Multiway resolution of spectrochromatographic measurements for the quantification of echinuline in marine-derived fungi Aspergillus chevalieri using parallel factor analysis

Zehra Ceren Ertekin; Hajar Heydari; Belma Konuklugil; Erdal Dinç

doi:10.1016/j.jchromb.2022.123181

Multiway resolution of spectrochromatographic measurements for the quantification of echinuline in marine-derived fungi Aspergillus chevalieri using parallel factor analysis

J Chromatogr B Analyt Technol Biomed Life Sci. 2022 Mar 15:1193:123181. doi: 10.1016/j.jchromb.2022.123181. Epub 2022 Feb 18.

Authors

Zehra Ceren Ertekin¹, Hajar Heydari², Belma Konuklugil³, Erdal Dinç⁴

Affiliations

¹ Ankara University, Faculty of Pharmacy, Department of Analytical Chemistry, Ankara, Turkey.
² Ankara University, Faculty of Pharmacy, Department of Pharmacognosy, Ankara, Turkey.
³ Lokman Hekim University, Faculty of Pharmacy, Department of Pharmacognosy, Ankara, Turkey.
⁴ Ankara University, Faculty of Pharmacy, Department of Analytical Chemistry, Ankara, Turkey. Electronic address: dinc@ankara.edu.tr.

PMID: 35203040
DOI: 10.1016/j.jchromb.2022.123181

Abstract

A multiway resolution of incomplete chromatographic separation was presented for spectrochromatographic quantification of echinuline in marine-derived fungi Aspergillus chevalieri. Two-dimensional spectrochromatographic maps of calibration, validation and real samples were recorded as a function of time and wavelength using UPLC-PDA instrument under non-optimized chromatographic conditions, which gave rise to co-elution of echinuline and the constituents of sample matrix. A three-way array was obtained by concatenating the data matrices of the spectrochromatographic maps. Then, parallel factor analysis was applied to the multiway array to extract the individual contribution of echinuline in three modes (time, wavelength and sample). While time and wavelength profiles were used for the characterization of echinuline, the sample profile was used for its quantitative determination of the analyte in validation set and in real samples. Validity of the analytical method was evaluated by analyzing the validation set, which consist of test samples, standard addition samples, intra-day and inter-day samples. The proposed multiway analysis method was then applied to marine-derived fungi extracts and echinuline content was found to be 31.9 µg/g based on the average of ten assay results. The assay results provided by PARAFAC model were statistically compared with those obtained by a newly developed classical UPLC method, which ensured the complete separation of echinuline in a run time of nine minutes. The assay results were found to be comparable due to the fact that there was no significant difference between the analysis results (F = 1.63, F_crit = 3.17; t = 0.69, t_crit = 2.11) at the significance level of 95%). Consequently, the PARAFAC method permitted the accurate determination of echinuline in fungal extracts despite the partial chromatographic separation with a run time of only three minutes.

Keywords: Echinuline; Multiway data; Natural products; Parallel factor analysis; UPLC.