Synthetic Methodology Development, Utilizing the Physical and Chemical Manipulation of Discrete Nanoscale Objects

拟议研究的智力价值集中在独特的纳米结构材料的制备，以及这样做的过程的发展。严格的表征技术将应用于合成的每个阶段。以迭代方式应用的超分子组装，以及模板策略和共价稳定，将用于开发新的合成方法，用于制备具有高阶复杂性的材料。研究工作将建立在过去成就的基础上，并将重点放在新的合成方法的发展上，主要涉及对源自超分子组装的纳米结构的迭代物理和化学操作，以增加结构偏离热力学衍生材料的程度。通过活性自由基聚合制备两亲性嵌段共聚物，结合保护基团策略，随后将其自组装成聚合物胶束或反胶束，通过壳交联实现共价稳定，然后操纵壳交联纳米结构。因此，基本组分将是壳交联聚合物胶束或逆胶束，建议的工作将包括：(1)合成具有亲水核的逆结构，该结构包含在疏水壳中，通过活性自由基交联聚合的发展来稳定；(2)研究了预先建立的壳交联纳米结构的反转，这一过程的可逆性和反转纳米结构的表面性质；(3)旨在发展热塑性和热固性方法的研究，以使预先建立的壳交联纳米结构的复杂形状超越热力学可达的球体、圆盘、棒、囊泡、环面等；(4)中空壳交联纳米结构的合成和纳米笼内外表面化学分化的合成方法的发展，包括在纳米笼内生长活性聚合物刷以产生回填的核心区域。这些材料将具有丰富的基本性质，研究表面附着和纳米约束对聚合物链的影响，作为先进的形状材料，可以根据复合核心区域聚合物链的结合和生长进行调整，并且作为那些呈现出独特的两亲性表面轮廓的材料，可以近似于蛋白质表面。拟议活动的更广泛影响将包括在多个层面上对学生进行跨学科培训，以及继续发展重要的社会教育和外展计划。教育活动将针对幼儿园学生、教师、研究生和博士后等多个层次。严谨的研究将为高等教育提供基础，而利用实践活动补充背景课程的正式课程将作为拓展活动继续和加强。“物质与能量，教育6009”课程将每两年为K-8教师开设一次，并且将开发一个更密集的暑期学院课程，为化学原理提供更坚实的基础。以教育示范和活动为主的小学参观活动将继续进行。将制定评价计划，通过评价完成正式课程或学校访问前后的态度和概念数据，增加这些活动可能产生的影响。

The intellectual merit of the proposed research centers upon the preparation of uniquenanostructured materials, and the development of processes to do so. Rigorous characterizationtechniques will be applied at each stage of the syntheses. Supramolecular assembly, applied in aniterative fashion, along with templating strategies and covalent stabilization, will be utilized for thedevelopment of new synthetic methodologies for the preparation of materials having high orders ofcomplexity. The research efforts will build from the past accomplishments and will focus upon thedevelopment of new synthetic methodologies, involving primarily iterative physical and chemicalmanipulation of nanostructures that originate from supramolecular assemblies to increase the degrees to which the structures can deviate from the thermodynamically-derived materials. The preparation of amphiphilic block copolymers via living radical polymerizations, in conjunction with protecting groupstrategies, will be followed by their self assembly into polymer micelles or inverse micelles, covalentstabilization through shell crosslinking, and then manipulation of the shell crosslinked nanostructures.Thus, the foundational component will be shell crosslinked polymer micelles or inverse micelles and the proposed work will include: (1) syntheses of inverse structures having hydrophilic cores contained within hydrophobic shells that are stabilized via the development of living radical crosslinking polymerizations;(2) studies of the inversion of pre-established shell crosslinked nanostructures, the reversibility of such a process and the surface properties of the inverted nanostructures; (3) studies aiming toward the development of thermoplastic and thermosetting methodologies for the complex shaping of preestablishedshell crosslinked nanostructures beyond thermodynamically accessible spheres, discs, rods,vesicles, toroids, etc.; (4) syntheses of hollowed shell crosslinked nanostructures and the development of synthetic methodologies for chemical differentiation of the external and internal surfaces of the resulting nanocages, including the living polymer brush growth within the nanocages to generate backfilled core domains. These materials will be rich with fundamental properties investigations of the effects of surface attachment and nanoconfinement upon polymer chains, as advanced shaped materials, which can be tuned in terms of the incorporation and growth of composite core domain polymer chains, and as those that present unique amphiphilic surface profiles that can approximate protein surfaces. The broader impacts from the proposed activity will include interdisciplinary training of students atmultiple levels, and the continued development of significant societal education and outreach programs.Educational activities will be directed at multiple levels from kindergarten students to teachers, graduate students and postdoctoral associates. Rigorous research studies will provide the foundation for higher education, whereas formal courses utilizing hands-on activities supplemented with the background curriculum will be continued and enhanced as outreach activities. The hands-on outreach, Matter and Energy, Education 6009 course will be offered every two years, for K-8 teachers, and a more intensive summer institute course will be developed to provide for a stronger foundation of chemistry principles. Educational demonstration-based and activities-filled visits to elementary schools will be continued. Assessment plans will be developed to increase the impact that these activities can provide, by evaluating attitudinal and conceptual data pre- and post-completion of the formal courses or school visits.