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件可以在刺激下经历受控的结构转变并产生不同的宏观现象。由于可控的响应性，它们已被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件至关重要。在这篇综述中，我们重点关注两亲性大分子组装体的结构决定因素及其在刺激下大分子水平的变化，例如亲水亲油平衡（HLB）的破坏、解聚、解交联以及组装体中分子堆积的变化，这些最终导致为实际目的而产生的一系列宏观现象。还根据刺激响应纳米组件的结构特征总结了其在传输、传感和成像方面的应用。我们希望这篇综述可以为读者提供纳米组件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。