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Metabolomic fingerprinting of saffron by LC/MS: novel authenticity markers

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Abstract

An untargeted metabolomic approach using liquid chromatography coupled to electrospray ionization time-of-flight mass spectrometry was developed in this work to identify novel markers for saffron authenticity which is an important matter related to consumer protection, quality assurance, active properties, and also economical impact (saffron is the most expensive spice). Metabolic fingerprinting of authentic and suspicious saffron samples from different geographical origin was obtained and analyzed. Different extracting protocols and chromatographic methodologies were evaluated to obtain the most adequate extracting and separation conditions. Using an ethanol/water mixture at pH 9.0 and an elution gradient with a fused core C18 column enabled obtaining the highest number of significant components between authentic and adulterated saffron. By using multivariate statistical analysis, predictive classification models for authenticity and geographical origin were obtained. Moreover, 84 and 29 significant metabolites were detected as candidates for markers of authenticity and geographical origin, respectively, from which only 34 metabolites were tentatively identified as authenticity markers of saffron, but none related to its geographical origin. Six characteristic compounds of saffron (kaempferol 3-O-glucoside, kaempferol 3-O-sophoroside, kaempferol 3,7-O-diglucoside, kaempferol 3,7,4′-O-triglucoside, kaempferol 3-O-sophoroside-7-O-glucoside, and geranyl-O-glucoside) were confirmed by comparing experimental MS/MS fragmentation patterns with those provided in scientific literature being proposed as novel markers of authenticity.

Metabolomic fingerprinting of saffron

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Acknowledgments

The authors thank financial support from the Spanish Ministry of Science and Innovation (project CTQ2009-09022), the Comunidad of Madrid (Spain) and European funding from FEDER program (project S2013/ABI-3028, AVANSECAL-CM), and the University of Alcalá (project UAH2011/EXP-020). M.G.D. thanks the Ministry of Science and Innovation for his predoctoral contract (BES-2010-033465). The authors also thank the kind gift of saffron samples by Carmencita Company and the group of Prof. Coral Barbas for the one-month stay of M.G.D. in her laboratory to work with the different chemometric techniques used in this work.

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  1. Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering, University of Alcalá, Ctra. Madrid-Barcelona Km. 33,600, 28871, Alcalá de Henares, Madrid, Spain

    Miguel Guijarro-Díez, Leonor Nozal, María Luisa Marina & Antonio Luis Crego

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  1. Miguel Guijarro-Díez
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  2. Leonor Nozal
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Correspondence to Antonio Luis Crego.

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Guijarro-Díez, M., Nozal, L., Marina, M.L. et al. Metabolomic fingerprinting of saffron by LC/MS: novel authenticity markers. Anal Bioanal Chem 407, 7197–7213 (2015). https://doi.org/10.1007/s00216-015-8882-0

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