Modeling the Effects of O -Sulfonation on the CID of Serine
Modeling the Effects of O -Sulfonation on the CID of Serine
复制标题
模拟 O-磺化对丝氨酸 CID 的影响
DOI：
10.1021/jasms.0c00037
复制
发表时间：
2020
影响因子：
3.2
通讯作者：
Barnes, George L.
中科院分区：
文献类型：
--
作者：
Lucas, Kenneth;Barnes, George L.
我们提出了直接动力学模拟和DFT计算的结果，旨在阐明o -磺化对丝氨酸碰撞诱导解离的影响。为此，在多个碰撞能量下对丝氨酸和硫丝氨酸进行了直接动力学模拟，并获得了理论质谱。与实验结果的比较对两种系统都有利。确定了与亚砜基团有关的峰，并探讨了反应动力学。特别地，我们分析了理论质谱中与亚砜基团直接相关的三个显著峰（m/z106、88和81）以及两个体系共有的主要峰。我们的分析表明，它们/z106峰是由分子内重排、初始断裂产物组成的配合物之间的分子间质子转移和高能侧链断裂引起的。他们/z88峰被发现含有多个构象异构体，包括一个以前没有考虑过的低能结构。还观察到RM1半经验方法不能获得硫丝氨酸实验中看到的所有主要峰。相比之下，PM6确实获得了所有主要的实验峰。
We present the results of direct dynamics simulations and DFT calculations aimed at elucidating the effect ofO-sulfonation on the collision-induced dissociation for serine. Toward this end, direct dynamics simulations of both serine and sulfoserine were performed at multiple collision energies and theoretical mass spectra obtained. Comparisons to experimental results are favorable for both systems. Peaks related to the sulfo group are identified and the reaction dynamics explored. In particular, three significant peaks (m/z106, 88, and 81) seen in the theoretical mass spectrum directly related to the sulfo group are analyzed as well as major peaks shared by both systems. Our analysis shows that them/z106 peaks result from intramolecular rearrangements, intermolecular proton transfer among complexes composed of initial fragmentation products, and at high energy side-chain fragmentation. Them/z88 peak was found to contain multiple constitutional isomers, including a previously unconsidered, low energy structure. It was also observed that the RM1 semiempirical method was not able to obtain all of the major peaks seen in experimens for sulfoserine. In contrast, PM6 did obtain all major experimental peaks.