Synthetic Self-Assembling Polyimides

9807470清水在自然界中，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典型的机械、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具有精确尺寸和组织的结构。由此得到的六角形阵列、交织薄片和构象开关是独一无二的，因为它们具有纳米尺度、高度有序的拓扑结构和完全合成的组成。因此，人们期待着新的仿生和材料特性。设想的应用如下：(1)理解生物自组装基本过程的模型；(2)合理设计的材料，如有机沸石和导体；(3)具有仿生特性的材料，如复制、特异性和模板能力。然而，所提出的聚合物最吸引人的属性是容易和低成本地合成这些自组织材料。这三种聚酰亚胺都是由1，3-二取代苯通过1，4，5，8-萘二亚胺连接而成的类似骨架。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原料中制备出来。与这种综合经济相辅相成的是自组装过程的效率。自发形成分子内和分子间接触的阵列，具有高度的保真度和特异性。最后，聚酰亚胺的人工可访问性及其组装的高度连贯的结构使其能够合理地细化到更复杂的扩展结构和材料中。这个项目应该会增强我们通过自组装过程设计新材料的能力，以自然为例，以直接和良性的方式。***

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. ***