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Application of a Novel Small-Scale Sample Cleanup Procedure Prior to MALDI-TOF-MS for Rapid Pigment Fingerprinting of Red Wines

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Abstract

This study evaluates the anthocyanin and derived pigment composition of Vitis vinifera red wines of Vranec, Merlot, and Cabernet Sauvignon produced in 2006, 2007, and 2008 vintages from the Tikveš wine region in the Republic of Macedonia. Their profile was established using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) technique. A total of 22 anthocyanins and derived pigments have been identified in the samples including 10 anthocyanins, 1 ethyl-bridged flavanol–anthocyanin adduct, and 11 pyranoanthocyanins. MALDI-TOF-MS analysis was performed after solid-phase extraction of the wines by using, for the first time, the Zip-Tip® C18 stationary phase, introducing a novel small-scale sample cleanup procedure prior to the rapid MALDI-TOF-MS fingerprinting of wine samples. 2′,4′,6′-Trihydroxyacetophenone (dissolved in acetonitrile/water 1:1, v/v) was used as a matrix. The qualitative screening of anthocyanins and derived pigments with MALDI-TOF-MS confirmed the presence of glucoside, acetylglucoside, and p-coumaroylglucoside derivatives of anthocyanins in the wine samples. Furthermore, pyranoanthocyanins formed by reactions of anthocyanins with pyruvic acid and acetaldehyde, as well as flavanol–pyranoanthocyanins and ethyl-bridged flavan-3-ol-anthocyanin adduct pigments have been detected in the samples.

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Acknowledgments

This work was financially supported by the Central European Exchange Program for University Studies (CEEPUS) Program realized through the CEEPUS network (CIII-HU-0010-06-Teaching and Learning Bioanalysis) covering the study stay of Violeta Ivanova Petropulos at the University of Pécs, Hungary. Á. D. acknowledges the support of the János Bolyai Research Scholarship (Hungarian Academy of Sciences). The authors express gratitude to Mr. Kire Trajkov from Tikveš Winery, Kavadarci, Republic of Macedonia, for providing the wine samples.

Conflict of Interest

Violeta Ivanova Petropulos declares that she has no conflict of interest. Ágnes Dörnyei declares that she has no conflict of interest. Marina Stefova declares that she has no conflict of interest. Trajče Stafilov declares that he has no conflict of interest. Borimir Vojnoski declares that he has no conflict of interest. László Márk declares that he has no conflict of interest. Isidro Hermosín-Gutiérrez declares that he has no conflict of interest. Ferenc Kilár declares that he has no conflict of interest. This article does not contain any studies with human or animal subjects.

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Correspondence to Violeta Ivanova Petropulos.

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Ivanova Petropulos, V., Dörnyei, Á., Stefova, M. et al. Application of a Novel Small-Scale Sample Cleanup Procedure Prior to MALDI-TOF-MS for Rapid Pigment Fingerprinting of Red Wines. Food Anal. Methods 7, 820–827 (2014). https://doi.org/10.1007/s12161-013-9687-4

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  • DOI: https://doi.org/10.1007/s12161-013-9687-4

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