RUI: Simulations of MS2 spectra: An examination of post-translational modification, secondary structure, and non-covalent complexes

有了这个奖项，化学结构，动力学和机制（CSDM-A）和化学测量和成像（CMI）的化学部支持教授乔治L。锡耶纳学院的巴恩斯研究肽分子在气相中高能碰撞后是如何分解或粘附在表面上的。这种碰撞发生在使用称为质谱仪的仪器分析分子时，质谱仪根据分子的质量和电荷识别分子及其碎片。质谱分析的准确性取决于对碰撞的理解程度。该项目研究了分子形状和常见的生物学修饰对碰撞和碰撞产生的分子产物的重要性。蛋白质在活细胞中由称为核糖体的分子机器合成，核糖体将储存在信使核糖核酸（mRNA）中的信息翻译成蛋白质。翻译后的蛋白质修饰被称为“翻译后”修饰（PTM）。巴恩斯教授对PTM如何影响气相碰撞的结果特别感兴趣。该项目积极参与本科生研究人员谁是交叉培训的理论和实验方法，并有机会在全国会议和其他科学会议上介绍他们的结果。一个相结合的计算和实验的方法，重点放在模型系统相关的串联质谱（MS 2）。特别是，一系列的质子化肽和它们的后修饰的版本被选择来研究二级结构对软着陆和碰撞诱导解离的影响。该研究阐明了非共价相互作用和复合物形成的肽片段的重要性。方法包括直接动力学模拟，从头计算，速率计算和实验串联质谱。 除了获得有关分子碰撞和反应的基本见解外，该项目还对生物分子质谱实验的优化和所得数据的解释具有直接影响。 反过来，这项研究可能对更广泛的生物和健康相关科学产生重要影响。 与普渡大学Julia Laskin教授的合作为巴恩斯教授的锡耶纳学院学生研究人员提供了大型研究型大学背景下的宝贵经验。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智力价值和更广泛的影响审查标准进行评估来支持。

With this award, the Chemical Structure, Dynamics, and Mechanisms (CSDM-A) and Chemical Measurement and Imaging (CMI) Programs of the Division of Chemistry support Professor George L. Barnes at Siena College to study how peptide molecules fall apart or stick to surfaces following high-energy collisions in the gas phase. Such collisions occur when molecules are being analyzed using instruments called mass spectrometers, which identify molecules and their fragments according to their mass and electric charge. The accuracy of the mass spectral analysis depends on how well the collisions are understood. This project examines the importance of the molecular shape and of common biological modifications on the collisions and the molecular products generated by the collisions. Proteins are synthesized in living cells by molecular machines called ribosomes, which translate the information stored in messenger ribonucleic acid (mRNA) into proteins. Modifications of the proteins after translation are called "post-translational" modifications (PTMs). Prof. Barnes is especially interested in how the PTMs affect the outcomes of gas phase collisions. This project actively involves undergraduate student researchers who are cross-trained in both theoretical and experimental methods and have the opportunity to present their results at national conferences and other scientific meetings. A combined computational and experimental approach is taken that focuses on model systems relevant to tandem mass spectrometry (MS2). In particular, a range of protonated peptides and their post-translationally modified versions are selected to investigate the impact of secondary structure on soft landing and collision-induced dissociation. The study elucidates the importance of non-covalent interactions and complex formation of peptide fragments. Methods include direct dynamics simulations, ab initio calculations, rate calculations, and experimental tandem mass spectrometry. In addition to the fundamental insights gained regarding molecular collisions and reactions, the project has direct implications for the optimization of mass spectrometric experiments on biomolecules and the interpretation of the resulting data. In turn, the research may have important implications for a wider range of biological and health-related sciences. Collaboration with Prof. Julia Laskin at Purdue University is providing valuable experience in the large research university context for Prof. Barnes' Siena College student researchers.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.