Fourier based partial least squares algorithm: new insight into influence of spectral shift in “frequency domain”

Developments in analytical chemistry technology, especially the combination between the partial least squares and spectroscopy, have contributed significantly to predicting the chemical concentrations and discriminating similar chemical analytes. However, spectral shift is an unwanted but inevitable factor for the spectroscopic analyzer, especially in practical application, which decreases the method's accuracy and stability. To remove the term of spectral shift completely and increase the robustness of spectroscopic analysis method, Fourier transform based partial least squares method was proposed. The approach used Fourier transform first to transform the spectral shift in the "time domain" to the phase term in the "frequency domain." The module of the Fourier transformed spectra was then calculated. As a result, the phase term was removed (the module of the phase term is 1), which means the spectral shift term was removed completely. Finally, the spectra modules were used to build the model and validate. The approach's advantages are: (i) that the approach provides a new insight to treat the spectral shift in spectroscopic analyzer; (ii) that the model is insensitive to spectral shift; (iii) that the approach makes partial least squares combined with spectroscopy more suitable for practical application, rather than lab experiment, because spectral shift is permitted, which means the decreased requirements of measure environment. As an example, blood species discrimination, using Raman spectroscopy, was used in order to demonstrate this approach's effectiveness.