Molecule self-assembly is a ubiquitous phenomenon and a key driving force for constructing nanostructures with diverse morphology and controllable size. Recently, interests in constructing environmentally responsive nanostructures have been growing, due to its diverse stimuli responsiveness. Thermoresponsive polymers as a class of smart materials, undergoes a phase transition by temperature stimuli, resulting assembly of molecules to construct diverse nanostructures with unique morphology and size. Over the past decades, supramolecular assembly in static solutions is well-established, while translating the self-assembly of synthetic molecules from the static controlled conditions to highly complex and dynamic environment of living systems is still challenging. In this review, we provide a brief overview of building blocks for constructing thermoresponsive polymer assemblies particularly those are suitable for in vivo self-assembly. Then we review recent contributions on molecular design and methods for constructing thermoresponsive polymer assemblies in vitro, particularly highlight those are instructive for the subsequent in vivo self-assembly. Furthermore, the tips for successful in vivo construction, self-assembly structure-property relationship, the advantages of in vivo self-assembled thermoresponsive materials for imaging or therapy and material topology-bioeffects relationship are emphasized.

分子自组装是一种普遍存在的现象，是构建具有多种形态和可控尺寸的纳米结构的关键驱动力。最近，由于其多样化的刺激响应性，构建环境响应纳米结构的兴趣一直在增长。热响应聚合物作为一类智能材料，在温度刺激下经历相变，导致分子组装以构建具有独特形态和尺寸的多种纳米结构。在过去的几十年中，静态溶液中的超分子组装已经成熟，而将合成分子的自组装从静态控制条件转化为高度复杂和动态的生命系统环境仍然具有挑战性。在本次审查中，体内自组装。然后我们回顾了最近在分子设计和体外构建热响应聚合物组装方法方面的贡献，特别强调了这些对随后的体内自组装具有指导意义。此外，还强调了体内构建成功的技巧、自组装结构-性能关系、体内自组装热响应材料在成像或治疗方面的优势以及材料拓扑-生物效应关系。