Charged Block Copolymer Assembly of Unique Nanoscale Objects

技术综述：带电嵌段共聚聚合物溶液组装将用于构建特殊的聚合物纳米结构。理解这种组件形成的机制，以及利用这些过程来获得定义明确的、可重复的纳米结构材料将是有帮助的。基于目前研究的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。我们将从根本上理解多价有机反离子与嵌段共聚物的带电晕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。这项工作将探索一系列为此目的的多胺。同样，还将制作一系列三嵌段与两嵌段共聚物，以探索链状结构和嵌段间相对组成的影响，以及新的疏水核心化学。新的核心化学允许混合实验，以便在同一组装的纳米结构中动力学地捕获多种分子类型。新的化学方法还将使实验得以进行，a)在纯水中进行，而不是在THF/H2O混合物中进行，从而极大地简化组装规程，以及b)允许疏水核心的光降解，以生产潜在功能的、多孔的聚合物纳米颗粒。总而言之，一种简单但具有变革性的溶液组装范例将被用来为潜在的技术创造复杂的聚合物纳米结构。非技术概述：拟议的材料科学将朝着两个重要需求努力。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的未来技术的现实。未来的技术需要更复杂的纳米结构，这项工作致力于创造新的方法来生产所需的纳米结构。其次，通过开展研究，研究生将在科学严谨的跨学科环境中接受培训，这些环境是他们未来在美国工作中取得成功的关键组成部分。在本科生和研究生层面，将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，在拟议的研究期间建立协作科学基础。知识和专业技能的交流将通过特拉华大学和德克萨斯农工大学之间的动态人员交流来实现。在四年的支持期间，每个学生都将通过进行多次和延长时间的现场交流来参与合作研究。也许这项拟议工作的最大可能结果之一是将知识统一地转化给参与研究的化学家和材料科学家/工程师。这项建议的更广泛影响在科学进步、教育推广和通过积极的导师促进学生发展方面具有深远的重要意义。这一合作研究计划构成了一个独特的研究和教育活动基地，每个活动都处于聚合物化学、物理化学、聚合物物理和材料科学领域的前沿。这笔合作赠款支持的研究生将通过参与制定和实施Wooley小组既定的外联活动来进行额外的培训，包括K-12教育外联活动(协助教授一学期长的K-8教师动手实验课程，通过材料意识方案或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费最多一周的时间参与K-12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.