- Email: [email protected]
Stability, antioxidant activity and phenolic composition of commercial and reverse osmosis obtained dealcoholised wines
LWT - Food Science and Technology 44 (2011) 1369e1375
Contents lists available at ScienceDirect
LWT - Food Science and Technology journal homepage: www.elsevier.com/locate/lwt
Stability, antioxidant activity and phenolic composition of commercial and reverse osmosis obtained dealcoholised wines M. Bogianchini a, Ana B. Cerezo a, A. Gomis b,1, F. López b, M.C. García-Parrilla a, * a
Department of Nutrition Food Science, Toxicology and Legal Medicine, Faculty of Pharmacy, University of Seville, c/. Professor García González 2, E-41012 Seville, Spain Grup d’Investigació en Tecnología d’Aliments (GITA), Departament d’Enginyeria Química, Facultat d’Enologia, Universitat Rovira i Virgili, Av. Països Catalans 26, 43007 Tarragona, Spain
b
a r t i c l e i n f o
a b s t r a c t
Article history: Received 26 July 2010 Received in revised form 20 January 2011 Accepted 31 January 2011
The purpose of this work is to evaluate the phenolic profile and the antioxidant activity of commercial dealcoholised wines and monitor the stability of their composition over time. This work also aims to test the influence of reverse osmosis (RO) process on phenolic compounds and on the antioxidant activity (AA) of dealcoholised wine. AA was measured by ORAC, DPPH and FRAP assays. Phenolic compounds were determined by LC-DAD. In the commercial dealcoholised wines, AA fell by between 33% and 54% and the concentration of phenolic compounds decreased significantly after 30 days of storage. However, RO process did not significantly affect any phenolic acids, regardless of their chemical structure (benzoic acids, cinnamic acids) and alcoholic degree. The AA and phenolic compounds of these products were monitored for seven months. No significant changes were observed. RO process therefore makes it possible to obtain a healthy, low-alcohol (<2% v/v) product with bioactive compounds that are stable in the product and are similar to those found in the original wine. Ó 2011 Elsevier Ltd. All rights reserved.
Keywords: Dealcoholised wine Antioxidant activity Polyphenols Stability
1. Introduction Wine e especially red wine e is renowned for being good for one’s health. Its phenolic composition has recently been reviewed (Monagas, Bartolomé, & Gómez-Cordovés, 2005) because of its health benefits and sensory properties (Noble, 2002). Wine is not the only polyphenol-rich product available on the market: there are a number of commercial ready-to-drink polyphenol-rich beverages whose marketing strategies centre around their antioxidant activity (Seeram et al., 2008). However, alcohol content limits wine consumption for several reasons. First, some people cannot drink ethanol or must not drink alcohol. Removing the alcohol allows these people to enjoy the benefits of the phenolic compounds in wines. Second, traffic regulations limit alcohol consumption before driving and alcohol abuse is a highly worrying issue for many authorities, and both governments and producers of alcoholic beverages have shown an interest in developing low-alcohol drinks. Finally, persons suffering from oxidative stress are also advised to avoid wine consumption because of the alcohol it
* Corresponding author. Tel.: þ34954556760; fax: þ34954233765. E-mail address: [email protected] (M.C. García-Parrilla). 1 Present address: Institut Català de la Vinya i el Vi (Incavi) Pl- Àgora 2-3, 08720-Vilafranca del Penedès (Spain). 0023-6438/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.lwt.2011.01.030
contains. Alcohol-free wines could therefore be an excellent source of antioxidants to protect persons who should not consume alcohol against oxidative damage. Wines with low-alcohol content can be obtained eliminating the alcohol from wine after it has been produced through the alcoholic fermentation. If maceration occurs and the alcohol is subsequently removed, the anthocyanin, flavan-3-ol and stilbene concentrations are expected to be higher than if the juice is simply pressed (Monagas et al., 2005). Low-alcohol and alcohol-free (with no alcohol at all) wines can be produced by different techniques: (i) distillation under vacuum or atmospheric pressure, (ii) evaporation, (iii) freeze concentration, (iv) membrane processes (dialysis, reverse osmosis and membrane contactors), (v) adsorption (on resins or on silica gels), and (vi) extraction using organic solvents or supercritical carbon dioxide. The systems most frequently used in the industry are the spinning cone column (SCC), vacuum distillation equipment, and reverse osmosis (RO) systems (BelisarioSánchez, Toboada-Rodríguez, Marín-Iniesta, & López-Gómez, 2009). RO and nanofiltration are the most promising processes for the production of wines with low-alcohol content, since they can operate at a low temperature and thereby preserve the aromatic profile of the wine (Labanda, Vichi, Llorens, & LópezTamames, 2009). In this paper, commercial low-alcohol wines are analysed for their AA and phenolic composition. The impact of RO on the
1370
M. Bogianchini et al. / LWT - Food Science and Technology 44 (2011) 1369e1375
phenolic composition of the products and AA is evaluated and the stability of these products is assessed over time. 2. Materials and methods 2.1. Samples A total of ten dealcoholised commercial wines available in the market were analysed: five dealcoholised red wines (R1eR5), three dealcoholised white wines (W1eW3) and two dealcoholised rosé wines (RS1eRS2). Two red wines (Sa and Sb) were also purchased for the stability study. The labels state that ascorbic acid (90 mg/L) is added to these wines. The wine used for the dealcoholisation process by RO was a red wine made with the Cabernet Sauvignon, Merlot and Tempranillo varieties (vintage 2008) from Cooperativa de Bellvei (DO Penedès, Tarragona, Spain). Table 1 shows the main analytical characteristics of the red wine used in this study. Samples were taken after different periods of storage: 0, 2 and 7 months.
Fig. 1. Scheme of the reverse osmosis unit used for removing alcohol from wine (1 feed tank, 2 - piston pump, 3 - membrane module, 4 - permeate reservoir, 5 - rotameters, 6 - on/off valves, 7 - temperature sensors, 8 - manometer).
2.2. Reverse osmosis equipment and procedure
wine) was recycled to the feed reservoir. The feed pressure and retentate flowrate were measured using a manometer and a rotameter respectively, which were adjusted using needle valves. The temperature was also measured in the feed tank and in the membrane module. Every hour distilled water previously removed from the permeate was added to the feed reservoir.
