The metabolic fate of red wine and grape juice polyphenols in humans assessed by metabolomics

The metabolic impact of polyphenol‐rich red wine and grape juice consumption in humans was studied using a metabolomics approach. Fifty‐eight men and women participated in a placebo‐controlled, double‐crossover study in which they consumed during a period of 4 wk, either a polyphenol‐rich 2:1 dry mix of red wine and red grape juice extracts (MIX) or only a grape juice extract (GJX). Twenty‐four‐hour urine samples were collected after each intervention. ¹H NMR spectroscopy was applied for global metabolite profiling, while GC‐MS was used for focused profiling of urinary phenolic acids. Urine metabolic profiles after intake of both polyphenol‐rich extracts were significantly differentiated from placebo using multilevel partial least squares discriminant analysis. A significant 35% increase in hippuric acid excretion (p<0.001) in urine was measured after the MIX consumption as) or only a red grape juice dry extract (GJX). 24‐h urine samples were collected after each intervention. 1H‐NMR spectroscopy was applied for global metabolite profiling, while gas chromatography‐mass spectrometry (GC‐MS) was used for focused profiling of urinary phenolic acids. Urine metabolic profiles after intake of both polyphenol‐rich extracts were significantly differentiated from placebo using multilevel partial least squares discriminant analysis (ML‐PLS‐DA). A significant 35% increase in hippuric acid excretion (p<0.001) in urine was measured after the MIX consumption compared with placebo, whereas no change was found after GJX consumption. GC‐MS‐based metabolomics of urine allowed identification of 18 different phenolic acids, which were significantly elevated following intake of either extract. Syringic acid, 3‐ and 4‐hydroxyhippuric acid and 4‐hydroxymandelic acid were the strongest urinary markers for both extracts. MIX and GJX consumption had a slightly different effect on the excreted phenolic acid profile and on endogenous metabolite excretion, possibly reflecting their different polyphenol composition.     

Physicochemical characterization of special persimmon fruit beers using bohemian pilsner malt as a base

This study involved the production of special fruit ale beers with different concentrations (100:0%, 75:25%, 50:50% and 25:75% v /v) of barley malt and persimmon juice from the ‘Rojo Brillante’ variety. Fermentation took place under beer quality control parameters and the influence of persimmon juice on beer quality was investigated. Colour, turbidity, pH, titratable acidity, total soluble solids, sugars, organic acids, total phenolic compounds, antioxidant capacity and ethanol formation were determined during the fermentation process. These fruit beers, whose alcoholic contents were within the standards (3.6–5.63% v /v ethanol), were characterized by a normal acid pH (3.97–4.13) with citric and lactic acids the most abundant organic acids, a clear golden colour without turbidity [2.05–2.83 European Brewery Convention units], intermediate total phenolic compound values (283.0–327.1 mg GAE/L) and antioxidant activities between 1.65 and 5.78 mm TE/L. The persimmon beverage which contained 75% fruit juice was the most valued and preferred by the panelists followed by the 50:50% wort–persimmon beer. Copyright © 2017 The Institute of Brewing & Distilling     

Characterisation of black cumin,pomegranate and flaxseed meals as sources of phenolic acids

The article focuses on the extraction of ten phenolic acids from black cumin (Nigella sativa L.), pomegranate (Punica granatum L.) and flax (Linum usitatissimum L.) seed meals. The extracts have been fractionated as free, esterified and insoluble‐bound phenolic compounds and quantitatively determined by HPLC–PDA. The analysed meals can be utilised for obtaining valuable phenolic acids. However, the distribution of phenolic compounds varies depending on the meal source. The insoluble‐bound fraction has been the richest for the black cumin meal, both qualitatively and quantitatively, containing all ten analysed phenolics. In the pomegranate meal, the main phenolic has been gallic acid, accounting for nearly 48% in free form. The esterified form of the flaxseed meal has been abundant with ferulic (1025.44 ± 3.99 mg kg^?1 dry weight), caffeic and p‐coumaric acids. The total amount of phenolic acids would be underestimated if only free fractions would be taken into account, while neglecting esterified (for the pomegranate and flax meals) and insoluble‐bound fractions (for the black cumin and pomegranate meals).     

