Structure and Reactivity of Organic Cations in the Gas Phase and Condensed Media

该项目探索携带电荷的有机分子的三维结构与其化学反应活性之间的关系。该计划的一个关键目标是比较离子在气相和凝聚相中的行为。尽管有许多相似之处，但离子在气相中的行为与它们在凝聚相中的行为之间的关系的图景仍然不完整。有些离子不能在溶液中生成，只能在气相中探索，但另一些离子可以在各种条件下生成。比较发现了溶剂的影响和与相反电荷配对的影响。拟议活动产生的更广泛的影响本科教学在传播新成果方面发挥了重要作用。PI投入了大量的精力来教授小部分(超出了他分配的教学负担)，以交流研究的见解。这些课程由加州大学河滨分校的荣誉项目提供，向学生介绍基于构象分析和小分子离子化学的假设检验。从2006年秋季到2008年底，国际学生联合会开设了一门课程，指导大约120名大二和大三学生(其中25%是代表不足的少数族裔，包括8名奇卡纳人，9名其他拉丁裔，11名太平洋岛民，3名非裔美国人)如何在计算机上独立进行分子建模，以期将计算预测与实验数据进行比较。关于研究出版物，开发分析细菌如何氧化烷烃的质谱学方法与全球石油开采和运输的环境问题密切相关。在多肽质谱学方面，开发检测和定量氨基酸和多肽立体异构体的MS/MS方法将使人们有可能更常规地评估通过氨基酸差向异构化而进行的翻译后修饰在生物系统中的普遍程度。在研究实验室中，一个主要目标是教育博士生将有机化学与仪器方法相结合。

This project probes the relationship between the 3-dimensional structure of organic molecules that carry an electric charge and their chemical reactivity. A key objective of this program is to compare the behavior of ions in the gas phase with those in condensed phases. The picture of how ions behave in the gas phase in relation to their behavior in condensed phases remains incomplete, although there are many parallels. Some ions cannot be made in solution and can be explored only in the gas phase, but others can be made under a variety of conditions. Comparison reveals the effects of solvent and of pairing with opposite charges. Broader impacts resulting from the proposed activity Undergraduate instruction plays an important role in disseminating new results. The PI has invested much effort in teaching small sections (beyond his assigned teaching load) to communicate insights from research. Offered through the UC Riverside's Honors' Program, these sections introduce students to hypothesis testing based on conformational analysis and ion chemistry of small molecules. The PI has developed a course in which, from fall 2006 through the end of 2008, approximately 120 sophomores and juniors (of whom 25% are under-represented minorities, including 8 Chicana/o, 9 other Latina/o, 11 Pacific Islander, 3 African American) have been instructed how to perform molecular modeling on a computer independently, with a view towards comparing computed predictions with experimental data. In regard to research publication, development of mass spectrometric methodology for analyzing how bacteria oxidize alkanes is germane to environmental issues regarding worldwide extraction and transportation of petroleum. With respect to peptide mass spectrometry, development of MS/MS methodology for detecting and quantitating amino acid and peptide stereoisomers will make it possible to assess more routinely how widespread post-translational modification via amino acid epimerization may turn out to be in biological systems. In the research laboratories, a major objective is the education of Ph.D. students to combine organic chemistry with instrumental methods.