The RO equipment used was a Permelab NF/OI Plant made by Permeare S.r.l. Milano (Italy). The system was made of stainless steel and consisted of a compact unit with a cartridge containing a 0.5 m2 polysulphone spiral membrane. It was equipped with a 2.2 kW piston pump. Fig. 1 shows a diagram of the configuration. The treatments were carried out at a constant pressure (30 bar), recycle flow rate and temperature (room temperature). A diafiltration mode was used to keep the concentration of solids constant and diminish the effect of gel polarisation. The water introduced in the process was obtained through the distillation of permeate produced during the dealcoholisation. The wine was pumped through the membrane module and the retentate (concentrated
2.3. Dealcoholisation of wine The volume of wine treated in the dealcoholisation process was 9 L. In the first stage of the treatment, the ethanol content of the wine was reduced from the initial value of 12.70% (v/v) to 4% (v/v)
Table 1 Analytical characteristics of original and dealcoholised wines obtained by reverse osmosis. Original wine
4% (v/v)
2% (v/v)
Dealcoholised wine (retentate)
Permeate
Dealcoholised wine (retentate)
Permeate
Parameter
X
s
X
s
X
s
X
s
X
s
Ethanol (%, v/v) Glucose (g/l) Fructose (g/l) Total sugar (G þ F) (g/l) Glycerol (g/l) Volatile acidity (g/l) Citric acid (g/l) Tartaric acid (g/l) Lactic acid (g/l) Succinic acid (g/l) Total acidity (g/l) Gelatin index (%) pH Total phenols index (a.u.) Total anthocyanins (mg/l m3og) Free anthocyanins (mg/l m3og) Total tannins (g/l) Abs 420 Abs 520 Abs 620 Modified colour intensity (MCI) Tonalitaty (tint) Cielab L* Cielab a* Cielab b*
12.70 3.36 0.60 3.97 8.18 0.32 0.17 2.50 1.40 3.09 4.50 57.80 3.46 46.18 286.00 227.00 1.54 2.67 3.80 0.78 7.25 0.70 21.30 52.6 34.4
0.02 0.01 0.00 0.01 0.00 0.00 0.00 0.02 0.05 0.01 0.00 0.12 0.01 1.03 2.00 1.00 0.06 0.01 0.01 0.01 0.03 0.00 0.20 0.3 0.3
4.37 3.26 0.57 3.83 7.45 0.54 0.14 2.44 1.28 2.82 4.70 58.40 3.45 44.3 239.00 186.00 1.39 2.87 4.74 0.87 8.48 0.60 18.6 50.0 31.0
0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.01 0.00 0.01 0.00 0.07 0.00 0.4 1.00 2.00 0.07 0.02 0.03 0.01 0.06 0.00 0.3 0.4 0.4
3.27 ea ea ea 0.20 0.39 ea ea 0.01 0.03 0.90 eb 3.45 eb eb eb eb eb eb eb eb eb eb eb eb
0.00 e e e 0.00 0.00 e e 0.00 0.00 0.01 e 0.01 e e e e e e e e e e e e
1.77 3.17 0.54 3.72 7.50 0.40 0.16 2.38 1.31 2.81 4.30 50.50 3.60 42.3 289.00 239.00 1.65 3.00 4.77 1.01 8.77 0.63 15.40 45.40 25.70
0.00 0.01 0.01 0.01 0.02 0.01 0.00 0.01 0.00 0.02 0.00 0.15 0.00 0.9 3.00 3.00 0.05 0.01 0.02 0.00 0.03 0.00 0.10 0.10 0.20
5.36 ea ea ea 0.38 eb ea ea 0.06 0.15 eb eb eb eb eb eb eb eb eb eb eb eb eb eb eb
0.00 e e e 0.00 e e e 0.01 0.12 e e e e e e e e e e e e e e e
m3og malvidin-3-O-glucoside. a not detected. b not determined.
M. Bogianchini et al. / LWT - Food Science and Technology 44 (2011) 1369e1375
1371
and 10 L of water were added to the feed tank. Secondly, the alcohol content was reduced further to 2% (v/v) and 25 L of water were added. In these two stages the wine was treated for 192 and 564 min respectively. The permeate rate was constant, with a value of 3 L/h (6 L/hm2) in both stages (Labanda et al., 2009). After the dealcoholisation of the wine, the total content of sulphur dioxide was adjusted to 80 mg/L. Then the wine was bottled.
concentration and the concentration after gelatine precipitation. The percentage was calculated by relating this astringency intensity to the total tannin concentration (Ribéreau-Gayon et al., 1998). This analysis was carried out using a UVeVIS spectrophotometer Perkin Elmer Lambda 20 with Colvin Perkin Elmer software v.1.0.
2.4. LC analysis of organic acids and sugars
The absorbances at wavelengths of 420, 520 and 620 nm and the CIELAB parameters (lightness (L*), red/green colour component (a*), and blue/yellow colour component (b*)) were determined by spectrophotometric methods (EEC, 1990; OIV, 2009). The colour was also characterised by the modified colour intensity (MCI), which is the sum of the absorbances at wavelengths of 420, 520 and 620 nm (1 cm path length). The tonality or tint was expressed by the ratio of the absorbances at 420 nm and 520 nm. By convention, the chromatic properties used to describe red and rosé wines are the colour intensity and the tint (EEC, 1990). The equipment used was the Perkin Elmer Lambda 20 UVeVIS spectrophotometer and the software was the Colvin Perkin Elmer v.1.0.
Organic acids (citric acid, tartaric acid, lactic acid, and succinic acid) and glucose, fructose, glycerol and ethanol were separated and simultaneously determined by liquid chromatography (LC) equipment Agilent Series 1100 with HP Chemstation software (Agilent, Waldbron, Germany). Sugars, glycerol and ethanol were measured using a refractive index detector (Agilent, Waldbron, Germany), while organic acids were measured using a diode array detector (Agilent, Waldbron, Germany). The column was a Transgenomic ICSepICE COREGEL-87H3, at an oven temperature of 50 C. The mobile phase was a solution of pH 2.20 prepared with concentrated H2SO4 (95e97%) in Milli-Q water, injection volume was 20 mL and the flow rate was 0.6 mL/min (López-Tamames, Puig-Deu, Teixeira & Buxaderas, 1996). Triplicate samples and mobile phase were filtered through cellulose acetate filters (Teknokroma) 0.45 mm before inyection. The standards: ethanol (>99.5%) and methanol (>99.9%) were provided by J.T. Baker, D-(þ)-glucose (>99.5%), fructose (99.0%), glycerol (>99.0%), citric (>99.5%), succinic (>99.0%), lactic (98%) and tartaric (>99.5%) acids by SigmaeAldrich. 2.5. LC-DAD analysis for phenolic compounds and furanic derivatives identification Phenolic compounds were analysed using an Agilent Series 1100 LC system equipped with a quaternary pump (Series 1100 G1311A), automatic injector (Series 1100 G1313A), degasser (Series 1100 G1379A), and UV/Vis diode detector (Series 1100 G1315B) coupled to a Chemstation HP A.10.02 (HP/Agilent). The column was an Agilent Zorbax SB-C18 (4.6 250 mm, 3.5 mm). Duplicate samples were filtered through a Millex-LCR 13 mm filter before injection. The chromatographic conditions had previously been described to analyse wine by Betes-Saura, Andres-Lacueva, and Lamuela-Raventos (1996). The method uses a binary gradient e A (glacial acetic acid/ water pH 2.65), B (20% A þ 80% acetonitrile) e programmed with the following gradient: 0 min (0% B); 5 min (2% B); 10 min (4% B); 15 min (10% B); 30 min (20% B); 35 min (30% B); 40 min (100% B); 45 min (0% B). The sample volume injected was 50 ml, the flow rate was 1.5 mL/min, and the temperature was set at 40 C. Quantification was performed by external calibration at their maximum absorbance. The standards were purchased from Fluka [caffeic acid, gallic acid, p-coumaric acid, ()-epicatechin, furfuryl alcohol], Sigma [vanillic acid, ellagic acid, ferulic acid, syringic acid, ()-catechin, resveratrol glucoside], Safc [5-hydroxymethylfurfural] and Chromadex [3-o-methylgallic acid, caftaric acid, procyanidin-B1, procianydin-B2]. Standards purity was higher than 98%. 2.6. Astringency analysis Gelatine index (GI) was obtained using the methods described by Ribéreau-Gayon, Glories, Maujean, and Dubourdieu (1998). A total of 100 mL of 70 g/L gelatine solution were added to 1000 mL of wine by duplicate, and centrifuged at 8000 rpm for 5 min (Eppendorf Centrifugue 5417C) after 3 days. The supernatants were assayed to determine the tannin concentration expressed as astringency intensity and as a percentage. Astringency intensity is calculated as the difference between the total solution tannin
