Synthetic Self-Assembling Polyimides

在自然界中，大分子自组装几乎是一个无处不在的过程，产生复杂的三维结构和体系结构。柔性多肽和多糖被折叠并组装成具有示例性机械、识别和催化性能的材料。提出了三种合成聚酰亚胺，它们类似地自组装成精确的尺寸和组织结构。由此产生的六角形阵列、交织片和构象开关由于其纳米级尺寸、高度组织的拓扑结构和完全合成的组成而独特。因此，新的仿生和材料特性被期待。设想的应用是：(1)模型来理解生物自组装的基本过程；(2)合理设计有机沸石、导体等材料；(3)具有仿生学特性的材料，如复制、特异性和模版能力。然而，所提出的聚合物最吸引人的特点是这些自组织材料的合成容易和低成本。这三种聚酰亚胺都是由由1,3 -二取代苯与1,4,5,8-萘二亚胺连接而成的类似框架形成的。这些合成聚合物可以通过传统的聚合和加工技术从廉价的起始材料制备。与这种合成经济相辅相成的是自组装过程的效率。自发地，分子内和分子间的接触阵列以高保真度和特异性形成。最后，聚酰亚胺的合成可及性及其组件的高度连贯结构使其能够合理地细化为更复杂的扩展结构和材料。%%%这个项目应该提高我们的能力，通过自组装过程，以自然为例，以直接和良性的方式设计新材料。＊＊＊

9807470 Shimizu In nature, macromolecular self-assembly is nearly an ubiquitous process, yielding complex three- dimensional structures and architectures. Flexible polypeptides and polysaccharides are folded and assembled into materials of exemplary mechanical, recognition, and catalytic properties. Proposed are three synthetic polyimides that similarly self-assemble into structures of precise dimensions and organization. The resulting, hexagonal array, interwoven sheets, and conformational switch are unique due to their nano-scale dimensions, highly organized topologies, and entirely synthetic composition. As a consequence, novel biomimetic and materials properties are anticipated. Envisioned are applications as: (1) models to understand the fundamental process of biological self-assembly; (2) rationally designed materials such as organic zeolites and conductors; (3) materials with biomimetic properties such as replication, specificity, and templating abilities. However, the most attractive attribute of the proposed polymers is ease and low cost with which these self- organizing materials can be synthesized. All three polyimides are fashioned from a similar framework composed of 1, 3- disubstituted benzenes linked by 1,4,5,8-naphthalene diimides. These synthetic polymers can be prepared by conventional polymerization and processing techniques from inexpensive starting materials. Complementing this synthetic economy is the efficiency of the self-assembly process. Spontaneously, arrays of intra-and intermolecular contacts are formed with high fidelity and specificity. Finally, the synthetic accessibility of the polyimides and highly coherent structures of their assemblies enable their rational elaboration into more complex extended architectures and materials. %%% This project should enhance our ability to design novel materials through self-assembling processes in a direct and benign way exemplified by nature. ***