Switching beyond the Molecule using Hydrazones

分子开关和分子机器的发展是当前科学推动小型化的重要组成部分。近年来，在设计新型分子开关、将其集成到块状材料中以及将其应用于新功能方面取得了显著进展。然而，在这种系统能够进入实际应用之前，仍有许多挑战需要解决。这项研究解决了其中一个问题，即缺乏对如何使分子开关和机器一起朝着一个有用的目标工作的基本理解-这是自然生物系统中已解决的问题。为了模仿自然，达特茅斯学院的阿普拉哈mian研究小组研究了分子开关与环境的相互作用。这些知识可能会导致动态，自适应和自我调节分子组装的工程，可用于药物输送和能源相关应用。这项研究的广泛影响包括参与美国化学学会的SEED计划，以及其他帮助不同教育水平（高中、本科和研究生）的学生留在科学领域的努力。阿普拉哈米安教授还使用互动演示来教育公众有关超分子化学的重要概念。这些活动预计将加强和扩展该组织与当地学校和科学博物馆的非正式和正式的科学教育伙伴关系和网络。在化学系大分子、超分子和纳米化学项目的支持下，本研究考察了锌（II）启动、配位偶联、腙开关去质子化（CCD）与其他金属的偶联，特别是钯（II）。这些反应扩展了目前已知的开关级联的能力，并为使用自组装笼的区隔化驱动催化开辟了道路。Aprahamian团队对控制ccd负反馈循环的因素有了更深入的了解，并揭示了导致分析性监管的潜在规则。最后，该小组开发了新的锌（II）光笼/开关，可以与CCD和反馈回路耦合，以实现振荡系统，分子钟和自调节组件的未来设计。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。

The development of molecular switches and machines is a vital part of the current scientific drive towards miniaturization. Appreciable advances have been made in recent years in the design of new molecular switches, integrating them into bulk materials, and applying them in new functions. However, there are still many challenges that need to be addressed before such systems can find their way into real-life applications. This research addresses one of these issues, which is the lack of a basic understanding of how to make molecular switches and machines work together towards a useful goal - a solved problem in natural biological systems. To mimic Nature, the Aprahamian research group at Dartmouth College studies the interactions of molecular switches with their environment. This knowledge may lead to the engineering of dynamic, adaptive and self-regulating molecular assemblies that can be used in drug delivery and energy-related applications. The broader impacts of this research include participation in the American Chemical Society's SEED Program and other endeavors to help retain students at different levels of education (high school, undergraduate, and graduate students) in the sciences. Professor Aprahamian also uses interactive demonstrations to educate the public about important concepts related to supramolecular chemistry. These activities are expected to strengthen and extend the group's informal and formal science education partnerships and networks with local schools and science museums.With the support from the Macromolecular, Supramolecular and Nanochemistry Program of the Division of Chemistry, this research examines the coupling of zinc(II)-initiated, coordination-coupled, deprotonation (CCD) of hydrazone switches with other metals, particularly palladium(II). These reactions extend the capabilities of currently known switching cascades and open the way for compartmentalization driven catalysis using self-assembled cages. The Aprahamian group gains a deeper understanding of the factors that control CCD-enabled negative feedback loops and uncovers the underlying rules that lead to analyte regulation. Finally, the group develops new zinc(II) photocages/switches that can couple with CCD and feedback loops to enable the future design of oscillating systems, molecular clocks, and self-regulating assemblies.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.