The project was carried out with the aim of finding new alternative and low environmental impact methods for the characterization of commercial and minor wines. In fact, the analyzes carried out at the Centro Interdipartimentale Grandi Strumenti (CIGS) in Modena permitted to analyze the wines of the Lambrusco family, which have now become among the most consumed and exported wines in the world; the wines of the Malvasia family, which are increasingly establishing on the market; the lesser known wines of Emilia-Romagna, produced by the Centro di Ricerca delle Produzioni Vegetali (CRPV) of Cesena, both red and white. Regarding to the red wines, metabolomics proved to be an effective approach, and the use of cutting-edge tools such as the high-resolution mass spectrometer Orbitrap Q Exactive, permitted to identify over 100 anthocyanin molecules. Among them, in addition to the most known forms such as glycosylated, acetyl-, coumaroyl- and caffeoyl-glycosylated, many other derivative forms were identified, such as di-glucosides, which are typical of American vines, but are present in traces also in the varieties of V. vinifera, as well as the combinations with catechins and gallocatechins, with higher molecular weight. In fact, with common analytical methods such as UV spectrophotometry or UV liquid chromatography, it is not possible to see the molecules present in low concentrations, due to the lower sensitivity of the detectors. In addition, UV spectrophotometers allow the identification of molecules only based on the retention times, which often co-elute with each other, even though the chromatographic method has been properly developed. By analyzing the data through the Principal Component Analysis (PCA), the Ancellotta was confirmed, both in terms of quantity and production stability, as the most interesting variety to produce blended wine. Even the Lambrusco Salamino, Grasparossa and Reggiano, are easily distinguishable and have also shown an excellent yield, in terms of color. From a technological point of view, it was possible to distinguish the Ancellotta vinified in red from that vinified in white. In fact, the red vinified one, especially in the 2019 vintage, stands out not only for the high contents of glycosylated anthocyanins, which are typically the most appreciated by winemakers, but also for the large amount of derived anthocyanins mentioned above. Among the minor vines, Festasio proved to be the wine with characteristics very similar to those of the wines already on the market, both in qualitative and quantitative terms, and it can be used as blended wine. Lambrusco di Fiorano (or Lambrusco del Pellegrino), typical of the Modena province, even if with a less abundant color, also showed interesting characteristics for the vinification of Lambrusco. As for the analysis of white wines, an analysis was conducted using mono-dimensional Nuclear Magnetic Resonance (1H-NMR), a typical approach of "untargeted" analysis. This type of analysis, despite being a more approximated analysis than mass spectrometry, allowed the characterization of the minor red wines described above, as well as the minor white wines of Caveccia, Vernaccia del Viandante, Bertinora and Vernaccina, once widespread especially in the coastal provinces of the Adriatic Sea, and the Melara, originally from the province of Piacenza. Moreover, it was possible to discriminate minor wines from wines already on the market, such as Lambrusco and Pignoletto. Of the latter, it was also possible to distinguish the commercial product, and therefore already refermented in the bottle, from the product not yet refermented, and thus with a higher content of residual sugars, and still low in alcohol.

Il progetto è stato svolto con l’obiettivo di trovare nuovi metodi alternativi ed a basso impatto ambientale per la caratterizzazione dei vini, commerciali e minori. Infatti, le analisi eseguite presso il Centro Interdipartimentale Grandi Strumenti (CIGS) di Modena, hanno permesso di analizzare i vini della famiglia dei Lambruschi, diventati ormai tra i vini più consumati ed esportati al mondo; i vini della famiglia delle Malvasie, che sempre più si stanno affermando sul mercato; i vini meno conosciuti dell’Emilia-Romagna, prodotti dal Centro di Ricerca delle Produzioni Vegetali (CRPV) di Cesena, sia rossi che bianchi. In particolare, per quel che riguarda i vini rossi, la metabolomica si è rivelata un approccio efficace, e l’utilizzo di strumenti di avanguardia quale lo spettrometro di massa ad alta risoluzione Orbitrap Q Exactive, ha permesso di individuare oltre 100 molecole di antocianine. Tra esse, oltre a quelle glicosilate, acetil-, coumaroil- e caffeoil-glicosilate, sono state individuate molte altre forme derivate, come ad esempio i di-glucosidi, che sono caratteristici delle viti americane, ma sono presenti in tracce anche nelle varietà di V. vinifera, così come le combinazioni con le catechine e le gallocatechine, a più alto peso molecolare. Infatti, i metodi analitici comuni quali spettrofotometria UV o cromatografia liquida UV, non permettono di vedere le molecole presenti in basse concentrazioni, a causa della minore sensibilità dei rivelatori. Inoltre, gli spettrofotometri UV permettono di individuare le molecole solo in base ai tempi di ritenzione di quest’ultime, che spesso co-eluiscono le une con le altre, nonostante il metodo cromatografico sia stato messo a punto in modo adeguato. Analizzando i dati tramite la Principal Component Analysis (PCA), l’Ancellotta è stata confermata, sia in termini di quantità sia come stabilità produttiva, come la varietà più interessante per la produzione di vino da taglio. Anche i Lambruschi Salamino, Grasparossa e Reggiano, sono facilmente distinguibili ed hanno dimostrato anch’essi un’ottima resa, in termini di colore. Dal punto di vista tecnologico, è stato possibile distinguere l’Ancellotta vinificata in rosso da quella vinificata in bianco. Infatti, quella vinificata in rosso, soprattutto nell’annata 2019, si distingue non solo per gli alti contenuti di antocianine glicosilate, che sono tipicamente le più ricercate dagli enologi, ma anche per la grande quantità di antocianine derivate citate precedentemente. Tra i vitigni minori, il Festasio si è rivelato il vino con delle caratteristiche molto simili a quelle dei vini già presenti in commercio, sia in termini qualitativi che quantitativi. Anche il Lambrusco di Fiorano (o Lambrusco del Pellegrino), tipico del Modenese, seppur con una colorazione meno abbondante, ha mostrato caratteristiche interessanti per la vinificazione del Lambrusco. Per quanto riguarda lo studio dei vini bianchi, è stata condotta un’analisi mediante Risonanza Magnetica Nucleare monodimensionale (1H-NMR), approccio tipico delle analisi “untargeted” delle matrici. Questo tipo di analisi, nonostante sia un’analisi più approssimativa rispetto alla spettrometria di massa, ha consentito di caratterizzare efficacemente i vini rossi minori descritti in precedenza, oltre ai vini bianchi minori di Caveccia, Vernaccia del Viandante, Bertinora e Vernaccina, un tempo diffuse soprattutto nelle province rivierasche del Mar Adriatico, e la Melara, originaria della provincia di Piacenza. In particolare, è stato possibile distinguere i vini minori dai vini già presenti in commercio, quali ad esempio i Lambruschi ed il Pignoletto. Di quest’ultimo, è stato inoltre possibile distinguere il prodotto commerciale, e quindi già rifermentato in bottiglia, dal prodotto non ancora rifermentato, con un contenuto alto di zuccheri residui, ed ancora di basso grado alcolico.

