Collaborative Research: Cooperative Processes at Surfaces: Ligand Binding at the Single Molecule Level

合作研究：表面合作过程：单分子水平的配体结合

• 批准号: 2306316
• 负责人: Ursula Mazur
• 金额: $ 47万
• 依托单位: Washington State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-06-01 至 2026-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2306316&HistoricalAwards=false
• 关键词: Collaborative; Research; Cooperative; Processes; Surfaces

With support from the Chemical Structure, Dynamics, and Mechanisms-A (CSDM-A) Program in the Division of Chemistry, Ursula Mazur and Kerry Hipps of Washington State University and Bhaskar Chilukuri of Illinois State University are exploring cooperative binding events using highly sensitive imaging and computational methods. Chemical processes such as chemical reactivity and detection sensitivity depend on cooperativity. Studying these cooperative interactions requires both surface techniques that are capable of single molecule detection and computational tools for quantifying the degree of interactions. Drs. Chilukuri, Hipps, and Mazur and their students will investigate how single molecules interact with one reactive site and how that system impacts beyond other nearby domains using both experimental and computational methods. The interplay among intermolecular, intramolecular, and substrate-induced effects on chemical reaction cooperativity at surfaces will be studied and analyzed. High school, graduate, and undergraduate students will be mentored in research, and an undergraduate course in nanoscale physical chemistry will be developed.Scanning tunneling microscopy (STM) measurements reveal contributions of both inter- and intramolecular communications to cooperativity on the submolecular level while density functional theory (DFT) and molecular dynamics provide a mechanism for quantifying the role of the substrate, inter and intramolecular interactions, spatial effects, and spin-spin interactions in producing cooperativity in axial complexation. Real-time STM imaging will be used to monitor the reaction between molecules in solution and/or the gas phase and reactive sites on surface supported metal complexes containing two or more reactive sites. Reactivity will be monitored as a function of temperature, reactant concentration, solvation environment, and nature of the support for the metal complexes. Several approaches will be used to model the STM experiments, including the grand canonical ensemble to parameterize the energetics of binding for each distribution over the reactive sites and periodic DFT calculations to provide insight into how electronic distributions affect binding cooperativity at reactive sites. Molecular dynamics calculations will be employed to model solvent effects. By developing a comprehensive model of reaction cooperativity at surfaces, improved predictability of reactivity in surface chemistry, catalysis, and sensor development is envisioned.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.

在化学结构，动力学和机制的支持下，华盛顿州立大学的厄休拉·马祖（Ursula Mazur）和伊利诺伊州立大学的Bhaskar Chilukuri正在使用高度敏感的绑定事件探索高度敏感的成像，和计算方法。化学过程（例如化学反应性和检测敏感性）取决于协同性。研究这些合作相互作用需要两个分子检测和计算工具来量化相互作用程度的表面技术。博士。 Chilukuri，Hipps和Mazur及其学生将研究单个分子如何与一个反应性位点相互作用，以及该系统如何使用实验和计算方法如何影响附近的其他域。将研究和分析分子间，分子内和底物诱导的化学反应协同作用的相互作用。高中，毕业生和本科生将在研究中得到指导，并将开发纳米级物理化学的本科课程。扫描的隧道显微镜（STM）测量结果揭示了分子间和分子内和分子内对余化水平的贡献的贡献功能理论（DFT）和分子动力学提供了一种量化底物，分子间相互作用和分子内相互作用，空间效应以及自旋旋转相互作用在产生轴向络合过程中的作用的机制。实时STM成像将用于监测溶液和/或气相中分子之间的反应，并在包含两个或多个反应性位点的表面支撑金属配合物上的反应性位点。反应性将根据温度，反应物浓度，溶剂化环境以及对金属配合物的支持的性质进行监测。将使用几种方法来对STM实验进行建模，包括大典型的集合，以参数化反应性位点上每个分布的结合能量和定期DFT计算，以提供有关电子分布如何影响反应性位点结合协同的洞察力。分子动力学计算将用于模拟溶剂效应。通过开发一个在表面上的反应合作性的综合模型，设想了表面化学，催化和传感器开发中反应性的可预测性。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的智力功能和更广泛的影响来评估的支持。审查标准。