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

• 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

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.

许多大分子有几个化学反应位点。通常这些位点的行为是独立的，在一个位点发生的化学反应对其他位点没有影响。然而，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个位点的化学反应性。反应位点之间的合作在从生物学到分子电子学的各种问题中起着重要作用。然而，研究协同性是具有挑战性的，因为许多实验方法难以区分反应位点。在化学系大分子、超分子和纳米化学以及化学、结构、动力学和机制A项目的支持下，华盛顿州立大学的Ursula Mazur、Bhaskar Chilukuri和K. W. Hipps教授正在利用高分辨率成像方法探索小分子在大型化学复合物附近位点结合的合作效应。这些发现有助于新材料的设计，并对传感、催化和光电子学等相关技术的进步具有广泛的影响。该项目的研究成果被纳入华盛顿州立大学的本科课程，提供了现代研究实例，以突出化学、材料科学和工程方面的概念。参与该项目的研究实验室还为研究生和本科生，包括一些女性和少数民族学生提供培训机会。Mazur、Chilukuri和Hipps教授与他们的学生一起合成了由多个熔融卟啉环组成的大型富电子分子，然后将它们沉积在导电基板上，如Au、石墨和MoS2。然后，研究小组将卟啉多聚体暴露于与金属中心反应的小分子（如O2、CO和NO）中。通过扫描隧道显微镜（STM）对产物进行成像，可以直接观察到协同结合。实验观察与分子动力学和密度泛函理论计算相比较，以确定通信是通过金属载体还是分子内pi结构发生的，以及分子间耦合发生的程度。Mazur、Chilukuri和Hipps教授参与了本科教育，并指导来自弱势群体的学生。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。

项目成果

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

Cooperative Binding of 1-Phenylimidazole to Cobalt(II) Octaethylporphyrin on Graphite: A Quantitative Imaging and Computational Study at Molecular Resolution

• DOI: 10.1021/acs.jpcc.0c05516
• 发表时间: 2020-08-27
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY C
• 影响因子: 3.7
• 作者: Korpany, Katalin, V;Chilukuri, Bhaskar;Mazur, Ursula
• 通讯作者: Mazur, Ursula

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

• DOI: 10.1021/acs.jpcc.2c06212
• 发表时间: 2022-11
• 期刊: The Journal of Physical Chemistry C
• 作者: K. N. Johnson;Shammi Rana;Bhaskar Chilukuri;K. W. Hipps;U. Mazur

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