Phenolic composition and antioxidant activity of white mulberry (Morus alba L.) fruits

Eight major mulberry cultivars [Nakhonratchasima 60 (NS 60), Buriram 60 (BR 60), Chumphon (CP), Wavee (WV), Chaingmai (CM), Pikultong (PT), Kamphaengsaen (KS) and Kamnanchul (KJ)] cultivated in Thailand were assessed for their flavonoid and phenolic acid composition using HPLC and tested for antioxidant potential using 2,2‐diphenyl‐1‐picrylhydrazyl hydrate (DPPH) assay. The total phenolic content (TPC) ranged from 104.78 to 213.53 mg GAE/100 g DW, and total flavonoid content (TFC) ranged from 69.58 to 211.01 mg CE/100 g DW. The major flavonoid compounds in mulberry fruit cultivars were (+)‐catechin (309.26–750.01 mg/100 g DW), procyanidin B1 (62.59–224.41 mg/100 g DW), quercetin (5.36–58.42 mg/100 g DW), rutin (18.73–26.90 mg/100 g DW) and (?)‐epicatechin (8.47–29.21 mg/100 g DW). Gallic acid, cinnamic acid and p‐hydroxybenzoic acid were found to be the major phenolic acids in mulberry fruit cultivars. The gallic acid and cinnamic acid contents ranged from 7.33 to 23.90 mg/100 g DW and from 11.64 to 15.05 mg/100 g DW, respectively. p‐Hydroxybenzoic acid content ranged from 1.77 mg/100 g DW (PT) to 7.13 mg/100 g DW (KJ). DPPH‐scavenging ability was excellent for ethanolic extract of NS 60, and EC₅₀ value of NS 60 (241.83 μg mL^?1) was significantly lower than those of the others (P < 0.05). TPC and TFC of the mulberry fruit were positively correlated with the DPPH‐scavenging ability.     

Antioxidant properties and phenolic content of sulla (Hedysarum spp.) honeys from Southern Italy

The geographical origin greatly influences the qualitative and nutraceutical characteristics of honey. In this study, a total of twenty‐four sulla honeys from eight different geographical areas of Southern Italy have been examined for total phenolic content (Folin–Ciocalteu method), antioxidant activity (FRAP and DPPH assays), colour intensity (ABS₄₅₀), and identification and quantification of phenolic acids (RP‐HPLC/UV‐VIS method). The total phenolic content ranged from 47.9 (Potentino honeys) to 248.3 mg GAE per kg honey (Penisola Sorrentina honeys). The antioxidant activity ranged from 47.06% (Basso Pollino honeys) to 88.25% (Penisola Sorrentina honeys), and from 98.26 μM Fe (II) (Potentino honeys) to 786.53 μm Fe (II) (Tarantino honeys) for DPPH and FRAP assays, respectively. Major phenolic acids identified in analysed samples were gallic, caffeic and ferulic acids. Correlations between the parameters analysed were statistically significant (P < 0.05). The results of the study showed that the parameters studied are greatly affected by the peculiarities of their production area.     

Determination of organic acids evolution during apple cider fermentation using an improved HPLC analysis method

An efficient method for analyzing ten organic acids in food, namely citric, pyruvic, malic, lactic, succinic, formic, acetic, adipic, propionic and butyric acids, using HPLC was developed. Boric acid was added into the mobile phase to separate lactic and succinic acids, and a post-column buffer solution [5 mmol/L p-toluensulfonic acid (p-TSA) + 20 mmol/L bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane (bis–tris) + 100 μmol/L sodium ethylenediaminetetraacetic (EDTA-2Na)] was used to improve the sensitivity of detection. The average spiked recoveries for the ten organic acids ranged from 82.9 to 127.9% with relative standard deviations of 1.44–4.71%. The linear ranges of determination were from 15 to 1,000 mg/L with correlation coefficients of 0.9995–0.9999. The metabolism of organic acids in cider, and the effect of nutrients including diammonium phosphate (DAP), thiamine, biotin, niacinamide and pantothenic acid on their metabolism, were studied using this method of analysis. We found that before cider brewing, additions of 200 mg/L DAP and 0.3 mg/L thiamine to apple juice concentrate results in a high quality cider. F. Zhou and B. Ji contributed equally to this work.     

