A novel systematic absence of cross peaks-based 2D-COS approach for bilinear data.
A novel systematic absence of cross peaks-based 2D-COS approach for bilinear data.
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DOI：
10.1016/j.saa.2019.05.008
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发表时间：
2019-09
期刊：
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通讯作者：
Ran Guo;Xin Zhang;An-qi He;Fei Zhang;Qing-bo Li;Zhuoyong Zhang;R. Tauler;Zhenqiang Yu;Shigeaki Morita;Yizhuang Xu;I. Noda;Y. Ozaki;Jinguang Wu
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文献类型：
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作者：
Ran Guo;Xin Zhang;An-qi He;Fei Zhang;Qing-bo Li;Zhuoyong Zhang;R. Tauler;Zhenqiang Yu;Shigeaki Morita;Yizhuang Xu;I. Noda;Y. Ozaki;Jinguang Wu
提出了一种利用二维相关光谱（2D-COS）分析双线性数据的新方法。在二维异步光谱中观察到一种称为交叉峰系统缺失（SACPs）的现象。推导了两个与sacp相关的定理。基于sacp的2D-COS方法已成功应用于混合样本（包括一个模型系统和两个实际系统）的双线性数据分析。即使不同成分的时间相关曲线严重重叠，也可以根据sacp的特征模式识别出隐式孤立峰，并将其分配给不同的成分。根据sacp的结果，可以检索到纯组分的光谱。sacp的识别仍然可以在工件存在的情况下实现。因此，噪声和基线漂移都不会对本文所述方法得到的结果产生显著影响。我们使用了几种成熟的化学计量方法，包括具有不同初始设置的N-Findr， VCA和MCR，在两个系统上可以使用2D-COS方法成功求解。由于时间相关谱线的严重重叠导致旋转模糊问题，上述化学计量方法无法提供正确的纯组分光谱。只有将2D-COS中sacp的信息作为MCR计算的附加约束，才能得到正确的光谱。也就是说，基于sacp的2D-COS方法提供了内在信息，这对于色谱光谱和类似数据的分析至关重要，即使不同组分的时间相关剖面严重重叠。
A novel approach to use two-dimensional correlation spectroscopy (2D-COS) to analyze bilinear data is proposed. A phenomenon called Systematic Absence of Cross Peaks (SACPs) is observed in a 2D asynchronous spectrum. Two theorems relevant to SACPs have been derived. The SACP-based 2D-COS method has been successfully applied on analyzing bilinear data from mixed samples (including one model system and two real systems). Implicit isolated peaks can be identified and assigned to different components based on characteristic pattern of SACPs even if the time-related profiles of different components are severely overlapped. Based on the results of SACPs, spectra of pure components can be retrieved. Identification of SACPs can still be achieved in the presence of artifacts. Thus, neither noise nor baseline drift can produce significant influence on the results obtained from the approach described in this paper. We have used several well-established chemometric methods, including N-Findr, VCA, and MCR with various initial settings, on two systems that can be successfully solved using the 2D-COS method. The chemometric methods mentioned above cannot provide correct spectra of pure components because of severe problem of rotational ambiguity derived from severe overlapping of the time-related profiles. Only when the information from SACPs in 2D-COS is used as additional constraints in MCR calculation, correct spectra can be obtained. That is to say, the SACP-based 2D-COS method provides intrinsic information which is crucial in the analysis of chromatographic-spectroscopic and analogous data even if the time-related profiles of different components overlap severely.