Chemical Stability of Thiol and Flavanol Sulfonation Products during Wine Aging Conditions.

Bisulfite (HSO3-) is the predominant form of sulfur dioxide, present as free and bound to wine relevant electrophiles under wine acidic pH. While sulfonation reactions of flavanols and thiols have been recently reported as key for wine preservation against oxidation, the transient mechanisms and physicochemical parameters responsible for that remain unknown. In the present study, sulfonation reaction kinetics of thiols and flavanols were monitored under simulated wine aging conditions. The reaction products were then characterized by liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis, and their chemical stability during time was determined by 1H NMR spectroscopy. Thiol and flavanol sulfonation reaction yields were both promoted by the presence of iron and oxygen, while their chemical stability was confirmed under the same conditions. The sulfonation derivatives of epicatechin and cysteine were synthesized and quantified in young and aged wines. Higher concentrations were reported for both metabolites in older wines, indicating their participation on the strongly bound sulfur dioxide fraction. These findings offer new prospects for more precise use of sulfur dioxide in winemaking.

1H NMR based sulfonation reaction kinetics of wine relevant thiols in comparison with known carbonyls.

Sulfite addition is a common tool for ensuring wines' oxidative stability via the activity of its free and weakly bound molecular fraction. As a nucleophile, bisulfite forms covalent adducts with wine's most relevant electrophiles, such as carbonyls, polyphenols, and thiols. The equilibrium in these reactions is often represented as dissociation rather than formation. Recent studies from our laboratory demonstrate, first, the acetaldehyde sulfonate dissociation, and second, the chemical stability of cysteine and epicatechin sulfonates under wine aging conditions. Thus, the objective of this study was to monitor by 1H NMR the binding specificity of known carbonyl-derived SO2 binders (acetaldehyde and pyruvic acid) in the presence of S-containing compounds (cysteine and glutathione). We report that during simulated wine aging, the sulfur dioxide that is rapidly bound to carbonyl compounds will be released and will bind to cysteine and glutathione, demonstrating the long-term sulfur dioxide binding potential of S-containing compounds. These results are meant to serve as a complement to existing literature reviews focused on molecular markers related to wines' oxidative stability and emphasize once more the importance of S-containing compounds in wine aging chemical mechanisms.

Direct NMR evidence for the dissociation of sulfur-dioxide-bound acetaldehyde under acidic conditions: Impact on wines oxidative stability.

SO2 reaction with electrophilic species present in wine, including in particular carbonyl compounds, is responsible for the reduction of its protective effect during wine aging. In the present study, direct 1H NMR profiling was used to monitor the reactivity of SO2 with acetaldehyde under wine-like oxidation conditions. The dissociation of acetaldehyde bound SO2 was evidenced suggesting that released free SO2 can further act as an antioxidant. EPR and DPPH assays showed an increasing antioxidant capacity of wine with the increase in the concentration of acetaldehyde sulfonate. The presence of acetaldehyde sulfonate in wines was correlated with the overall antioxidant activity of wines. The first evidence of acetaldehyde bound SO2 dissociation provides a completely new representation of the long-term protection efficiency of SO2 during bottle aging.

NMR Spectroscopy Protocols for Food Metabolomics Applications.

NMR spectroscopy has become an indispensable tool for the metabolic profiling of foods and food products. In the present protocol, we report an analytical approach based on liquid-state NMR for the determination of polar and nonpolar metabolites in some common liquid (wine, spirits, juice) and solid (cheese, coffee, honey) foods. Although the diversity of foods precludes the use of a single protocol, with small modifications, the proposed methodologies can be adapted to a broader range of foodstuffs.