Fruit Phenolic Composition of Different Elderberry Species and Hybrids

The aim of this study was to investigate a detailed composition and content of phenolic compounds in fruits of 4 elderberry species (Sambucus nigra, S. cerulea, S. ebulus, and S racemosa) and 8 interspecific hybrids. Hydroxycinnamic acids (HCAs) represented the major share of phenolics in analyzed elderberries; caffeoylquinic and p‐coumaroylquinic acids were most abundant. Flavanols (catechin, epicatechin, and different procyanidins) were the second major phenolic group detected in range from 2% to 30% of total analyzed phenolics. From the group of flavonols, 13 different quercetin glycosides, 7 kaempferol glycosides, and 8 isorhamnetin glycosides have been quantified. Rutin was the major flavonol in all studied genotypes. S. ebulus was characterized by the highest level of total HCAs, catechin, epicatechin, and most flavonols. Some elderberry hybrids, for example JA × RAC, CER × NI, and JA × (JA × NI), are perspective for further studies because they have high content of phenolic compounds. The results of research could contribute to breed cultivars, which may prove interesting for food‐processing industries.     

Phenolic content,antioxidant and physico‐chemical properties of Sardinian monofloral honeys

In this study, fifty‐one monofloral Sardinian honeys from ten various floral origins were screened for their phenolic content, antioxidant activity, colour and electrical conductivity. The total phenolic amounts have been evaluated by Folin–Ciocalteu method, whereas quantification of several phenolic compounds (phenolic acids and flavonoids) has been carried out by HPLC‐DAD technique. The richest sample in phenolic compounds resulted strawberry tree honey with about 40 mg GAE/100 g, as well FRAP test and DPPH˙ test confirm that antioxidant activity of strawberry tree honey extract exceed both honey extracts and synthetic antioxidants like BHA and BHT. Among the studied phenolic compounds a total of five phenolic acids (ferulic, syringic, trans‐cinnamic, chlorogenic and p‐hydroxycinnamic) and nine flavonoids (catechin, kaempferol, rutin, quercetin, luteolin, apigenin, galangin, pinocembrin and pinobanksin) were identified. Our results show good correlations between total polyphenol amount and antioxidant activity and between colour and electrical conductivity.     

Phenolic acid concentrations in organically and conventionally cultivated spring and winter wheat

BACKGROUND: Organic crops are often thought to contain more phenolic secondary metabolites than conventional ones. This study evaluated the influence of organic and conventional farming on concentrations of phenolic acids in spring and winter wheat cultivars. RESULTS: Five phenolic acids were identified: ferulic, sinapic, p‐coumaric, vanillic and p‐hydroxybenzoic acid. Ferulic acid was the main phenolic acid in the grain of all tested wheat varieties. Significant differences among the examined cultivars in concentration of particular compounds were observed. Concentrations of phenolic acids varied significantly in organic and conventional wheat. Levels of ferulic and p‐coumaric acids, as well as the total phenolic acid content were higher in organic crops. Concentrations of sinapic acid in spring wheat, as well as vanillic and p‐hydroxybenzoic acid levels in both types of wheat were significantly higher in conventional grains. The 1000 kernel weight (TKW) of spring and winter wheat was significantly lower in organic crops. CONCLUSION: Organically produced spring and winter wheat had significantly higher concentrations of ferulic and p‐coumaric acid as well as the total phenolic acid content than conventional wheat, though the differences in the levels of phenolics were not large. However, these differences are probably caused mainly by smaller size of organic wheat kernels (lower TKW). Copyright © 2011 Society of Chemical Industry     

Determination of volatile carboxylic acids (C1–C5i) and lactic acid in aqueous acid extracts of silage by high performance liquid chromatography

A simple isocratic h.p.l.c. technique was developed for the simultaneous quantitative analysis of lactic, formic, acetic, propionic, isobutyric, n-butyric and isovaleric acids in aqueous acid extracts of silage. An Aminex HPX-87H strong cation exchange resin column at 41°C, 0.0025M H₂SO₄ mobile phase and ultraviolet detector at 210 nm were utilised. Estimated recoveries of acids added to silage ranged from 98.2 to 103.5%.     

