A Supramolecular Chemistry Approach to Precisely Controlled Multi-Porphyrin Arrays in Water

杜兰大学Jayawickramarajah教授的研究重点是在竞争性水介质中定义良好的多卟啉阵列的自组装，该研究得到了大分子、超分子和纳米化学（MSN）计划和刺激竞争性研究实验计划（EPSCoR）的支持。本项目旨在利用疏水驱动的主客体相互作用，以协调和多价的方式(a)开发由多卟啉阵列组成的定向纳米线，并精确控制卟啉间特性（如卟啉间间距和卟啉-卟啉结合常数），以及(b)通过溶液和表面组合方法的结合，构建具有阵列尺寸和组成控制的卟啉阵列。在制备之后，将探索阵列的光物理和电子特性（特别是光诱导能量迁移）。这项研究是跨学科的，涉及与Schmehl教授的光化学小组和Diebold教授的表面物理小组的合作。除了推进分子识别和水中自组装的基础知识外，这项工作还有望为以可持续和环境友好的方式生产功能卟啉材料奠定基础，从而造福社会，这些材料具有作为人工光收集材料组件、传感器、催化剂和抗菌平台的潜在应用。其他更广泛的影响包括通过参与从合成和自组装到微观和光谱表征的跨学科研究活动，推进从本科到博士后水平的研究人员的科学教育。此外，该奖项将通过(a)他们直接参与研究项目，以及(b)通过Jayawickramarajah教授开发的延伸课程的继续，加强未被充分代表的群体在化学教育和研究中的参与，该课程涉及杜兰大学的大一和大二本科生在新奥尔良市中心的一所公立学校进行以化学为中心的服务学习活动。

The research of Professor Jayawickramarajah at Tulane University focusing on the self-assembly of well-defined multi-porphyrin arrays in competitive aqueous media is supported by the Macromolecular, Supramolecular, and Nanochemistry (MSN) program and the Experimental Program to Stimulate Competitive Research (EPSCoR). This project aims to use hydrophobically driven host-guest interactions in a coordinated and multivalent manner to (a) develop directional nanowires composed of multi-porphyrin arrays with precise control over inter-porphyrin characteristics (such as inter-porphyrin spacing and porphyrin-porphyrin association constants), and (b) to construct porphyrin arrays with control over array dimensions and composition, via a combination of solution- and surface-based assembly methods. Subsequent to preparation, the photophysical and electronic properties (in particular, photo-induced energy migration) of the arrays will be explored. This research endeavor is inter-disciplinary involving collaborations with the photochemistry group of Prof. Schmehl and the surface physics group of Prof. Diebold.In addition to advancing fundamental knowledge in molecular recognition and self-assembly in water, this work is expected to benefit society by laying a foundation for functional porphyrinic materials, produced in a sustainable and environmentally friendly manner, with potential applications as components in artificial light harvesting materials, as sensors, catalysts, and anti-microbial platforms. Additional broader impacts include advancing the scientific education of researchers from the undergraduate through post-doctoral levels via their integral involvement in cross-disciplinary research activities ranging from synthesis and self-assembly to microscopic and spectroscopic characterizations. Further, this award will enhance the participation of under-represented groups in chemistry education and research via (a) their direct involvement in research projects, and (b) through the continuation of an outreach course developed by Prof. Jayawickramarajah that involves freshman and sophomore undergraduate students from Tulane conducting chemistry-centered service learning activities at an inner-city New Orleans public school.