2.7. Determination of chromatic properties
2.8. Antioxidant activity (AA) 2.8.1. ORAC assay The ORAC assay is based on a previously reported method, with slight modifications (Ou, Hampsch-Woodill, & Prior, 2001). In this method, 50 ml of a sample or Trolox are mixed with 100 ml of Fluorescein (45 nM) and 50 ml of AAPH (15 mM). Fluorescence is recorded for 60 min (the excitation wavelength is set at 485 nm and the emission wavelength at 528 nm). Measurements were taken in triplicate in a multi-detector microplate reader (Synergy HT, BiotekÒ). Trolox was used as a calibration standard (0.5e9.5 mM). The results were calculated as ORAC values from the differences between the blank and the sample areas under the fluorescein decay curve. They are expressed as mM Trolox equivalents. 2.8.2. FRAP method The FRAP reagent consists of acetate buffer (300 mM, pH 3.6), TPTZ (10 Mm in HCl 40 Mm) and FeCl3 6H20 (20 mM) (10:1:1, v/v/v). A total of 3 ml of FRAP reagent was mixed with 300 ml of Mili-Q water and a 100 ml sample. Absorbance was measured after 8 min at 593 nm. An aqueous solution of FeSO4x7H2O in the 0e1 mM range was used for calibration. All determinations were performed in triplicate. Results are expressed as mmol of Feþ2/L of wine (Benzie & Strain, 1996). Absorbance measurements were recorded on a Hitachi UV-2800Ò spectrophotometer thermostated with a Peltier system at 25 C. 2.8.3. DPPH method 0.1 mL of sample or Trolox (0.000e1.000 mM) was added to 3.9 mL of DPPH (0.063 mM), all in methanolic solution. Absorbance was measured at 515 nm after 60 min (when the reaction reached equilibrium) (Sánchez-Moreno, Larrauri, & Saura-Calixto, 1998). The blank reference cuvette contained methanol. All measurements were performed in triplicate. Results are expressed as mM Trolox equivalents. Absorbance measurements were recorded on a Hitachi UV-2800Ò spectrophotometer thermostated with a Peltier system at 25 C. 2.9. Ascorbic acid addition A Spanish wine was dealcoholised in the laboratory by means of rotavapor set at 38 C and operating under vacuum. Subsequently, a total of 90 mg/L of ascorbic acid was added. ORAC AA was
7226 7091 609 9.71 1.11 1855 7561 222 12.4 0.7 4671 6712 185 8.9 0.3 2324 10478 301 11.0 0.6 3040 11021 344 11.81 0.19 3926 850 72 1.89 0.16 1123 1560 328 1.45 0.09 1078 749 55 0.51 0.13 1836 769 88 0.57 0.13 932 752 31 2.36 0.03
measured before and after ascorbic acid addition to evaluate the effect of this ascorbic acid content in the AA of the final product. 2.10. Other parameters
ea 132.82 ea 190.41 ea 342.89 a e 201.30 a e 207.10 a e 64.50 1.74 0.01 33.30 0.61 0.00 21.95 ea 35.71 2.28 0.02 119.35
ea 22.4 0.01 29.9 0.5 27.58 0.02 22.0 0.3 ea 1.98 0.01 2.6 0.5 ea 18.36 0.15
ea 15.3 0.3 ea ea ea ea ea ea ea 13.28 0.25
ea 44.9 0.4 92.57 0.19 18.5 0.4 39.41 1.21 ea ea ea ea ea
0.00 82.50 122.49 46.04 61.42 0.00 1.98 2.61 0.00 31.64
68839 74968 62347 87149 89043 21250 11517 10274 8516 24357
Total and volatile acidity and pH were determined using Fourier Transform Infrared (FTIR) technology by means of a WineScanÔ Flex equipment with a Foss and Flexible Foss Integrator Software platform, a liquid flow system and a 0.4 mm calcium fluoride cuvette (Foss, Foss Electric España, S.A) to generate the FTIR spectra. The calibration provided with the equipment has allowed us to analyse immediately the pH and volatile acidity, adapting following to the resolution OIV/OENO 390/2010. The samples were automatically thermostated at 20 C in the spectrometer before analysis. The IR spectrum was scanned between 2.000 nm and 10.000 nm (NIR and MIR). The spectra were obtained in duplicate and averaged for each sample. Sulphur dioxide was determined using the reference method (Paul, 1958). Phosphoric acid was added to the sample then connected to a bubbler and passed through a hydrogen peroxide solution. The resulting hydrogen peroxide solution was neutralised and the acid which formed with the 0.01 M sodium hydroxide solution was titrated to determinate the free sulphur dioxide. All of the sulphur dioxide is purged from the wine by entrainment at high temperature. Total phenol Index was determined by both most used methods: by recording absorbance at 280 nm (Commission Regulation (EEC) No. 2676/90) and Folin Ciocalteu method (Waterhouse, 2001). Results are expressed as absorbance units (a.u.) and as mg/L of gallic acid equivalents respectively. The equipment used was UVeVIS spectrophotometer Perkin Elmer Lambda 20 with Colvin Perkin Elmer software v.1.0. Total anthocyanins (TA) were determined by measuring the absorbance at 520 nm (Zoecklein, Fugelsang, Gump, & Nury, 1995). Absorbance (A) was measured at 520 nm in 1M HCL and sodium metabisulfite solution (20% wt/vol) buffers using the following equation: TA ¼ 20 (AHCl(520nm)(5/3)ASO2(520nm)),the 5/3 correction factor is used to get a more accurate measure of monomeric anthocyanin in wine. Results are expressed as mg/L of maldivine3-O-glucoside. Free anthocyanins (FA) expresses as mg/L of maldivine-3-Oglucoside is calculated by: FA ¼ 20 (A(520nm)ASO2(520nm)), were A(520nm) is the absorbance at 520 nm of a wine dilution of 200 mL of wine in 10 mL of deionised water. The equipment used to measure total anthocyanins was UVeVIS spectrophotometer Perkin Elmer Lambda 20 with Colvin Perkin Elmer software v.1.0. 2.11. Statistical analysis Statistical software (Statsoft, 2001) was used to test significant differences (t-test; p < 0.05). Rered wine; Wewhite wine; RSerosé wine. a no detected.
ea ea ea ea ea ea 13.5 0.5 ea ea ea 2.75 0.02 ea 6.77 0.06 ea ea ea ea ea ea 8.9 0.7 R1 R2 R3 R4 R5 W1 W2 W3 RS1 RS2
1802 2460 828 2487 2451 1105 528 2360 218 701
30.5 55.2 282 221 51.4 32.1 52.9 119 14.1 14.1
28.0 1.5 34.93 0.00 43.9 0.3 72.43 0.10 36.65 0.20 4.88 0.00 5,1 0,3 ea 3.6 0.3 16.01 0.06
ea 11.76 0.07 ea 10.7 0.3 12.8 0.6 ea ea ea ea ea
28.00 118.6 46.69 190.4 43.88 342.9 96.63 183.1 49.45 190.2 7.63 64.50 11.87 29.44 0.00 19.46 3.60 34.56 24.91 117.07
3.7 0.3 11.6 0.3 0.3 0.03 0.02 0.01 0.15 0.11
14.22 0.19 ea ea 18.19 0.01 16.80 0.00 ea 2.12 0.01 1.88 0.01 1.15 0.00 ea
()Epicatechin (þ)Catechin
Flavanols (mg/L)
p-Coumaric Total Acid Caffeic Acid
Cinnamic acids (mg/L)
Total Caftaric Acid Ellagic acid Vanillic acid Syringic acid Gallic Acid
Benzoic acids (mg/L) Sample TPI (mg/L)
Table 2 Total phenolic index (mg/L of GAE), antioxidant activity and concentration of phenolic compounds (mg/L) detected in commercial dealcoholised wine.