Characterization of the phenolic acid profile and in vitro bioactive properties of white beetroot products

The impact of boiling, baking and fermentation treatment on the phenolic acid profile, antioxidant capacity (AC) and angiotensin-1 converting enzyme (ACE) activity of white beetroot was investigated. The phenolic acids were analysed by liquid chromatography–mass spectrometry (micro-HPLC-MS/MS), while AC and ACE were determined by in vitro assays. Phenolic acids concentration was between 87.55 and 100.98 ng g⁻¹ d.m. Ferulic and p-coumaric acids were the main compounds among the nine phenolic acids identified. Boiling increased the phenolic acid content by 3%; however, baking and fermentation reduced the level of these acids by approximately 6% and 11%, respectively. A significant positive correlation was observed between the results of all AC assays and sinapic and caffeic acid content. The ACE inhibitory activity of white beetroot products may be attributable to the combined effect of the syringic, 4-hydroxybenzoic, ferulic and p-coumaric acids. Our study indicates that white beetroot as a novel product may be a valuable source of phenolic acids and functional properties.     

Development of a reversed-phase high performance liquid chromatography (RP-HPLC) procedure for the simultaneous determination of phenolic compounds in peanut skin extracts

A reversed-phase high performance liquid chromatography (RP-HPLC) procedure was developed for simultaneous determination of five phenolic acids, two stilbenes and eight flavonoids in peanut skin extract. A C₁₈ column fitted with diode array detection at 250 and 320, 280 and 370, and 306 nm for phenolic acids, flavonoids and stilbenes, respectively, with mobile phase consisting of 0.1% formic acid in water and 0.1% formic acid in 100% acetonitrile. Phenolic compounds were eluted with good resolution (Rs > 1.5) within 95 min as follows: gallic, protocatechuic, epigallocatechin, catechin, β-resorcylic (internal standard), caffeic, procyanidin B₂, epicatechin, epigallocatechin gallate, p-coumaric, ferulic, piceid, epicatechin gallate, catechin gallate, resveratrol and quercetin. The variation in recovery and reproducibility in peak area was <11 and <2.5%, respectively. The correlation coefficients, r, of calibration curves of the 15 compounds were >0.999. The method was used to quantify phenolic compounds in peanut skin extracts from Runner, Virginia and Spanish peanuts.     

Phenolic acids, flavonoids, vitamin C and antioxidant capacity of strawberry juices processed by high-intensity pulsed electric fields or heat treatments

The effect of high-intensity pulsed electric fields (HIPEF) processing (35 kV/cm for 1,700 μs in bipolar 4-μs pulses at 100 Hz) on individual phenolic compounds (phenolic acids and flavonoids), vitamin C and antioxidant capacity of strawberry juice was evaluated and compared to heat (90 °C for 60 or 30 s) and fresh juice as a reference. Although strawberry juice underwent a substantial depletion of health-related compounds with storage time irrespective of the treatment conducted, ellagic acid was enhanced. HIPEF-treated strawberry juice maintained higher amounts of phenolic acids (ellagic and p-coumaric acid) and total anthocyanins than the thermally treated juices during the storage period. Regarding the antioxidant capacity, similar DPPH and ABTS values were obtained so that differences among pasteurized juices were non significant. HIPEF processing may be a technology as effective as thermal treatments not only to achieve safe and stable juices, but also to obtain juices with a high content of antioxidant compounds.     

Effects of roasting degree on radical scavenging activity,phenolics and volatile compounds of Arabica coffee beans (Coffea arabica L. cv. Catimor)

We investigated the effect of roasting degree on volatile and phenolic compounds of coffee beans (Coffea Arabica L. cv. Catimor). The colour, 1,1‐diphenyl‐2‐picrylhydrazyl radical‐scavenging activity and phenolic acids of the aqueous extracts were studied. For the colour, L and b values were increased with an increase in roasting degree. Increasing roasting degrees led to a decrease in radical‐scavenging activity. Maximum radical‐scavenging activity was observed for the light‐roasted coffee. Chlorogenic acid was the most predominant amongst the ten phenolic acids identified, in green and all roasted beans. Syringic acid, p‐coumaric acid, gallic acid and sinapic acid increased with an increase in roasting degree. The volatile compounds were analysed using gas chromatography and mass spectroscopy. Aldehyde was the major volatile compound in green coffee. Our study has demonstrated that light‐roasted coffee gave the most desirable quality of roasted coffee with respect to phenolic content and radical‐scavenging activities.     

