Discrimination of rosé wines using shotgun metabolomics with a genetic algorithm and MS ion intensity ratios.

A rapid Ultra Performance Liquid Chromatography coupled with Quadrupole/Time Of Flight Mass Spectrometry (UPLC-QTOF-MS) method was designed to quickly acquire high-resolution mass spectra metabolomics fingerprints for rosé wines. An original statistical analysis involving ion ratios, discriminant analysis, and genetic algorithm (GA) was then applied to study the discrimination of rosé wines according to their origins. After noise reduction and ion peak alignments on the mass spectra, about 14 000 different signals were detected. The use of an in-house mass spectrometry database allowed us to assign 72 molecules. Then, a genetic algorithm was applied on two series of samples (learning and validation sets), each composed of 30 commercial wines from three different wine producing regions of France. Excellent results were obtained with only four diagnostic peaks and two ion ratios. This new approach could be applied to other aspects of wine production but also to other metabolomics studies.

Effect of polyvinylpolypyrrolidone treatment on rosés wines during fermentation: Impact on color, polyphenols and thiol aromas.

Fining treatment with polyvinylpolypyrrolidone (PVPP) is often used during winemaking of rosé wines. It can modulate the intensity and hue of their pink color and prevent some organoleptic degradations. In this paper, the effect of PVPP treatments on rosé wine during fermentation was investigated by measuring color, polyphenol content and thiol aromas. As expected, colorimetry results showed a decrease in color, indicating some adsorption of anthocyanins and other pigments. This was confirmed by UPLC-ESI-MS/MS analyses. Specific adsorption of certain families of polyphenols was evidenced. Flavonols, flavanols and anthocyanins, especially coumaroylated anthocyanins were preferentially adsorbed by PVPP. The thiol content (3-sulfanylhexyl acetate (3SHA) and 3-sulfanylhexan-1-ol (3SH)) was usually higher after PVPP treatments, in a dose dependent manner. A possible explanation is that the partial adsorption of some polyphenols at an early stage of fermentation would later limit the amount of quinone compounds able to trap thiol aromas.

Rosé Wine Fining Using Polyvinylpolypyrrolidone: Colorimetry, Targeted Polyphenomics, and Molecular Dynamics Simulations.

Polyvinylpolypyrrolidone (PVPP) is a fining agent polymer used in winemaking to adjust rosé wine color and to prevent organoleptic degradations by reducing polyphenol content. The impact of this polymer on color parameters and polyphenols of rosé wines was investigated, and the binding specificity of polyphenols toward PVPP was determined. Color measured by colorimetry decreased after treatment, thus confirming the adsorption of anthocyanins and other pigments. Phenolic composition was determined before and after fining by targeted polyphenomics (Ultra Performance Liquid Chromatography (UPLC)-Electrospray Ionization(ESI)-Mass Spectrometry (MS/MS)). MS analysis showed adsorption differences among polyphenol families. Flavonols (42%) and flavanols (64%) were the most affected. Anthocyanins were not strongly adsorbed on average (12%), but a specific adsorption of coumaroylated anthocyanins was observed (37%). Intermolecular interactions were also studied using molecular dynamics simulations. Relative adsorptions of flavanols were correlated with the calculated interaction energies. The specific affinity of coumaroylated anthocyanins toward PVPP was also well explained by the molecular modeling.