CAREER: Small Molecule Activations Enabled by Coordination-Driven Self-Assembly

自然界提供了许多催化剂（加速反应的分子）的例子，这些催化剂在其活性位点含有多个金属原子。这些催化剂在将小分子转化为更理想的产物方面非常有效，并在许多关键过程中发挥作用，例如光合作用和呼吸作用。了解多个金属原子如何协同工作需要控制给定催化剂的大小和形状。在这个项目中，库克博士正在使用自组装方法设计高度可调的催化剂，其大小和形状可以系统地改变，以观察它们如何影响小分子。他的团队可以改变金属中心之间的距离，存在的金属类型，以及支持有机构建块的性质。这些系统的研究提供了对小分子活化的更深层次的理解。最终，它们可以作为设计催化剂的指南，使可再生能源和更环保的化工原料路线成为可能。在这个研究项目的同时，库克博士正在使用3d打印技术作为一种工具，通过课堂上的互动、动态模型来说明自组装和其他基本化学概念。这些努力包括与布法罗公立学校系统合作，为教师在课堂材料的设计和使用方面提供研究机会和专业发展。在化学部门化学催化项目的资助下，布法罗大学的库克博士正在使用自组装作为一种合成方法来构建结构，其中含金属卟啉、二氧肟和相关的聚吡咯大环作为催化活性位点。这些自组装反应使用金属-配体键形成作为组织共面几何形状的驱动力。这种合成方法提供了模块化和控制金属-金属分离，衬底访问，结构刚性和分子修饰来调整电子结构。这些参数对分子氧、质子和二氧化碳的电化学还原的作用正在通过活性研究、电化学方法和结构分析来确定。由此产生的有关结构-活性关系的信息以及控制选择性、周转频率和催化剂稳定性的机制见解，为小分子活化提供了更深入的理解。Cook博士积极设计以互动、动态模型为中心的STEM教育课堂材料，以说明高中教师和本科讲师使用的自组装和一般化学概念。这些活动通过研究机会和教师专业发展涉及布法罗公立学校系统。该奖项反映了美国国家科学基金会的法定使命，并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，被认为值得支持。

Nature provides many examples of catalysts (molecules that speed reactions up) that contain multiple metal atoms in their active sites. These catalysts are very effective at changing small molecules into more desirable products and play a role in many critical processes, such as photosynthesis and respiration. Understanding how multiple metal atoms can work together requires control over the size and shape of a given catalyst. In this project, Dr. Cook is using self-assembly methods to design highly tunable catalysts in which size and shape can be systematically changed to see how they affect small molecules. His group can change the distance between metal centers, the type of metals present, and the nature of the supporting organic building blocks. The study of these systems provides a deeper understanding of small molecule activations. Ultimately, they may serve as guides for the design of catalysts that enable renewable energy and greener routes to chemical feedstocks. In parallel with this research program, Dr. Cook is using 3D-printing technology as a tool to illustrate self-assembly and other fundamental chemistry concepts with interactive, dynamic models for the classroom. These efforts include a partnership with the Buffalo Public School System to provide research opportunities and professional development for teachers in the design and use of classroom materials.With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Cook of the University at Buffalo is using self-assembly as a synthetic methodology to construct architectures in which metal-containing porphyrins, diglyoximes, and related polypyrrole macrocycles serve as catalytically active sites. These self-assembly reactions use metal-ligand bond formation as a driving force to organize cofacial geometries. This synthetic approach provides modularity and control over metal-metal separation, substrate access, structural rigidity, and molecular modifications to tune electronic structure. The role of these parameters on the electrochemical reduction of molecular oxygen, protons and carbon dioxide is being established using activity studies, electrochemical methods, and structural analyses. The resulting information about the structure-activity relationships and mechanistic insight governing selectivity, turnover frequency, and catalyst stability is providing a deeper understanding of small molecule activations. Dr. Cook is actively designing classroom materials for STEM education centered on interactive, dynamic models to illustrate self-assembly and general chemistry concepts for use by high school teachers and undergraduate lecturers. These activities involve the Buffalo Public School System through research opportunities and teacher professional development.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.