Zarghani Maryam, Parastar Hadi
Department of Chemistry, Sharif University of Technology, P.O. Box 11155-3516, Tehran, Iran.
Department of Chemistry, Sharif University of Technology, P.O. Box 11155-3516, Tehran, Iran.
J Chromatogr A. 2017 Nov 17;1524:188-201. doi: 10.1016/j.chroma.2017.09.060. Epub 2017 Sep 27.
The objective of the present work is development of joint approximate diagonalization of eigenmatrices (JADE) as a member of independent component analysis (ICA) family, for the analysis of gas chromatography-mass spectrometry (GC-MS) and comprehensive two-dimensional gas chromatography-mass spectrometry (GC×GC-MS) data to address incomplete separation problem occurred during the analysis of complex sample matrices. In this regard, simulated GC-MS and GC×GC-MS data sets with different number of components, different degree of overlap and noise were evaluated. In the case of simultaneous analysis of multiple samples, column-wise augmentation for GC-MS and column-wise super-augmentation for GC×GC-MS was used before JADE analysis. The performance of JADE was evaluated in terms of statistical parameters of lack of fit (LOF), mutual information (MI) and Amari index as well as analytical figures of merit (AFOMs) obtained from calibration curves. In addition, the area of feasible solutions (AFSs) was calculated by two different approaches of MCR-BANDs and polygon inflation algorithm (FACPACK). Furthermore, JADE performance was compared with multivariate curve resolution-alternating least squares (MCR-ALS) and other ICA algorithms of mean-field ICA (MFICA) and mutual information least dependent component analysis (MILCA). In all cases, JADE could successfully resolve the elution and spectral profiles in GC-MS and GC×GC-MS data with acceptable statistical and calibration parameters and their solutions were in AFSs. To check the applicability of JADE in real cases, JADE was used for resolution and quantification of phenanthrene and anthracene in aromatic fraction of heavy fuel oil (HFO) analyzed by GC×GC-MS. Surprisingly, pure elution and spectral profiles of target compounds were properly resolved in the presence of baseline and interferences using JADE. Once more, the performance of JADE was compared with MCR-ALS in real case. On this matter, the mutual information (MI) values were 1.01 and 1.13 for resolved profiles by JADE and MCR-ALS, respectively. In addition, LOD values (μg/mL) were respectively 1.36 and 1.24 for phenanthrene and 1.26 and 1.09 for anthracene using MCR-ALS and JADE which showed outperformance of JADE over MCR-ALS.
本工作的目标是开发本征矩阵联合近似对角化方法（JADE），作为独立成分分析（ICA）家族的一员，用于分析气相色谱 - 质谱联用（GC - MS）和全二维气相色谱 - 质谱联用（GC×GC - MS）数据，以解决复杂样品基质分析过程中出现的不完全分离问题。在此方面，对具有不同组分数、不同重叠程度和噪声的模拟GC - MS和GC×GC - MS数据集进行了评估。在同时分析多个样品的情况下，在JADE分析之前，对GC - MS采用列向增强，对GC×GC - MS采用列向超增强。根据失拟统计参数（LOF）、互信息（MI）和阿马里指数以及从校准曲线获得的分析优度指标（AFOMs）对JADE的性能进行了评估。此外，通过MCR - BANDs和多边形膨胀算法（FACPACK）这两种不同方法计算了可行解区域（AFS）。此外，将JADE的性能与多元曲线分辨交替最小二乘法（MCR - ALS）以及平均场ICA（MFICA）和互信息最小相关成分分析（MILCA）等其他ICA算法进行了比较。在所有情况下，JADE都能成功解析GC - MS和GC×GC - MS数据中的洗脱和光谱图，具有可接受的统计和校准参数，且其解位于可行解区域内。为检验JADE在实际案例中的适用性，将JADE用于通过GC×GC - MS分析的重质燃料油（HFO）芳烃馏分中菲和蒽的解析和定量。令人惊讶的是，使用JADE在存在基线和干扰的情况下能够正确解析目标化合物的纯洗脱和光谱图。再次，在实际案例中将JADE的性能与MCR - ALS进行了比较。在此方面，JADE和MCR - ALS解析谱图的互信息（MI）值分别为1.01和1.13。此外，使用MCR - ALS和JADE时，菲的检测限（μg/mL）分别为1.36和1.24，蒽的检测限分别为1.26和1.09，这表明JADE优于MCR - ALS。