Procyanidin Total B2
ORAC (mM)
DPPH FRAP (mmolFe2þ/L) (mM)
M. Bogianchini et al. / LWT - Food Science and Technology 44 (2011) 1369e1375
Antioxidant Activity
1372
3. Results and discussion 3.1. Phenolic composition and antioxidant activity of commercial dealcoholised wines Table 2 shows the phenolic content of the different types of commercial dealcoholised wines. A total of 10 phenolic compounds were identified, caftaric acid being the most abundant compound, followed by procyanidin B2, (þ)-catechin and gallic acid (Table 2). Their concentrations were found to be similar to those described for normal French (Landrault et al., 2001) and Spanish wines (Guerrero, García-Parrilla, Puertas, & Cantos-Villar, 2009). The
M. Bogianchini et al. / LWT - Food Science and Technology 44 (2011) 1369e1375
1373
Table 3 Concentration (mg/L) of phenolic acids and antioxidant activity determination of commercial dealcoholised wines (Sa and Sb) during the storage of bottles (T1 - T30). Wine
Benzoic acids (mg/L) Gallic Acid
SaT1 SaT7 SaT15 SaT30 SbT1 SbT15 SbT30
85.0 93.10 66.70 72.42 50.6 52.15 48.1
0.3b 0.03c 0.08d 0.02e 1.7b 0.09b 0.3b
Cinnamic acids (mg/L)
Vanillic acid
Ellagic acid
17.0 1.4b 21.40 0.09b 12.91 0.07b 15.01 0.07b ea ea ea
7.11 4.73 5.23 4.07 4.6 4.23 3.31
Total
Caftaric Acid
0.02b 109.07 228.30 7.22b 0.09c 119.26 225.7 1.9b 0.16c 84.84 165.1 13.7c 0.11c 91.50 171.1 0.5c 0.3b 55.18 397.4 2.6b 0.02b 56.38 364.9 1.4b 0.00c 51.43 315.8 1.3c
Antioxidant Activity
Caffeic Acid
Ferulic Acid
Total
ORAC (mM)
26.8 0.3b 20.53 0.02c 15.46 0.19d eae ea ea ea
ea ea ea ea 0.89 0.02b 0.8 0.3b eab
255.07 246.18 180.57 171.10 398.27 365.68 315.84
13378 17942 14026 8990 15590 15848 9964
3647b 1807b 1090b 2284b 1343b 1571b 665c
FRAP (mmolFe2þ/L) DPPH (mM) 2.99 2.55 2.39 1.39 3.34 2.74 2.20
0.17b 0.18b 0.07b 0.07c 0.16b 0.18b 0.51b
17.4 22.3 14.1 10.72 12.0 10.42 5.7
0.4b 0.6c 0.4d 1.02e 0.3b 0.21b 0.4c
Different superscript letters within the same sample indicate significant differences among the different times of storage (p < 0.05). a no detected; T e time in days.
alcohol lost in the medium does not lead to precipitation of these compounds and can therefore be considered a source of bioactive compounds. Certain process to dealcoholise wines involves heating to evaporate ethanol and therefore 5-hydroxymethylfurfural (5-HMF) could be present in commercial samples. This compound, like other furfuryl alcohol derivatives, was studied by the Scientific Panel on Food Additives, Flavouring, Processing Aids and Materials in Contact with Food (EFSA, 2005) to evaluate the implication of these substances for human health. The Scientific Panel concluded that 5-HMF and four other furfuryl alcohol derivatives, insofar as their metabolism includes the formation of furfural, a known reactive hepatotoxic aldehyde, cannot be predicted to be metabolised to innocuous or endogenous products. 5-HMF has been shown to be bioactivated in vitro to reactive genotoxic intermediates by sulfotransferases (EFSA, 2005). However, 5-HMF is present only at low concentrations (0.02e4.6 mg/L) similar to the concentrations found in orange juices, normal white or red wines (Yuan & Chen, 1999). The concentration of 5-HMF is important for producers as they must guarantee their products are safe. The AA of commercial dealcoholised wines is shown in Table 2. As expected, dealcoholised red wines showed higher AA values for the ORAC, DPPH and FRAP assays than dealcoholised rosé and white wines. These results are coherent with reported data for red wines (Fernández-Pachón, Villano, García-Parrilla, & Troncoso, 2004). However, most of these commercial dealcoholised wines presented an ORAC AA value three times higher than reported values for wines (Fernández-Pachón et al., 2004; Granato, Katayama, & Castro, 2010). Because the concentration of polyphenolic compounds (Table 2) is within the same range of French and Spanish wines (Guerrero et al., 2009; Landrault et al., 2001), this high AA value may be caused by the addition of ascorbic acid (90 mg/L) for product stability purpose. The label on these products states that ascorbic acid (90 mg/L) is added. We tested whether this concentration of ascorbic acid might explain the AA values by dealcoholising the wine in the laboratory (rotavapor set at 38 C and operating under vacuum) and adding ascorbic acid afterwards. The ORAC value of the wine was 13672 2108 mM Trolox equivalents initially and 26137 4824 mM Trolox equivalents after ascorbic acid had been added, which explains the increase in AA. The phenolic composition and AA of commercial dealcoholised wines was monitored over time to check their stability. Commercial dealcoholised wines lost 33e54% of AA e as determined by ORAC, FRAP and DPPH e after 30 days of storage (Table 3). The lesser solubility of certain phenolic compounds in a medium without ethanol can explain this fact. Indeed, in most of the commercial dealcoholised wines, phenolic compounds significantly decreased after 30 days of storage. Specifically, caffeic acid disappeared, while the concentrations of caftaric acid and ellagic acid decreased by around 25% and 43%, respectively (Table 3). It does not have the allergic effects associated with SO2, which is an advantage in terms
of health. However, the data in Table 3 show that the phenolic concentration is not stable. Recent research studies report that ascorbic acid has a pro-oxidant effect on model wine matrix containing (þ)-catechin (Bradshaw, Cheynier, Scollary, & Prenzler, 2003). Our results agree with these latest findings. 3.2. Effects of RO on dealcoholised wines 3.2.1. Effects of RO on enological parameters Table 1 shows the analytical characteristics of the original red wine and of the dealcoholised products following RO. As can be seen, the retention of glucose, the main organic acids and glycerol was higher than 90% for both retentates at 4% and 2% (v/v). The total acidity increased in the first stage and fell in the second one, while the volatile acidity increased in both stages. On the other hand, RO did not affect the analysed parameters as the pH, fructose, and tartaric acid content of dealcoholised wines (4% and 2% alcoholic degree), which remained the same as in the original wine. The treatment caused the free and total sulphur dioxide content to fall by around 25% and 75% for the retentate of 4% and 2% (v/v), respectively. This fall must be controlled during the treatment to avoid any wine oxidation. Astringency (expressed as the gelatine index), on the other hand, increased slightly during the first stage of the treatment and decreased during the second stage. However, the values of the index of gelatin obtained (50e60%), and the concentration of tannins (around 1.5 g/L) in wine indicates that wines are slightly astringent. These values have not a relevant impact on astringency (Goldner & Zamora, 2010; Llaudy et al., 2004). The modified colour intensity increased by around 20% in both stages dealcoholised wines and the tonality diminishes around 15%. This could have been due to the reduction in sulphur dioxide, which is known to produce a reversible reaction that affects the colour (Zoecklein et al., 1995). All absorbances at 420 nm (yellow), 520 nm (red), and 620 nm (blue) increased, but the absolute increase was higher for 420 and 520 nm than for 620 nm, resulting in a higher red and yellow component and therefore a more purple colour. Nevertheless, this increase could be affected by the lower alcohol content, since Somers and Evans (1979) observed an increase in colour at both 420 and 520 nm when the concentration of alcohol was reduced. The CIELAB parameters were lower when the alcoholic strength was reduced. The decrease in the red/green value (a*) led to a greener colour and the decrease in the blue/yellow value (b*) led to a more blueness colour. All these changes in colour parameters can be easily explained by the effect of ethanol on copigmentation phenomena. It is knew that ethanol decrease the anthocyanin copigmentation (Boulton, 2001). Consequently, a decrease in ethanol content implies a greater proportion of flavilium form of anthocyanins which must increase the colour intensity and decrease the hue. The consequence is an increase of the blueness
44b 132b 59b 155b 231b 193b 153b 223b 301b
hue which characterises the colour of young wines. All this data is confirmed by the changes observed in CIELAB coordinates.
