From Programmed Macromolecules to Complex Functional Architectures with Chemical Organization on All Levels

技术概要：该提案将详细说明用于合成程序化合成大分子的策略，这些大分子被指示自组装和自组织成具有各级化学组织的复杂功能纳米结构。这个概念目前仅在生物系统中可用。程序化合成大分子是具有精确的一级结构的大分子，其包括单分散分子量分布、组成、序列分布和立体化学，其被指示自组装成提供特定功能所需的三维（3-D）纳米结构。这种架构必须在其第二、第三和第四级进行控制，称为复杂功能架构。目前可用的聚合方法不能用于设计程序化的大分子。因此，通过逆转录结构分析的加速设计策略将用于通过发散和收敛迭代合成方法的组合开发程序化大分子库。 同时，将阐述自中断聚合方法。该方法有望应用于所有已知的链式和分步聚合，并产生第一种生产单分散合成大分子的聚合方法。程序化的大分子库，自组装成各种生物模拟物，如多孔蛋白质，中空球状蛋白质，超分子胶囊，手性超分子纳米结构的非手性积木，和超分子纳米球，表现出分子内手性将被开发。这些纳米结构将有助于获得非常有效的生物功能，如跨膜通道，抗菌剂，可逆封装和递送，酶样催化，电子材料，随机传感，新能源，分离过程，记忆效应，以及放大已知的材料特性。 非技术性总结：目前对具有特定性质的材料的方法是成本和时间效率低下的，并且只能产生最小的改进。该提案旨在将生物纳米结构原理应用于具有特定功能的合成纳米材料的设计。一项加速设计战略涉及化学、物理和生物学专业知识，并与美国和国外的大学、政府实验室和工业界合作，将开发出将材料性能放大几个数量级所需的原理。极有效的分离过程，酶样催化，传感，新能源和新的医学方法有望从这项研究中出现。这项研究将改变我们在最基本的层面上设计材料性能的方式，并相应地影响新一代研究生、本科生和高中生的教育。

TECHNICAL SUMMARY: This proposal will elaborate strategies for the synthesis of programmed synthetic macromolecules that are instructed to self-assemble and self-organize into complex functional nanoarchitectures with chemical organization on all levels. This concept is currently available only in biological systems. A programmed synthetic macromolecule is a macromolecule with precise primary structure, that includes monodisperse molecular weight distribution, composition, sequence distribution and stereochemistry, that is instructed to self-assemble into the 3-dimensional (3-D) nanoarchitecture required to provide a specific function. This architecture must be controlled at its seconday, tertiary and quaternary levels and is called complex functional architecture. Currently available polymerization methods cannot be used to design programmed macromolecules. Therefore, an accelerated design strategy via retrostructural analysis will be used to develop libraries of programmed macromolecules via combinations of divergent and convergent iterative synthetic methods. Simultaneously, a self-interrupted polymerization method will be elaborated. This method is expected to apply to all chain and step polymerizations known and generate the first polymerization method that will produce monodisperse synthetic macromolecules. Libraries of programmed macromolecules that self-assemble into various biological mimics such us porous proteins, hollow globular protein, supramolecular capsules, chiral supramolecular nanostructures from achiral building blocks, and supramolecular nanospheres that exhibit intramolecular chirality will be developed. These nanoarchitectures will facilitate access to extremely efficient biological functions such as transmembrane channels, antimicrobials, reversible encapsulation and delivery, enzymatic-like catalysis, electronic materials, stochastic sensing, new sources of energy, separation processes, memory effects and also amplify already known material properties. NON-TECHNICAL SUMMARY: Current approaches to materials with specific properties are cost and time inefficient and generate only minimal improvements. This proposal intends to apply biological nanostructural principles to the design of synthetic nanomaterials with specific functions. An accelerated design strategy that involves expertise from chemistry, physics and biology with collaboration between universities in US and abroad, governmental laboratories and industry will develop the principles required to amplify materials properties by up to several orders of magnitude. Extremely efficient separation processes, enzymatic-like catalysis, sensing, new sources of energy and new approaches to medicine are expected to emerge from this research. This research will change our way to design materials properties at the most fundamental level and affect accordingly the education of a new generation of graduate, undergraduate and high school students.