CAREER: Nanoreactors for Dual Catalysis Under Polymer Confinement

在化学系大分子、超分子和纳米化学（MSN）项目的支持下，宾夕法尼亚州立大学的Elacqua博士将合成和研究由单个聚合物链上的多个催化单元组成的聚合物纳米反应器。自然界和化学工业都使用催化剂来加快化学反应的速度。本研究项目旨在对近限制性共催化剂对活性的影响提供基本的理解，并最终为协同催化转化开发新的策略。除了为本科生和研究生提供有机和聚合物合成方面的研究培训外，该项目还包括突出当代化学和多学科研究基础设施的课程活动。额外的重点将放在增加有机化学的可及性，并制定积极的招聘和保留计划，以最大限度地减少STEM职业的障碍。本课题主要研究用于光氧化还原催化的聚合物纳米反应器。双光氧化还原催化和串联反应是一个特别的焦点。将开发合成策略，将多种催化剂合并到单链聚合物中，这些聚合物可以可控地折叠，形成具有高催化剂密度的离散纳米级结构。通过改变聚合物链的化学结构来调节溶解度，这种纳米反应器可以作为均相催化剂。将在共催化剂的存在下研究光引发反应性，其中聚合物限制可以导致加速反应并提供额外的机理见解。这些研究有望为新的协同催化策略提供有用的信息。具体来说，本研究将深入了解近端催化剂定位对催化效率的影响，旨在解决共催化反应中的扩散限制。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。

With the support of the Macromolecular, Supramolecular, and Nanochemistry (MSN) Program in the Division of Chemistry, Dr. Elacqua of The Pennsylvania State University will synthesize and study polymer nanoreactors that consist of multiple catalytic units in a single polymer chain. Both nature and chemical industry use catalysts to speed up the rate of chemical reactions. This research project aims to provide fundamental understanding of the effects of proximally confining cocatalysts on activity and, ultimately, to develop novel strategies for cooperative catalytic transformations. In addition to providing research training to undergraduate and graduate students in organic and polymer synthesis, this project includes curricular activities that highlight contemporary chemistry and feature a multidisciplinary research infrastructure. Additional focus will be placed on increasing the accessibility of organic chemistry and developing active recruitment and retention initiatives that minimize barriers to STEM careers. This research focuses on studying polymer nanoreactors for photoredox catalysis. Dual photoredox catalysis and tandem reactions are a particular focus. Synthetic strategies will be developed to incorporate multiple catalysts into single-chain polymers that fold controllably to form discrete, nanometer-sized structures with high catalyst density. By tuning the solubility through modifying the chemical structure of the polymer chain, such nanoreactors can function as homogeneous catalysts. Light-initiated reactivity will be studied in the presence of co-catalysts, wherein polymeric confinement can lead to accelerated reactions and provide additional mechanistic insight. These studies are expected to provide useful information on novel strategies for cooperative catalysis. Specifically, this research will provide insight into the effects of proximal catalyst localization upon catalytic efficiency, with the aim of tackling diffusion limitations in co-catalytic reactions.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.