Nanoparticle Brushes: Macromolecular Ligands for Materials Synthesis
Nanoparticle Brushes: Macromolecular Ligands for Materials Synthesis
复制标题
纳米粒子刷：用于材料合成的高分子配体
DOI：
10.1021/acs.accounts.3c00160
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发表时间：
2023
影响因子：
18.3
通讯作者：
Macfarlane, Robert J.
中科院分区：
文献类型：
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作者：
Hueckel, Theodore;Luo, Xin;Aly, Omar F.;Macfarlane, Robert J.
结论胶体纳米颗粒具有独特的特性，可用于合成具有奇异特性的材料，但利用这些特性需要对颗粒之间及其周围环境的相互作用进行精细控制。传统上，吸附在纳米颗粒表面的小分子作为配体来控制这些相互作用，提供了一种确保胶体稳定性和决定颗粒组装行为的手段。或者，纳米科学越来越感兴趣的是使用形成定义明确的聚合物刷子的大分子配体，因为这些刷子提供了更可定制的表面配体，在组成和配体大小方面都具有明显更大的通用性。虽然这一领域的初步研究前景看好，但合成能够适当形成刷子结构的大分子仍然是它们更广泛使用的障碍，并限制了对影响刷子接枝颗粒形成功能材料能力的基本化学和物理原理的理解。因此，提高聚合物接枝纳米粒子作为材料合成工具的能力需要多学科的努力，特别是开发新的合成路线以获得聚合物刷涂纳米粒子，并研究刷子使能的结构-性能关系。在这个帐户中，我们描述了我们最近在开发纳米粒子的聚合物刷子涂层方面的工作，我们使用这种涂层来根据需要调节粒子的行为，选择特定的纳米结构来形成，并通过设计支持传统的本体聚合物来形成更坚固的材料。根据聚合物的类型和性能，这里讨论了三类纳米颗粒：纳米复合材料Tecton(NCTs)，它使用末端官能化的合成聚合物，能够引导其组装；可编程原子当量(PAE)，包含合成DNA的刷子，使用Watson-Crick碱基对来编码粒子结合相互作用；以及可交联纳米颗粒(XNPs)，它可以稳定纳米颗粒在溶液和聚合物基质中，随后形成多价交联来增强聚合物复合材料。我们描述了这些刷子是如何通过“嫁接自”和“嫁接到”策略形成的，并举例说明了对未来发展很重要的方面。我们还研究了刷子提供的新功能，密切关注动态聚合物过程，这些过程提供了对颗粒组装状态的控制。最后，我们简要概述了纳米粒子与聚合物刷子的技术应用，重点介绍了纳米粒子与传统材料的集成以及纳米粒子加工成块状固体。
ConspectusColloidal nanoparticles have unique attributes that can be used to synthesize materials with exotic properties, but leveraging these properties requires fine control over the particles’ interactions with one another and their surrounding environment. Small molecules adsorbed on a nanoparticle’s surface have traditionally served as ligands to govern these interactions, providing a means of ensuring colloidal stability and dictating the particles’ assembly behavior. Alternatively, nanoscience is increasingly interested in instead using macromolecular ligands that form well-defined polymer brushes, as these brushes provide a much more tailorable surface ligand with significantly greater versatility in both composition and ligand size. While initial research in this area is promising, synthesizing macromolecules that can appropriately form brush architectures remains a barrier to their more widespread use and limits understanding of the fundamental chemical and physical principles that influence brush-grafted particles’ ability to form functional materials. Therefore, enhancing the capabilities of polymer-grafted nanoparticles as tools for materials synthesis requires a multidisciplinary effort, with specific focus on both developing new synthetic routes to polymer-brush-coated nanoparticles and investigating the structure–property relationships the brush enables.In this Account, we describe our recent work in developing polymer brush coatings for nanoparticles, which we use to modulate particle behavior on demand, select specific nanoscopic architectures to form, and bolster traditional bulk polymers to form stronger materials by design. Distinguished by the polymer type and capabilities, three classes of nanoparticles are discussed here: nanocomposite tectons (NCTs), which use synthetic polymers end-functionalized with supramolecular recognition groups capable of directing their assembly; programmable atom equivalents (PAEs) containing brushes of synthetic DNA that employ Watson–Crick base pairing to encode particle binding interactions; and cross-linkable nanoparticles (XNPs) that can both stabilize nanoparticles in solution and polymer matrices and subsequently form multivalent cross-links to strengthen polymer composites. We describe the formation of these brushes through “grafting-from” and “grafting-to” strategies and illustrate aspects that are important for future advancement. We also examine the new capabilities brushes provide, looking closely at dynamic polymer processes that provide control over the assembly state of particles. Finally, we provide a brief overview of the technological applications of nanoparticles with polymer brushes, focusing on the integration of nanoparticles into traditional materials and the processing of nanoparticles into bulk solids.