Impact of Dealcoholization by Osmotic Distillation on Metabolic Profile, Phenolic Content, and Antioxidant Capacity of Low Alcoholic Craft Beers with Different Malt Compositions

Abstract

Beer antioxidants originate mainly from malts, classified as colored, caramel, and roasted, according to the malting process. This study aimed to characterize, in terms of phenolic antioxidants, three types of Pale Ale craft beers brewed using increasing percentage of dark malt (0, 5, and 15% Caraamber malt, called PA100, PA95, PA85, respectively) and to evaluate the impact of dealcoholization by osmotic distillation (OD) on the same antioxidants. All the alcoholic (PA, 6.2–6.8 vol %) and low alcoholic (LA-PA, 1 vol %) beers were analyzed by HPLC-ESI-MS/MS, total phenolic content (TPC), and antioxidant activity (AA): similar phenolic profiles were evidenced and 43 compounds identified or tentatively identified. Some differences were found among PA100, PA95, and PA85: PA85 was richer in free phenolic compounds (10.55 mg/L) and had a higher TPC (463.7 GAE mg/L) and AA (852.1 TE mg/L). LA-PA beers showed the same phenolic profile and similar TPC and AA compared to PA beers; however, there were some differences regarding LA-PA85 (5.91 mg/L). Dealcoholization by OD seemed to weakly affect the phenolic fraction. ESI-MS/MS infusion experiments evidenced oligosaccharides, small organic acids, and amino acids, whose presence was confirmed and quantitated by NMR: besides ethanol and other alcohols, weak to strong loss of low-molecular-weight metabolites was evidenced in LA-PA beers.

Targeted phenolic profile of radler beers by HPLC-ESI-MS/MS: the added value of hesperidin to beer antioxidants

“…In detail, numbered according to the elution order (t R , Table 3 ): 3,4,5-trihydroxybenzoic acid 1 (gallic acid, GA), 3,5-dihydroxybenzoic acid 2 (3,5-DHBA), 3,4-dihydroxybenzoic acid 3 (protocatecuic acid, PCA), 5-caffeoylquinic acid 4 (5CQA), 2,5-dihydroxybenzoic acid 5 (2,5-DHBA, gentisic acid), catechin 6 (Cat), 4-caffeoylquinic acid 7 (4CQA), p -hydroxybenzoic acid 8 (pHBA), vanillic acid 9 (VA), caffeic acid 10 (CA), syringic acid 11 (SyA), m -hydroxybenzoic acid 12 (mHBA), 2,6-dihydroxybenzoic acid 13 (2,6-DHBA), coumaric acid 14 (CuA), sinapic acid 15 (SA), ferulic acid 16 (FA), rutin 17 (Ru), myricitrin 18 (My), quercetin-3-O-glucoside 19 (Q3G), kampferol-3-O-rutinoside 20 (K3R), salicylic acid 21 (SaA), hesperidin 22 (He), quercetin 23 (Q), kampferol 24 (K), isoxanthohumol 25 (IsoX), xanthohumol 26 (X). The analysis was carried out by an HPLC-ESI-MS/MS in SIR mode method previously developed for 14 compounds ( 1 , 3 , 4 , 8 – 12 , 14 – 17 , 23 , 24 ) (Petrucci et al 2020b , 2021 ) and herein slightly modified to include 12 more compounds ( 2 , 5 – 7 , 13 , 18 – 22 , 25 , 26 ), whose quality-of-analysis parameters are resumed in Table 2 . Briefly, all calibration curves showed a good linearity in the investigated concentration range 10 ÷ 80 µg/L, as evidenced by the R 2 values ranging within 0.9715 ÷ 1 (the minimum value 0.9715 was found for X), reported in Table 2 ; LOD and LOQ values were in the concentration ranges 0.070 ÷ 10.23 µg/L and 0.22 ÷ 31.01 µg/L, respectively (the higher LOD and LOQ values were found for SaA).…”

“…CQAs 4 and 7 , and the hydroxybenzoic acids (HBAs) 1 , 2 , 5 and 12 were not detected in any of the samples; conversely, HBAs 8 , 9 , 11 and 21 were identified and quantitated in B and R1, 13 was identified in B, R1 and R2, 3 was found in trace only in L. Therefore, the investigated HBAs seemed not to be characteristic components of the Sicilian lemon, used for L. Noteworthy, the phenolic acids profile of lemon has been sparingly reported and the few papers are aligned with our results (Alu’datt et al 2017 ; Gorinstein et al 2001 ; Singh et al 2020 ; Xi et al 2017 ). Some differences between R1 and R2 (different brand) are likely due to different starting materials (malts and/or hops) used for the beers (Cheiran et al 2019 ; Cortese et al 2020 ; Gouvinhas et al 2021 ; Petrucci et al 2020b , 2021 ). Conversely, similarity between B and R1 might be expected, since R1 is likely prepared with B (same brand): in fact, B and R1 were not significantly different (p < 0.05) for HBAs, except for VA 9 .…”

“…Q 23 and K 24 are typical of beer too (Di Matteo P. et al, 2021 ; Gouvinhas et al 2021 ; Petrucci et al 2020b , 2021 ; Quifer-Rada et al 2015 ), mainly coming from hops. Quercetin was found in the free form ( 23 ) and in the bonded form, identified as Q3G 19 ; conversely, kampferol was present mainly as the bonded form, identified as K3R 20 , though it was detected also in the free form ( 24 ) in B and R1.…”

“…Calibration curves, LOD and LOQ of the other 14 standards (GA, PCA, pHBA, mHBA, 5CQA, VA, SyA, CA, FA, CuA, SA, Ru, Q, K) were used as previously reported in the literature (Petrucci et al 2020b(Petrucci et al , 2021.…”

Recent Advances in Electrochemical Chitosan-Based Chemosensors and Biosensors: Applications in Food Safety

“…Chromatographic techniques, coupled with different kinds of detector, from spectrophotometric ones to mass spectrometry ones, are the most commonly used methods for the determination of phenolic compounds, including HAs [56][57][58], although sophisticated equipment and laborious analytical procedures are required. Nevertheless, the use of electrochemical methods for analytical purposes is receiving increasing interest [55,59], and interesting examples of CHI-based electrochemical sensors and biosensors are reported in Table 1.…”