• ageing;
  • fingerprint;
  • MS/MS;
  • pyranoanthocyanin;
  • wine


Background and Aims

Pyranoanthocyanins are a type of derivative formed by the cycloaddition reaction of different compounds with anthocyanins during wine maturation and ageing, and show a characteristic pyranic ring. This ring provides a high stability to the pigment, and the ring does not fragment in mass spectrometric experiments. Thus, aglycone ions of these derivatives in tandem mass spectrometry show the same fragmentation pattern as that of the corresponding precursor anthocyanin. The aim of this work was the identification of pyranoanthocyanins present in Rioja aged wines using mass spectrometric features to differentiate among isomeric compounds.

Methods and Results

The application to three Rioja aged red wines of a methodology that combines column chromatography, solid-phase extraction and high-performance liquid chromatography–diode array detection–electrospray ionisation collision-induced dissociation–tandem mass spectrometry has allowed the identification of 72 pyranoanthocyanin derivatives.


This paper provides an overview of pyranoanthocyanin derivatives present in aged red wines with the identification of 72 compounds, some of them derivatives that appear in low concentration, and it assesses the importance of mass spectrometric analysis in the differentiation among isomeric derivatives.

Significance of the Study

The methodology described allows the identification of derivatives at low concentration and the establishment of characteristic fingerprints of native anthocyanins, which provide an effective tool for pyranoanthocyanin identification, allowing the differentiation among isomeric derivatives.