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Structurally Specific Isotopic Shifts Across Analytical Separations

分析分离过程中结构特异性同位素的变化

基本信息

批准号：
2105182
负责人：
Alexandre Shvartsburg
金额：
$ 47.49万
依托单位：
Wichita State University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2021
资助国家：
美国
起止时间：
2021-07-15 至 2025-06-30
项目状态：
未结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2105182&HistoricalAwards=false
关键词：
Structurally Specific Isotopic Shifts Across

项目摘要

With support from the Chemical Measurement and Imaging (CMI) Program in the Division of Chemistry and partial co-funding from the Division of Biological Infrastructure (DBI), Alexandre Shvartsburg at Wichita State University is developing fundamentally new analytical approaches to molecular structure characterization based on separations of natural isotopologues - species with different isotopes (elemental forms) for one or more atoms. The Shvartsburg group combines sophisticated analytical methods including mass spectrometry (MS), ion mobility spectrometry (IMS), and advanced chromatography to assess the impact of isotope substitution on the separations of isotopologues in various media to determine their molecular geometries. The resulting new methods are expected to enable identification of a wide range of molecules, such as metabolites in biological samples, environmental contaminants, and explosives and chemical agents relevant to topical forensic and security applications. This research project will provide hands-on training for next-generation scientists, as well as broad educational opportunities for undergraduate and graduate students at WSU and regional universities through courses and stand-alone lectures on IMS and MS methods and applications.This research relies on the dependence of the transport of ions or molecules on their isotopic composition in a structurally specific manner. Measured shifts of separation parameters between natural isotopologues can reflect analyte geometry, enabling identification of isomers and disentangling their mixtures. Isotopic envelopes have long been used in MS, but not in analytical separations limited resolution. For this reason, observed shifts in liquid chromatography (LC) elution times as a function of isotopic substitution have generally been treated mass effects without structural significance. Recently, the major gains in resolving power of IMS have enabled detection of isotopic shifts in both linear IMS--based on absolute mobility--and differential IMS--capturing the mobility increment in strong electric fields. MS selection after separation combined with replicate statistics will allow the Shvartsburg team to exploit the small shifts between non-isomeric isotopologues. Dr. Shvartsburg and his group are exploring this capability and extending it with instrumental upgrades utilizing ultrahigh-resolution Orbitrap MS to disentangle nominal isobars to extract information about exact isotopologues. This project will expand this methodology to the study of a range of organic compound classes, morphologies, and elemental compositions, including anabolic steroids and fatty acids with transposed double bonds. If successful in these endeavors, the Shvartsburg team's ability to extract structural information from the splitting of isotopic envelopes is expected to find broad application in separation science.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学部化学测量和成像（CMI）计划的支持下，以及生物基础设施部（DBI）的部分共同资助下，威奇托州立大学的Alexandre Shvartsburg正在开发基于分离天然同位素体（一个或多个原子具有不同同位素（元素形式）的物种）的分子结构表征的全新分析方法。Shvartsburg小组结合了复杂的分析方法，包括质谱法（MS），离子迁移谱法（IMS）和先进的色谱法，以评估同位素取代对各种介质中同位素体分离的影响，以确定其分子几何形状。由此产生的新方法预计将能够识别广泛的分子，如生物样品中的代谢物，环境污染物以及与局部法医和安全应用相关的爆炸物和化学制剂。该研究项目将为下一代科学家提供实践培训，并通过IMS和MS方法和应用的课程和独立讲座为WSU和区域大学的本科生和研究生提供广泛的教育机会。天然同位素体之间分离参数的测量位移可以反映分析物的几何形状，从而能够识别异构体并解开它们的混合物。同位素包络线长期以来一直用于MS，但不用于有限分辨率的分析分离。由于这个原因，观察到的变化，液相色谱（LC）洗脱时间作为同位素取代的函数，一般被处理的质量效应没有结构意义。最近，IMS的分辨能力的主要增益使得能够在线性IMS（基于绝对迁移率）和差分IMS（捕获强电场中的迁移率增量）中检测同位素位移。分离后的MS选择与重复统计相结合，将使Shvartsburg团队能够利用非异构体同位素之间的微小变化。Shvartsburg博士和他的团队正在探索这种能力，并利用超高分辨率的Orbitrap MS进行仪器升级，以解开标称同量异位素，从而提取有关精确同位素的信息。该项目将把这种方法扩展到一系列有机化合物类别、形态和元素组成的研究，包括合成代谢类固醇和具有转置双键的脂肪酸。如果在这些努力中取得成功，那么Shvartsburg团队从同位素包层的分裂中提取结构信息的能力有望在分离科学中得到广泛的应用。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的知识价值和更广泛的影响审查标准进行评估来支持。