0.01b
0.03b 0.00b 0.08b
0.11b 0.06b 0.02b 0.4b 0.00b 0.8b 0.02b 0.06b 0.01b
3.29 3.53 3.60 3.25 3.45 3.3 3.26 2.82 3.25
0.04b 0.03b 0.12b 0.06b 0.05b 0.3b 0.03b 0.07b 0.12b
0.38 eab eab 0.88 0.68 1.01 eab eab 0.19
0.01b
9.70 9.83 9.91 8.7 8.3 8.05 9.76 9.71 9.73
0.15b 0.23b 0.12b 0.4b 0.3b 0.14b 0.03b 0.13b 0.05b
20496 20335 20433 19619 19845 19838 18835 19336 19055
3.2.2. Effects of RO on phenolic composition and AA Table 4 shows the phenolic composition, furfuryl alcohol and AA of a red wine and of the products resulting from RO. The resulting products were dealcoholised wines with 4% and 2% (v/v) alcoholic degree. Total anthocyanins were 286.00 2.00 mg/L for the original wine and 289.00 3.00 mg/L for the dealcoholised 2% (v/v) wine. Therefore, no significant differences were observed as a result of this process. As Table 4 shows, RO did not significantly affect any phenolic acid, irrespective of their chemical structure (benzoic acids, cinnamic acids). However, flavanols are affected in some extent. Concerning the stability of these products, the concentration for phenolic compounds of the wines dealcoholised by RO did not significantly change after 7 months of storage (Table 4). Their AA did not change significantly either. It is important to bear in mind that samples were stabilised by sulphurous dioxide, which is commonly used in winemaking. The results show that the RO method does not alter the phenolic profile and antioxidant properties of the final product, enabling a healthy product to be obtained with a low-alcohol content (2% v/v) and stable bioactive compounds that are similar to those found in normal wine.
0.01b 0.04b
0.00b 0.00b 0.00b 0.07b
4. Conclusions Wewine; DWedealcoholised wine; Tetime in months. Different superscript letters within the same sample indicate significant differences among the different times of storage (p < 0.05). a no detected.
12.67 14.49 14.46 13.3 13.70 12.9 12.89 11.50 13.10 0.8b 0.20b 0.6b 0.08b 0.13b 2.23b 2.5b 0.22b 0.13b 50.4 41.76 41.3 34.86 49.10 47.10 38.5 31.55 47.97 0.4b 0.07b 0.12c 0.12b 0.3c 0.5c 0.03b 0.4b 0.3b 12.0 11.10 7.95 7.81 15.0 12.7 8.70 9.3 8.8 21.5 0.3b 16.7 0.15c 14.9 0.5c 13.8 0.8b 16.9 0.4b eac 13.60 0.03b 10.71 0.06b 9.80 0.15b ea ea ea eab 32.4 0.5c 29.23 1.19c eab 18.8 0.6c 19.1 0.5c eab eab 1.12 1.11 1.00 0.97 eab 0.87 0.95 0.16b 0.01b 0.07b 0.03b 0.06b 0.24b 0.09b 0.02b 0.14b 3.04 2.71 3.12 2.68 2.53 3.30 3.37 2.21 3.26 2.9b 0.8b 0.3b 0.5b 1.4b 5.9b 1.9b 0.3b 0.4b 84.3 83.4 88.4 82.5 82.9 83.3 86.9 73.7 87.6 W 12 T0 W 12 T2 W 12 T7 DW 4 T0 DW 4 T2 DW 4 T7 DW 1 T0 DW 1 T2 DW 1 T7
Furfural derived Antioxidant activity Cinnamic acids Stilben Flavanols
Protocatechuic acid 3-O-Methylgallic acid (þ)-Catechin ()-Epicatechin Procianidin B2 Procianidin B1 Caftaric acid Gallic acid
Benzoic acids Samples
Resveratrol glucoside Furfuryl alcohol DPPH (mM) FRAP (mmolFe2þ/L)
M. Bogianchini et al. / LWT - Food Science and Technology 44 (2011) 1369e1375
Table 4 Concentration (mg/L) of phenolic compounds, furfuryl alcohol and antioxidant activity of dealcoholised wines obtained by reverse osmosis during the storage of bottles (T0 - T7).
1374
We determined the AA and the phenolic composition of dealcoholised wines and the results led us to conclude that the dealcoholised wines provide a good source of polyphenols without the disadvantages of alcohol intake. We tested the influence of bottle storage on the polyphenolic composition and AA in commercial dealcoholised wines and observed a significant decrease in these two parameters after 30 days of storage. This may prove important for labelling the optimum time of consumption in terms of AA for consumers who want to drink wine with antioxidant properties. RO is a process suitable for obtaining dealcoholised wines that maintain their phenolic compounds and AA. The bioactive composition of dealcoholised wines obtained in this way is more stable than in dealcoholised wines obtained by other methods. Acknowledgements The authors are grateful to the University of Milan for Michele Bogianchini’s fellowship and to the Spanish Ministry of Science and Innovation for its financial support (Research project AGL 200764622). References Belisario-Sánchez, Y. Y., Taboada-Rodríguez, A., Marín-Iniesta, F., & López-Góméz, A. (2009). Dealcoholised wines by spinning cone column distillation: phenolic compounds and antioxidant activity measured by the 1.1-diphenyl-2-picrylhydrazyl method. Journal of Agriculture and Food Chemistry, 57(15), 6770e6778. Benzie, I. F., & Strain, J. J. (1996). The ferric reducing ability of plasma (FRAP) as a measure of “antioxidant power”: the FRAP assay. Analytical Biochemistry, 239, 70e76. Betes-Saura, C., Andres-Lacueva, C., & Lamuela-Raventos, R. M. (1996). Phenolics in white free run juices and wines from Pened’es by high-performance liquid chromatography: changes during vinification. Journal of Agricultural and Food Chemistry, 44(10), 3040e3046. Boulton, R. (2001). The copigmentation of anthocyanins and its role in the color of red wine: a critical review. American Journal of Enology and Viticulture, 52(2), 67e87. Bradshaw, M. P., Cheynier, V., Scollary, G. R., & Prenzler, P. D. (2003). Defining the ascorbic acid crossover from anti-oxidant to pro-oxidant in a model wine matrix containing (þ)-catechin. Journal of Agriculture and Food Chemistry, 51(14), 4126e4132. Commission Regulation (EEC) No. 2676/90. (October 3 1990). Commission regulation (EEC) No. 2676/90 determining community methods for the analysis of wines. Official Journal, L272, 1e192. EFSA. (2005). Opinion of the scientific panel on food additives, flavourings, processing aids and materials in contact with food (afc) on a request from the
M. Bogianchini et al. / LWT - Food Science and Technology 44 (2011) 1369e1375 commission related to flavouring group evaluation 13: furfuryl and furan derivatives with and without additional side-chain substituents and heteroatoms from chemical group 14. Question number EFSA-Q-2003-156. Adopted on 27 April 2005. The EFSA Journal, 215, 1e73. Fernández-Pachón, M. S., Villano, D., García-Parrilla, M. C., & Troncoso, A. M. (2004). Antioxidant activity of wines and relation with their polyphenolic composition. Analitica Chimica Acta, 513(1), 113e118. Goldner, M. C., & Zamora, M. C. (2010). Effect of polyphenol concentrations on astringency perception and its correlation with gelatine index of red wine. Journal of Sensory Studies, 25(5), 761e777. Granato, D., Katayama, F. C. U., & Castro, I. A. (2010). Assesing the association between phenolic compounds and the antioxidant activity of Brazilian red wines using chemometrics. LWT- Food Science and Technology, 43, 1542e1549. Guerrero, R. F., García-Parrilla, M. C., Puertas, B., & Cantos-Villar, E. (2009). Wine, resveratrol and health: a review. Natural Product of Communications, 4(5), 635e658. International Organisation of Vine and Wine (OIV). (2009) Compendium of international methods of wine and must analysis, vols 1 and 2. Labanda, J., Vichi, S., Llorens, J., & López-Tamames, E. (2009). Membrane separation technology for the reduction of alcoholic degree of a white model wine. LWT - Food Science and Technology, 42, 1390e1395. Landrault, N., Poucheret, P., Ravel, P., Gasc, F., Cros, G., & Teissedre, P. L. (2001). Antioxidant capacities and phenolics levels of French wines from different varieties and vintages. Journal of Agriculture and Food Chemistry, 49(7), 3341e3348. Llaudy, M. C., Canals, R., Canals, J. M., Rozès, N., Arola, L., & Zamora, F. (2004). New method for evaluating astringency in red wine. Journal of Agriculture and Food Chemistry, 52(2), 742e746. López-Tamames, E., Puig-Deu, M. A., Teixeira, E., & Buxaderas, S. M. (1996). Organic acids, sugars, and glycerol content in white winemaking products determined by HPLC: relationship to climate and varietal factors. American Journal of Enology and Viticulture, 47(2), 193e198. Monagas, M., Bartolomé, B., & Gómez-Cordovés, C. (2005). Updated knowledge about the presence of phenolic compounds in wine. Critical Review in Food Science and Nutrition, 45(2), 85e118.
