terclim by ICS banner
IVES 9 IVES Conference Series 9 USE OF 13C CP/MAS NMR AND EPR SPECTROSCOPIC TECHNIQUES TO CHARACTERIZE MACROMOLECULAR CHANGES IN OAK WOOD(QUERCUS PETRAEA) DURING TOASTING

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

Abstract

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.

In this study, we characterised the structural changes of the main components (cellulose, hemicellulose and lignin) of oak wood staves subjected to heat treatments (non-toasted to 240 °C) by cross-polarisation/magic angle spinning nuclear magnetic resonance (CP/MAS NMR, 800 MHz) and electron para-magnetic resonance (EPR, X-band) spectroscopy techniques applied to solids. Furthermore, the results will be compared to those obtained by quantitative GC-MS (EI) analysis of oak wood volatile compounds generated by the same heat treatments. The 13C CP/MAS NMR data highlighted concomitant phenomena of demethoxylation and depolymerisation of syringyl units leading to the formation of guaiacyl units and the release of monomer units. EPR results revealed the same phenomena and led us to hypothesize that the nature of the radical formed evolved during toasting from syringyl to guaiacyl form. Our results are consistent with data on others wood species and confirm that 200 °C is a threshold temperature above which degradation of the macromolecular structure leads to the formation of radicals and volatile compounds. Overall, the study offers interesting perspectives for the application of spectroscopic techniques, particularly EPR spectroscopy, to monitor radical formation during barrel aging and, consequently, to assess the oxidative stability of wine.

DOI:

Publication date: February 9, 2024

Issue: OENO Macrowine 2023

Type: Poster

Authors

Marie Courregelongue 1,2,3, Mathieu Duttine ⁴, Axelle Grélard ⁵, Alexandre Pons 1,2,3

1. Univ. Bordeaux, Bordeaux INP, INRAE, OENO, UMR 1366, ISVV, F-33140 Villenave d’Ornon, France
2. Bordeaux Sciences Agro, F-33170 Gradignan, France
3. Seguin Moreau Cooperage, ZI Merpins, F-16103 Cognac, France
4. Univ. Bordeaux, CNRS, Bordeaux INP, ICMCB, UMR 5026, F-33600 Pessac, France
5. Univ. Bordeaux, CNRS, Bordeaux INP, CBMN, UMR 5248, IECB, F-33600 Pessac, France

Contact the author*

Keywords

oak wood, thermal degradation, macromolecular components, aroma compounds

Tags

IVES Conference Series | oeno macrowine 2023 | oeno-macrowine

Citation

Related articles…

THE POTENTIAL USE OF SOLUBLE POLYSACCHARIDES TO PREVENT THE OXIDATION OF ROSÉ WINES

Lately, rosé wine is rapidly increasing its popularity worldwide. Short-time macerations with the red skin of the grapes cause the partial extraction of anthocyanins, which are responsible for the pinki-sh-salmon hue of rosé wines. However, the low quantity of tannins (antioxidants) and richness in phenolic acids, which can be easily oxidized into yellowish pigments, tend to predispose rosé wines to an undesirable browning. Although the use of SO₂ for the prevention of oxidation is highly extended, this practice is expected to be reduced. Therefore, the search for alternative oenological adjuvants that prevent the oxidation and browning of rosé wines is highly desired.

NEW INSIGHTS INTO THE FATE OF MARKERS INVOLVED IN FRESH MUSHROOM OFF-FLAVOURS DURING ALCOHOLIC FERMENTATION

The fresh mushroom off-flavour (FMOff) has been appearing in wines since the 2000s. Some C8 compounds such as 1-octen-3-one, 1-octen-3-ol, 1-hydroxyoctan-3-one, 3-octanol and others are involved in this specific off-flavour [1-3]. At the same time, glycosidic precursors of some FMOff compounds have been identified in musts contaminated by Crustomyces subabruptus [4], highlighting the role of aroma precursors in this specific taint. However, the fate of these volatile molecules and glycosidic fractions during fermentation is not well known.

HYBRID GRAPEVINE CV BACO BLANC, BETWEEN TRADITION AND MODERNISM: FOCUS ON ENDOGENOUS EUGENOL AS RESISTANCE FACTOR TO BOTRYTIS CINEREA

The well-known antifungal and antibiotic molecule, eugenol, is widely spread in various plants including clove, basil and bay. It is also abundant in the hybrid grapevine cultivar (cv) Baco blanc (Vitis vi-nifera x Vitis riparia x Vitis labrusca), created by François Baco (19th century) in the Armagnac region. This study confirmed this cv as highly resistant to Botrytis cinerea by comparing fruit rot incidence and severity with two Vitis vinifera cultivars: Folle Blanche and Ugni Blanc. We have demonstrated the efficiency of eugenol in vitro, by further investigating the effect of small concentrations of eugenol, 3 to 4 ppm (corresponding to IC10), on B. cinerea. By comparing the two major modes of action (direct or volatile antibiosis), the vapour inhibiting effect of eugenol was more powerful. In the skin of Baco blanc berry, the total eugenol concentration reached a maximum at veraison, i.e. 1118 to 1478 μg/kg.

UNEXPECTED PRODUCTION OF DMS POTENTIAL DURING ALCOOLIC FERMENTATION FROM MODEL CHAMPAGNE-LIKE MUSTS

The overall quality of aged wines is in part due to the development of complex aromas over a long period (1.) The apparition of this aromatic complexity depends on multiple chemical reactions that include the liberation of odorous compounds from non-odorous precursors. One example of this phenomenon is found in dimethyl sulphide (DMS) which, with its characteristic odor truffle, is a known contributor to the bouquet of premium aged wine bouquet (1). DMS supposedly accumulates during the ten first years of ageing thanks to the hydrolysis of its precursor dimethylsulfoniopropionate (DMSp.) DMSp is a possible secondary by-product from the degradation of S-methylmethionine (SMM), an amino acid iden- tified in grapes (2), which can be metabolized by yeast during alcoholic fermentation.

VOLATILE AND GLYCOSYLATED MARKERS OF SMOKE IMPACT: EVOLUTION IN BOTTLED WINE

Smoke impact in wines is caused by a wide range of volatile phenols found in wildfire smoke. These compounds are absorbed and accumulate in berries, where they may also become glycosylated. Both volatile and glycosylated forms eventually end up in wine where they can cause off-flavors. The impact on wine aroma is mainly attributed to volatile phenols, while in-mouth hydrolysis of glycosylated forms may be responsible for long-lasting “ashy” aftertastes (1).