Evaluation of the QCxMS2 Method for the Calculation of Collision-Induced Dissociation Spectra via Automated Reaction Network Exploration

IF 2.7 2区 化学 Q2 BIOCHEMICAL RESEARCH METHODS
Johannes Gorges, , , Marianne Engeser*, , and , Stefan Grimme*, 
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Abstract

Collision-induced dissociation mass spectrometry (CID-MS) is an important tool in analytical chemistry for the structural elucidation of unknown compounds. The theoretical prediction of the CID spectra plays a critical role in supporting and accelerating this process. To this end, we adapt the recently developed QCxMS2 program originally designed for the calculation of electron ionization (EI) spectra to enable the computation of CID-MS. To account for the fragmentation conditions characteristic of CID within the automated reaction network discovery approach of QCxMS2 we adapted the internal energy distribution to match the experimental conditions. This distribution can be adjusted via a single parameter to approximate various activation settings, thereby eliminating the need for explicit simulations of the collisional process. We evaluate our approach on a test set of 13 organic molecules with diverse functional groups, compiled specifically for this study. All reference spectra were recorded consistently under the same measurement conditions, including both CID and higher-energy collisional dissociation (HCD) modes. Overall, QCxMS2 achieves a good average entropy similarity score (ESS) of 0.687 for the HCD spectra and 0.773 for the CID spectra. The direct comparison to experimental data demonstrates that the QCxMS2 approach, even without explicit modeling of collisions, is generally capable of computing both CID and HCD spectra with reasonable accuracy and robustness. This highlights its potential as a valuable tool for integration into structure elucidation workflows in analytical mass spectrometry.

Abstract Image

QCxMS2方法在自动反应网络探索中计算碰撞诱导解离谱的评价
碰撞诱导解离质谱法(CID-MS)是分析化学中未知化合物结构解析的重要工具。CID光谱的理论预测在支持和加速这一过程中起着至关重要的作用。为此,我们采用了最近开发的QCxMS2程序,该程序最初是为计算电子电离(EI)谱而设计的,用于计算CID-MS。考虑到QCxMS2自动反应网络发现方法中CID的破碎条件特点,我们调整了内能分布以匹配实验条件。这种分布可以通过一个参数来调整,以近似各种激活设置,从而消除了对碰撞过程的显式模拟的需要。我们在13个具有不同官能团的有机分子的测试集上评估了我们的方法,这些测试集专门为本研究编写。所有参考光谱在相同的测量条件下记录一致,包括CID和高能碰撞解离(HCD)模式。总体而言,QCxMS2的HCD光谱和CID光谱的平均熵相似度得分(ESS)分别为0.687和0.773。与实验数据的直接比较表明,即使没有明确的碰撞建模,QCxMS2方法也能以合理的精度和鲁棒性计算CID和HCD光谱。这突出了它作为一种有价值的工具集成到分析质谱的结构阐明工作流程的潜力。
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来源期刊
CiteScore
5.50
自引率
9.40%
发文量
257
审稿时长
1 months
期刊介绍: The Journal of the American Society for Mass Spectrometry presents research papers covering all aspects of mass spectrometry, incorporating coverage of fields of scientific inquiry in which mass spectrometry can play a role. Comprehensive in scope, the journal publishes papers on both fundamentals and applications of mass spectrometry. Fundamental subjects include instrumentation principles, design, and demonstration, structures and chemical properties of gas-phase ions, studies of thermodynamic properties, ion spectroscopy, chemical kinetics, mechanisms of ionization, theories of ion fragmentation, cluster ions, and potential energy surfaces. In addition to full papers, the journal offers Communications, Application Notes, and Accounts and Perspectives
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