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Application of MALDI-TOFMS Combined with Partial Least Square Regression for the Determination of Mercury and Copper in Canned Tuna, Using Dithizone as the Complexing Agent and Ag(I) as Internal Standard

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Abstract

In this work, a procedure for the determination of mercury and copper in canned tuna samples is presented, based on the extraction of their respective dithizone complexes and quantification by conventional MALDI-TOFMS with the aid of partial least square regression (PLS2). Methanolic dithizone solution (1 ml, 0.01% m/v) containing Ag(I) as internal standard was added to the calibration solutions and to the acid-digested samples (5 ml, pH 3); copper, mercury, and silver complexes were extracted to cyclohexane (1.5 ml), and after evaporation, the residues were re-constituted in acetone (100 μl). The samples were prepared by dried droplet crystallization with α-cyano-4-hydroxycinnamic acid. The experimental and MALDI-TOFMS instrument operating conditions were set up under criteria of as high as possible detectability and repeatability. When univariate calibration was carried out using the most intense ion of Cu or Hg complex normalized by internal standard, determination seemed feasible yet precision of the results was poor. Taking baseline-corrected spectra in m/z range 560–725, PLS2 model was constructed for the prediction of two elements with the method quantification limits 63 μg kg−1 for Cu and 75 μg kg−1 for Hg, respectively. For different brands of canned tuna, the results obtained by MALDI-TOFMS combined with PLS2 and by ICP-MS were in good agreement. The proposed procedure is an attractive alternative for the determination of trace metals in foods because of the procedural simplicity, micro-scale dimension, high speed of data acquisition/processing, and the cost of instrument operation lower as compared to any atomic spectrometry technique.

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Funding

This study was funded by CONACYT, Mexico (grants 123732 and 253879) and by the University of Guanajuato (grants 800/2016 and 721/2016).

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  1. Department of Chemistry, University of Guanajuato, L de Retana No. 5, 36000, Guanajuato, Mexico

    Manuel Mendez Garcia, Kazimierz Wrobel, Alejandra Sarahi Ramirez Segovia, Eunice Yanez Barrientos, Alma Rosa Corrales Escobosa, Oracio Serrano, Francisco Javier Acevedo Aguilar & Katarzyna Wrobel

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  1. Manuel Mendez Garcia
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  2. Kazimierz Wrobel
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Correspondence to Katarzyna Wrobel.

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Manuel Mendez Garcia declares that he has no conflict of interest. Kazimierz Wrobel declares that he has no conflict of interest. Alejandra Sarahi Ramirez Segovia declares that she has no conflict of interest. Eunice Yanez Barrientos declares that she has no conflict of interest. Alma Rosa Corrales Escobosa declares that she has no conflict of interest. Oracio Serrano declares that he has no conflict of interest. Francisco Javier Acevedo Aguilar declares that he has no conflict of interest. Katarzyna Wrobel declares that she has no conflict of interest.

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Garcia, M.M., Wrobel, K., Segovia, A.S.R. et al. Application of MALDI-TOFMS Combined with Partial Least Square Regression for the Determination of Mercury and Copper in Canned Tuna, Using Dithizone as the Complexing Agent and Ag(I) as Internal Standard. Food Anal. Methods 11, 2835–2846 (2018). https://doi.org/10.1007/s12161-018-1272-4

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