Phenolic acids from malt are efficient acetylcholinesterase and butyrylcholinesterase inhibitors

Anticholinesterase activities of mashes produced using wheat (‘Wheat Pale’) or barley malts (‘Pilsner’, ‘Pale Ale’, ‘Munich Light’, ‘Carahell’ or ‘Carared’) were studied by spectrophotometric method. The highest inhibition of acetylcholinesterase and butyrylcholinesterase was observed at 52 °C and/or 64 °C, followed by a decrease or stabilization of the activity at 72 °C. Changes in the total phenolics content in the test mashes were correlated with changes in the acetylcholinesterase and/or butyrylcholinesterase activities. Phenolic acids were singled out from phenolic compounds for more detailed studies owing to their simplicity and structural similarity to well‐known cholinesterase inhibitors. The main phenolic acids in the test malts were ferulic, gallic, p‐coumaric and vanillic acids followed by chlorogenic, caffeic, syringic, p‐OH‐benzoic, sinapic and protocatechuic acids. The anticholinesterase activities of the phenolic acids were studied using model standard solutions at concentrations similar to the maximal content of these compounds in the test mashes. Among the phenolic acids, p‐coumaric acid had the largest share in the anticholinesterase activity, even though it was present in the test mashes at a significantly lower concentration (~0.38 mm L^?1) than ferulic acid (~1.00 mm L^?1). Sinapic acid and p‐OH‐benzoic acid (0.03 and 0.01 mm L^?1, respectively) were equally efficient inhibitors as ferulic acid at ~1.00 mm L^?1. This preliminary study should be extended to other phenolic compounds from malt (wort) in the near future. Copyright © 2012 The Institute of Brewing & Distilling     

The effect of addition of chokeberry, flowering quince fruits and rhubarb juice to strawberry jams on their polyphenol content, antioxidant activity and colour

The aim of the study was to establish whether the addition of berries (flowering quince, chokeberry) and rhubarb juice during jam processing improves its colour and enriches jams in polyphenol compounds other than those found in strawberries. The sum of phenolic compounds determined by HPLC was distributed in a wide concentration range depending on the cultivar. Jams prepared from Elkat cultivar had 27% more total phenolic compounds than jams prepared from Senga Sengana. The following compounds were identified in jams prepared from strawberries: p-coumaric, ferulic and ellagic acids, quercetin, kaempferol, anthocyanins, (+)-catechin, (−)-epicatechin and proanthocyanidins. Proanthocyanidins and ellagic acid are the major polyphenol compounds of all strawberries jams. The Elkat cultivar (47.34 mg/100 g) contained higher amounts of proanthocyanidins compared to Senga Sengana (29.95 mg/100 g). The addition of 10% of flowering quince and chokeberry to jams during their preparation resulted in the increase in the content of phenolic components in final products, especially for proanthocyanidins. The highest level of total polyphenols (P < 0.05) was found in strawberry mixed with chokeberry, 237.82 mg/100 g for Senga Sengana and 260.61 mg/100 g for Elkat. There has been a marked increase of proanthocyanidins content (5.4 and 4.0 times) in jams made from Senga Sengana and Elkat cultivars mixed with chokeberry. However, the addition of rhubarb juice did not increase the content of polyphenol in Senga Sengana jam (not statistically significant). Antioxidant activity of strawberry jam was determined by 2,2′azinobis-(3-ethylbenzthiazoline-6-sulphonic acid (ABTS), 1,1-Diphenyl-2-picrylhydrazyl radical (DPPH) and ferric reducing/antioxidant power methods (FRAP). The antioxidant activity of this mixed jam was more than two times higher (P < 0.05) than control sample of strawberry jam. Rhubarb juice had high effect on L* (lightness) value in case of all strawberry varieties. The redness (a*), and yellowness (b*) were significantly different in jams with supplement. Strawberry jam with chokeberries had smaller L* value than control and other samples, and the lowest a* and b* values. This variation could be due to the nature of the pigments in these fruit cultivars and the content of anthocyanins which resulted in more reddish colour.     