1375
Noble, A. C. (2002). In Astringency and bitterness of flavonoid phenols. ACS Symposium Series, vol. 825 (pp. 192e201). OIV, Oeno Resolution 390/2010. (June, 25th 2010). Guidelines on infrared analyser in oenology. Tbilisi. Ou, B., Hampsch-Woodill, M., & Prior, L. R. (2001). Development and validation of an improved oxygen radical absorbance capacity assay using fluorescein as the fluorescent probe. Journal of Agriculture and Food Chemistry, 49, 4619e4626. Paul, F. (1958). Die alkalimetrische Bestimmung der Freien, gebundenen und gesamten schwefeligen Sw, ure mittels des Apparates von Lieb und Zacherl. Mitt. Rebe u. Wein, Ser. A., Klosterneuberg, 8, 21e7. Ribéreau-Gayon, P., Glories, Y., Maujean, A., & Dubourdieu, D. (1998). In Traité d’œnologie. Chimie du vin, Stabilisation et traitement, Tome 2. France: Dunod. Sánchez-Moreno, C., Larrauri, J. A., & Saura-Calixto, F. (1998). A procedure to measure the antiradical efficiency of polyphenols. Journal of the Science of Food and Agriculture, 76(2), 270e276. Seeram, N. P., Aviram, M., Zhang, Y., Henning, S. M., Feng, L., Dreher, M., et al. (2008). Comparison of antioxidant potency of commonly consumed polyphenol-rich beverages in the United States. Journal of Agriculture and Food Chemistry, 56(4), 1415e1422. Somers, T. C., & Evans, M. E. (1979). Grape pigment phenomena: interpretation of major colour losses during vinification. Journal of the Science of Food and Agriculture, 30, 623e633. Statsoft, Inc.. (2001). STATISTICA for Windows [Computer program manual]. Tulsa, OK: Staftsoft, Inc.. 2300 East 14th Street74104e74442. Waterhouse, A. L. (2001). Determination of total phenolics. In R. E. Wrolstad, T. E. Acree, E. A. Decker, M. H. Penner, D. S. Reid, S. J. Schwartz, C. F. Shoemaker, D. M. Emith, & P. Sporns (Eds.), Handbook of food analytical chemistry (pp. 464e465). New York: Wiley, Unit I1.1. Yuan, J. P., & Chen, F. (1999). Simultaneous separation and determination of sugars, ascorbic acid and furanic compounds by HPLC-dual detection. Food Chemistry, 64(3), 423e427. Zoecklein, B. W., Fugelsang, K. C., Gump, B. H., & Nury, F. S. (1995). Wine analysis and production. New York, NY: Champman & Hall.
Contents lists available at ScienceDirect
LWT - Food Science and Technology journal homepage: www.elsevier.com/locate/lwt
Stability, antioxidant activity and phenolic composition of commercial and reverse osmosis obtained dealcoholised wines M. Bogianchini a, Ana B. Cerezo a, A. Gomis b,1, F. López b, M.C. García-Parrilla a, * a
Department of Nutrition Food Science, Toxicology and Legal Medicine, Faculty of Pharmacy, University of Seville, c/. Professor García González 2, E-41012 Seville, Spain Grup d’Investigació en Tecnología d’Aliments (GITA), Departament d’Enginyeria Química, Facultat d’Enologia, Universitat Rovira i Virgili, Av. Països Catalans 26, 43007 Tarragona, Spain
b
a r t i c l e i n f o
a b s t r a c t
Article history: Received 26 July 2010 Received in revised form 20 January 2011 Accepted 31 January 2011
The purpose of this work is to evaluate the phenolic profile and the antioxidant activity of commercial dealcoholised wines and monitor the stability of their composition over time. This work also aims to test the influence of reverse osmosis (RO) process on phenolic compounds and on the antioxidant activity (AA) of dealcoholised wine. AA was measured by ORAC, DPPH and FRAP assays. Phenolic compounds were determined by LC-DAD. In the commercial dealcoholised wines, AA fell by between 33% and 54% and the concentration of phenolic compounds decreased significantly after 30 days of storage. However, RO process did not significantly affect any phenolic acids, regardless of their chemical structure (benzoic acids, cinnamic acids) and alcoholic degree. The AA and phenolic compounds of these products were monitored for seven months. No significant changes were observed. RO process therefore makes it possible to obtain a healthy, low-alcohol (<2% v/v) product with bioactive compounds that are stable in the product and are similar to those found in the original wine. Ó 2011 Elsevier Ltd. All rights reserved.
Keywords: Dealcoholised wine Antioxidant activity Polyphenols Stability
1. Introduction Wine e especially red wine e is renowned for being good for one’s health. Its phenolic composition has recently been reviewed (Monagas, Bartolomé, & Gómez-Cordovés, 2005) because of its health benefits and sensory properties (Noble, 2002). Wine is not the only polyphenol-rich product available on the market: there are a number of commercial ready-to-drink polyphenol-rich beverages whose marketing strategies centre around their antioxidant activity (Seeram et al., 2008). However, alcohol content limits wine consumption for several reasons. First, some people cannot drink ethanol or must not drink alcohol. Removing the alcohol allows these people to enjoy the benefits of the phenolic compounds in wines. Second, traffic regulations limit alcohol consumption before driving and alcohol abuse is a highly worrying issue for many authorities, and both governments and producers of alcoholic beverages have shown an interest in developing low-alcohol drinks. Finally, persons suffering from oxidative stress are also advised to avoid wine consumption because of the alcohol it
* Corresponding author. Tel.: þ34954556760; fax: þ34954233765. E-mail address: [email protected] (M.C. García-Parrilla). 1 Present address: Institut Català de la Vinya i el Vi (Incavi) Pl- Àgora 2-3, 08720-Vilafranca del Penedès (Spain). 0023-6438/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.lwt.2011.01.030
contains. Alcohol-free wines could therefore be an excellent source of antioxidants to protect persons who should not consume alcohol against oxidative damage. Wines with low-alcohol content can be obtained eliminating the alcohol from wine after it has been produced through the alcoholic fermentation. If maceration occurs and the alcohol is subsequently removed, the anthocyanin, flavan-3-ol and stilbene concentrations are expected to be higher than if the juice is simply pressed (Monagas et al., 2005). Low-alcohol and alcohol-free (with no alcohol at all) wines can be produced by different techniques: (i) distillation under vacuum or atmospheric pressure, (ii) evaporation, (iii) freeze concentration, (iv) membrane processes (dialysis, reverse osmosis and membrane contactors), (v) adsorption (on resins or on silica gels), and (vi) extraction using organic solvents or supercritical carbon dioxide. The systems most frequently used in the industry are the spinning cone column (SCC), vacuum distillation equipment, and reverse osmosis (RO) systems (BelisarioSánchez, Toboada-Rodríguez, Marín-Iniesta, & López-Gómez, 2009). RO and nanofiltration are the most promising processes for the production of wines with low-alcohol content, since they can operate at a low temperature and thereby preserve the aromatic profile of the wine (Labanda, Vichi, Llorens, & LópezTamames, 2009). In this paper, commercial low-alcohol wines are analysed for their AA and phenolic composition. The impact of RO on the
1370
M. Bogianchini et al. / LWT - Food Science and Technology 44 (2011) 1369e1375
phenolic composition of the products and AA is evaluated and the stability of these products is assessed over time. 2. Materials and methods 2.1. Samples A total of ten dealcoholised commercial wines available in the market were analysed: five dealcoholised red wines (R1eR5), three dealcoholised white wines (W1eW3) and two dealcoholised rosé wines (RS1eRS2). Two red wines (Sa and Sb) were also purchased for the stability study. The labels state that ascorbic acid (90 mg/L) is added to these wines. The wine used for the dealcoholisation process by RO was a red wine made with the Cabernet Sauvignon, Merlot and Tempranillo varieties (vintage 2008) from Cooperativa de Bellvei (DO Penedès, Tarragona, Spain). Table 1 shows the main analytical characteristics of the red wine used in this study. Samples were taken after different periods of storage: 0, 2 and 7 months.
