含硒动态共价化学

The study of molecular self-assembly during the last few decades has proven that the discovery of every dynamic covalent bond would invoke a huge wave of research interest and promote the development of research fields, including supramolecular science, polymer science, material science and life science, etc. The objectives of this project are: (1) to develop a series of selenium-containing dynamic covalent bonds, to understand its nature and to master the rules of transition between different selenium-containing dynamic covalent bonds, which would provide novel driving force for molecular self-assembly. (2) to establish the quantitative relations between selenium-containing dynamic covalent bonds in polymer systems and force-induced chemoselectivity, conversion ratio with polymer structure, force field condition, from single-molecule level to macroscale level. (3) to prepare novel selenium-containing dynamic covalent materials, including mechanical property-adjustable macromolecular materials, shape memory polymer networks and selenium-containing biomaterials, etc. During the implement of the project, we would strive to take the leading position in the research field of selenium-containing dynamic covalent bonds and to offer a solid foundation for the establishing and developing of selenium-containing polymer chemistry with our own characteristics.

分子自组装领域近几十年的研究表明，每一种新型动态共价键的出现，都会促进超分子科学、高分子科学、材料科学和生命科学等学科和领域的发展，引起研究热潮。本项目的研究旨在：（1）发展一系列新的含硒动态共价键，认识含硒动态共价键的本质，掌握含硒动态共价键之间的转换规律，为分子自组装提供新的推动力;（2）从单分子水平到宏观水平，建立含硒动态共价键在高分子体系中力诱导化学反应选择性、转化率与高分子结构、力场条件的定量关系；（3）制备新型含硒动态共价材料，包括力学性能可调的宏观聚合物材料、形状记忆材料和含硒生物医用材料等。通过项目的实施，力争使我们在含硒动态共价键的研究领域处于领先地位，为建立和发展具有我国特色的高分子硒化学体系提供基础。

通过5年的资助，我们发现了一系列含硒动态共价键，推动了含硒/碲高分子在生物医学领域的应用，含硒动态共价键已被认为是具有独特光响应性的新型动态共价键，含硒/碲高分子已被国际同行广泛认为是两类可用于调控活性氧的材料。含硒动态共价化学以及含硒/碲高分子的研究已经成为具有中国学者标签的工作。该项目实施以来取得了如下具体成果:.1. 在含硒动态共价键/配位键的力学本质方面：通过研究在单分子链拉伸、渗透压作用以及超声作用下的含硒动态共价键/配位键的断裂以及动态共价键之间的转换，从单分子水平到宏观水平获得了关于含硒动态共价键强弱的信息。.2. 在含硒动态共价键的转换与调控方面：探索了含硒动态共价键之间的转换规律，实现了可利用波长调控以及主客体交换调控的含硒动态共价交换，为推动含硒动态共价键在材料领域的应用打下基础。.3. 在含硒动态共价材料的制备及应用方面：通过光、医用射线等手段实现对含硒动态共价键断裂和相互转换的调控，制备了力学性能可调的宏观聚合物材料，实现了免疫疗法与放/化疗的结合。.项目执行期间，发表学术论文76篇，期中包括J. Am. Chem. Soc. 2篇， Angew. Chem. Int. Ed. 5篇， Adv. Mater. 3篇， CCS Chem. 4篇， Biomaterials 4篇；授权中国发明专利3项，国际发明专利2项；培养博士后5名、博士生16名，4篇论文获评清华大学优秀博士学位论文。.在环太平洋地区高分子大会“Functional and self-assembled materials”分会、全国高分子学术论文报告会“高分子组装与超分子体系”分会、IUPAC International Symposium on Ionic Polymerization 2019 (IP’19)，14th International Conference on the Chemistry of Selenium and Tellurium (ICCST-14)等国内外会议做邀请报告15次。举办International Symposium on Functional Soft Materials 2次。