Switching beyond the Molecule using Hydrazones

使用腙超越分子

• 批准号: 1807428
• 负责人: Ivan Aprahamian
• 金额: $ 43万
• 依托单位: Dartmouth College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-08-01 至 2022-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1807428&HistoricalAwards=false
• 关键词: Switching; beyond; Molecule; using; Hydrazones

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.

分子开关和机器的发展是当前科学向小型化发展的重要组成部分。近年来，在设计新型分子开关、将其集成到块体材料中以及将其应用于新功能方面取得了显著进展。然而，在这种系统能够找到进入现实生活应用的方法之前，仍然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共同努力实现有用目标的基本理解-这是自然生物系统中解决的问题。为了模仿自然，达特茅斯学院的Aprahamian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工程的动态，自适应和自我调节的分子组件，可用于药物输送和能源相关的应用。这项研究的更广泛的影响包括参与美国化学学会的种子计划和其他努力，以帮助留住学生在不同层次的教育（高中，本科和研究生）的科学。 Aprahamian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大该集团的非正式和正式的科学教育伙伴关系和网络，与当地学校和科学博物馆。在支持的大分子，超分子和纳米化学计划的化学部，本研究探讨耦合锌（II）发起的，协调耦合，去质子化（CCD）的腙开关与其他金属，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室化驱动的催化开辟了道路。 Aprahamian小组对控制CCD负反馈回路的因素有了更深入的了解，并揭示了导致分析物调节的基本规则。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，使未来的振荡系统，分子钟和自调节组件的设计成为可能。该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

The Future of Molecular Machines

• DOI: 10.1021/acscentsci.0c00064
• 发表时间: 2020-03-25
• 期刊: ACS CENTRAL SCIENCE
• 影响因子: 18.2
• 作者: Aprahamian, Ivan

Planarization‐Induced Activation Wavelength Red‐Shift and Thermal Half‐Life Acceleration in Hydrazone Photoswitches

腙光电开关中的平坦化 - 诱导激活波长红移和热半衰期加速

• DOI: 10.1002/open.201900340
• 发表时间: 2020
• 期刊: ChemistryOpen
• 影响因子: 2.3
• 作者: Shao, Baihao;Aprahamian, Ivan
• 通讯作者: Aprahamian, Ivan

Hydrazones as New Molecular Tools

• DOI: 10.1016/j.chempr.2020.08.007
• 发表时间: 2020-09-10
• 期刊: CHEM
• 影响因子: 23.5
• 作者: Shao, Baihao;Aprahamian, Ivan
• 通讯作者: Aprahamian, Ivan

Photon Energy Storage in Strained Cyclic Hydrazones: Emerging Molecular Solar Thermal Energy Storage Compounds

• DOI: 10.1021/jacs.2c05384
• 发表时间: 2022-07-08
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Qiu, Qianfeng;Yang, Sirun;Han, Grace G. D.
• 通讯作者: Han, Grace G. D.

pH‐Induced Fluorescence and Thermal Relaxation Rate Modulation in a Hydrazone Photoswitch

• DOI: 10.1002/cptc.201900119
• 发表时间: 2019-06
• 期刊: ChemPhotoChem
• 影响因子: 3.7
• 作者: Baihao Shao;I. Aprahamian