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…

USE OF 13C CP/MAS NMR AND EPR SPECTROSCOPIC TECHNIQUES TO CHARACTERIZE MACROMOLECULAR CHANGES IN OAK WOOD(QUERCUS PETRAEA) DURING TOASTING

For coopers, toasting process is considered a crucial step in barrel production during which oak wood (Q. petraea) develops several aromatic nuances released to the wine during its maturation. Toasting consists of applying different degrees of heat to a barrel for a specific period. As the temperature increases, thermal degradation of oak wood structure produces a huge range of chemical compounds. Many studies have identified the main key aroma volatile compounds (whisky-lactone, furfural, eugenol, guaiacol, vanillin). However, detailed information on how the chemical structure of oak wood degrades with increasing toasting level is still lacking.

Read More

IDENTIFICATION OF NEW RESVERATROL DERIVATIVES FORMED IN RED WINE AND THEIR BIOLOGICAL PROPERTIES

Stilbenes are natural bioactive polyphenols produced by grapevine. Recently, we have reviewed the na- tural presence of these compounds in wines [1]. This study showed that the resveratrol and its glycoside, the piceid, are the most abundant stilbenes in wines. Resveratrol is a well-known stilbene with a wide range of biological activities. Due to its specific structure, resveratrol can be oxidized in wines to form various derivatives including oligomers [2]. In this study, we investigate the resveratrol and piceid transformation in wines.

Read More

HOW OXYGEN CONSUMPTION INFLUENCES RED WINES VOLTAMMETRIC PROFILE

Phenolic compounds play a central role in sensory characteristics of wine, such as colour, mouthfeel, flavour and determine its shelf life. Furthermore, the major non-enzymatic wine oxidation process is due to the catalytic oxidation of phenols in quinones. Due their importance, during the years have been developed different analytical methods to monitor the concentration of phenols in wine, such as Folin-Ciocalteu method, spectrophotometric techniques and HPLC. These methods can also be used to follow some oxidation-related chemical transformations.

Read More

FOURIER TRANSFORM INFRARED SPECTROSCOPY IN MONITORING THE WINE PRODUCTION

The complexity of the wine matrix makes the monitoring of the winemaking process crucial. Fourier Transform Infrared Spectroscopy (FTIR) along with chemometrics is considered an effective analytical tool combining good accuracy, robustness, high sample throughput, and “green character”. Portable and non-portable FTIR devices are already used by the wine industry for routine analysis. However, the analytical calibrations need to be enriched, and some others are still waiting to be thoroughly developed.

Read More

IDENTIFICATION AND LEVELS OF PHENOLIC COMPOUNDS (TANINS, ANTHO-CYANS) IN RED VARIETAL WINES (PROKUPAC AND BLACK TAMJANIKA) FROM SERBIA

The phenolic compounds of red wines represent a source of numerous benefits for human health, which is why they are a constant subject of scientific research. Winemaking in Serbia has a growing economic significance, with particularly autochthonous varieties included [1]. This research identifies and quantifies phenolic compounds of Serbian red varietal wines of Prokupac and Black Tamjanika varieties. Quantification of the level of phenolics has been conducted, including molecular tannins [(+)-catechin, (-)-epicatechin, procyanidin dimers B1, B2, B3, B4], molecular anthocyanins, and the mean degree of polymerization of tannins by HPLC by UV detection, total antioxidant capacity via spectrophotometric methods and chromatic characteristics via CIELAB.

Read More