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…

RED WINE AGING WITHOUT SO₂: WHAT IMPACT ON MICROBIAL COMMUNITY?

Nowadays, the use of food preservatives is controversial, SO2 being no exception. Microbial communities have been particularly studied during the prefermentary and fermentation stages in a context of without added SO2. However, microbial risks associated with SO2 reduction or absence, particularly during the wine aging process, have so far been little studied. The microbiological control of wine aging is a key issue for winemakers wishing to produce wines without added SO2. The aim of the present study is to evaluate the impact of different wine aging strategies according to the addition or not of SO2 on the microbiological population levels and diversity.

AGEING BOTTLED WINES SUBMERGED IN SEA: DOES IT IMPACT WINE COMPOSITION?

Aging wines is a common practice in oenology, which in recent years has undergone some innovations. Currently, we are witnessing the practice of aging bottled wine in depth, immersed in the sea or in reservoirs, for variable periods of time, but so far, little is known about the impact of aging in depth on the physicochemical properties, of wines.
The objective of this work was to evaluate the impact of this practice on the physicochemical characteristics, in particular to verify changes in the volatile composition of wines bottled and subsequently immersed in depth. A red wine from Cabernet Sauvignon was bottled and a set of bottles were submerged from July to February (2020), another set of bottles were submerged from February to September (2020) and another set was kept in the wine cellar. Bottles from each set were analyzed (in triplicate) in July 2021.

NOVEL BENZENETHIOLS WITH PHENOLS CAUSE ASHY, SMOKE FLAVOR PERCEPTION IN RED WINES

Smoke impacts on wines are becoming a worldwide problem; the size and severity of wildfires increasing due to influences from changing climates.¹ For over a century, wines have been known to have a unique issue of absorbing chemical compounds derived from wildfire smoke wherein the flavor of the subsequent wine becomes ashy, rubbery, campfire-like, and smoky.² The economic impacts of a smoke-impacted wine can last for years depending on the grape varietal, costing Oregon and Washington states in the United States over a billion dollars from the 2020 wildfires, as an example.³ While years of research have indicated elevated concentrations of smoke-related compounds, such as guaiacol and syringol, in wines after smoke events, unfortunately, replicating the sensory experience using smoke-associated phenols has not had much success.⁴

ANALYZING THE ROLE OF ELEMENTAL SULFUR IN GRAPE JUICE ON THE DEVELOPMENT OF POLYFUNCTIONAL MERCAPTANS IN SAUVIGNON BLANC WINES

Sauvignon blanc is characterized by distinctive aromas, both fruity and herbaceous. The “green” character has been attributed to the methoxypyrazines, while the “fruity” character is associated with polyfunctional mercaptans . Polyfunctional mercaptans are of great significance due to their high impact on wines and associated low perception thresholds.
Elemental sulfur (S⁰) is widely used to protect grapevines from powdery mildew.

EFFECT OF FUMARIC ACID ON SPONTANEOUS FERMENTATION IN GRAPE MUST

Malolactic fermentation (MLF)¹, the decarboxylation of L-malic acid into L-lactic acid, is performed by lactic acid bacteria (LAB). MLF has a deacidifying effect that may compromise freshness or microbiological stability in wines² and can be inhibited by fumaric acid [E297] (FA). In wine, can be added at a maximum allowable dose of 0.6 g/L³. Its inhibition with FA is being studied as an alternative strategy to minimize added doses of SO₂⁴. In addition, wine yeasts are capable of metabolizing and storing small amounts of FA and during alcoholic fermentation (AF).