terclim by ICS banner
IVES 9 IVES Conference Series 9 UNRAVELING THE CHEMICAL MECHANISM OF MND FORMATION IN RED WINE DURING BOTTLE AGING : IDENTIFICATION OF A NEW GLUCOSYLATED HYDROXYKETONE PRO-PRECURSOR

UNRAVELING THE CHEMICAL MECHANISM OF MND FORMATION IN RED WINE DURING BOTTLE AGING : IDENTIFICATION OF A NEW GLUCOSYLATED HYDROXYKETONE PRO-PRECURSOR

Abstract

During bottle aging, the development of wine aroma through low and gradual oxygen exposure is often positive in red wines, but can be unfavorable in many cases, resulting in a rapid loss of fresh, fruity flavors. Prematurely aged wines are marked by intense prune and fig aromatic nuances that dominate the desirable bouquet achieved through aging (Pons et al., 2013). This aromatic defect, in part, is caused by the presence of 3-methyl-2,4-nonanedione (MND). MND content was shown to be lower in nonoxidized red wines and higher in oxidized red wines, which systematically exceeds the odor detection threshold (62 ng/L). Concentrations up to 340 ng/L were evidenced in the most oxidized red wines as well as MND content up scaling was observed whatever the oxidation level. Very recently, we identified two new hydroxyketones (2-hydroxy-3-methylnonan-4-one) associated with MND distribution in aged red wines. We demonstrated that in red wine, their oxidation can produce MND (Peterson et al., 2020). To date, the origin of these precursors were not studied. During preliminary experiments, the presence in wine of a glycosylated form of this hydroxyketone was suggested by hydrolysis experiments. Based on the literature, we hypothesized the presence of a corresponding glucosylated precursor and developed a strategy for its organic multi-step synthesis. First, the MND hydroxylated precursor of MND was synthesized by aldolization (Crévisy et al., 2001). Then, based on literature, we optimized strategies for the O- glycosidation step. For this, the tetrabenzylated glucose was activated by imidation reaction (Chatterjee et al., 2018). Several deprotection methods for the glucoside moiety were then experimented. Finally, the use of palladium on carbon for the hydrogenolytic debenzylation lead to the target compound. A multi-step purification process (LC, HPLC) was carried out to reach sufficient purity. Glycosylated standard was characterized by Nuclear Magnetic Resonance (NMR) and by High Resolution Mass Spectrometry (HRMS) and then used to develop an LC-MS/MS for its identification in grapes and wines. The first analytical results lead to look deeper into the search for glucosylated compounds in various oenolo-gical samples (grapes, musts, red wines), affected or not by the nuances of “dried fruits”.

 

1. Peterson, A.; Cholet, C.; Geny, L.; Darriet, P.; Landais, Y.; Pons, A. Identification and analysis of new α- and β-hydroxy ketones related to the formation of 3-methyl-2,4-nonanedione in Musts and red wines. Food Chem. 2020, 305, 12548.
2. Pons, A.; Lavigne, V.; Darriet, P.; Dubourdieu, D. Role of 3-methyl-2,4-nonanedione in the flavor of aged red wines. J. Agric. Food Chem. 2013, 61 (30), 7373–7380.
3. Crévisy, C.; Wietrich, M.; Le Boulaire, V.; Uma, R.; Grée, R. From allylic alcohols to aldols via a novel, tandem isomerization–condensation catalyzed by Fe(CO)5. Tetrahedron Lett. 2001, 42 (3), 395–398.
4. Chatterjee, S.; Moon, S.; Hentschel, F.; Gilmore, K.; Seeberger, PH. An Empirical Understanding of the Glycosylation Reaction. J Am Chem Soc. 2018, 140 (38), 11942-11953.

DOI:

Publication date: February 9, 2024

Issue: OENO Macrowine 2023

Type: Poster

Authors

D. Lamliji1,2,3, C. Thibon2,3, S. Shinkaruk1,2,3, A. Pons2,3,4
1. Univ. Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400 Talence, France.
2. Univ. Bordeaux, Bordeaux INP, INRAE, OENO, UMR 1366, ISVV, F-33140 Villenave d’Ornon, France.
3. Bordeaux Sciences Agro, Bordeaux INP, INRAE, OENO, UMR 1366, ISVV, F-33170 Gradignan, France.
4. Seguin Moreau France, Z.I. Merpins, BP 94, 16103 Cognac, France.

