CAREER: CAS: Structured Assemblies of Block Copolymers and Macrocycles with the Novel Halogen Bond

在化学系大分子、超分子和纳米化学计划的支持下，密歇根州罗切斯特市奥克兰大学的Ngong Kodiah Beyeh将开发一种新的方法，将超分子化学和聚合物科学相结合，组装由具有持久内腔的有机大环组成的聚合物结构。类似于被广泛研究的在许多自然和合成体系中发挥重要作用的“氢键”，“卤素”键可以作为识别位点，将复杂结构中的组分结合在一起，但人们对它们的研究较少。这个项目将提供关于卤键作用的新的基础知识，并研究这类新的功能聚合物的性质。这些多孔结构的内腔可以用作特定客体分子(例如甲烷和二氧化碳)的感测、吸收、分离或存储的识别位置。卤键的可逆形成赋予了自我修复性能和循环利用的可能性。该项目还将包括对下一代多样化的科学技术劳动力的教育、培训和指导。这个项目的多学科性质确保了学生，包括高中生，将在有机化学和材料化学方面发展广泛的技能。学生参与这个项目，包括讨论职业选择的研讨会和座谈会，将促进他们在科学领域的职业追求。这个项目的一个重要目标是充分阐明卤键在组装功能聚合物结构中作为识别“粘性”位置的能力和性质。Beyeh博士和他的学生将合成几个间苯二酚大环和嵌段共聚物库。间苯二酚大环为客体结合提供了持久的内部空腔，将用官能团来装饰，以与不同的嵌段共聚物形成卤键。卤素键合的混合结构将得到充分的表征。这些杂化结构的卤素键合性能、稳定性和自愈效率将被研究。将评估它们的形态、孔隙率和客体吸收特性。如果成功，该项目将提供有关卤键及其性质在构建新型功能聚合物中的作用的新的基础知识。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Ngong Kodiah Beyeh of Oakland University in Rochester, Michigan, will develop a novel approach that combines supramolecular chemistry and polymer science to assemble polymeric structures that consist of organic macrocycles with persistent internal cavities. Analogous to the widely researched “hydrogen” bonds that play important roles in many natural and synthetic systems, “halogen” bonds could serve as recognition sites holding together the components in complex structures, but they are less explored. This project will provide new fundamental knowledge on the roles of halogen bonds and investigate the properties of this new class of functional polymers. The internal cavities of these porous structures may serve as recognition sites for sensing, uptake, separation, or storage of specific guest molecules, e.g., methane and carbon dioxide. The reversible formation of halogen bonds bestows self-healing properties and the possibility of recycling. This project will also incorporate educational training and mentoring of the next generation of a diverse workforce in science and technology. The multidisciplinary nature of this project ensures that students, including high school students, will develop broad skills in both organic and materials chemistry. Student participation in the project, including workshops and colloquia focusing on career options, will foster their pursuit of careers in science.An important objective of this project is to fully elucidate the capabilities and properties of halogen bonds as recognition "sticky" sites in the assembly of functional polymeric structures. Dr. Beyeh and his students will synthesize several libraries of resorcinarene macrocycles and block copolymers. The resorcinarene macrocycles, which provide persistent internal cavities for guest binding, will be decorated with functional groups to form halogen-bonds with different block copolymers. The halogen-bonded hybrid structures will be fully characterized. The halogen-bonding properties, stability, and self-healing efficiency of these hybrid structures will be studied. Their morphology, porosity, and guest-uptake properties will be evaluated. If successful, this project will provide new fundamental knowledge on the roles of halogen bonds and their properties in building new classes of functional polymers.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.