Quantitative assessment of non-covalent interactions in aqueous medium and in hydrophobic cavities using Cucurbiturils

使用葫芦脲定量评估水介质和疏水腔中的非共价相互作用

• 批准号: 1905238
• 负责人: Eric Masson
• 金额: $ 45.5万
• 依托单位: Ohio University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1905238&HistoricalAwards=false
• 关键词: Quantitative; assessment; non; covalent; interactions

Living organisms, from single cells to human beings, thrive as a result of an extremely large number of interactions and reactions between molecules that include proteins, DNA, sugars and lipids. Drugs also interact with these chemical structures to counteract symptoms and diseases. A more precise knowledge of how different chemical structures interact (or "stick" together) has the potential to enable a better understanding of biochemical processes involved in diseases and to facilitate drug design. With the support of the NSF Macromolecular, Supramolecular and Nanochemistry (MSN) Program, the research group of Professor Eric Masson at Ohio University designs and synthesizes hollow, pumpkin-shaped molecules that can accommodate two chemical entities in its hollow center. By bringing two chemical entities together, the Masson group seeks to determine how well they interact and to quantify the strength of their interactions at the molecular level. The research project involves graduate and undergraduate students (including students from underprivileged backgrounds) and trains them in organic, analytical and computational chemistry. Among other outreach activities, Professor Masson also co-organizes a yearly science communication and policy workshop held at Ohio University and at the University of Leipzig, Germany. The workshop brings together students from chemistry, journalism and international studies at both institutions around scientific themes of societal interest. Through the workshop, students learn to communicate scientific concepts to non-scientists.For the purpose of quantifying non-covalent interactions in both aqueous medium and in hydrophobic cavities surrounded by an aqueous environment, Professor Masson's group designs supramolecular systems that are water-compatible, versatile for evaluating a wide range of non-covalent interactions; and geometrically well-defined and far less complex than natural systems, to avoid secondary perturbations. There are three specific aims in this project. In the first aim, the Cucurbituril (CB[n]) family of macrocycles is used to encapsulate highly hydrophilic guests and determine the strengths of the intramolecular hydrogen bonds formed inside the hydrophobic cavity of CB[n]. In the second aim, "2:1 stacked" ternary complexes of a variety of 4'- substituted platinum(II) terpyridyl complexes in curcubit[8]urils (CB[8]) are designed. These ternary complexes serve as self-sorting probes for quantifying Coulombic interactions between peptides as well as aryl-aryl "pi-pi" and aryl-cycloalkenyl CH-pi interactions in aqueous medium. The last aim exploits the use of the "2:1 stacked" ternary complexes as supramolecular balances for quantifying dispersive "pi-pi" and CH-pi interactions in aqueous medium. The supramolecular balance is formed by self-sorting of a platinum complex connected to a triptycene unit (the "wheel") with another platinum complex without triptycene (the "shaft") in CB[8]. The novel ternary complexes that are composed of one "shaft" and one "wheel" in CB[8] or two "wheels" in CB[8] may represent new families of supramolecular brakes and spur gears.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.

从单细胞到人类，生物体的繁衍生息是蛋白质、DNA、糖和脂质等分子之间大量相互作用和反应的结果。药物还与这些化学结构相互作用以对抗症状和疾病。更准确地了解不同化学结构如何相互作用（或“粘”在一起）有可能更好地理解疾病所涉及的生化过程并促进药物设计。在NSF高分子、超分子和纳米化学（MSN）计划的支持下，俄亥俄大学Eric Masson教授的研究小组设计并合成了空心南瓜形分子，其空心中心可容纳两种化学实体。通过将两种化学实体结合在一起，马森小组试图确定它们相互作用的程度，并在分子水平上量化它们相互作用的强度。该研究项目涉及研究生和本科生（包括来自贫困家庭的学生），并对他们进行有机、分析和计算化学方面的培训。除其他外展活动外，马森教授还在俄亥俄大学和德国莱比锡大学共同组织了年度科学传播和政策研讨会。 该研讨会汇集了两所院校化学、新闻和国际研究专业的学生，​​围绕社会感兴趣的科学主题。通过研讨会，学生们学习向非科学家传达科学概念。为了量化水介质和水环境包围的疏水腔中的非共价相互作用，Masson 教授的团队设计了与水兼容的超分子系统，用途广泛，可用于评估各种非共价相互作用；并且几何形状定义明确，并且比自然系统复杂得多，以避免二次扰动。 该项目有三个具体目标。第一个目标是使用葫芦脲 (CB[n]) 大环家族来封装高度亲水的客体，并确定 CB[n] 疏水空腔内形成的分子内氢键的强度。 第二个目标是设计各种4'-取代铂(II)三联吡啶配合物在葫芦[8]脲(CB[8])中的“2:1堆叠”三元配合物。这些三元复合物用作自分选探针，用于定量肽之间的库仑相互作用以及水介质中的芳基-芳基“pi-pi”和芳基-环烯基CH-pi相互作用。最后一个目标利用“2:1堆叠”三元配合物作为超分子天平来量化水介质中分散的“pi-pi”和CH-pi相互作用。超分子平衡是通过CB[8]中连接有三蝶烯单元的铂配合物（“轮”）与另一个不含三蝶烯的铂配合物（“轴”）的自排序而形成的。由CB[8]中的一个“轴”和一个“轮”或CB[8]中的两个“轮”组成的新型三元复合物可能代表了超分子制动器和正齿轮的新家族。该奖项反映了NSF的法定使命和通过使用基金会的智力优点和更广泛的影响审查标准进行评估，该项目被认为值得支持。

项目成果

Light- and Chemical-Doping-Induced Magnetic Behavior of Eu Molecular Systems

• DOI: 10.1021/acs.inorgchem.3c01154
• 发表时间: 2023-07-28
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Rajh，Tijana;Masson，Eric;Hla，Saw-Wai
• 通讯作者: Hla，Saw-Wai