Perfecting Complex Assemblies of Covalent and Supramolecular Polymers via Biological Principles

第一部分：非技术概述生物大分子如蛋白质、核酸、碳水化合物及其与脂质的缀合物是自然界产生的最常见的结构单元。 它们的性质是由它们的原子在其结构和复杂组装中的完美排列决定的。尽管合成聚合物广泛应用于我们的日常生活以及许多健康、国防和其他技术应用中，但它们的性能无法与金属和生物大分子相匹配。 该研究计划旨在利用生物学原理构建聚合物及其复杂组件，以提高合成聚合物的结构精度，使其达到金属和天然大分子的结构精度，并将其在日常生活中的应用扩展到生物系统中遇到的精度和复杂性。 该项目涉及设计，合成和表征大分子到各种复杂的组件，然后研究其结构和性质。 该项目将为高中生、本科生、研究生和博士后（包括少数民族）提供跨学科教育，包括有机、聚合物、超分子合成、催化、物理、生物学、合成生物学、纳米科学、纳米医学和超级计算等学科的接口。小组成员将在PI和宾夕法尼亚大学同事的实验室工作，与美国和国外的科学家合作，并与工业界互动。从这个项目中获得的原则和经验教训将适用于科学，工业和社会的复杂系统。第2部分：技术概述复杂的组件产生的金属原子和大的生物大分子是惊人的不同的概念，但在其非凡的结构完善和功能的水平相同。 合成的共价聚合物和超分子聚合物具有统计的链长分布、手性、组成和序列。因此，它们不能提供无机和生物组装体的结构完美性和性质水平。该项目将使用单分散，纯手性和序列定义的组件来阐明生产非共价超分子和共价聚合物所需的原理，这些聚合物将自组织成复杂的组装体，表现出无机和生物组装体的精确性。将研究以下主题：（1）Frank-Kasper相的自组织原理将被阐明;这些在金属，金属合金，某些气体，脂质，甚至在某些病毒中看到，最近还在窄分子量分布聚合物，单分散聚合物组分和超分子聚合物中。 连同它们的超分子取向记忆Frank-Kasper相将提供第一次获得生物精确度。(2)齿轮双螺旋，帽形去消旋化和“刚性”立体角烟草花叶病毒样超分子螺旋聚合伴随去消旋化的一般性将被研究和阐明。它们将提供具有生物精确度甚至更高的纯手性组装体，其含有通过去外消旋化获得的序列限定的和单分散的组分。(3)将研究和阐明通过非迭代方法合成单分散生物类聚合物的自中断活性聚合的范围和局限性。还将探索合成单分散聚合物的替代方法。该奖项反映了NSF的法定使命，并被认为是值得通过使用基金会的知识价值和更广泛的影响审查标准进行评估的支持。

PART 1: NON-TECHNICAL SUMMARYBiological macromolecules such as proteins, nucleic acids, carbohydrates and their conjugates to lipids are the most common building blocks produced by nature. Their properties are determined by a perfect arrangement of their atoms in their structure and in their complex assemblies. Even though they are pervasively used in our daily lives and in many health, defense and other technological applications, synthetic polymers are not able to match the properties of metals and biological macromolecules. This research program aims to use biological principles in the construction of polymers and their complex assemblies to increase the level of structural precision of synthetic polymers to that of metals and natural macromolecules and expand their applications in daily life to the precision and sophistication encountered in biological systems. The project involves design, synthesis, and characterization of macromolecules to a variety of complex assemblies, followed by study of their structure and properties. This project will provide interdisciplinary education for high school, undergraduate, graduate students and postdocs, including minorities, at the interface of disciplines including organic, polymer, supramolecular synthesis, catalysis, physics, biology, synthetic biology, nanoscience, nanomedicine, and supercomputing. Group members will work in the laboratories of the PI and colleagues at Penn, collaborated with scientists in the US and abroad, and interact with industry. The principles and lessons learned from this project will be applicable to scientific, industrial and societal complex systems.PART 2: TECHNICAL SUMMARY Complex assemblies generated from metal atoms and from large biological macromolecules are strikingly dissimilar as concepts but identical in their extraordinary level of structural perfection and functions. Synthetic covalent and supramolecular polymers have statistical chain length distribution, chirality, composition and sequence. Therefore, they cannot provide the level of structural perfection and properties of inorganic and biological assemblies. This project will use monodisperse, homochiral and sequence-defined components to elucidate principles required to produce noncovalent-supramolecular and covalent polymers that will self-organize into complex assemblies exhibiting the precision of inorganic and biological assemblies. The following topics will be investigated: (1) The principles of self-organization of Frank-Kasper phases will be elucidated; these are seen in metals, metal alloys, some gases, lipids and even in some viruses and recently also in narrow molecular-weight-distribution polymers, monodisperse polymer components, and supramolecular polymers. Together with their supramolecular orientational memory Frank-Kasper phases will provide a first access to biological precision. (2) The generality of the cogwheel double-helix, hat-shape deracemizing and “rigid” solid-angle tobacco mosaic virus-like supramolecular helical polymerizations accompanied by deracemization will be investigated and elucidated. They will provide homochiral assemblies, of biological precision and even higher, containing sequence-defined and monodisperse components obtained by deracemization. (3) The scope and limitations of self-interrupted living polymerization for the synthesis of monodisperse biological-like polymers by non-iterative methods will be investigated and elucidated. Alternative methodologies for the synthesis of monodisperse polymers will also be explored..This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.