Detailed characterization of glycosylated sensory-active volatile phenols in smoke-exposed grapes and wine.

The exposure of Vitis vinifera L. vines to smoke from wildland fires can alter the chemical composition of the berries, such that the resulting wine can possess a defect known as smoke-taint. This work constitutes a complete method for the analysis of simple volatile phenol glycosides (VP-glycosides) that can be elevated in berries and wine following smoke exposure. We synthesized 16 model VP-glycosides, four of which are not reported previously, to facilitate method development. Fragmentation analysis using high-resolution accurate-mass spectrometry demonstrated that the glycone and aglycone influenced the fragmentation pattern of VP-glycosides. Diagnostic fragmentation patterns for the synthesized VP-glycosides were applied to identify several VP-glycosides in smoke-exposed berries and wine. The fragmentation pattern of VP-disaccharides should facilitate the characterization of modified glycones. Putative non-VP glycosides elevated in smoke-exposed berries are demonstrated for the first time. In tandem with VP-glycosides, such compounds may contribute to the expression of smoke taint.