RUI: Collaborative Research: Intrinsic Gas-phase Properties of Peptides: Thermochemistry, Fragmentation Mechanisms, H/D exchange and IRMPD Spectroscopy.

有了这个奖项，化学结构、动力学和机制项目将支持威廉和玛丽学院的约翰·c·普茨玛教授和老道明大学的詹妮弗·普茨玛教授的合作研究。John Poutsma教授采用基于质谱的实验来研究肽结构与其气相能量特性之间的微妙相互作用。他研究了含有非蛋白氨基酸（NPAA）的多肽，这种氨基酸天然存在于植物和真菌中，但不用于天然蛋白质合成。许多NPAAs对人类和其他动物有毒，部分原因是它们与20种常见的蛋白质氨基酸（PAA）中的一种或多种结构相似。NPAAs可以在多种生物途径中与PAAs竞争，包括错误地结合到蛋白质和肽中。研究NPAAs被系统取代的肽的行为有助于理解肽之间的关系。S结构及其在质谱仪中的表现。最终，这种增强的理解可能会导致蛋白质组学实验中自动肽测序算法的改进。Jennifer Poutsma教授进行密度泛函理论计算，以预测支持和指导实验研究的结构和能量学。这两个研究项目通过培养本科生研究人员，将研究和教育结合起来。这项研究是由威廉玛丽大学和老道明大学的本科生进行的。进行独立研究不仅可以教会这些学生发现的乐趣，还可以教会他们如何处理和克服现实世界科学中不可避免的失败。本研究采用1)扩展动力学方法，2)氢氘交换，3)红外多光子解离光谱，4)肽片段研究和5)密度泛函计算来确定肽及其片段的固有气相性质。这些研究的最终目的是建立氨基酸结构与热化学性质之间的关系，更好地了解分子内氢键对氨基酸和肽气相化学的影响，并解释选择性？低能串联质谱实验中的碎片。这些详细的知识可以整合到肽测序方法中，这样他们就可以更好地解释不寻常氨基酸的存在，以及选择性片段。该奖项反映了美国国家科学基金会的法定使命，并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，被认为值得支持。

With this award, the Chemical Structure, Dynamics and Mechanisms program is supporting the collaborative research of Professor John C. Poutsma at the College of William and Mary and Professor Jennifer Poutsma at Old Dominion University. Professor John Poutsma employs mass spectrometry-based experiments to study the subtle interplay between the structure of peptides and their gas-phase energetic properties. He studies peptides containing non-protein amino acids (NPAA), which are found naturally in plants and fungi, but are not used in natural protein synthesis. Many NPAAs are toxic to humans and other animals in part due to structural similarity to one or more of the twenty common protein amino acids (PAA). NPAAs can compete with PAAs in a variety of biological pathways including being mis-incorporated into proteins and peptides. Studying the behavior of peptides into which NPAAs have been systematically substituted helps to understand the relationship between a peptide?s structure and its behavior in the mass spectrometer. Ultimately this enhanced understanding may lead to improved automated peptide sequencing algorithms for proteomics experiments. Professor Jennifer Poutsma performs density functional theory calculations to predict structure and energetics that support and guide the experimental studies. Both research programs integrate research and educational components through the training of undergraduate researchers. This research is carried out by undergraduates at William and Mary and Old Dominion University. Performing independent research helps to teach these students not only the joy of discovery but also how to handle and work through the inevitable failures that accompany real-world science.In this research, intrinsic gas-phase properties of peptides and their fragments are determined using 1) the extended kinetic method, 2) hydrogen deuterium exchange, 3) infrared multiphoton dissociation spectroscopy, 4) peptide fragmentation studies and 5) density functional computations. The ultimate goals of these studies are to establish the relationship between amino acid structure and thermochemical properties, to better understand the effects of intramolecular hydrogen bonding on the gas-phase chemistry of amino acids and peptides, and to explain the mechanisms for ?selective? fragmentations in low-energy tandem mass spectrometry experiments. This detailed knowledge may be integrated into peptide sequencing methods so that they can better account for the presence of unusual amino acids, and for selective fragmentations.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.