Quantitative Examination and Mechanistic Insights of Polymer Chain Conformation Confined in Nanopores by Time-Resolved Fluorescence Resonance Energy Transfer

IF 5.1 Q1 POLYMER SCIENCE

ACS Macro Letters Pub Date : 2024-11-07 DOI:10.1021/acsmacrolett.4c00640

Ying Wang, Zihao Meng, Zhenyang Luo, Zhiqiang Song, Bo Du, Yongsheng Zhang, Pengjin Ye, Linling Li, Yucheng He, Ye Sha

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Abstract

The conformational studies of polymers confined at the nanoscale remain challenging and controversial due to the limitations of characterization techniques. In this study, we utilized the high sensitivity of time-resolved fluorescence resonance energy transfer (trFRET) and a site-specific dye-labeling strategy to characterize the conformation of polymer chains confined in anodic aluminum oxide (AAO) nanopores. This strategy introduced a fluorescent donor (carbazole) and acceptor (anthracene) at the center of poly(butyl methacrylate) (PBMA) chains grown by atom transfer radical polymerization (ATRP). By quantitatively analyzing fluorescence decay through the Förster mechanism and the Drake–Klafter–Levitz (DKL) formalism, we can determine both the energy transfer efficiency and the spatial distribution of the dyes. This analysis revealed that the PBMA chains, with a molecular weight of 40 kDa, maintained their bulk-like conformation even when confined within nanopores as small as 10 nm in diameter. This study is the first to demonstrate the use of trFRET for investigating chain conformation in confined polymer systems, which can be generalized to other polymer types and polymer topologies in different confined geometries.

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通过时间分辨荧光共振能量转移定量检测纳米孔中限制的聚合物链构象并揭示其机理

由于表征技术的局限性，纳米尺度限制聚合物的构象研究仍然具有挑战性和争议性。在这项研究中，我们利用时间分辨荧光共振能量转移（trFRET）的高灵敏度和特定位点染料标记策略来表征封闭在阳极氧化铝（AAO）纳米孔中的聚合物链的构象。该策略在通过原子转移自由基聚合（ATRP）生长的聚（甲基丙烯酸丁酯）（PBMA）链中心引入了荧光供体（咔唑）和受体（蒽）。通过福斯特机制和德雷克-克拉夫特-莱维茨（DKL）形式主义对荧光衰减进行定量分析，我们可以确定染料的能量传递效率和空间分布。分析表明，分子量为 40 kDa 的 PBMA 链即使被限制在直径仅为 10 nm 的纳米孔中，也能保持其大块状构象。这项研究首次证明了利用 trFRET 来研究封闭聚合物体系中的链构象，并可推广到其他聚合物类型和不同封闭几何形状的聚合物拓扑结构中。

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来源期刊

ACS Macro Letters 化学-

CiteScore

10.40

自引率

3.40%

发文量

209

审稿时长

1 months

期刊介绍： ACS Macro Letters publishes research in all areas of contemporary soft matter science in which macromolecules play a key role, including nanotechnology, self-assembly, supramolecular chemistry, biomaterials, energy generation and storage, and renewable/sustainable materials. Submissions to ACS Macro Letters should justify clearly the rapid disclosure of the key elements of the study. The scope of the journal includes high-impact research of broad interest in all areas of polymer science and engineering, including cross-disciplinary research that interfaces with polymer science. With the launch of ACS Macro Letters, all Communications that were formerly published in Macromolecules and Biomacromolecules will be published as Letters in ACS Macro Letters.