Self-Assembly of Regioselective Polymer-Tethered Gold Nanorods in Selective Solvents

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-01-16 DOI:10.1021/acs.macromol.4c02257

Rui Ren, Fan Li, Han Zhang, Yingying Wang, Bijin Xiong, Jintao Zhu

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Abstract

The self-assembly of regioselective polymer-tethered gold nanorods (AuNRs) offers significant potential for creating functional nanoscale architectures with applications in optoelectronics, sensing, and nanomedicine. In this study, we synthesized AuNRs with well-defined dimensions and modified them regioselectively with polystyrene (PS) at the ends and poly(4-vinylpyridine) (P4VP) on the sidewalls. Controlled self-assembly was achieved using selective solvent methods, resulting in distinct end-to-end and side-by-side configurations depending on the solvent environment. The study further explored the influence of the molecular weight of the polymer ligands and the AuNR core size on the assembly structures. Additionally, the assembly process were investigated in real-time using small-angle X-ray scattering (SAXS) and UV–visible spectroscopy, revealing a two-stage assembly process significantly affected by solvent composition. The results demonstrated that the evaporation rate of the solvent plays a critical role in the final assembly morphology. Slow solvent evaporation led to the formation of well-ordered thin films due to the gradual aggregation of side-by-side arranged AuNRs, while faster evaporation favored the formation of vesicles or micelles. These structures are a result of the differential solubility and phase separation of the polymer ligands under varying solvent conditions. This study provides a comprehensive understanding of the assembly mechanisms and the dynamic processes governing the formation of different nanostructures, offering a foundation for the design of AuNR-based nanomaterials with precise structural and functional control.

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区域选择性聚合物系留金纳米棒在选择性溶剂中的自组装

区域选择性聚合物系链金纳米棒（aunr）的自组装为创建具有光电子学、传感和纳米医学应用的功能纳米级结构提供了巨大的潜力。在这项研究中，我们合成了具有明确尺寸的aunr，并在末端用聚苯乙烯（PS）和侧壁用聚（4-乙烯基吡啶）（P4VP）对其进行了区域选择性修饰。使用选择性溶剂方法实现了受控的自组装，根据溶剂环境产生不同的端到端和并排配置。本研究进一步探讨了聚合物配体的分子量和AuNR核尺寸对组装结构的影响。此外，利用小角x射线散射（SAXS）和紫外可见光谱实时研究了组装过程，揭示了溶剂成分对两阶段组装过程的显著影响。结果表明，溶剂的蒸发速率对最终组装的形貌起着关键作用。缓慢的溶剂蒸发导致有序薄膜的形成，这是由于并排排列的aunr逐渐聚集，而更快的蒸发有利于囊泡或胶束的形成。这些结构是聚合物配体在不同溶剂条件下的不同溶解度和相分离的结果。该研究全面了解了不同纳米结构形成的组装机制和动态过程，为设计具有精确结构和功能控制的基于ar的纳米材料提供了基础。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.