RESUMO
Anthocyanin profiles of juices from blueberry (Vaccinium myrtillus L.) and different grape varieties (Vitis labrusca L. cv. Concord, Vitis vinifera L. cvs. Accent, Dunkelfelder, Dakapo, and GM 674-1) were characterized by ultra-high performance liquid chromatography (UHPLC) coupled to trapped ion mobility spectrometry-quadrupole time-of-flight tandem mass spectrometry (TIMS-QTOF-MS/MS). Ion mobility and collision cross section (CCS) values of over 50 structurally related anthocyanins based on delphinidin, cyanidin, petunidin, peonidin, and malvidin were determined. Relations between molecular mass, mobility values, and specific structural features were revealed. The mass-to-charge (m/z) ratio of the molecular ions (M+) was found to be the major factor influencing anthocyanin ion mobilities, but structural characteristics also contributed to their variability. We were able to differentiate positional and geometrical isomers and certain epimers by their respective mobility values. For instance, whereas 3-O-hexosides (i.e., 3-O-glucosides and 3-O-galactosides) were separated by TIMS, epimers of 3-O-pentosides assessed could not be distinguished.
RESUMO
Potentially health-promoting concentrations of flavan-3-ols were previously shown to be retained in apple juices produced with the emerging spiral filter press. Due to the novelty of this technology, the factors governing the stability of flavan-3-ol-rich apple juices have only scarcely been studied. Therefore, we produced flavan-3-ol-rich apple juices and concentrates (16, 40, 70 °Brix) supplemented with ascorbic acid (0.0, 0.2, 1.0 g/L) according to common practice. Flavan-3-ols (DP1-7) and twelve flavan-3-ol reaction products were comprehensively characterized and monitored during storage for 16 weeks at 20 and 37 °C, employing RP-UHPLC- and HILIC-DAD-ESI(-)-QTOF-HR-MS/MS. Flavan-3-ol degradation followed a second-order reaction kinetic, being up to 3.5-times faster in concentrates (70 °Brix) than in single strength juices (16 °Brix). Furthermore, they diminished substantially faster compared to other phenolic compounds. For instance, after 16-weeks at 20 °C, the maximum loss of flavan-3-ols (-70 %) was greater than those of hydroxycinnamic acids (-18 %) and dihydrochalcones (-12 %). We observed that flavan-3-ols formed adducts with sugars and other carbonyls, such as 5-(hydroxymethyl)furfural and the ascorbic acid-derived L-xylosone. Increased degradation rates correlated particularly with increased furan aldehyde levels as found in concentrates stored at elevated temperatures. These insights could be used for optimizing production, distribution, and storage of flavan-3-ol-rich apple juices and other foods and beverages.
Assuntos
Aldeídos , Ácido Ascórbico , Flavonoides , Armazenamento de Alimentos , Sucos de Frutas e Vegetais , Malus , Ácido Ascórbico/química , Malus/química , Sucos de Frutas e Vegetais/análise , Flavonoides/análise , Aldeídos/análise , Manipulação de Alimentos/métodos , Açúcares/química , Espectrometria de Massas em Tandem , Cromatografia Líquida de Alta Pressão , Filtração , Cinética , Frutas/químicaRESUMO
The retention of flavan-3-ols and other phenolic compounds during apple juice production at pilot plant scale (200 kg, cv. Boskoop) was investigated. An oxygen-excluding spiral filter press and a conventional decanter were used with and without pectinase mash treatment. Phenolic compounds were comprehensively identified and quantitated by RP-UHPLC and HILIC, both coupled to DAD-FLD and DAD-ESI(-)-QTOF-HR-MS/MS. These techniques combined with using a NIST cocoa flavan-3-ol standard allowed for the first time an individual quantification of flavan-3-ol fractions (DP 1-7) in apple juices. Spiral filter-pressed juices were exposed to less oxidation and exhibited four times higher total phenolic compound levels than decanter-made juices (1016 vs. 262 mg/L). Apple juices derived from pectinase-treated mashes had lower total phenolic compound levels than their non-treated counterparts. However, those made by spiral filter press still retained significantly higher concentrations (780 vs. 104 mg/L). Flavan-3-ols were especially well retained by spiral filter press processing, reaching unprecedentedly high concentrations of up to 713 mg/L. A 280 mL serving of non-treated spiral filter-pressed juice would therefore suffice to provide the daily intake of 200 mg flavan-3-ols, equaling the dose of cocoa flavan-3-ols associated with an authorized European health claim for healthy blood flow.