CAREER: Tailoring the Nanostructure and Morphology of Hydrogen-Bonded Supramolecular Liquid Crystals Using Immiscible Polymer Side Chains

这一职业发展计划旨在实现对具有不相容聚合物侧链的超分子柱状液晶(LCS)中新的纳米结构和形态的基本了解，并在纳米长度尺度上操纵微相分离的单个LC柱中的自发曲率。合理的材料设计和超分子柱状液晶自发自组装的精确工程在新一代纳米材料的开发中变得越来越重要。为了实现这些目标，提出了具体目标。(1)设计并合成了两端带有酰胺核和多个不相容聚合物侧链的新型非介晶性分子。(2)理解由不同长度尺度上的层级分子间相互作用(如液晶形成和微相分离)之间的相互关系和相互依赖所决定的柱状LC相。(3)利用自发曲率原理在单根液晶纳米纤维中实现了新颖的螺旋线圈形态。基于分子量和选择性溶剂的影响，我们将系统地研究自发曲率。这一建议的科学价值有几个。首先，将不相容的聚合物侧链连接到超分子柱状液晶上，形成一种新型的液晶材料。新的LC聚合物将弥合我们对小分子和聚合物之间的结构-性能关系的理解的差距。第二，柱内微相分离的独特物理性质将在自组装柱状液晶中诱导出新的螺旋螺旋形态，这可能模拟生物相关脂小管中的卷曲不稳定性。第三，提出的螺旋形态可能具有潜在的技术应用，如环境响应型纳米致动器。为了实现更广泛的影响，提出了一项综合研究和教育计划，将面向当地高中教师和学生的推广与聚合物结构与形态研究生课程中的新型聚合物纳米技术组件的开发相结合。首先，这样的努力将提高当地社区对具有重要技术意义的聚合物纳米材料的认识，同时与高中教师和代表不足的年轻学生建立实质性的联系，否则他们不会接触到聚合物的概念和应用。计划中的外展工作将包括两个主要部分：教育和研究。在教育部分，国际学生联合会将与当地高中科学教师合作，为代表不足的学生开发一门新课程，让他们学习与日常聚合物材料相关的基本科学和工程概念。计划定期访问当地的高中，安排精心设计的聚合物实验和项目，以激发学生对科学和工程的兴趣。在研究计划中，PI将为高中教师和学生发起暑期实习，与聚合物研究人员合作，开发用于高中课堂的聚合物形态研究的动手实验室实验。聚合物纳米结构和形态课程将有助于弥合不同水平的聚合物纳米技术研究和教育之间的现有差距。研究成果将通过在科学期刊上发表文章、在全国会议上发表报告以及与行业合作等方式广泛传播。

This CAREER development plan seeks to achieve fundamental understanding of novel nanostructure and morphology in supramolecular columnar liquid crystals (LCs) with immiscible polymer side chains, and to manipulate spontaneous curvature in a microphase-separated single LC column on nanometer length scales. Rational material design and precise engineering of the spontaneous self-assembly of the supramolecular columnar LCs have become increasingly important in the development of a new generation of nanomaterials for nanotechnology. In order to achieve these goals, specific objectives are proposed. (1) Design and synthesize novel non-mesogenic molecules with an amide core and multiple immiscible polymer side chains at each end. (2) Understand the columnar LC phases determined by the interrelationship and interdependence between hierarchical intermolecular interactions, such as liquid crystal formation and microphase separation, on different length scales. (3) Achieve novel helical coil morphology in single LC nanofiber using the principle of spontaneous curvature. The spontaneous curvature will be systematically investigated based upon the effects from molecular weight and selectivesolvent.The scientific merits of this proposal are several. First, attaching immiscible polymer side chainsonto supramolecular columnar liquid crystals generates a new type of LC material. The new LCpolymers will bridge the gap in our understanding of structure-property relationship between small molecules and polymers. Second, the unique physical property of intra-columnar microphase separation will induce novel helical coil morphology in self-assembled columnar LCs, which may mimic the coiling instability in bio-related lipid tubules. Third, the proposed helical morphology may have potential technological applications such as environment-responsive nanoactuators.To achieve broader impact, an integrated research and education plan is proposed to combineoutreach to local high school teachers and students with the development of novel polymernanotechnology component in a graduate course on Polymer Structure and Morphology. First, such an effort is going to improve the local community's awareness of technologically important polymer nanomaterials, while creating substantive ties to high school teachers and underrepresented young students who otherwise would have no exposure to polymer concepts and applications. The planned outreach effort will feature two major components: education and research. In the education part, the PI will collaborate with local high school science teachers to develop a new curriculum for underrepresented students to learn basic science and engineering concepts related to everyday polymeric materials. Regular visits to the local high school are planned with well-designed polymer experiments and projects to stimulate student interest in science and engineering. In the research program, the PI will initiate a summer internship for high school teachers and students to team with polymer research faculty to develop hands-on laboratory experiments in polymer morphology research for the use in high school classrooms.The polymer nanostructure and morphology course will help bridge the existing gap between different levels of research and education in polymer nanotechnology. The research results will be widely disseminated through publications in scientific journals, presentations at national meetings, and collaborations with industries.***