Complex Functional Materials Accessed Uniquely through Selective Covalent and Non-covalent Macromolecular Interactions

第一部分：有机聚合物材料，通常被认为是塑料，对人类生活的各个方面都至关重要，从我们穿的衣服到我们使用的计算机，到我们驾驶的轮胎，再到药物管理的设备。 由于聚合物的大的大分子尺寸，在整个分子框架中或在特定的子区域中，有很大的机会改变化学组成和结构，以实现材料性质的显著变化：即，柔性与刚性、导电与绝缘等。随着聚合物的化学结构变得越来越复杂，它们的性能和技术应用也常常增加。 拟议工作的预期意义将是在合成化学方法的进步，允许简单，可扩展的生产聚合物材料，具有复杂的复杂性，并表现出独特的物理和机械性能。 一个重点是构建聚合物，使其具有“瓶刷状”分子结构，使其能够作为预制的超大型大分子存在，这些大分子包含设计用于程序化组装或降解的子区域。 然后可以从这些大分子生产功能性纳米结构物体。 这样的物体可以能够用作合成疫苗的病毒的合成版本，或者用作水净化、气体分离或其他运输和分离应用的多孔薄膜。 其他目标结构将包括能够通过磁性回收来清理溢油的纳米结构。 预计产生的基础知识将影响化学，物理和工程学科，该项目还将包括多方面的教育组成部分。 随着这些新材料的实用性，包括具体的目标应用进行研究，工业利益可能会预期，这可能会转化为产品提供额外的社会beneficies.PART 2：技术总结拟议的工作的活动将涉及先进的合成方法的发展，以提供具有增强的组合物，结构和功能的纳米材料。 一个目的是通过首先将线性聚合物前体动力学捕获到具有预定区域化学分布的官能度的共价分子刷结构中来增加材料组成、结构和性质的复杂性。 第二个目标是发展的形态和性能，可以产生从组装所得的分子刷积木在溶液中，薄膜和散装的理解。 除了分子结构对组装过程和所得性质的作用之外，多肽片段将作为侧链接枝物并入以提供活性二级结构相互作用，并且可降解多肽或聚磷酸酯部分将被内置以允许对整体材料的纳米级结构域内的密度进行异质调节。 除了基本目标之外，具体目标将包括离散的纳米笼框架，在球状蛋白组装成病毒衣壳之后建模，以及扩展的薄膜或散装多孔聚合物网络材料，每个受控的尺寸和孔隙率用于运输和分离应用。 另一个目的是进一步研究混合无机-有机异质结构，其被设计为在其原油采收能力方面优于我们最近开发的磁性壳交联的膝状（MSCK）纳米颗粒。将采用的方法将包括聚合和化学改性反应的组合以构建结构，均相或非均相超分子组装方法以提供复杂的形态，选择性区域的交联以稳定那些形态，以及在某些情况下，材料内的选择性结构域的降解。 在整个工作中，将进行严格的表征研究。 一个广泛的教育和推广方案是该项目的一部分。

PART 1: NON-TECHNICAL SUMMARYOrganic polymer materials, commonly thought of as plastics, are of critical importance to every aspect of human life, from the clothes that we wear to the computers that we use to the tires on which we drive to the devices through which medicines are administered. Due to the large, macromolecular size of polymers, there is great opportunity to vary the chemical composition and structure, throughout the entire molecular framework or in specific sub-regions, to achieve significant variation in the materials properties: i.e., flexible vs. rigid, conducting vs. insulating, etc. As the chemical structure of polymers becomes increasingly complex, their properties and technological applications also often increase. The expected significance of the proposed work will be in the advancement of synthetic chemistry approaches that allow for simple, scalable production of polymer materials that possess intricate complexity and exhibit unique physical and mechanical properties. A focus is on building the polymers to have a "bottle-brush-like" molecular architecture enabling them to exist as pre-fabricated super-size macromolecules that contain sub-regions designed for programmed assembly or degradation. From these macromolecules functional nanostructured objects can then be produced. Such objects may be able to be used as synthetic versions of viruses for synthetic vaccines, or as porous thin films for water purification, gas separation or other transport and separations applications. Other target structures will include nanostructures that are capable of oil spill clean-up with magnetic recovery. The fundamental knowledge generated is expected to impact chemistry, physics and engineering disciplines, and the project will also include multifaceted educational components. With the practical applicability of these new materials, including the specific target applications to be studied, industrial interest may be anticipated, which may translate to products offering additional societal benefits.PART 2: TECHNICAL SUMMARYThe activities of the proposed work will involve the development of advanced synthetic methodologies to afford nanoscopic materials having enhanced compositions, structures and functions. One objective is to increase the complexity of materials compositions, structures and properties, by first kinetically-trapping linear polymer precursors into covalent molecular brush architectures having pre-determined regiochemical distributions of functionalities. A second objective is to develop an understanding of the morphologies and properties that can be generated from the assembly of the resulting molecular brush building blocks in solution, thin films and the bulk. In addition to the roles of molecular architecture on the assembly processes and resulting properties, polypeptide segments will be incorporated as side chain grafts to provide for active secondary structural interactions, and degradable polypeptide or polyphosphoester portions will be built-in to allow for heterogeneous modulation of the density within nanoscopic domains of the overall materials. Beyond the fundamental objectives, specific targets will include discrete nanocage frameworks, modeled after the assembly of globular proteins into viral capsids, and extended thin-film or bulk porous polymer network materials, each of controlled dimensions and porosities for potential use in transport and separations applications. An additional objective is to further investigate hybrid inorganic-organic heterostructures that are designed to outperform our recently-developed magnetic shell crosslinked knedel-like (MSCK) nanoparticles in their capacity for crude oil recovery efforts. The methods that will be employed will include combinations of polymerization and chemical modification reactions to build up the structures, homogeneous or heterogeneous supramolecular assembly methods to afford complex morphologies, crosslinking of selective regions to stabilize those morphologies, and, in some cases, degradation of selective domains within the materials. Throughout the work, rigorous characterization studies will be conducted. A broad educational and outreach program is part of this project.