efficiency in producing the desired polymer materials. In this study, we propose a novel approach to harness this side reaction for the creation of a lignin-containing, sustainable, and solvent-resistant dynamic dual network using a one-pot synthesis strategy. Initially, a lignin-based macroinitiator with low polydispersity index (PDI) was synthesized to facilitate the precise formation of well-defined star polymers functionalized with epoxy groups. Subsequent to this, the first network, composed of star-shaped lignin-grafted copolymers, was successfully established through the utilization of the free radical bimolecular termination reaction. Following this, the second dynamic crosslinked network was formed via vitrimer chemistry between epoxy and carboxylic acid. The resulting dynamic dual network, accessible through a straightforward one-pot method, exhibited excellent reprocessability and solvent resistance, rendering it suitable for applications as high-performance adhesives. This study introduces a novel strategy for the synthesis of dynamic dual networks based on star-shaped lignin-grafted copolymers, offering promising prospects for the advancement of sustainable biomaterial synthesis.
研究领域:
材料科学
·
可持续化学
✓ 已验证
产品关联
DOI
高影响因子
SCIENCE AND TECHNOLOGY OF ADVANCED MATERIALS
·
2026
·
IF 6.6
Wei Ma,Hongyan Yang,Xinyue Ma,Jiao Huang,Li Chen,Atsushi Takahara
The development of polymer prodrugs with well-defined architectures capable of forming stable nanomicelles is important for achieving precise and efficient drug delivery. Compared with conventional linear systems, star-shaped copolymer prodrugs offer enhanced micellar stability owing to their covalently tethered architecture. However, many existing synthetic approaches rely on transition-metal catalyzed polymerization and customized monomers, which limit their sustainability and practical applicability. Herein, we report a pH-responsive doxorubicin (DOX)-conjugated benzaldehyde-functionalized star-shaped copolymer synthesized via an environmentally benign metal-free atom transfer radical polymerization (ATRP) strategy. A hydroxyl-functionalized star-shaped copolymer scaffold was first prepared from readily available monomers and subsequently modified to introduce pendant benzaldehyde groups, enabling DOX conjugation through acid-labile imine linkages. This approach affords well-controlled polymer architectures while avoiding transition-metal residues and the need for pre-functionalized monomers. The resulting DOX-conjugated star-shaped copolymers form unimolecular micelles with high colloidal stability and exhibit pH-triggered drug release under acidic conditions. In vitro studies further demonstrate effective cellular internalization and a moderated cytotoxic profile toward human large-cell lung carcinoma (H460) cells, supporting the functional viability of this micellar system as a polymer prodrug delivery platform.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
RSC Advances
·
2015
·Vol. 5
·期 68
·55048-55058
·
IF 3.84
Aizhao Pan,Shao Yang,Ling He
Polyhedral oligomeric silsesquioxane (POSS) tethered fluorinated diblock copolymers including linear-shaped ap-POSS–PMMA-b-PDFHM and star-shaped s-POSS–(PMMA-b-PDFHM)16 are synthesized by octakis(dibromoethyl)POSS (POSS-(Br)16) and aminopropylisobutyl POSS (ap-POSS) initiating methylmethacrylate (MMA) and dodecafluoroheptylmethacrylate (DFHM). In THF solution, both diblock copolymers could self-assemble into 200 nm core/shell micelles with a POSS/PDFHM core and 70–80 nm PMMA shell. These micelles are able to produce typical films with a fluorine-rich top-surface and POSS-gathered sub-surface. Although PDFHM segments and POSS cages are competitively migrating onto the film surface, the migration of the PDFHM segments is actually improved by the POSS cages. Comparatively, the surface of the ap-POSS–PMMA-b-PDFHM film is much more rough and fluorine-rich than the s-POSS–(PMMA-b-PDFHM)16 film, therefore, the ap-POSS–PMMA-b-PDFHM film has higher viscoelasticity and higher oleophobicity, but a little lower hydrophobicity than the s-POSS–(PMMA-b-PDFHM)16 film. The hydrophobic application of both linear- and star-shaped topologies to glass, cotton fabric and stone substrates reveals that the treated samples exhibit superhydrophobicity for the cotton fabric (>150°) and obvious hydrophobicity for the stone and glass (>135°) in terms of resistance to water and other liquids like coffee, milk, coke and green tea. It is believed that the properties of self-assembled films and the hydrophobic applications are related closely to the topologies of block copolymers.
