Improved Discrimination of Mass Spectral Isomers Using the High-Dimensional Consensus Mass Spectral Similarity Algorithm

IF 1.9 3区 化学 Q3 BIOCHEMICAL RESEARCH METHODS
Deborah F. McGlynn, Nirina Rabe Andriamaharavo, Anthony J. Kearsley
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Abstract

This study employs a high-dimensional consensus mass spectral (HDCMS) similarity scoring technique to discriminate isomers collected using an electron ionization mass spectrometer. The HDCMS method was previously introduced and applied to the discrimination of mass spectra of constitutional isomers, methamphetamine and phentermine, collected with direct analysis real-time mass spectrometry (DART-MS). The method formulates the problem of discriminating mass spectra in a mathematical Hilbert space and is hence called “high dimensional.” It requires replicate mass spectra to build a Gaussian model and evaluate the inner products between these functions. The resulting measurement variability is used as a signature by which to discriminate spectra. In this work, HDCMS is tested on electron impact ionization (EI) mass spectra of 7 terpene and terpene-related (C10H16 and C10H14) isomers with experimental retention indices that differ by less than 30 and with traditional cosine similarity scores greater than 0.9, on a scale of 0 to 1, when compared with at least one other compound in the test set. Using identical instrument parameters, 15 replicate gas chromatography–electron ionization–mass spectrometry (GC-EI-MS) spectra of each isomer were collected and separated into distinct library and query sets. The HDCMS algorithm discriminated each isomer, indicating the method's potential. Because the method requires replicate measurements, observations from a simple heuristic study of the number of replicates required to discriminate these isomers is presented. The paper concludes with a discussion of compound discrimination using HDCMS and the benefits and drawbacks of applying the method to EI-MS data.

Abstract Image

利用高维共识质谱相似性算法提高质谱同分异构体的鉴别能力
本研究采用高维共识质谱(HDCMS)相似性评分技术,对使用电子电离质谱仪收集的异构体进行鉴别。HDCMS 方法之前已被引入并应用于鉴别用直接分析实时质谱法(DART-MS)收集的甲基苯丙胺和芬特明的同分异构体质谱。该方法将质谱鉴别问题置于数学希尔伯特空间中,因此被称为 "高维"。它需要复制质谱来建立高斯模型,并评估这些函数之间的内积。由此产生的测量变异性被用作识别光谱的特征。在这项工作中,HDCMS 对 7 种萜烯和萜烯相关(C10H16 和 C10H14)异构体的电子碰撞电离 (EI) 质谱进行了测试,这些异构体的实验保留指数相差小于 30,并且与测试集中至少一种其他化合物相比,其传统余弦相似度得分大于 0.9(0 至 1 分)。使用相同的仪器参数,收集了 15 份每种异构体的重复气相色谱-电离质谱(GC-EI-MS)光谱,并将其分为不同的库集和查询集。HDCMS 算法对每种异构体都进行了鉴别,显示了该方法的潜力。由于该方法需要重复测量,因此本文介绍了对区分这些异构体所需的重复测量次数进行的简单启发式研究的结果。论文最后讨论了使用 HDCMS 进行化合物鉴别以及将该方法应用于 EI-MS 数据的利弊。
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来源期刊
Journal of Mass Spectrometry
Journal of Mass Spectrometry 化学-光谱学
CiteScore
5.10
自引率
0.00%
发文量
84
审稿时长
1.5 months
期刊介绍: The Journal of Mass Spectrometry publishes papers on a broad range of topics of interest to scientists working in both fundamental and applied areas involving the study of gaseous ions. The aim of JMS is to serve the scientific community with information provided and arranged to help senior investigators to better stay abreast of new discoveries and studies in their own field, to make them aware of events and developments in associated fields, and to provide students and newcomers the basic tools with which to learn fundamental and applied aspects of mass spectrometry.
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