Contact the author*

Keywords

cooked fruit aroma, 3-methyl-2,4-nonanedione, glucosylated precursors, identification

Tags

IVES Conference Series | oeno macrowine 2023 | oeno-macrowine

Citation

Related articles…

SHIRAZ FLAVONOID EXTRACTABILITY IMPACTED BY HIGH AND EXTREME HIGH TEMPERATURES

Climate change is leading to an increase in average temperature and in the severity and occurrence of heatwaves, and is already disrupting grapevine phenology. In Australia, with the evolution of the weather of grape growing regions that are already warm and hot, berry composition including flavonoids, for which biosynthesis depends on bunch microclimate, are expected to be impacted [1]. These compounds, such as anthocyanins and tannins, contribute substantially to grape and wine quality. The goal of this research was to determine how flavonoid extraction is impacted when bunches are exposed to high (>35 °C) and extreme high (>45 °C) temperatures during berry development and maturity.

ABOUT THE ROLE PLAYED BY THE DIFFERENT POLYPHENOLS ON OXYGEN CONSUMPTION AND ON THE ACCUMULATION OF ACETALDEHYDE ANDSTRECKER ALDEHYDES DURING WINE OXIDATION

In a previous work1, it was suggested that the different contents in delphinidin and catechin of the grapes were determinant on the O2 consumption and Strecker aldehyde (SAs) accumulation rates. Higher delphinidin seemed to be related to a faster O2 consumption and a smaller SAs accumulation rate, and the opposite was observed regarding catechin.
In the present paper, these observations were fully corroborated by adding synthetic delphinidin to a wine model containing polyphenolic fractions (PFs) extracted from garnacha and synthetic catechin to a wine model containing PF extracted from tempranillo: The delphinin-containing garnacha model consumed O₂ significantly faster and accumulated significantly smaller amounts of SAs than the original garnacha model, and the catechin-containing tempranillo model, consumed O2 significantly slower and accumulated significantly higher amounts of SAs than the original tempranillo model.

MOUSY OFF-FLAVOURS IN WINES: UNVEILING THE MICROORGANISMS BEHIND IT

Taints and off-flavours are one of the major concerns in the wine industry and even if the issues provoked by them are harmless, they can still have a negative impact on the quality or on the visual perception of the consumer. Nowadays, the frequency of occurrence of mousy off-flavours in wines has increased.
The reasons behind this could be the significant decrease in sulphur dioxide addition during processing, the increase in pH or even the trend for spontaneous fermentation in wine. This off-flavour is associated with Brettanomyces bruxellensis or some lactic acid bacteria metabolisms.

METHYL SALICYLATE, A COMPOUND INVOLVED IN BORDEAUX RED WINES PRODUCED WITHOUT SULFITES ADDITION

Sulfur dioxide (SO₂) is the most commonly used additive during winemaking to protect wine from oxidation and from microorganisms. Thus, since the 18th century, SO₂ was almost systematically present in wines. Recently, wines produced without any addition of SO₂ during all the winemaking process including bottling became more and more popular for consumers. A recent study dedicated to sensory characterization of Bordeaux red wines produced without added SO₂, revealed that such wines were perceived differently from similar wines produced with using SO₂ and were characterized by specific fruity aromas and coolness1,2.

CHANGES IN METABOLIC FLUXES UNDER LOW PH GROWTH CONDITIONS: CAN THE SLOWDOWN OF CITRATE CONSUMPTION IMPROVE OENOCOCCUS OENI ACID-TOLERANCE?

Oenococcus oeni is the main Lactic Acid Bacteria responsible for malolactic fermentation, converting malic acid into lactic acid and carbon dioxide in wines. Following the alcoholic fermentation, this second fermentation ensures a deacidification and remains essential for the release of aromatic notes and the improvement of microbial stability in many wines. Nevertheless, wine is a harsh environment for microbial growth, especially because of its low pH (between 2.9 and 3.6 depending on the type of wine) and nutrient deficiency. In order to maintain homeostasis and ensure viability, O. oeni possesses different cellular mechanisms including organic acid metabolisms which represent also the major pathway to synthetize energy in wine.