Hydrogen Rearrangement Rules: Computational MS/MS Fragmentation and Structure Elucidation Using MS-FINDER Software.
Hydrogen Rearrangement Rules: Computational MS/MS Fragmentation and Structure Elucidation Using MS-FINDER Software.
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DOI：
10.1021/acs.analchem.6b00770
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发表时间：
2016-08-16
影响因子：
7.4
通讯作者：
Arita M
中科院分区：
文献类型：
--
作者：
Tsugawa H;Kind T;Nakabayashi R;Yukihira D;Tanaka W;Cajka T;Saito K;Fiehn O;Arita M
从准确的质谱/质谱谱图中鉴定化合物是非靶向代谢组学的瓶颈。在这项研究中，我们提出了九个规则的氢重排（HR）在低能量碰撞诱导解离（CID）的键断裂。这些规则是基于经典的偶电子规则，并涵盖杂原子和多级碎裂。我们通过MassBank MS/MS光谱的统计数据以及焓计算来评估我们的HR规则，产生三个级别的计算MS/MS注释：“解析”（遵循HR规则的规则HR行为）、“半解析”（不规则HR行为）和“公式指定”（缺乏结构指定）。使用这种命名法，MassBank数据库中总共18506个MS/MS碎片离子中的78.4%和GNPS数据库中总共36370个MS/MS碎片离子中的84.8%通过预测的键裂解（半）解析。我们还介绍了MS-FINDER结构解析软件。根据精确的质量、同位素比和产物离子信息确定前体离子的分子式。从代谢组数据库中检索预测公式的所有异构体结构，并通过计算机模拟预测MS/MS碎片。考虑键离解能，质量精度，片段连接，最重要的是，九个HR规则的组合加权评分的结构进行排名。该程序通过其正确计算5063 MassBank MS/MS记录的分子式的能力进行了验证，准确度为98.0%，并在前3名候选者中产生正确的结构异构体，准确度为82.1%。在对来自人血浆的非靶向HILIC-QTOF MS数据集的936个手动识别的光谱进行的测试中，在90.4%的情况下正确预测了公式，并且在前3名候选者中以80.4%的概率检索到正确的异构体结构，包括质谱库中不存在的化合物。MS-FINDER软件可在http://prime.psc.riken.jp/上免费获得。
Compound identification from accurate mass MS/MS spectra is a bottleneck for untargeted metabolomics. In this study, we propose nine rules of hydrogen rearrangement (HR) during bond cleavages in low-energy collision-induced dissociation (CID). These rules are based on the classic even-electron rule and cover heteroatoms and multistage fragmentation. We evaluated our HR rules by the statistics of MassBank MS/MS spectra in addition to enthalpy calculations, yielding three levels of computational MS/MS annotation: “resolved” (regular HR behavior following HR rules), “semiresolved” (irregular HR behavior), and “formula-assigned” (lacking structure assignment). With this nomenclature, 78.4% of a total of 18506 MS/MS fragment ions in the MassBank database and 84.8% of a total of 36370 MS/MS fragment ions in the GNPS database were (semi−) resolved by predicted bond cleavages. We also introduce the MS-FINDER software for structure elucidation. Molecular formulas of precursor ions are determined from accurate mass, isotope ratio, and product ion information. All isomer structures of the predicted formula are retrieved from metabolome databases, and MS/MS fragmentations are predicted in silico. The structures are ranked by a combined weighting score considering bond dissociation energies, mass accuracies, fragment linkages, and, most importantly, nine HR rules. The program was validated by its ability to correctly calculate molecular formulas with 98.0% accuracy for 5063 MassBank MS/MS records and to yield the correct structural isomer with 82.1% accuracy within the top-3 candidates. In a test with 936 manually identified spectra from an untargeted HILIC-QTOF MS data set of human plasma, formulas were correctly predicted in 90.4% of the cases, and the correct isomer structure was retrieved at 80.4% probability within the top-3 candidates, including for compounds that were absent in mass spectral libraries. The MS-FINDER software is freely available at http://prime.psc.riken.jp/.
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HMDB：人类代谢组数据库。
影响因子：
14.9
作者：
Wishart, David S;Tzur, Dan;Knox, Craig;Eisner, Roman;Guo, An Chi;Young, Nelson;Cheng, Dean;Jewell, Kevin;Arndt, David;Sawhney, Summit;Fung, Chris;Nikolai, Lisa;Lewis, Mike;Coutouly, Marie-Aude;Forsythe, Ian;Tang, Peter;Shrivastava, Savita;Jeroncic, Kevin;Stothard, Paul;Amegbey, Godwin;Block, David;Hau, David D;Wagner, James;Miniaci, Jessica;Clements, Melisa;Gebremedhin, Mulu;Guo, Natalie;Zhang, Ying;Duggan, Gavin E;Macinnis, Glen D;Weljie, Alim M;Dowlatabadi, Reza;Bamforth, Fiona;Clive, Derrick;Greiner, Russ;Li, Liang;Marrie, Tom;Sykes, Brian D;Vogel, Hans J;Querengesser, Lori
通讯作者：
Querengesser, Lori
影响因子：
3
作者：
Wolf S;Schmidt S;Müller-Hannemann M;Neumann S
通讯作者：
Neumann S
影响因子：
7.4
作者：
Ma, Yan;Kind, Tobias;Yang, Dawei;Leon, Carlos;Fiehn, Oliver
通讯作者：
Fiehn, Oliver
DOI：
10.1255/ejms.304
发表时间：
1999-01-01
期刊：
EUROPEAN MASS SPECTROMETRY
影响因子：
--
作者：
Nakata, H
通讯作者：
Nakata, H
影响因子：
3.8
作者：
Rochfort, Simone J.;Trenerry, V. Craige;Jones, Rod
通讯作者：
Jones, Rod