Fig. 1. Scheme of the reverse osmosis unit used for removing alcohol from wine (1 feed tank, 2 - piston pump, 3 - membrane module, 4 - permeate reservoir, 5 - rotameters, 6 - on/off valves, 7 - temperature sensors, 8 - manometer).
2.2. Reverse osmosis equipment and procedure
wine) was recycled to the feed reservoir. The feed pressure and retentate flowrate were measured using a manometer and a rotameter respectively, which were adjusted using needle valves. The temperature was also measured in the feed tank and in the membrane module. Every hour distilled water previously removed from the permeate was added to the feed reservoir.
The RO equipment used was a Permelab NF/OI Plant made by Permeare S.r.l. Milano (Italy). The system was made of stainless steel and consisted of a compact unit with a cartridge containing a 0.5 m2 polysulphone spiral membrane. It was equipped with a 2.2 kW piston pump. Fig. 1 shows a diagram of the configuration. The treatments were carried out at a constant pressure (30 bar), recycle flow rate and temperature (room temperature). A diafiltration mode was used to keep the concentration of solids constant and diminish the effect of gel polarisation. The water introduced in the process was obtained through the distillation of permeate produced during the dealcoholisation. The wine was pumped through the membrane module and the retentate (concentrated
2.3. Dealcoholisation of wine The volume of wine treated in the dealcoholisation process was 9 L. In the first stage of the treatment, the ethanol content of the wine was reduced from the initial value of 12.70% (v/v) to 4% (v/v)
Table 1 Analytical characteristics of original and dealcoholised wines obtained by reverse osmosis. Original wine
4% (v/v)
2% (v/v)
Dealcoholised wine (retentate)
Permeate
Dealcoholised wine (retentate)
Permeate
Parameter
X
s
X
s
X
s
X
s
X
s
Ethanol (%, v/v) Glucose (g/l) Fructose (g/l) Total sugar (G þ F) (g/l) Glycerol (g/l) Volatile acidity (g/l) Citric acid (g/l) Tartaric acid (g/l) Lactic acid (g/l) Succinic acid (g/l) Total acidity (g/l) Gelatin index (%) pH Total phenols index (a.u.) Total anthocyanins (mg/l m3og) Free anthocyanins (mg/l m3og) Total tannins (g/l) Abs 420 Abs 520 Abs 620 Modified colour intensity (MCI) Tonalitaty (tint) Cielab L* Cielab a* Cielab b*
12.70 3.36 0.60 3.97 8.18 0.32 0.17 2.50 1.40 3.09 4.50 57.80 3.46 46.18 286.00 227.00 1.54 2.67 3.80 0.78 7.25 0.70 21.30 52.6 34.4
0.02 0.01 0.00 0.01 0.00 0.00 0.00 0.02 0.05 0.01 0.00 0.12 0.01 1.03 2.00 1.00 0.06 0.01 0.01 0.01 0.03 0.00 0.20 0.3 0.3
4.37 3.26 0.57 3.83 7.45 0.54 0.14 2.44 1.28 2.82 4.70 58.40 3.45 44.3 239.00 186.00 1.39 2.87 4.74 0.87 8.48 0.60 18.6 50.0 31.0
0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.01 0.00 0.01 0.00 0.07 0.00 0.4 1.00 2.00 0.07 0.02 0.03 0.01 0.06 0.00 0.3 0.4 0.4
3.27 ea ea ea 0.20 0.39 ea ea 0.01 0.03 0.90 eb 3.45 eb eb eb eb eb eb eb eb eb eb eb eb
0.00 e e e 0.00 0.00 e e 0.00 0.00 0.01 e 0.01 e e e e e e e e e e e e
1.77 3.17 0.54 3.72 7.50 0.40 0.16 2.38 1.31 2.81 4.30 50.50 3.60 42.3 289.00 239.00 1.65 3.00 4.77 1.01 8.77 0.63 15.40 45.40 25.70
0.00 0.01 0.01 0.01 0.02 0.01 0.00 0.01 0.00 0.02 0.00 0.15 0.00 0.9 3.00 3.00 0.05 0.01 0.02 0.00 0.03 0.00 0.10 0.10 0.20
5.36 ea ea ea 0.38 eb ea ea 0.06 0.15 eb eb eb eb eb eb eb eb eb eb eb eb eb eb eb
0.00 e e e 0.00 e e e 0.01 0.12 e e e e e e e e e e e e e e e
m3og malvidin-3-O-glucoside. a not detected. b not determined.
M. Bogianchini et al. / LWT - Food Science and Technology 44 (2011) 1369e1375
1371
and 10 L of water were added to the feed tank. Secondly, the alcohol content was reduced further to 2% (v/v) and 25 L of water were added. In these two stages the wine was treated for 192 and 564 min respectively. The permeate rate was constant, with a value of 3 L/h (6 L/hm2) in both stages (Labanda et al., 2009). After the dealcoholisation of the wine, the total content of sulphur dioxide was adjusted to 80 mg/L. Then the wine was bottled.
concentration and the concentration after gelatine precipitation. The percentage was calculated by relating this astringency intensity to the total tannin concentration (Ribéreau-Gayon et al., 1998). This analysis was carried out using a UVeVIS spectrophotometer Perkin Elmer Lambda 20 with Colvin Perkin Elmer software v.1.0.
2.4. LC analysis of organic acids and sugars
The absorbances at wavelengths of 420, 520 and 620 nm and the CIELAB parameters (lightness (L*), red/green colour component (a*), and blue/yellow colour component (b*)) were determined by spectrophotometric methods (EEC, 1990; OIV, 2009). The colour was also characterised by the modified colour intensity (MCI), which is the sum of the absorbances at wavelengths of 420, 520 and 620 nm (1 cm path length). The tonality or tint was expressed by the ratio of the absorbances at 420 nm and 520 nm. By convention, the chromatic properties used to describe red and rosé wines are the colour intensity and the tint (EEC, 1990). The equipment used was the Perkin Elmer Lambda 20 UVeVIS spectrophotometer and the software was the Colvin Perkin Elmer v.1.0.
