Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02143, United States.
J Am Chem Soc. 2018 Feb 7;140(5):1596-1599. doi: 10.1021/jacs.7b12696. Epub 2018 Jan 22.
Deciphering the significance of length, sequence, and stereochemistry in block copolymer self-assembly remains an ongoing challenge. A dearth of methods to access uniform block co-oligomers/polymers with precise stereochemical sequences has precluded such studies. Here, we develop iterative exponential growth methods for the synthesis of a small library of unimolecular stereoisomeric diblock 32-mers. X-ray scattering reveals that stereochemistry modulates the phase behavior of these polymers, which we rationalize based on simulations carried out on a theoretical model system. This work demonstrates that stereochemical sequence can play a crucial role in unimolecular polymer self-assembly.
解析嵌段共聚物自组装中长度、序列和立体化学的意义仍然是一个持续的挑战。缺乏获得具有精确立体化学序列的均匀嵌段共低聚物/聚合物的方法，使得这些研究受到限制。在这里，我们开发了迭代指数增长方法，用于合成具有单分子立体异构体的二嵌段 32 聚体的小库。X 射线散射表明立体化学调节了这些聚合物的相行为，我们基于对理论模型体系进行的模拟来合理化这些行为。这项工作表明，立体化学序列可以在单分子聚合物自组装中发挥关键作用。
