Cooperative dynamics in ligand binding reactions at the solution/solid interface

溶液/固体界面配体结合反应的协同动力学

基本信息

批准号：
1800070
负责人：
Ursula Mazur
金额：
$ 60.91万
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：
2018
资助国家：
美国
起止时间：
2018-08-01 至 2023-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800070&HistoricalAwards=false
关键词：
Cooperative dynamics ligand binding reactions

项目摘要

Many large molecules have several chemically reactive sites. Oftentimes these sites behave independently, with the chemical reactions occurring at one site having no effect on the others. This is not always the case, however. In some instances, the binding at one site can change the chemical reactivity of another. Cooperation between reactive sites plays an important role in problems ranging from biology to molecular electronics. However, investigating cooperativity is challenging, since many experimental methods have trouble distinguishing the reactive sites. With support from the Macromolecular, Supramolecular, and Nanochemistry and the Chemical, Structure, Dynamics and Mechanisms A programs in the Division of Chemistry, Professors Ursula Mazur, Bhaskar Chilukuri, and K. W. Hipps at Washington State University are exploring cooperative effects in the binding of small molecules on nearby sites in large chemical complexes using a high resolution imaging method. The discoveries could aid in the design of new materials, as well as have broad implications for advancing technologies related to sensing, catalysis, and optoelectronics. The project's findings are incorporated into undergraduate courses at Washington State University, providing modern research examples to highlight concepts in chemistry, materials science, and engineering. The research labs involved in the project also provide training opportunities for graduate and undergraduate students, including a number of female and minority students.Working with their students, Professors Mazur, Chilukuri, and Hipps are synthesizing large, electron-rich molecules that consist of multiple fused porphyrin rings, and then depositing them on conducting substrates such as Au, graphite, and MoS2. The team then exposes the porphyrin multimers to small molecules (e.g. O2, CO, and NO) that react with the metal centers. By imaging the products with scanning tunneling microscopy (STM), they can directly observe of cooperative binding. Experimental observations are compared with molecular dynamics and density functional theory calculations to determine if communication occurs through the metal support or the intramolecular pi structure, as well as the extent to which intermolecular coupling occurs. Professors Mazur, Chilukuri, and Hipps are involved in undergraduate education and mentoring students from underrepresented groups.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.

许多大分子具有几个化学反应性位点。通常，这些地点的行为是独立的，而化学反应发生在一个地点，对其他地点没有影响。但是，情况并非总是如此。在某些情况下，一个位点的结合可以改变另一种位置的化学反应性。反应性位点之间的合作在从生物学到分子电子的问题中起着重要作用。但是，研究协作性是具有挑战性的，因为许多实验方法难以区分反应性位点。在大分子，超分子和纳米化学以及化学，结构，动力学和机制的支持下，化学部门的程序，Ursula Mazur教授，Bhaskar Chilukuri教授，Bhaskar Chilukuri和K. W. Hipps在华盛顿州立大学正在探索小型与小的结合效应。使用高分辨率成像方法，在大型化学复合物中附近位点上的分子。这些发现可以帮助设计新材料，并对与传感，催化和光电子学相关的推进技术具有广泛的影响。该项目的发现被纳入华盛顿州立大学的本科课程中，提供了现代研究示例，以突出化学，材料科学和工程学的概念。参与该项目的研究实验室还为研究生和本科生提供了培训机会，包括许多女性和少数族裔学生。融合的卟啉环，然后将它们沉积在导电基质（例如AU，石墨和MOS2）上。然后，团队将卟啉多聚体暴露于与金属中心反应的小分子（例如O2，CO和NO）。通过使用扫描隧道显微镜（STM）对产物进行成像，它们可以直接观察到合作结合。将实验观察结果与分子动力学和密度功能理论计算进行比较，以确定是否通过金属支撑或分子内PI结构进行通信以及发生分子间耦合的程度。 Mazur，Chilukuri和Hipps教授参与了本科教育，并指导了来自代表性不足的小组的学生。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优点评估来支持的，并具有更广泛的影响。

项目成果

期刊论文数量（7）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Single molecule level studies of reversible ligand binding to metal porphyrins at the solution/solid interface

DOI：
10.1142/s1088424620300049
发表时间：
2020-06
期刊：
Journal of Porphyrins and Phthalocyanines
影响因子：
1.5
作者：
U. Mazur;K. W. Hipps
通讯作者：
U. Mazur;K. W. Hipps

Role of the Supporting Surface in the Thermodynamics and Cooperativity of Axial Ligand Binding to Metalloporphyrins at Interfaces

支持表面在界面处轴向配体与金属卟啉结合的热力学和协同性中的作用

DOI：
10.2174/1385272826666220209122508
发表时间：
2022
期刊：
Current Organic Chemistry
影响因子：
2.6
作者：
Johnson, Kristen N.;Chilukurib, Bhaskar;Fisherb, Zachary E.;Hippsa, K. W.;Mazura, Ursula
通讯作者：
Mazura, Ursula

In Situ Imaging and Computational Modeling Reveal That Thiophene Complexation with Co(II)porphyrin/Graphite Is Highly Cooperative