研究领域:
高分子化学
·
材料科学
·
表面科学
·
纳米技术
·
功能材料
✓ 已验证
DOI
高影响因子
ACS Applied Energy Materials
·
2021
·
IF 6.024
Jingyu Ma,Xiaoyan Ma,Chengchen Luo,Xinghua Guan,Fang Chen,Yibo Chen,Jingwen Tu
The low ionic conductivity and mechanical strength are important factors impeding the application of solid polymer electrolytes. Herein, we design synthesize an organic/inorganic hybrid star-shaped polymer of octa(poly(methyl methacrylate)–poly(poly(ethylene glycol) methyl ether methacrylate) cage oligomeric silsesquioxanes (POSS–(PMMA–PPEGMEM)8) by one-step free atom transfer radical polymerization (ATRP), and compound with Li6.4La3Zr1.4Ta0.6O12 (LLZTO) to prepare a composite polymer electrolyte membrane (LP-CPEM). The star-shaped structure of the POSS–(PMMA–PPEGMEM)8 induced by octachloropropyl polyhedral cage oligomeric silsesquioxane (OCP-POSS) is beneficial to reduce the crystallinity of polymer and increase the movement of the polymer chain to form a continuous interconnected ion migration channel. The LLZTO fillers in the LP-CPEM could simultaneously hinder the orderly arrangement of polymer chains and provide other ion transport paths to increase the ion conductivity of LP-CPEM. The LP-CPEM with 7.5 wt % LLZTO has higher ionic conductivity of 3.8 × 10–4 S cm–1 at 30 °C and high mechanical strength (5.2 MPa). Additionally, Li/Li symmetric cells demonstrate stable constant current charging/discharging during 1000 h at 0.1 mA cm–2, and the all-solid-state batteries fabricated by the LP-CPEM exhibit good cyclic stability. It is promising for the development of next-generation high-safety all-solid-state lithium metal batteries.
研究领域:
材料科学
·
电化学
·
储能技术
·
聚合物化学
·
固态电池
✓ 已验证
DOI
高影响因子
Science Advances
·
2021
·Vol. 7
·期 28
·
IF 14.143
Qi Cao,Yongjiang Li,Hong Zhang,Jiabao Yang,Jian Han,Ting Xu,Shuangjie Wang,Zishuai Wang,Bingyu Gao,Junsong Zhao,Xiaoqiang Li,Xiaoyan Ma,Shaik Mohammed Zakeeruddin,Wei E. I. Sha,Xuanhua Li,Michael Grätzel
Stabilizing high-efficiency perovskite solar cells (PSCs) at operating conditions remains an unresolved issue hampering its large-scale commercial deployment. Here, we report a star-shaped polymer to improve charge transport and inhibit ion migration at the perovskite interface. The incorporation of multiple chemical anchor sites in the star-shaped polymer branches strongly controls the crystallization of perovskite film with lower trap density and higher carrier mobility and thus inhibits the nonradiative recombination and reduces the charge-transport loss. Consequently, the modified inverted PSCs show an optimal power conversion efficiency of 22.1% and a very high fill factor (FF) of 0.862, corresponding to 95.4% of the Shockley-Queisser limited FF (0.904) of PSCs with a 1.59-eV bandgap. The modified devices exhibit excellent long-term operational and thermal stability at the maximum power point for 1000 hours at 45°C under continuous one-sun illumination without any significant loss of efficiency.
研究领域:
材料科学
·
高分子科学
·
光伏技术
·
纳米技术
✓ 已验证
DOI
高影响因子
COLLOID AND POLYMER SCIENCE
·
2012
·Vol. 291
·期 4
·789-803
·
IF 2.331
Zhang Xiaojing,Wang Chaojun,Fang Shaoming,Sun Jiashu,Li Chong,Hu Yuelei
In this paper, a series of hybrid star PLLA (sPLLA) with different arm lengths was synthesized via the hydrosilylation between octakis(dimethylsiloxy) silsesquioxane (Q 8 M 8 ) and functionalized PLLA macromolecules with vinyl end groups (mPLLA). mPLLA was synthesized by ring-opening polymerization of l -lactide using 2-hydroxyethylmethacryl as an initiator in the presence of stannous 2-ethylhexanoate as a catalyst. The obtained sPLLA has low polydispersity with polydispersity index values from 1.29 to 1.30. The arm numbers of sPLLA vary from 5 to 7 and decrease with the increase in the length of the mPLLA arm due to the steric hindrance, which are estimated by 1 H NMR analysis. The branched structure of sPLLA is also evidenced by the lower intrinsic viscosity when compared with the linear mPLLA with similar molecular weight. Both the glass transition temperatures ( T
g ’s) and melting temperatures ( T
m ’s) of sPLLAs are higher than those of the mPLLA arms. The incorporation of polyhedral oligomeric silsesquioxane (POSS) does not change the crystalline structure of PLLA, while the crystallinity of sPLLA is enhanced as the result that the POSS core acts as a heterogeneous nucleating agent in the matrix to promote the crystallization ability of PLLA. High-resolution transmission electron microscopy observation suggests that POSS disperses in the crystalline PLLA matrix as 5–20 nm aggregates. Microspheres of sPLLA with mean diameter 1 to 2 μm were prepared via emulsion solvent evaporation method. The sPLLA microspheres have higher loading capacity and encapsulation efficiency and lower drug release rate than mPLLA microspheres.
