Impact of harvest maturity on the aroma characteristics and chemistry of Cascade hops used for dry-hopping.

The impact of ripening on the dry-hop aroma potential and chemical development of Cascade hops is not well understood. Therefore, 5-6 weekly hop samples were collected over the 2014, 2015 and 2016 harvests. Concentrations of humulones did not change as a function of harvest date, while total hop essential oil content displayed significant positive trends. Concentrations of thiol precursors decreased over harvest while concentrations of free thiols increased. These weekly samples were used to dry-hop an unhopped base beer. Overall hop aroma intensity and citrus quality attributed to beer during dry-hopping increased as a function of harvest date. These results suggest that for brewers to maximize the efficiency of hop usage, early harvested Cascades might be better for bittering, while, later harvested Cascades might be better for dry-hopping or aroma additions because they attributed more intense citrusy aromas to beer and had higher concentrations of free thiols and terpene alcohols.

Revisiting the evaluation strategy of varietal thiol biogenesis.

The varietal thiols 3-mercaptohexan-1-ol (3MH), 3-mercaptohexyl acetate (3MHA), and 4-mercapto-4-methylpentan-2-one (4MMP) are key aroma compounds in wine due to the tropical notes they impart. They are released by yeast during alcoholic fermentation from different precursors. However, a large part of 3MH origin remains unknown. In this study, we focused on dipeptide forms arising from glutathione S-conjugates to 3MH and 4MMP. Using labelled tracers, we showed in spiked must the release of varietal thiols from 4 different compounds. We highlighted the interconversion between different forms of precursors under defined enological conditions. Cysteinyl-glycine S-conjugates are partially degraded into cysteine S-conjugates, contrary to γ-glutamyl-cysteine S-conjugates. Glutathione S-conjugate to 3MH can be partially degraded to γ-glutamyl-cysteine S-conjugate to 3MH. For the first time, all these labeled forms of precursors were found to release 3MH or 4MMP between 0.17 and 1% molar conversion yield. Two different yeasts were compared without any significant difference.

First identification and quantification of S-3-(hexan-1-ol)-γ-glutamyl-cysteine in grape must as a potential thiol precursor, using UPLC-MS/MS analysis and stable isotope dilution assay.

Varietal thiols are key aroma compounds in wine issued from multiple and complex origins. Several precursor families have been identified in grapes and must and have been widely studied. But a large part of thiol origin still remains unknown. Thus, we only have an incomplete picture of thiol precursors and there is a lack of knowledge on pre-fermentative mechanisms that can impact their levels. Our study focused on the formal identification and the quantification of new varietal thiol precursors in must. First of all, we synthesized natural and labeled standards using an original multi-step strategy, then we developed and validated a UPLC-MS/MS method that allowed us to identify and quantify for the first time a dipeptide S-conjugate to 3MH, the γGluCys-3MH, in Sauvignon B. We observed the S-4-mercapto-4-methylpentan-2-one-l-cysteinyl-glycine (CysGly-4MMP) and S-4-mercapto-4-methylpentan-2-one-N-(l-γ-glutamyl)-l-cysteine (γGluCys-4MMP) but at too low concentration to be quantified.

Innovative analysis of 3-mercaptohexan-1-ol, 3-mercaptohexylacetate and their corresponding disulfides in wine by stable isotope dilution assay and nano-liquid chromatography tandem mass spectrometry.

Both 3-mercaptohexan-1-ol (3MH) and 3-mercaptohexyl acetate (3MHA) were largely studied for the last 20 years due to their pleasant olfactory notes conferred to wine. Until now, many analytical methods focused only on the free forms of both 3MH and 3MHA in wine that provided partial information in the wine aroma evolution. Our study proposes new analytical measurements which allow quantification of both free and disulfide forms of 3MH and 3MHA to better understand the redox phenomenon occurring in wines and further, to orientate wine aroma evolution. Free thiols were analyzed by an original method based on maleimide derivatization allowing in-situ disulfide reduction followed by SIDA-LC-MS/MS analyses exhibiting excellent performances. Indeed, the accuracy ranged from 95 to 110% in three different wine matrices and the repeatability and intermediate reproducibility were inferior to 15% (RSD measurements). Our method exhibited very low limits of detection, which are below to 0.5ng/L and inferior to the perception thresholds of both compounds. Then, this method was applied to three different wines exposed to several oxidative conditions. On the one hand, it was demonstrated that copper sulfate treatment firstly destroyed the total amount of free 3MH to the benefit of thioether and disulfides compounds, with proportions that could be slightly modified by glutathione addition. On the other hand, oxygenation of wines resulted in partial free 3MH destruction to the benefit of thioether compounds. We proposed for the first time an innovative analysis that gives a complete picture of wine aroma, which can be really useful to winemakers to manage wine aroma evolution and to take advantage of the disulfide reservoir.