自修复膜为柔性间隔层的宏观超分子组装机理及其应用研究

Macroscopic supramolecular assembly (MSA) has been a recent progress in supramolecular chemistry. MSA mainly focuses on studies of the building blocks with the size beyond ten micrometer and the multivalent interactions between these interactive building blocks to realize the process of collision, identification and assembly. MSA since being proposed has been rapidly developed due to its interdisciplinary integration, which is expected to provide a new approach for the design and manufacture of bulk supramolecular materials with specific functions. However, the current problem of MSA is that the type of as-prepared flexible spacing coating is single and the judged basis is not clear. Herein, inspired by the mechanism of intrinsic self-healing film, we have proposed that polyelectrolyte multilayers capable of self-healing can function as the flexible spacing coating based on the common characteristic of highly flowable property, thus providing guidance to select flexible spacing coating. Furthermore, MSA based on self-healing film as a flexible spacing coating provides the new principle and method for fabricating the bulk supramolecular materials and realizing their application in the field of biomaterials and sensor.

宏观超分子组装是超分子科学领域的新兴前沿研究方向，其主要研究对象是尺寸在十微米及以上、修饰有大量超分子识别基团的构筑基元，以及它们之间基于超分子多重相互作用的碰撞、识别和组装的过程。自宏观超分子组装提出以来，因其与多学科的交叉共融而得到快速的发展，有望为设计和制备具有特定功能的体相超分子材料提供崭新的途径。目前，针对宏观超分子组装中柔性间隔层类型单一、判据不明确等问题，本项目拟借鉴本征型自修复膜的基本原理，从自修复膜和柔性间隔层共有的高柔顺和流动性特点出发，提出基于自修复膜为刚性构筑基元柔性间隔层的策略，为柔性间隔层的选择提供重要的判据，丰富和发展宏观超分子组装的适用范围，为制备体相超分子材料及实现其在生物材料和传感领域的应用提供新原理和新方法。

宏观超分子组装，是指在十微米以上的构筑基元表面，通过表面化学修饰引入超分子识别基团，再利用界面组装构筑超分子材料的过程。自提出以来，因其与多学科的交叉共融而得到快速的发展，有望为设计和制备具有特定功能、特定形状的超分子材料提供崭新的途径。然而，随着构筑基元尺寸的增大，体系中布朗运动不足以推动宏观构筑基元自发运动，难以实现宏观构筑基元界面间的超分子组装。针对此，一方面，需要借助于外部作用力（如震荡摇床）来为构筑基元提供驱动力，与此同时，根据构筑基元的基本设计原则，协同“柔性间隔层”概念，实现宏观构筑基元的超分子组装；另一方面，通过对构筑基元表面功能化修饰，如构筑稳定功能超疏水表面，减小构筑基元在体系中的运动阻力，进而协同“柔性间隔层”概念，实现构筑基元的宏观超分子组装。在本项目的支持下，我们提出了基于本征自修复膜作为刚性构筑基元“柔性间隔层”的重要判据，拓展了“柔性间隔层”的普适性研究；开发了稳定超疏水表面的设计策略，解决了构筑基元在组装过程中阻力大的难题；实现了单相体系中宏观构筑基元的精准超分子组装，获得了不同拓扑结构精准有序组装体的构筑。本项目既定的研究目标基本完成，三年来，本项目研究成果共计发表SCI论文7篇（Cell Reports Physical Science, Polymer, Composite Science and Technology, Advanced Materials Interfaces, Materials, Journal of Materials Research and Technology等），申请中国发明专利1项，本项目执行期间，共培养硕士生3名。