RUI: Resonance and Inductive Effects in Fundamental Chemical Systems

在这个由化学部化学结构，动力学和机制计划资助的项目中，埃隆大学的Joel Karty教授将确定共振和诱导效应对各种基本有机反应背后的驱动力的能量贡献。该项目将结合实验和计算方法。 在实验方法中，将确定涉及感兴趣物种同系物的各种反应的反应动力学和热力学。 然后将结果外推，以得出涉及感兴趣物种的值。 一种计算方法，称为乙烯基外推法，采用了类似的策略，通过利用标准分子轨道理论计算，以确定共振和诱导的贡献，对涉及同系物的感兴趣的物种的反应。第二种计算方法是块局域波函数方法，最简单的变化价键理论，它允许直接计算共振能。 更广泛的影响主要围绕在化学研究的教学和培训本科生，并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些知识。此外，这些结果有可能接触到更广泛的受众，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诱导效应在整个化学中所起作用的普遍理解。 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起始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.