Department of Environmental Chemistry, IDAEA-CSIC, Jordi Girona 18-26, Barcelona 08034, Spain.
Anal Chem. 2023 May 16;95(19):7519-7527. doi: 10.1021/acs.analchem.2c05704. Epub 2023 May 5.
New data-independent acquisition (DIA) modes coupled to chromatographic separations are opening new perspectives in the processing of massive mass spectrometric (MS) data using chemometric methods. In this work, the application of the regions of interest multivariate curve resolution (ROIMCR) method is shown for the simultaneous analysis of MS1 and MS2 DIA raw data obtained by liquid chromatography coupled to quadrupole-time-of-flight MS analysis. The ROIMCR method proposed in this work relies on the intrinsic bilinear structure of the MS1 and MS2 experimental data which allows us for the fast direct resolution of the elution and spectral profiles of all sample constituents giving measurable MS signals, without needing any further data pretreatment such as peak matching, alignment, or modeling. Compound annotation and identification can be achieved directly by the comparison of the ROIMCR-resolved MS1 and MS2 spectra with those from standards or from mass spectral libraries. ROIMCR elution profiles of the resolved components can be used to build calibration curves for the prediction of their concentrations in complex unknown samples. The application of the proposed procedure is shown for the analysis of mixtures of per- and polyfluoroalkyl substances in standard mixtures, spiked hen eggs, and gull egg samples, where these compounds tend to accumulate.
新的数据非依赖性采集（DIA）模式与色谱分离相结合，为使用化学计量学方法处理大量质谱（MS）数据开辟了新的前景。在这项工作中，应用了感兴趣区域多元曲线分辨（ROIMCR）方法，同时分析了通过液相色谱与四极杆飞行时间 MS 分析获得的 MS1 和 MS2 DIA 原始数据。这项工作中提出的 ROIMCR 方法依赖于 MS1 和 MS2 实验数据的固有双线性结构，这使得我们能够快速直接解析所有具有可测量 MS 信号的样品成分的洗脱和光谱轮廓，而无需进行任何进一步的数据预处理，如峰匹配、对齐或建模。通过将 ROIMCR 解析的 MS1 和 MS2 光谱与标准品或质谱库中的光谱进行比较，可以直接进行化合物注释和鉴定。解析成分的 ROIMCR 洗脱曲线可用于构建校准曲线，以预测其在复杂未知样品中的浓度。所提出的方法应用于标准混合物、加标鸡蛋和海鸥蛋样品中全氟和多氟烷基物质混合物的分析，这些化合物往往会在这些样品中积累。