研究领域:
材料科学
·
药物递送
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
Polymer Chemistry
·
2013
·Vol. 4
·期 6
·1950-1959
·
IF 5.231
Xiaofang Shi,Miao Miao,Zesheng An
Homoarm and heteroarm core cross-linked star (CCS) polymers based on poly(N,N-dimethylacrylamide) (PDMA) as the high-polarity arm and poly(2-methoxyethylacrylate) (PMEA) as the low-polarity arm were efficiently prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization in a dispersion polymerization system. PDMA and PMEA arm polymers exhibited similar conversion rates, such that their composition in the heteroarm CCS polymers was easily controlled by the feed ratio in the synthesis. The ability to control the arm composition allowed facile tuning of the polarity of the CCS polymers. Heteroarm CCS polymers self-assembled in water to form aggregates and their size was related to the composition and polarity of the CCS polymers. The composition and polarity of the CCS polymers significantly affected the emulsifying behaviour of the CCS polymers as emulsifiers. Oil-in-water (o/w) emulsions were favoured for CCS polymers with relatively high polarity and lowering the polarity of CCS polymers to a certain degree enhanced the stability of the emulsions. Multiple emulsions, both o/w and water-in-oil (w/o), were gradually produced when the polarity of CCS polymers was gradually lowered and the oil fraction in the emulsion samples was gradually increased, and at the same time the emulsions also became increasingly less stable.
研究领域:
聚合物科学
·
材料化学
·
胶体科学
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
Nano Research
·
2020
·Vol. 13
·期 1
·160-172
·
IF 8.183
Zhang Amin,Zhang Qian,Alfranca Gabriel,Pan Shaojun,Huang Zhicheng,Cheng Jin,Ma Qiang,Song Jie,Pan Yunxiang,Ni Jian,Ma Lijun,Cui Daxiang
Distinctively different metabolism between tumor cells and normal cells endows tumor tissues unique microenvironment. In this regard, we have successfully prepared a sequential catalytic platform based on Au/Pt star for tumor theragnostic. The multifunctional probes consisted of a gold/platinum star-shaped core (Au/Pt star) conjugated with a GSH-sensitive disulfide bond (S–S), a targeting ligand (rHSA-FA), a near-infrared fluorophore (IR780) and glucose oxidase (GO x ). When systemically administered in a xenografted murine model, the probes specifically targeted the tumor sites. As the disulfide linker was cleaved by intracellular GSH, the IR780 molecules could be released for photo-thermal therapy & photodynamic therapy (PTT&PDT) and imaging. Subsequently, the Pt nanolayer of the Au/Pt star and the GO x formed a sequential catalytic system: GO x effectively catalyzed intracellular glucose by consuming oxygen to generate H 2 O 2 and enhance the local acidity, and the Pt layer exhibited peroxidase-like property to catalyze H 2 O 2 producing toxic ·OH for tumor oxidative damage. Here we demonstrated that our probes simultaneously possessed a GSH-sensitive release, real-time imaging ability, and synergetic cancer starving-like therapy/enzyme oxidative therapy/PTT/PDT features, which provides a potential strategy for effective tumor theragnostic.
✓ 已验证
产品关联
DOI
高影响因子
COLLOID AND POLYMER SCIENCE
·
2017
·Vol. 295
·期 9
·1609-1619
·
IF 1.723
Ding Amin,Zhou Yifeng,Chen Pengpeng,Nie Wangyan
Amphiphilic star-shaped copolymers based on star-shaped poly(L-lactide) (s-PLLA) and poly(ethylene glycol) (PEG) (s-PLLA-PEG) were synthesized with variable molecular weights (M w ) of PEG, and the relationship between the PEG block molecular weight of s-PLLA-PEG copolymers and their micelle properties were investigated. The structure and M w of s-PLLA-PEG were characterized with 1 H NMR, GPC, DSC, and XRD. The ibuprofen (IBU)-loaded s-PLLA-PEG micelles were prepared by dialysis method. The effects of PEG block molecular weight on the morphology, particle size, zeta potential, drug loading content (LC), drug encapsulation efficiency (EE), and in vitro drug release behavior of prepared micelles were investigated. Results indicated that the average diameters, LC, and EE of IBU-loaded s-PLLA-PEG micelles increased with increasing the M w of PEG in s-PLLA-PEG copolymers. The in vitro study showed that the IBU accumulative release can be depressed by increasing the M w of the s-PLLA-PEG, and the release profiles of IBU from s-PLLA-PEG followed the Baker-Lonsdale model equation. The results suggest that structural tailoring of PEG length from s-PLLA-PEG copolymers could provide a new strategy for designing drug carriers of high efficiency.
