含氮氧化物的聚（2-恶唑啉）具有双刺激响应行为和自由基捕获活性。

IF 5.4 2区化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Biomacromolecules Pub Date : 2025-02-10 Epub Date: 2025-01-30 DOI:10.1021/acs.biomac.4c01598

Milad Ghorbani , Nicholas P. C. Roxburgh , Mai P. Tran , James P. Blinco , Kristian Kempe

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引用次数: 0

摘要

2,2,6,6-四甲基哌啶- n -氧（TEMPO）结构具有有效的抗氧化活性，在生物医学上具有应用。在亲水性聚合物上固定TEMPO是改善其性能的有效策略；然而，它主要局限于可逆失活自由基聚合或聚合后方法。在这里，我们通过阳离子开环聚合（CROP）将TEMPO单元固定在亲水聚（2-乙基-2-恶唑啉）（PEtOx）骨架上，这种新型2-恶唑啉单体具有甲氧基保护的TEMPO -2取代基（2-乙基-2-恶唑啉）（EtOx）。调整EtOx/TempOx的比例以优化氮氧化物含量，同时在脱保护时保持所得到的P（EtOx -stat-TempOx- oy•）共聚物的合适水溶性。P（EtOx40-stat-TempOx-O10•）和P（EtOx33-stat-TempOx-O17•）表现出双重刺激响应行为，并在水介质中表现出显著的自由基捕获活性。特别是，当TempOx-O•固定为P（EtOxx-stat-TempOx-Oy•）时，其活性显著增强。P（EtOx40-stat-TempOx-O10•）体系在水中表现出更持久的活性，统计上与抗氧化剂铁他汀-1 （fer1）相当。总的来说，本研究介绍了一种生物相容性聚合物平台用于TEMPO固定，增强了其自由基捕获活性，并提供了可控的刺激响应特性。

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Nitroxide-Containing Poly(2-oxazoline)s Show Dual-Stimuli-Responsive Behavior and Radical-Trapping Activity

2,2,6,6-Tetramethylpiperidine-N-oxyl (TEMPO) structures possess potent antioxidant activities for biomedical applications. TEMPO immobilization on hydrophilic polymers is a powerful strategy to improve its properties; however, it is mostly limited to reversible-deactivation radical polymerizations or postpolymerization approaches. Here, we immobilized TEMPO units on a hydrophilic poly(2-ethyl-2-oxazoline) (PEtOx) backbone through cationic ring-opening polymerization (CROP) of a new 2-oxazoline monomer bearing a methoxy-protected TEMPO 2-substituent with 2-ethyl-2-oxazoline (EtOx). The ratios of EtOx/TempOx were adjusted to optimize the nitroxide content while maintaining suitable water solubility of the resulting P(EtOx_x -stat-TempOx-O_y ^•) copolymers upon deprotection. P(EtOx₄₀ -stat-TempOx-O₁₀ ^•) and P(EtOx₃₃ -stat-TempOx-O₁₇ ^•) showed a dual stimuli-responsive behavior and demonstrated significant radical-trapping activities in aqueous media. Particularly, a meaningful augmentation in the activity of TempOx-O^• was observed when it was immobilized as P(EtOx_x -stat-TempOx-O_y ^•). The P(EtOx₄₀ -stat-TempOx-O₁₀ ^•) system exhibited a longer-lasting activity in water, statistically comparable to that of the antioxidant ferrostatin-1 (Fer-1). Overall, this study introduces a biocompatible polymeric platform for TEMPO immobilization that augments its radical-trapping activity and offers controllable stimuli-responsive properties.

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来源期刊

Biomacromolecules 化学-高分子科学

CiteScore

10.60

自引率

4.80%

发文量

417

审稿时长

1.6 months

期刊介绍： Biomacromolecules is a leading forum for the dissemination of cutting-edge research at the interface of polymer science and biology. Submissions to Biomacromolecules should contain strong elements of innovation in terms of macromolecular design, synthesis and characterization, or in the application of polymer materials to biology and medicine. Topics covered by Biomacromolecules include, but are not exclusively limited to: sustainable polymers, polymers based on natural and renewable resources, degradable polymers, polymer conjugates, polymeric drugs, polymers in biocatalysis, biomacromolecular assembly, biomimetic polymers, polymer-biomineral hybrids, biomimetic-polymer processing, polymer recycling, bioactive polymer surfaces, original polymer design for biomedical applications such as immunotherapy, drug delivery, gene delivery, antimicrobial applications, diagnostic imaging and biosensing, polymers in tissue engineering and regenerative medicine, polymeric scaffolds and hydrogels for cell culture and delivery.