RUI: Resonance and Inductive Effects in Fundamental Chemical Systems

在这个由化学部门化学结构、动力学和机制项目资助的项目中，伊隆大学的Joel Karty教授将确定共振和感应效应对各种基本有机反应背后驱动力的能量贡献。该项目将结合实验和计算方法。在实验方法中，反应动力学和热力学将被确定为涉及感兴趣的同种同系物的各种反应。然后将结果外推，以得到涉及感兴趣物种的值。一种计算方法，称为乙烯链外推法，采用了类似的策略，通过利用标准分子轨道理论计算来确定涉及感兴趣的同种同系物的反应的共振和归纳贡献。第二种计算方法是块定域波函数方法，这是价键理论的最简单变化，它允许直接计算共振能量。更广泛的影响主要围绕化学研究的教学和培训本科生，以及通过在主要期刊上发表论文和在专业会议上发表报告来传播这些知识。此外，研究结果有可能触及更广泛的受众，例如通过将其纳入本科教科书，以及开发本科教学实验室。这项工作将促进对共振和感应效应在整个化学过程中所起作用的一般理解。此外，该项目的具体结果可能对合理的药物设计，以及对氨基酸精氨酸在某些类型癌症的发生和增殖中的作用的理解产生深远的影响。

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.