结晶驱动自组装形成的三维聚合物胶束

IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Jingjie Jiang,  and , Mitchell A. Winnik*, 
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引用次数: 0

摘要

聚合物自组装在生物医学、催化、光电等领域发挥着至关重要的作用。多年来,溶液中的自组装引起了人们极大的兴趣。2007年,我们的团队与Ian Manners教授合作,在《科学》杂志上发表了一篇开创性的文章,内容是两亲性嵌段共聚物的活结晶驱动自组装(CDSA),具有结晶核形成的嵌段。本文主要研究了聚二茂铁基硅烷嵌段共聚物(PFS bcp)。活性CDSA的操作类似于活性聚合,可以精确地制造具有可预测形状和尺寸的胶束。成核块的结晶性质促进了低界面曲率结构的形成,如圆柱体和片状结构,这些结构在传统的基于微相分离的自组装技术中很少形成。在过去的二十年中,我们率先采用了一系列策略,通过CDSA创建一维、二维、三维和分层统一的PFS BCP结构。该方法也已推广到其他半结晶聚合物体系,以生产规则和均匀的组件。虽然1D和2D胶束已经被广泛研究,但3D结构的制造仍然相对较少。然而,大自然拥有精致的3D结构。尽管CDSA已经生成了一些3D结构,但它还没有达到自然界的复杂性。研究人员继续推动边界,以创造更复杂的3D结构。本文综述了CDSA技术在三维结构制造方面的研究进展。体系的自由能受各种因素的影响,最终决定胶束形态和生长行为。我们的工作通过多步骤种子生长过程,将PFS均聚物(HP)与PFS BCP结合,控制冷却速度,调整电晕块组成,控制聚合物分散性和不同溶剂,导致分支结构的形成。进一步的创新包括使用有机牺牲模板来生产中空纤维篮聚合体,以及应用无机基质进行表面胶束生长,从而产生具有定制功能的有机-无机杂化材料。一个重要的突破是在溶液中生成均匀聚合物球粒及其前体的协议的发展。虽然球粒在块状聚合物材料和地质学、生物学等领域的材料中很常见,但在溶液中的块状聚合物中尚未观察到球粒。我们发现了一种新的CDSA机制,其中层状前体中的缺陷作为构建3D架构的关键驱动因素。为了实现复杂的、仿生的和统一的3D结构,进一步的努力将集中在加强结构控制和集成多功能特性上。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Three-Dimensional Polymer Micelles Formed by Crystallization-Driven Self-Assembly

Polymer self-assembly plays a crucial role across various fields, such as biomedicine, catalysis, and optoelectronics. Over the years, self-assembly in solution has attracted significant interest. In 2007, our group, in collaboration with Prof. Ian Manners, published a groundbreaking article in Science on living crystallization-driven self-assembly (CDSA) of amphiphilic block copolymers featuring a crystalline core-forming block. This study focused on polyferrocenylsilane block copolymers (PFS BCPs). Living CDSA operates similarly to living polymerization, enabling the precise fabrication of micelles with predictable shapes and dimensions. The crystalline nature of the core-forming block promotes the formation of structures with low interfacial curvature, such as cylinders and platelets, which are rarely formed in traditional self-assembly techniques based on microphase separation.

Over the past two decades, we have pioneered a range of strategies to create one-dimensional (1D), 2D, 3D, and hierarchical uniform PFS BCP structures via CDSA. This method has also been extended to other semicrystalline polymer systems to produce regular and uniform assemblies. While 1D and 2D micelles have been extensively studied, the fabrication of 3D structures remains relatively rare. Nature, however, possesses exquisite 3D structures. Although CDSA has generated some 3D structures, it has not yet achieved the complexity found in nature. Researchers continue to push boundaries toward creating more intricate 3D structures.

In this Account, we summarize our research advancements on 3D structure fabrication via CDSA. The free energy of the system, influenced by various factors, ultimately determines micellar morphology and growth behavior. Our work has led to the formation of branched structures through multistep seeded growth processes, incorporating PFS homopolymers (HP) with PFS BCP, manipulating the cooling rate, adjusting the corona block composition, controlling polymer dispersity, and varying solvents. Further innovations involved the use of organic sacrificial templates to produce hollow fiber-basket polymersomes and the application of inorganic substrates for surface micelle growth, yielding organic–inorganic hybrid materials with tailored functionalities. A significant breakthrough was the development of protocols for generating uniform polymeric spherulites and their precursors in solution. Although spherulites are common in bulk polymer materials and materials found in fields such as geology and biology, they have not been observed from block polymers in solution. We uncovered a novel CDSA mechanism in which defects in lamellar precursors act as a critical driver for constructing 3D architectures. To achieve intricate, bioinspired, and uniform 3D structures, further efforts will focus on enhancing structural control and integrating multifunctional properties.

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来源期刊
Accounts of Chemical Research
Accounts of Chemical Research 化学-化学综合
CiteScore
31.40
自引率
1.10%
发文量
312
审稿时长
2 months
期刊介绍: Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.
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