Evolution of anthocyanin content during grape ripening and characterization of the phenolic profile of the resulting wine by comprehensive two-dimensional liquid chromatography.

The typical phenolic profile in grapes is characterized by its complexity both in terms of number of diverse chemical structures and their variation during ripening. Besides, the specific phenolic composition of grapes directly influences the presence of those components in the resulting wine. In this contribution, a new method based on the application of comprehensive two-dimensional liquid chromatography coupled to a diode array detector and tandem mass spectrometry has been developed to obtain the typical phenolic profile of Malbec grapes cultivated in Brazil. Moreover, the method has been demonstrated to be useful to study how the phenolic composition in grapes evolved during a 10-week ripening period. Main detected compounds in grapes and in the wine derived from them were anthocyanins, although a good number of polymeric flavan-3-ols were also tentatively identified, among other compounds. Results show how the amount of anthocyanins present in grapes was increased during ripening up to 5-6 weeks and then decreased towards week 9. The two-dimensional approach applied was demonstrated to be useful for the characterization of the complex phenolic profile of these samples, involving more than 40 different structures and has the potential to be further applied to the study of this important fraction is different grapes and wines systematically.

Fate of enniatins in the Ale beer production stages analyzed by a validated method based on matrix-matched calibration and LC-QToF-MS.

Enniatins (ENA, ENA1, ENB and ENB1) are emerging mycotoxins reported in malt used for brewing. This study aimed to assess the fate of ENA, ENA1, ENB and ENB1 throughout Ale beer brewing using a validated method based on matrix-matched calibration (MMC) and liquid chromatography with quadrupole time-of-flight mass spectrometry detection. MMC avoided the inaccurate quantification of all enniatins, since the matrix effects that cause signal suppression have been overcome. The validated method displayed linearity (R2 > 0.99), recovery (>88%), repeatability and intermediate precision (RSD < 9.0%) in accordance with the different guidelines of method validation. The values of LOD (<0.1 µg kg-1) and LOQ (<0.5 µg kg-1) were sensitive enough to detect enniatins throughout brewing. In the Ale beer production stages, enniatins levels were significantly reduced, ensuring that beers were free of these mycotoxins. In contrast, enniatins were found in all by-products of beer production due to their low water solubility.