Stimuli-responsive nano-assemblies from amphiphilic macromolecules could undergo controlled structural transformations and generate diverse macroscopic phenomenon under stimuli. Due to the controllable responsiveness, they have been applied for broad material and biomedical applications, such as biologics delivery, sensing, imaging, and catalysis. Understanding the mechanisms of the assembly-disassembly processes and structural determinants behind the responsive properties is fundamentally important for designing the next generation of nano-assemblies with programmable responsiveness. In this review, we focus on structural determinants of assemblies from amphiphilic macromolecules and their macromolecular level alterations under stimuli, such as the disruption of hydrophilic-lipophilic balance (HLB), depolymerization, decrosslinking, and changes of molecular packing in assemblies, which eventually lead to a series of macroscopic phenomenon for practical purposes. Applications of stimuli-responsive nano-assemblies in delivery, sensing and imaging were also summarized based on their structural features. We expect this review could provide readers an overview of the structural considerations in the design and applications of nano-assemblies and incentivize more explorations in stimuli-responsive soft matters.

来自两亲性大分子的刺激响应纳米组装体可以经历受控的结构转变，并在刺激下产生多样化的宏观现象。由于响应性可控，它们已应用于广泛的材料和生物医学应用，例如生物制剂输送、传感、成像和催化。了解组装-拆卸过程的机制和响应特性背后的结构决定因素对于设计具有可编程响应性的下一代纳米组装至关重要。在这篇综述中，我们重点讨论了两亲性大分子组装体的结构决定因素及其在刺激下的大分子水平改变，例如亲水亲脂平衡 （HLB） 的破坏、解聚、解交和组装体中分子堆积的变化，最终导致一系列实际的宏观现象。还根据刺激响应纳米组件的结构特征总结了刺激响应纳米组件在递送、传感和成像中的应用。我们期望这篇综述可以为读者提供纳米组装体设计和应用中的结构考虑因素的概述，并激励对刺激响应软物质的更多探索。