Handling time misalignment and rank deficiency in liquid chromatography by multivariate curve resolution: Quantitation of five biogenic amines in fish

Biogenic amines (BAs) are used for identifying spoilage in food. The most common are tryptamine (TRY), 2-phenylethylamine (PHE), putrescine (PUT), cadaverine (CAD) and histamine (HIS). Due to lack of chromophores, chemical derivatization with dansyl was employed to analyze these BAs using high performance liquid chromatography with a diode array detector (HPLC-DAD). However, the derivatization reaction occurs with any primary or secondary amine, leading to co-elution of analytes and interferents with identical spectral profiles, and thus causing rank deficiency. When the spectral profile is the same and peak misalignment is present on the chromatographic runs, it is not possible to handle the data only with Multivariate Curve Resolution and Alternative Least Square (MCR-ALS), by augmenting the time, or the spectral mode. A way to circumvent this drawback is to receive information from another detector that leads to a selective profile for the analyte. To overcome both problems, (tri-linearity break in time, and spectral mode), this paper proposes a new analytical methodology for fast quantitation of these BAs in fish with HPLC-DAD by using the icoshift algorithm for temporal misalignment correction before MCR-ALS spectral mode augmented treatment. Limits of detection, relative errors of prediction (REP) and average recoveries, ranging from 0.14 to 0.50 µg mL⁻¹, 3.5–8.8% and 88.08%–99.68%, respectively. These are outstanding results obtained, reaching quantification limits for the five BAs much lower than those established by the Food and Agriculture Organization of the United Nations and World Health Organization (FAO/WHO), and the European Food Safety Authority (EFSA), all without any pre-concentration steps. The concentrations of BAs in fish samples ranged from 7.82 to 29.41 µg g⁻¹, 8.68–25.95 µg g⁻¹, 4.76–28.54 µg g⁻¹, 5.18–39.95 µg g⁻¹ and 1.45–52.62 µg g⁻¹ for TRY, PHE, PUT, CAD, and HIS, respectively. In addition, the proposed method spends less than 4 min in an isocratic run, consuming less solvent in accordance with the principles of green analytical chemistry.