研究领域:
材料科学
·
药剂学
✓ 已验证
产品关联
DOI
高影响因子
Polymer Chemistry
·
2014
·Vol. 5
·期 14
·4277-4284
·
IF 5.368
Xueteng Cao,Chunlei Zhang,Songbai Wu,Zesheng An
We have developed a highly efficient, one-step approach for the synthesis of core cross-linked star (CCS) polymers using commercial macromonomers (polyethylene glycol methyl ether methacrylates) as the arms via RAFT-mediated emulsion polymerization in aqueous media. This approach employs a small molecular chain transfer agent (CTA), commercial macromonomer, hydrophobic cross-linker, and optional hydrophobic spacing monomer as the polymerization recipe to synthesize CCS polymers via direct one-step polymerization in aqueous buffer solution. Various polymerization parameters, including buffer concentration and molar ratio of macromonomer/cross-linker/spacing monomer relative to CTA, were investigated. CCS polymers of high yield and low dispersity were obtained within 4 h under a wide range of conditions. Analysis of polymerization kinetics and macromolecular parameters of the generated polymeric species during the polymerization process led to insights into the mechanistic aspects of the CCS formation process, which was proposed to involve three stages, i.e., polymer chain growth, cross-linking to form CCS, and CCS growth. Finally, synthesis of CCS polymers using macromonomers of different molecular weights pointed to the necessity for optimization of the polymerization conditions for each macromonomer, possibly due to different polymerization rates and steric hindrance.
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
AICHE JOURNAL
·
2014
·Vol. 61
·期 1
·35-45
·
IF 2.581
Feng Xu,Jing-Wen Xu,Bi-Xia Zhang,Luo Yan-Ling
Novel tri-armed star polystyrene-block-poly(N-isopropylacrylamide) block copolymers with trimesic acid as central molecules were synthesized by successive two-step atom transfer radical polymerization, and confirmed by Fourier-transform infrared spectra, 1 H nuclear magnetic resonance, and laser light scattering gel chromatography system. The copolymers could self-assemble into spherical core-shell micelles in aqueous media independent on drug loading. Physicochemical properties of the blank and drug-loaded micelles were examined by surface tension, fluorescence spectroscopy, UV-vis, transmission electron microscope, and dynamic light scattering measurements. The copolymer micelles exhibited thermo-triggered phase transition, with low critical solution temperature of 33.7 and 34.6°C, varying with copolymer compositions. The critical aggregate concentrations were 11.62 and 47.61 mg L −1 , and hydrodynamic diameters from 200 to 220 nm. Water-insoluble 10-hydroxycamptothecine was encapsulated into the micelle aggregates to investigate the change in the resulting physicochemical parameters, thermo-triggered in vitro drug release, and the applicability as drug targeting release carriers. MTT assays were carried out to uncover cytotoxicity of the newly developed micelle-based drug formulations. © 2014 American Institute of Chemical Engineers AIChE J , 61: 35–45, 2015
研究领域:
材料科学
·
药学
·
肿瘤学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2016
·Vol. 134
·期 2
·
IF 1.866
Weitao Ye,Wei Wei,Xiaoma Fei,Rongjie Lu,Na Liu,Jing Luo,Ye Zhu,Xiaoya Liu
A six-arm star-shaped poly( ε -caprolactone) (s-PCL) based on cyclophosphazene core was obtained by presynthesis of a hydroxy-teminated cyclophosphazene derivative and subsequent initiation of the ring-opening polymerization of ε -caprolactone, and its use in different proportions as toughening modifier of diglycidylether of bisphenol A/anhydride thermosets was studied. The star-shaped polymer was characterized to have approximately 30 caprolactone units per arm. Differential scanning calorimetry revealed a nonsignificant influence on the curing process of the epoxy-anhydride formulation by the addition of s-PCL. The s-PCL-modified epoxy thermosets exhibited a great improvement in both toughness and strength compared with the neat resin, as the result of a joint effort by the internal rigid core and the external ductile polyester chains of s-PCL. When the addition of the modifier was 3 wt %, an optimal mechanical and thermomechanical performance was achieved. The impact resistance and tensile strength of the cured epoxy resin were enhanced by 150% and 30%, respectively. The glass transition temperature was also increased slightly. Moreover, the addition of the star-shaped modifier had little harmful effect on the thermal stability of the material. Thus s-PCL was proved to be a superior toughening agent without sacrificing thermal and mechanical properties of the thermosets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44384.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）