Charged Block Copolymer Assembly of Unique Nanoscale Objects

技术概述：带电嵌段共聚物溶液组装将用于构建非凡的聚合物纳米结构。将寻求对这些组装形成的机制的理解，以及利用这些过程来实现定义良好、可再生的纳米结构材料。基于当前研究和新的嵌段化学的嵌段共聚物的合成和实验将有助于产生这种理解。将寻求对多价有机反离子与嵌段共聚物的带电电冕链络合对带电嵌段构象以及聚合物自组装过程中形成的整体形态的影响的基本理解。这项工作将探索一系列的多胺来实现这一目的。同样，将制作一系列三嵌段与二嵌段共聚物，以探索链结构和嵌段之间的相对组成的影响，以及新的疏水核心化学。新的核心化学允许混合实验，以便在相同的组装纳米结构中动态捕获多种分子类型。新的化学物质还将允许实验a)在纯水中进行，而不是在THF/H2O混合物中进行，从而大大简化了组装方案；b)允许光降解疏水核心，以生产具有潜在功能的多孔聚合物纳米颗粒。总之，将寻求一种简单但具有变革性的解决方案组装范式，用于创建潜在技术的复杂聚合物纳米结构。非技术总结：拟建的材料科学将致力于两个重要的需求。首先，技术成果将有助于使纳米技术成为从能源到生物医学应用等未来技术的现实。未来的技术需要更复杂的纳米结构，而这项工作努力创造新的方法来生产所需的纳米结构。其次，通过进行研究，研究生将在科学严谨的跨学科环境中接受培训，这是他们未来在美国劳动力中取得成功的关键组成部分。在本科和研究生阶段，通过整合合成聚合物化学、物理化学、聚合物物理和材料科学与工程等多学科和跨学科领域的教育专业知识，将在拟议的研究期间发展合作科学基础。知识和专业知识的交流将通过特拉华大学和德克萨斯农工大学之间的人员交流来实现。在每四年的资助中，每位学生都将通过多次和长时间的现场交流参与合作研究。也许这项工作最大的可能成果之一是将知识统一地传递给参与研究的化学家和材料科学家/工程师。这一提议的广泛影响在科学进步、教育推广和通过积极的指导促进学生发展方面具有深远的重要性。这项合作研究计划构成了一个独特的研究和教育活动的基础，每个都在聚合物化学，物理化学，聚合物物理和材料科学领域的前沿。这项合作基金支持的研究生将通过参与Wooley集团既定的推广活动的发展和实施来接受额外的培训，包括K-12教育推广活动（协助为K-8教师讲授一学期的动手实验课程，通过材料意识计划或MAP对纽瓦克当地大学预科学生进行教育访问）。预计每个学生每年将花一周的时间参与K-12的活动。

TECHNICAL SUMMARY:Charged block copolymer solution assembly will be used to construct extraordinary polymer nanostructures. The understanding of the mechanisms by which such assemblies form, and the harnessing of those processes to achieve well-defined, reproducible nanostructured materials, will be sought.The syntheses of, and experiments with, block copolymers based on both currently studied and new block chemistries will help produce this understanding. A fundamental understanding will be sought of the effects that multivalent, organic counterions complexing with charged corona chains of block copolymers have on the charged block conformation as well as the overall morphology formed during polymer self-assembly. The work will explore a series of multiamines towards this purpose. Likewise a series of triblock vs. diblock copolymers will be made to explore the effects of chain architecture and relative composition between blocks, as well as new hydrophobic core chemistry. The new core chemistry allows for blending experiments in order to kinetically trap multiple molecule types in the same assembled nanostructure. The new chemistries will also allow experiments toa) be performed in pure water as opposed to THF/H2O mixtures thus greatly simplifying assembly protocols as well as b) permit the photodegradation of hydrophobic cores for the production of potentially functional, porous polymer nanoparticles. In summary, a simple but transformative solution assembly paradigm for creation of complex polymer nanostructures for potential technology will be sought.NON-TECHNICAL SUMMARY:The proposed materials science will work towards two important needs.First, the technical results will help work towards making nanotechnology a reality for future technology ranging from energy to biomedical applications. More complex nanostructures are needed for future technology, and this work strives to create new methods to produce the needed nanostructure. Second, by performing the research, graduate students will be trained in scientifically rigorous, interdisciplinary environments, critical components for their future successes in the U.S. work force.At the undergraduate and graduate levels, collaborative scientific foundations will be developed during the proposed research by integrating educational expertise in the multi- and interdisciplinary fields of synthetic polymer chemistry, physical chemistry, polymer physics and materials science and engineering. Exchange of knowledge and expertise will be accomplished by a dynamic exchange of personnel between the University of Delaware and Texas A&M University. In each of the four years of support, each of the students will engage in collaborative research by conducting site exchanges for multiple and extended periods of time. Perhaps one of the greatest possible outcomes of the proposed work is the translation of knowledge uniformly to the chemists and materials scientists/engineers involved in the research.The broader impacts of this proposal are of far reaching importance in terms of scientific advances, educational outreach, and student development through active mentorship. This collaborative research proposal constitutes a unique base for research and educational activities, each at the forefront of the fields of polymer chemistry, physical chemistry, polymer physics and materials science. The graduate students supported by this collaborative grant will be trained additionally through involvement with the development and implementation of established outreach activities in the Wooley group including K-12 educational outreach activities (assisting with the teaching of a semester-length course on hands-on experiments for K-8 teachers, educational visits to and by local pre-college students in Newark through the Materials Awareness Program or MAP), and it is expected that each student will spend up to a week per year involved in K-12 activities.