Release of phenolic acids from defatted rice bran by subcritical water treatment

BACKGROUND: Oil production from rice bran, an undervalued by‐product of rice milling, produces defatted rice bran (DRB) as a waste material. Although it is considered a less valuable product, DRB still contains useful substances such as phenolic compounds with antioxidant, UV‐B‐protecting and anti‐tumour activities. In this study the phenolic acids in DRB were extracted with subcritical water at temperatures of 125, 150, 175 and 200 °C. RESULTS: Analysis of total phenolics using Folin–Ciocalteu reagent showed about 2–20 g gallic acid equivalent kg^?1 bran in the extracts. High‐performance liquid chromatography analysis showed low contents of phenolic acids (about 0.4–2 g kg^?1 bran). Ferulic, p‐coumaric, gallic and caffeic acids were the major phenolic acids identified in the extracts. Thermal analysis of the phenolic acids was also done. The thermogravimetric curves showed that p‐coumaric, caffeic and ferulic acids started to decompose at about 170 °C, while gallic acid did not start to decompose until about 200 °C. CONCLUSION: Subcritical water can be used to hydrolyse rice bran and release phenolic compounds, but the high temperatures used in the extraction can also cause the decomposition of phenolic acids. Copyright © 2010 Society of Chemical Industry     

Phenolic profile of blackberry wine produced using Korean winemaking techniques in earthenware jars

This research evaluated the winemaking potential of ‘Natchez’ and ‘Triple Crown’ blackberries grown in Oklahoma and examined the phenolic composition of blackberry wines made using modified Korean traditional winemaking techniques. The winemaking variables were fermentation temperature (21.6 vs 26.6°C), and fermentation type (yeast inoculation vs wild fermentation). High‐performance liquid chromatography was used to examine the phenolic compounds in blackberry juice and wine. The phenolic compounds consisted of anthocyanins (kuromanin, keracyanidin, delphinidin) and phenolic acids (gallic acid, catechin, caffeic acid, epicatechin, p‐coumaric acid). The ‘Natchez’ berries had higher concentrations of anthocyanins (kuromanin) while ‘Triple Crown’ berries had higher levels of phenolic acids (p‐coumaric acid). For many compounds, a higher fermentation temperature generally corresponded to higher concentrations of the phenolic compound in the wine after three months aging, but this was not universally observed. Accordingly, fermentation temperature may best be matched with individual cultivars via experimentation in order to maximise extraction and retention of phenolic compounds in the finished wines. Overall, the Korean traditional winemaking technique may be a good technique to add value to wines made from blackberries suited for production in a mid‐continental climate such as the central USA. © 2018 The Institute of Brewing & Distilling     

The Effect of Hydroxycinnamic Acids and Volatile Phenols on Beer Quality

To the consumer, beer should be an agreeable beverage of attractive colour, clarity, pleasing flavour and should carry no toxic substances. One of the major constituents of barley is phenolic acids and their direct effect on the quality of beer is still a mystery. The aim of the study therefore was to investigate the relationship between phenolic acids during mashing at different temperatures and the quality of the beer. The mash regime and liquor to malt ratios were optimised and the carbohydrates obtained were analysed at 3.5 L of water per kg of malt and a total mash time of 105 min. Carbohydrate and phenolic acid analyses were performed by HPLC coupled with a UV‐vis detector. The three different malts used had a phenolic acid content of 33.25 μg/mL, 25.44 μg/mL and 19.98 μg/mL for malt A, B and C, respectively. The plot of 1/T versus Ln(t) gave a negative slope with activation energy (E_a) = 209 KJ/mol, rate constant (k) = 4.6 × 10^?4 mg/L min, which are comparable to similar data reported in the literature. The kinetics studies showed that the optimised mashing temperature of 90°C was adequate to form 4‐vinylguaiacol by thermal decarboxylation from the hydroxycinnamic acids. This study has shown that there is no direct correlation between phenolic acids and oxidative flavour stability of beer while the corresponding volatile phenols may affect beer flavour.