RUI: Resonance and Inductive Effects in Fundamental Chemical Systems

RUI：基础化学系统中的共振和感应效应

• 批准号: 1058833
• 负责人: Joel Karty
• 金额: $ 18.11万
• 依托单位: Elon University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-06-01 至 2015-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1058833&HistoricalAwards=false
• 关键词: RUI; Resonance; Inductive; Effects; Fundamental

In this project funded by the Chemical Structure, Dynamics and Mechanisms Program of the Chemistry division, Professor Joel Karty of Elon University will determine the energetic contributions by resonance and inductive effects toward the driving force behind a variety of fundamental organic reactions. The project will incorporate both experimental and computational methodologies. In the experimental methodology, reaction kinetics and thermodynamics will be determined for a variety of reactions involving homologs of the species of interest. The results will then be extrapolated to arrive at the values involving the species of interest. One computational methodology, called a vinylogue extrapolation methodology, incorporates a similar strategy, by utilizing standard molecular orbital theory calculations to determine resonance and inductive contributions toward reactions involving homologs of the species of interest. The second computational methodology is a block-localized wavefunction methodology, the simplest variation of valence bond theory, which allows for the calculations of resonance energies directly. The broader impacts largely surround teaching and training undergraduates in chemistry research, and in the dissemination of that knowledge via publication in major journals, and presentations at professional meetings. Furthermore, the results have the potential to reach broader audiences, such as through their inclusion in undergraduate textbooks, and the development of undergraduate teaching labs.This work will advance the general understanding of the roles that resonance and inductive effects play throughout chemistry. Moreover, the specific results of this project could have far-reaching impacts on rational drug design, and on the understanding of the role that the amino acid arginine has in the initiation and proliferation of certain types of cancer.

在这个由化学系化学结构、动力学和机理计划资助的项目中，伊隆大学的乔尔·卡尔蒂教授将通过共振和诱导效应确定各种基本有机反应背后的驱动力的能量贡献。该项目将包括实验方法和计算方法。在实验方法中，将确定涉及感兴趣物种的同系物的各种反应的反应动力学和热力学。然后，结果将被外推，以得出涉及感兴趣物种的值。一种被称为Venylogue外推方法的计算方法采用了类似的策略，通过使用标准分子轨道理论计算来确定涉及感兴趣物种的同系物的反应的共振和诱导贡献。第二种计算方法是块局域波函数方法，这是价键理论最简单的变体，它允许直接计算共振能量。更广泛的影响主要围绕着化学研究方面的本科生的教学和培训，以及通过在主要期刊上发表文章和在专业会议上发表演讲来传播这一知识。此外，这些结果有可能影响到更广泛的受众，例如通过将它们纳入本科教科书，以及本科教学实验室的发展。这项工作将促进对共振和诱导效应在整个化学中所起作用的总体理解。此外，该项目的具体结果可能会对合理的药物设计以及对氨基酸精氨酸在某些类型癌症的启动和增殖中所起作用的理解产生深远的影响。