Saffron authentication based on liquid chromatography high resolution tandem mass spectrometry and multivariate data analysis.

Saffron is one of the oldest and most expensive spices, which is often target of fraudulent activities. In this research, a new strategy of saffron authentication based on metabolic fingerprinting was developed. In the first phase, a solid liquid extraction procedure was optimized, the main aim was to isolate as maximal representation of small molecules contained in saffron as possible. In the second step, a detection method based on liquid chromatography coupled with high-resolution mass spectrometry was developed. Initially, principal component analysis (PCA) revealed clear differences between saffron cultivated and packaged in Spain, protected designation of origin (PDO), and saffron packaged in Spain of unknown origin, labeled Spanish saffron. Afterwards, orthogonal partial least square discriminant analysis (OPLS-DA) was favorably used to discriminate between Spanish saffron. The tentative identification of markers showed glycerophospholipids and their oxidized lipids were significant markers according to their origin.

[1]  Juan Cacho,et al.  Characterisation of aroma active compounds of Spanish saffron by gas chromatography–olfactometry: Quantitative evaluation of the most relevant aromatic compounds , 2011 .

[2]  J. Hajšlová,et al.  Metabolic fingerprinting based on high-resolution tandem mass spectrometry: a reliable tool for wine authentication? , 2014, Analytical and Bioanalytical Chemistry.

[3]  Zhide Hu,et al.  Quantitative Structure-Retention relationship study of the constituents of saffron aroma in SPME-GC-MS based on the projection pursuit regression method. , 2008, Talanta.

[4]  G. Alonso,et al.  Solid-phase extraction for picrocrocin determination in the quality control of saffron spice (Crocus sativus L.) , 2009 .

[5]  Jana Hajslova,et al.  Liquid chromatography–mass spectrometry-based metabolomics for authenticity assessment of fruit juices , 2012, Metabolomics.

[6]  Miguel Herrero,et al.  Metabolomics approaches based on mass spectrometry for food safety, quality and traceability , 2013 .

[7]  Julien Boccard,et al.  A consensus orthogonal partial least squares discriminant analysis (OPLS-DA) strategy for multiblock Omics data fusion. , 2013, Analytica chimica acta.

[8]  Laura Ruth Cagliani,et al.  Evaluation of saffron (Crocus sativus L.) adulteration with plant adulterants by (1)H NMR metabolite fingerprinting. , 2015, Food chemistry.

[9]  A. Granell,et al.  Metabolite and target transcript analyses during Crocus sativus stigma development. , 2009, Phytochemistry.

[10]  Josep Rubert,et al.  Advances in high-resolution mass spectrometry based on metabolomics studies for food – a review , 2015, Food additives & contaminants. Part A, Chemistry, analysis, control, exposure & risk assessment.

[11]  Monica Bononi,et al.  Gas chromatography of safranal as preferable method for the commercial grading of saffron (Crocus sativus L.). , 2015, Food chemistry.

[12]  Gonzalo L. Alonso,et al.  Rapid determination of safranal in the quality control of saffron spice (Crocus sativus L.) , 2011 .

[13]  K. Srinivasan Antioxidant Potential of Spices and Their Active Constituents , 2014, Critical reviews in food science and nutrition.

[14]  K. Héberger,et al.  Supervised pattern recognition in food analysis. , 2007, Journal of chromatography. A.

[15]  Javad Asili,et al.  1H NMR metabolic fingerprinting of saffron extracts , 2010, Metabolomics.

[16]  Reza Heidari,et al.  Determination of volatile components of saffron by optimised ultrasound-assisted extraction in tandem with dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry. , 2014, Food chemistry.

[17]  Gordana Ivosev,et al.  Dimensionality reduction and visualization in principal component analysis. , 2008, Analytical chemistry.

[18]  Carsten Fauhl-Hassek,et al.  Potential and limitations of non-targeted fingerprinting for authentication of food in official control , 2014 .

[19]  G. Alonso,et al.  Determination of free amino acids and ammonium ion in saffron (Crocus sativus L.) from different geographical origins , 2009 .

[20]  J. Spink,et al.  Development and application of a database of food ingredient fraud and economically motivated adulteration from 1980 to 2010. , 2012, Journal of food science.

[21]  D. Wishart Metabolomics: applications to food science and nutrition research , 2008 .

[22]  Marco Rito-Palomares,et al.  Recovery of crocins from saffron stigmas (Crocus sativus) in aqueous two-phase systems. , 2012, Journal of chromatography. A.

[23]  Manuel Carmona,et al.  Geographical origin differentiation of saffron spice (Crocus sativus L. stigmas) - Preliminary investigation using chemical and multi-element (H, C, N) stable isotope analysis. , 2011, Food chemistry.

[24]  Massimo F. Marcone,et al.  Chemical and biological properties of the world's most expensive spice: Saffron , 2010 .

[25]  M. Rantalainen,et al.  OPLS discriminant analysis: combining the strengths of PLS‐DA and SIMCA classification , 2006 .