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Polymers · 2017 ·Vol. 9 ·期 7 ·301 · IF 3.364

Synthesis and Phase Transition of Poly(N-isopropylacrylamide)-Based Thermo-Sensitive Cyclic Brush Polymer

Xiaoyan Tu,Chao Meng,Zhe Liu,Lu Sun,Xianshuo Zhang,Mingkui Zhang,Mingrui Sun,Liwei Ma,Mingzhu Liu,Hua Wei

Polymers with advanced topological architectures are promising materials for wide applications due to their structure-generated unique properties different from that of the linear analogues. The elegant integration of stimuli-responsive polymers with such advanced architectures can create novel materials with virtues from both moieties, are thus a hot subject of research for both fundamental and practical investigations. To fabricate cyclic brush polymer-based intelligent materials for biomedical applications, herein, we designed and synthesized thermo-sensitive cyclic brush polymers with poly(N-isopropylacrylamide) (PNIPAAm) brushes by controlled living radical polymerization using cyclic multimacroinitiator. The thermo-induced phase transition behaviors of the resultant cyclic brush polymers with different compositions were investigated in detail by temperature-dependent optical transmittance measurements, and compared with the properties of bottlebrush and linear counterparts. Interestingly, the cloud point transition temperature (Tcp) of cyclic brush PNIPAAm could be regulated by the chain length of PNIPAAm brush. Although the bottlebrush polymers with the same composition exhibited similarly structurally dependentTcps behaviors to the cyclic brush polymers, the cyclic brush PNIPAAm did show higher critical aggregation concentration (CAC) and enhanced stability against dilution than the bottlebrush counterpart. The readily tailorableTcps together with the ability to form highly stable nanoparticles makes thermo-sensitive cyclic brush PNIPAAm a promising candidate for controlled drug delivery.Keywords:cyclic brush polymer;thermo-sensitivity;poly(N-isopropylacrylamide)

CAS / MDL: 3030-47-5
研究领域: 材料科学 · 生物医学工程
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LANGMUIR · 2025 · IF 3.9

Construction of Loop Polyzwitterion Brushes on PET Sheets via the Chain-End Closure Strategy To Improve Antifouling and Hemocompatible Properties

Zhaoyan Ge,Yushuang Shang,Yu Sun,Xinyu Zhang,Fengni Liu,Jian Shen,Jiang Yuan

Steric stabilization and lubrication give loop polymer brushes enhanced antifouling properties. In the study, linear zwitterionic poly(NMASMCMS) brushes were first constructed on a poly(ethylene terephthalate) (PET) surface through surface-initiated reversible addition–fragmentation chain-transfer (SI-RAFT) polymerization. The tethered linear brushes on sheets were then thiolated with ethanolamine, followed by oxidation to form loop brushes. The chain-end closure strategy to form loop brushes is facile, with a high transformation rate. The physical and chemical structures were characterized by the water contact angle (WCA), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Loop brush grafted sheets (PET-L) exhibited better lubricity than linear brush grafted sheets (PET-B) due to the rigidity of loop brush structures. The two brushes exhibited good antifouling and hemocompatible properties on low protein adsorption, bacteria adhesion, platelet adhesion, and hemolysis. In comparison, loop brushes performed with antifouling properties superior to those of linear brushes.

研究领域: 材料科学 · 生物医学工程
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BIOMACROMOLECULES · 2023 · IF 6.2

Topology Effects of Poly(2-ethyl-2-oxazoline) Brushes with Various Architectures for Antifouling Behavior under Shear Flow

Songlin Xing,Qiqi Wang,Yang He,Li Chen

Polymer brushes with different topological architectures exhibit unparalleled interfacial and physicochemical properties and are being widely utilized in antifouling applications. However, there is an absence of a thorough understanding of the antifouling process of dynamic flow mediated by the topological structure of polymer brushes. Here, it is highlighted how the interface parameters related to biofouling in flowing carrier fluid are tuned by topologically different architectures. The mechanism by which three brushes with various topological structures (cyclic, looped, and linear brushes) encounter biological media was revealed by relating protein adhesion with nanomechanics and protein conformational transitions on poly(2-ethyl-2-oxazoline) (PEtOx) brushes. In contrast to the classically linear analogue, the cyclic PEtOx brushes confered an enhanced steric barrier and excellent lubrication at the critical density region. The impenetrable and smoother layer prevented the approach and shortened the residence time for protein on the surface, providing optimal antifouling properties at low shear rates. The looped brushes also significantly inhibited protein adhesion under prolonged high shear rates due to their unshakable conformational characteristics. These findings detailed a new evaluation framework behind polymer brushes of topology-driven biofouling repulsion under flow conditions and pointed the way toward a promising approach for the effectiveness of biomaterial design.

CAS / MDL: 10431-98-8 6165-76-0
研究领域: 聚合物科学 · 材料科学 · 生物医学工程 · 表面化学 · 生物物理学
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MACROMOLECULAR BIOSCIENCE · 2018 ·Vol. 18 ·期 7 ·1800022 · IF 3.392

Fabrication of Reduction-Sensitive Amphiphilic Cyclic Brush Copolymer for Controlled Drug Release

Xiao-Yan Tu,Chao Meng,Xiao-Long Zhang,Miao-Ge Jin,Xian-Shuo Zhang,Xue-Zhi Zhao,Yun-Fei Wang,Li-Wei Ma,Bao-Yan Wang,Ming-Zhu Liu,Hua Wei

The cyclic brush polymers, due to the unique topological structure, have shown in the previous studies higher delivery efficacy than the bottlebrush analogues as carriers for drug and gene transfer. However, to the best of knowledge, the preparation of reduction-sensitive cyclic brush polymers for drug delivery applications remains unexplored. For this purpose, a reduction-sensitive amphiphilic cyclic brush copolymer, poly(2-hydroxyethyl methacrylate-g-poly(ε-caprolactone)-disulfide link-poly(oligoethyleneglycol methacrylate)) (P(HEMA- g -PCL-SS-POEGMA)) with reducible block junctions bridging the hydrophobic PCL middle layer and the hydrophilic POEGMA outer corona is designed and synthesized successfully in this study via a “grafting from” approach using sequential ring-opening polymerization (ROP) and atom transfer free radical polymerization (ATRP) from a cyclic multimacroinitiator PHEMA. The resulting self-assembled unimolecular core–shell–corona (CSC) micelles show sufficient salt stability and efficient destabilization in the intracellular reducing environment for a promoted drug release toward a greater therapeutic efficacy relative to the reduction-insensitive analogues. The overall results demonstrate the reducible cyclic brush copolymers developed herein provides an elegant solution to the tradeoff between extracellular stability and intracellular high therapeutic efficacy toward efficient anticancer drug delivery.

研究领域: 高分子化学 · 药学 · 纳米技术 · 药物递送系统
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