Caratterizzazione dei vini dell’Emilia-Romagna mediante spettrometria di massa ad alta risoluzione e risonanza magnetica nucleare: caso di studio sui Lambruschi commerciali e sui vini di varietà minori di Vitis vinifera L. neoiscritti al Registro Nazionale delle Varietà di Vite / Leonardo Setti , 2021 Mar 19. 33. ciclo, Anno Accademico 2019/2020.

Caratterizzazione dei vini dell’Emilia-Romagna mediante spettrometria di massa ad alta risoluzione e risonanza magnetica nucleare: caso di studio sui Lambruschi commerciali e sui vini di varietà minori di Vitis vinifera L. neoiscritti al Registro Nazionale delle Varietà di Vite

SETTI, LEONARDO
2021

Abstract

The project was carried out with the aim of finding new alternative and low environmental impact methods for the characterization of commercial and minor wines. In fact, the analyzes carried out at the Centro Interdipartimentale Grandi Strumenti (CIGS) in Modena permitted to analyze the wines of the Lambrusco family, which have now become among the most consumed and exported wines in the world; the wines of the Malvasia family, which are increasingly establishing on the market; the lesser known wines of Emilia-Romagna, produced by the Centro di Ricerca delle Produzioni Vegetali (CRPV) of Cesena, both red and white. Regarding to the red wines, metabolomics proved to be an effective approach, and the use of cutting-edge tools such as the high-resolution mass spectrometer Orbitrap Q Exactive, permitted to identify over 100 anthocyanin molecules. Among them, in addition to the most known forms such as glycosylated, acetyl-, coumaroyl- and caffeoyl-glycosylated, many other derivative forms were identified, such as di-glucosides, which are typical of American vines, but are present in traces also in the varieties of V. vinifera, as well as the combinations with catechins and gallocatechins, with higher molecular weight. In fact, with common analytical methods such as UV spectrophotometry or UV liquid chromatography, it is not possible to see the molecules present in low concentrations, due to the lower sensitivity of the detectors. In addition, UV spectrophotometers allow the identification of molecules only based on the retention times, which often co-elute with each other, even though the chromatographic method has been properly developed. By analyzing the data through the Principal Component Analysis (PCA), the Ancellotta was confirmed, both in terms of quantity and production stability, as the most interesting variety to produce blended wine. Even the Lambrusco Salamino, Grasparossa and Reggiano, are easily distinguishable and have also shown an excellent yield, in terms of color. From a technological point of view, it was possible to distinguish the Ancellotta vinified in red from that vinified in white. In fact, the red vinified one, especially in the 2019 vintage, stands out not only for the high contents of glycosylated anthocyanins, which are typically the most appreciated by winemakers, but also for the large amount of derived anthocyanins mentioned above. Among the minor vines, Festasio proved to be the wine with characteristics very similar to those of the wines already on the market, both in qualitative and quantitative terms, and it can be used as blended wine. Lambrusco di Fiorano (or Lambrusco del Pellegrino), typical of the Modena province, even if with a less abundant color, also showed interesting characteristics for the vinification of Lambrusco. As for the analysis of white wines, an analysis was conducted using mono-dimensional Nuclear Magnetic Resonance (1H-NMR), a typical approach of "untargeted" analysis. This type of analysis, despite being a more approximated analysis than mass spectrometry, allowed the characterization of the minor red wines described above, as well as the minor white wines of Caveccia, Vernaccia del Viandante, Bertinora and Vernaccina, once widespread especially in the coastal provinces of the Adriatic Sea, and the Melara, originally from the province of Piacenza. Moreover, it was possible to discriminate minor wines from wines already on the market, such as Lambrusco and Pignoletto. Of the latter, it was also possible to distinguish the commercial product, and therefore already refermented in the bottle, from the product not yet refermented, and thus with a higher content of residual sugars, and still low in alcohol.
Characterization of Emilia-Romagna wines by high resolution mass spectrometry and nuclear magnetic resonance: case study on commercial Lambrusco and minor variety wines of Vitis vinifera L. newly registered in the national register of varieties
19-mar-2021
MASINO, Francesca
ANTONELLI, Andrea
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