DMREF: Collaborative Research: Self-assembled peptide-pi-electron supramolecular polymers for bioinspired energy harvesting, transport and management

非技术描述：在光合作用过程中，大自然巧妙地控制关键色素和染料的空间排列，以利用太阳能。通过分子和分子排列的量身定制设计，可以在合成材料中模拟可控的染料排列。然而，在关键的10-100纳米“中尺度”范围内，对工程分子材料的组装施加可靠的控制，仍然是难以实现的。这种介观分子结构将电荷和能量转移活动与在生物溶液中组装的能力以及与生物环境的兼容性结合在一起。考虑到分子设计的多种可能性，实验程序必须结合计算机建模和数据驱动的筛选来指导实验设计和合成。计算和实验的紧密结合和相互促进的反馈可以揭示分子组装的基本设计规律，加速具有定制结构和功能的多分子组装的发现和发展。该项目将合作开发这些功能性分子超结构，包括分子合成、类似于生物系统的自组装、组件的结构和电学性质的建模，以及利用组件来管理光和电之间的相互作用。私人投资机构致力于在该项目中培训和发展劳动力，指导具有不同社会经济背景的下一代材料和数据科学家使用最先进的工具，并使他们接触到将定义未来研究的综合跨学科工作模式。技术描述：pi共轭超分子体系的光物理和电学性质主要取决于分子间电子相互作用的明确性质。这些相互作用是由精确的分子结构和化学以及新出现的超分子排列决定的。PI开发了一种多肽结构，它提供了一种途径，通过剪裁空间体积和可变的组分序列的疏水性来影响分子间取向、高阶原纤化和特定的电子结果，从而对新出现的超分子结构施加这种控制。他们最初使用爱迪生方法来发现这些变化，但这个项目的目标是通过紧密集成的原子模拟和电子结构计算来使用显式工程控制。研究活动建立在S团队的坚实基础上，以实现两个具体目标：(I)开发具有先进光电功能的尖端多肽半导体材料；(Ii)开发新的组装范例，导致具有化学和电子梯度以及局部电场的异质多肽纳米材料。这项工作的实施将需要研究小组在(I)合成新的pi电子单元和新的自组装肽，(Ii)分子和数据驱动的纳米材料聚集体及其更高阶组装的模拟，以及(Iii)纳米材料内的电子传输的表征方面的相互关联的努力。该项目将为本科生、女性和代表性不足的少数族裔提供特别的研究机会。PIS将培训和指导研究人员使用最先进的实验和计算工具，并使他们接触到一种综合的跨学科工作模式。K-12外展活动将激发学生对材料科学的兴奋和认识，并鼓励学生在科学、技术、工程和数学(STEM)领域接受高等教育。

Non-technical Description: Nature exquisitely controls the spatial arrangement of key pigments and dyes in the process of photosynthesis to harness solar energy. Mimicry of controlled dye arrangements in synthetic materials can be realized through tailored design of molecules and molecular arrangements. However, exerting reliable control over the assembly of engineered molecular materials in the crucial 10-100 nanometer "mesoscale" regime, thousands of times smaller than a millimeter, remains elusive. Such mesoscale molecular structures will combine charge and energy transfer activities with capabilities for assembly in biological solutions, and compatibility with biological environments. Given the multitude of molecular design possibilities, it is essential that experimental programs incorporate computer modeling and data-driven screening to guide experimental design and synthesis. Tight integration and mutually reinforcing feedback between computation and experiment can reveal fundamental design rules for molecular assembly, and accelerate the discovery and development of multi-molecule assemblies with tailored structure and function. This project will develop these functional molecular superstructures in a collaboration encompassing molecular synthesis, self-assembly analogous to biological systems, modeling of the structures and electrical properties of the assemblies, and utilizing the assemblies to manage interactions between light and electricity. The PIs are committed to workforce training and development within this project, guiding the next generation of materials and data scientists of diverse socio-economic background in state-of-the-art tools and exposing them to an integrated interdisciplinary mode of work that will define future research. Technical Description: The photophysical and electrical properties of pi-conjugated supramolecular systems depend critically on the explicit nature of the intermolecular electronic interactions. These interactions are governed by the precise molecular structure and chemistry and emergent supramolecular arrangements. The PIs developed a peptide construct that offer a pathway to exert such control over emergent supramolecular structure through tailoring of steric bulk and variable hydrophobicity of the component sequences to influence intermolecular orientations, higher-order fibrilization, and specific electronic outcomes. They initially used an Edisonian approach to uncover these variations, but the goals of this project are to wield explicit engineered control through tightly integrated atomistic simulations and electronic structure calculations. The research activities build upon the team?s strong foundation to accomplish these goals in two specific objectives: (i) the development of sophisticated peptidic semiconductor materials with advanced optoelectronic functionality and (ii) the development of new assembly paradigms leading to heterogeneous peptidic nanomaterials with chemical and electronic gradients and localized electric fields. The execution of this work will entail interconnected efforts by the research team in the (i) synthesis of new pi-electron units and new self-assembling peptides, (ii) molecular and data-driven modeling of the nanomaterial aggregates and their higher-order assemblies, and (iii) characterization of electrical transport within the nanomaterials. This project will make special provision for research opportunities for undergraduate students, women, and underrepresented minorities. The PIs will train and mentor researchers in state-of-the-art experimental and computational tools and expose them to an integrated interdisciplinary mode of work. K-12 outreach activities will inspire excitement and awareness of materials science and encourage students to pursue higher education in science, technology, engineering, and math (STEM) fields.