Molecular Recognition in the Gas Phase: Rates, Structures, and Energetics Without Solvents or Counterions

有机动力学计划的这笔赠款支持以下工作： 德州大学阿灵顿分校的迪尔登教授。的 研究将探讨内在的分子识别 冠醚和相关配体的性质 在气相中使用离子回旋共振的分子离子， 串联质谱技术。具体领域涉及 (a)表现出以下特征的化学系统的识别 识别效果，（B）测量主客体亲和力， （c）研究气相反应的速率和机理 识别反应。将研究的分专题是：（a） 改变腔体尺寸以及腔体的数量和类型的影响 配体供体原子，（B）天然存在的配体供体原子的固有反应性， 离子载体，和（c）离子-分子反应中的手性识别。 %%% 大卫D. Dearden的气相研究 冠醚和金属/分子离子之间的相互作用将 补充现有的关于溶液中分子识别的数据， 从而能够区分内在的和 溶剂效应该研究还涉及手性识别和 包括天然存在的生物活性离子载体 （促进离子通过膜的分子）。的 这项研究的结果将有助于识别和 选择性反应的笼型试剂的表征 大小和形状的基础。

This grant from the Organic Dynamics Program supports the work of Professor Dearden at the University of Texas at Arlington. The study will investigate the intrinsic molecular recognition properties of crown ethers and related ligands for metal and molecular ions in the gas phase using ion cyclotron resonance and tandem mass spectrometric techniques. The specific areas concern (a) the identification of chemical systems which exhibit recognition effects, (b) the measurement of host-guest affinities, and (c) the investigation of the rates and mechanisms of gas phase recognition reactions. Subtopics that will be studied are (a) the effects of varying the cavity size and the number and types of ligand donor atoms, (b) intrinsic reactivity of naturally occurring ionophores, and (c) chiral recognition in ion-molecule reactions. %%% The results from Professor David D. Dearden's gas phase study on the interaction between crown ethers and metal/molecular ions will complement data available on molecular recognition in solution and will thereby enable the differentiation between intrinsic and solvent effects. The study also addresses chiral recognition and includes naturally-occurring, biologically-active ionophores (molecules facilitating ion transport through membranes). The outcome of this research will enable an identification and characterization of cage-type reagents which react selectively on the basis of size and shape.