Hydrogen Bonds, Conformations, Reactivity, and Solvation

由于这是一个基于性能的建议，Perrin实验室的建议研究涵盖了广泛的主题，包括氢键（h键）的对称性，构象分析，异构效应，离子溶剂化的空间位阻，同位素对酸度的影响，核磁共振偶联常数，以及对苯和丙二酸酐的化学反应性。技术包括多核核磁共振，核磁共振滴定法，量热法和计算。这些项目的一个常见主题是溶剂化，它(1)通过打破局部环境的对称性影响氢键，(2)对空间阻碍离子基团变得不那么有效，(3)通过氢键与孤对成键影响IEs，(4)降低亲核试剂对对苯的反应性。具体项目的例子包括：研究某些有机小分子中正确定位的电子对对阴离子稳定化产生的反常效应；核磁共振滴定法研究氘离子对酸度及其构象依赖性；计算醚、胺、硫醚及其衍生物中核磁共振偶联常数的构象依赖性。这些研究对推进发现的更广泛的影响仍然是相当长远的，因为这些研究的目标不是实际应用，而是发展对一些基础化学的透彻理解，以指导物理有机化学的进一步研究。这些研究对教育的广泛影响是深远的。学生学会提问和回答问题，解决问题，批判性思考。近年来，他们中的许多人受到启发进入学术界。此外，Perrin教授还被选为2006年戈登同位素会议的主席，在那里他特别努力鼓励研究生和博士后研究人员的参与，并为他们提供资金支持。

Since this is a performance based proposal, the proposed research of the Perrin Laboratory perforce covers a wide range of topics, including symmetry of hydrogen bonds (H-bonds), conformational analysis, anomeric effects, steric hindrance to ionic solvation, isotope effects (IEs) on acidity, NMR coupling constants, and the chemical reactivity of para-benzynes and malonic anhydrides. Techniques include multinuclear NMR, NMR titration, calorimetry, and computation. A frequent theme of these projects is solvation, which (1) affects H-bonds by breaking the symmetry of the local environment, (2) becomes less effective for sterically hindered ionic groups, (3) affects IEs by H-bonding to lone pairs, and (4) reduces the reactivity of nucleophiles toward para-benzynes. Examples of specific projects include the study of anomeric effects on stabilizations of anions that arise from properly positioned electron pairs in certain small organic molecules, NMR titration studies on deuterium IEs on acidity and their conformational dependence, and calculations of the conformational dependence of NMR coupling constants in ethers, amines, thioethers and their derivatives.The broader impact of these studies for advancing discovery remains quite long-range, since the studies are not aimed at practical application but at developing a thorough understanding of some fundamental chemistry, to guide further research in physical organic chemistry. The broader educational impact of these studies is far-reaching. Students learn to ask and answer questions, to solve problems, and to think critically. In recent years many of them have been inspired to enter academia. In addition, Prof. Perrin was elected chair of the 2006 Gordon Conference on Isotopes, where he made special efforts to encourage participation by graduate students and postdoctoral researchers, and provided financial support to them.