Achieving second order advantage with multi-way partial least squares and residual bi-linearization with total synchronous fluorescence data of monohydroxy–polycyclic aromatic hydrocarbons in urine samples

• Chemometrics of urine metabolites with total synchronous fluorescence data.
• Second-order advantage is obtained either with U-PLS/RBL or N-PLS/RBL.
• Five PAH metabolites are determined in the presence of strong spectral interference.

An attractive approach to handle matrix interference in samples of unknown composition is to generate second- or higher-order data formats and process them with appropriate chemometric algorithms. Several strategies exist to generate high-order data in fluorescence spectroscopy, including wavelength time matrices, excitation–emission matrices and time-resolved excitation–emission matrices. This article tackles a different aspect of generating high-order fluorescence data as it focuses on total synchronous fluorescence spectroscopy. This approach refers to recording synchronous fluorescence spectra at various wavelength offsets. Analogous to the concept of an excitation–emission data format, total synchronous data arrays fit into the category of second-order data. The main difference between them is the non-bilinear behavior of synchronous fluorescence data. Synchronous spectral profiles change with the wavelength offset used for sample excitation. The work presented here reports the first application of total synchronous fluorescence spectroscopy to the analysis of monohydroxy-polycyclic aromatic hydrocarbons in urine samples of unknown composition. Matrix interference is appropriately handled by processing the data either with unfolded-partial least squares and multi-way partial least squares, both followed by residual bi-linearization.

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