Development of cryogenic ion spectroscopy as a structural tool for complex ions extracted from solution and spectroscopic characterization of non-covalent interactions

开发低温离子光谱作为从溶液中提取复杂离子的结构工具以及非共价相互作用的光谱表征

• 批准号: 1213634
• 负责人: Mark Johnson
• 金额: $ 52万
• 依托单位: Yale University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-09-01 至 2015-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1213634&HistoricalAwards=false
• 关键词: Development; cryogenic; ion; spectroscopy; structural

In this award funded by the Chemical Structure, Dynamics and Mechanisms Program of the Division of Chemistry, Professor Mark A. Johnson of Yale University will continue his integration of vibrational spectroscopy with cryogenic mass spectrometry to create a new, generally applicable structural probe for chemical analysis with dramatically enhanced resolution and sensitivity. This development exploits very recent technological advances that allow increasingly complex species to be extracted from solution, frozen into well-defined structures near 10 K, mass-selected, and then characterized with vibrational, electronic and (in the case of anions) photoelectron spectroscopies. The most important aspect of these gas-phase studies is that, because species are quenched into configurations with minimal thermal fluctuations, much sharper band patterns are recovered than are observed in condensed media. Johnson's program will extend and expand the utility of cryogenic vibrational spectroscopy to elucidate the particular H-bond donor-acceptor pairs of folded structures of biopolymers as well as those at play in non-covalently bonded host-guest complexes. Special emphasis will be placed on identifying scenarios which yield highly selective docking of substrate molecules to biomimetic peptide catalysts. An important aspect of the study will be to elucidate the relationship between the conformations obtained in the gas phase and those found in solution, which will be accomplished by following the dependence of ion structure on the number of solvent molecules retained in the gas-phase cluster. Because these measurements are carried out using methods specifically built for this application, his program dedicates significant effort toward refinement of the experimental approach, including temperature control and micro-solvation of the isolated species.Johnson's program directly interfaces physical chemistry students with immediate challenges addressed by synthetic colleagues, and thus prepares a new generation of scientists with a versatile skill set, well centered in the chemical sciences. His program contributes to the strong foundation of an emerging branch of chemical analysis where complex systems are subjected to structural characterization in the ansatz of a supermolecule. The generality of the approach is ideally suited to engage young researchers and established colleagues alike, with exciting and powerful new ways to explore chemical structure.

在这个由化学系的化学结构，动力学和机制计划资助的奖项中，马克A。耶鲁大学的约翰逊将继续他的振动光谱与低温质谱的整合，以创建一个新的，普遍适用的结构探针，用于化学分析，具有显着提高的分辨率和灵敏度。 这一发展利用了最近的技术进步，允许越来越复杂的物种从溶液中提取，冷冻成10 K附近的明确定义的结构，质量选择，然后用振动，电子和（在阴离子的情况下）光电子光谱进行表征。这些气相研究的最重要的方面是，因为物种被淬火成具有最小热波动的配置，比在冷凝介质中观察到的更尖锐的带图案被恢复。约翰逊的计划将扩展和扩大低温振动光谱的实用性，以阐明生物聚合物折叠结构的特定H-键供体-受体对以及在非共价键合的主-客体复合物中发挥作用的H-键供体-受体对。 特别强调将被放置在识别方案，产生高度选择性对接的底物分子仿生肽催化剂。该研究的一个重要方面将是阐明在气相中获得的构象和那些在溶液中发现的构象之间的关系，这将通过以下的依赖性的离子结构上保留在气相簇中的溶剂分子的数量来完成。由于这些测量是使用专门为此应用构建的方法进行的，因此他的项目致力于改进实验方法，包括温度控制和分离物质的微溶剂化。约翰逊的项目直接将物理化学学生与合成同事所面临的直接挑战联系起来，从而为新一代科学家提供多功能技能，以化学科学为中心。 他的计划有助于化学分析的一个新兴分支的坚实基础，其中复杂的系统受到超分子的结构表征。这种方法的普遍性非常适合年轻的研究人员和资深的同事，他们可以用令人兴奋和强大的新方法来探索化学结构。