Organic acids (citric acid, tartaric acid, lactic acid, and succinic acid) and glucose, fructose, glycerol and ethanol were separated and simultaneously determined by liquid chromatography (LC) equipment Agilent Series 1100 with HP Chemstation software (Agilent, Waldbron, Germany). Sugars, glycerol and ethanol were measured using a refractive index detector (Agilent, Waldbron, Germany), while organic acids were measured using a diode array detector (Agilent, Waldbron, Germany). The column was a Transgenomic ICSepICE COREGEL-87H3, at an oven temperature of 50 C. The mobile phase was a solution of pH 2.20 prepared with concentrated H2SO4 (95e97%) in Milli-Q water, injection volume was 20 mL and the flow rate was 0.6 mL/min (López-Tamames, Puig-Deu, Teixeira & Buxaderas, 1996). Triplicate samples and mobile phase were filtered through cellulose acetate filters (Teknokroma) 0.45 mm before inyection. The standards: ethanol (>99.5%) and methanol (>99.9%) were provided by J.T. Baker, D-(þ)-glucose (>99.5%), fructose (99.0%), glycerol (>99.0%), citric (>99.5%), succinic (>99.0%), lactic (98%) and tartaric (>99.5%) acids by SigmaeAldrich. 2.5. LC-DAD analysis for phenolic compounds and furanic derivatives identification Phenolic compounds were analysed using an Agilent Series 1100 LC system equipped with a quaternary pump (Series 1100 G1311A), automatic injector (Series 1100 G1313A), degasser (Series 1100 G1379A), and UV/Vis diode detector (Series 1100 G1315B) coupled to a Chemstation HP A.10.02 (HP/Agilent). The column was an Agilent Zorbax SB-C18 (4.6 250 mm, 3.5 mm). Duplicate samples were filtered through a Millex-LCR 13 mm filter before injection. The chromatographic conditions had previously been described to analyse wine by Betes-Saura, Andres-Lacueva, and Lamuela-Raventos (1996). The method uses a binary gradient e A (glacial acetic acid/ water pH 2.65), B (20% A þ 80% acetonitrile) e programmed with the following gradient: 0 min (0% B); 5 min (2% B); 10 min (4% B); 15 min (10% B); 30 min (20% B); 35 min (30% B); 40 min (100% B); 45 min (0% B). The sample volume injected was 50 ml, the flow rate was 1.5 mL/min, and the temperature was set at 40 C. Quantification was performed by external calibration at their maximum absorbance. The standards were purchased from Fluka [caffeic acid, gallic acid, p-coumaric acid, ()-epicatechin, furfuryl alcohol], Sigma [vanillic acid, ellagic acid, ferulic acid, syringic acid, ()-catechin, resveratrol glucoside], Safc [5-hydroxymethylfurfural] and Chromadex [3-o-methylgallic acid, caftaric acid, procyanidin-B1, procianydin-B2]. Standards purity was higher than 98%. 2.6. Astringency analysis Gelatine index (GI) was obtained using the methods described by Ribéreau-Gayon, Glories, Maujean, and Dubourdieu (1998). A total of 100 mL of 70 g/L gelatine solution were added to 1000 mL of wine by duplicate, and centrifuged at 8000 rpm for 5 min (Eppendorf Centrifugue 5417C) after 3 days. The supernatants were assayed to determine the tannin concentration expressed as astringency intensity and as a percentage. Astringency intensity is calculated as the difference between the total solution tannin
2.7. Determination of chromatic properties
2.8. Antioxidant activity (AA) 2.8.1. ORAC assay The ORAC assay is based on a previously reported method, with slight modifications (Ou, Hampsch-Woodill, & Prior, 2001). In this method, 50 ml of a sample or Trolox are mixed with 100 ml of Fluorescein (45 nM) and 50 ml of AAPH (15 mM). Fluorescence is recorded for 60 min (the excitation wavelength is set at 485 nm and the emission wavelength at 528 nm). Measurements were taken in triplicate in a multi-detector microplate reader (Synergy HT, BiotekÒ). Trolox was used as a calibration standard (0.5e9.5 mM). The results were calculated as ORAC values from the differences between the blank and the sample areas under the fluorescein decay curve. They are expressed as mM Trolox equivalents. 2.8.2. FRAP method The FRAP reagent consists of acetate buffer (300 mM, pH 3.6), TPTZ (10 Mm in HCl 40 Mm) and FeCl3 6H20 (20 mM) (10:1:1, v/v/v). A total of 3 ml of FRAP reagent was mixed with 300 ml of Mili-Q water and a 100 ml sample. Absorbance was measured after 8 min at 593 nm. An aqueous solution of FeSO4x7H2O in the 0e1 mM range was used for calibration. All determinations were performed in triplicate. Results are expressed as mmol of Feþ2/L of wine (Benzie & Strain, 1996). Absorbance measurements were recorded on a Hitachi UV-2800Ò spectrophotometer thermostated with a Peltier system at 25 C. 2.8.3. DPPH method 0.1 mL of sample or Trolox (0.000e1.000 mM) was added to 3.9 mL of DPPH (0.063 mM), all in methanolic solution. Absorbance was measured at 515 nm after 60 min (when the reaction reached equilibrium) (Sánchez-Moreno, Larrauri, & Saura-Calixto, 1998). The blank reference cuvette contained methanol. All measurements were performed in triplicate. Results are expressed as mM Trolox equivalents. Absorbance measurements were recorded on a Hitachi UV-2800Ò spectrophotometer thermostated with a Peltier system at 25 C. 2.9. Ascorbic acid addition A Spanish wine was dealcoholised in the laboratory by means of rotavapor set at 38 C and operating under vacuum. Subsequently, a total of 90 mg/L of ascorbic acid was added. ORAC AA was
7226 7091 609 9.71 1.11 1855 7561 222 12.4 0.7 4671 6712 185 8.9 0.3 2324 10478 301 11.0 0.6 3040 11021 344 11.81 0.19 3926 850 72 1.89 0.16 1123 1560 328 1.45 0.09 1078 749 55 0.51 0.13 1836 769 88 0.57 0.13 932 752 31 2.36 0.03
measured before and after ascorbic acid addition to evaluate the effect of this ascorbic acid content in the AA of the final product. 2.10. Other parameters
ea 132.82 ea 190.41 ea 342.89 a e 201.30 a e 207.10 a e 64.50 1.74 0.01 33.30 0.61 0.00 21.95 ea 35.71 2.28 0.02 119.35
ea 22.4 0.01 29.9 0.5 27.58 0.02 22.0 0.3 ea 1.98 0.01 2.6 0.5 ea 18.36 0.15
ea 15.3 0.3 ea ea ea ea ea ea ea 13.28 0.25
ea 44.9 0.4 92.57 0.19 18.5 0.4 39.41 1.21 ea ea ea ea ea
0.00 82.50 122.49 46.04 61.42 0.00 1.98 2.61 0.00 31.64
68839 74968 62347 87149 89043 21250 11517 10274 8516 24357
Total and volatile acidity and pH were determined using Fourier Transform Infrared (FTIR) technology by means of a WineScanÔ Flex equipment with a Foss and Flexible Foss Integrator Software platform, a liquid flow system and a 0.4 mm calcium fluoride cuvette (Foss, Foss Electric España, S.A) to generate the FTIR spectra. The calibration provided with the equipment has allowed us to analyse immediately the pH and volatile acidity, adapting following to the resolution OIV/OENO 390/2010. The samples were automatically thermostated at 20 C in the spectrometer before analysis. The IR spectrum was scanned between 2.000 nm and 10.000 nm (NIR and MIR). The spectra were obtained in duplicate and averaged for each sample. Sulphur dioxide was determined using the reference method (Paul, 1958). Phosphoric acid was added to the sample then connected to a bubbler and passed through a hydrogen peroxide solution. The resulting hydrogen peroxide solution was neutralised and the acid which formed with the 0.01 M sodium hydroxide solution was titrated to determinate the free sulphur dioxide. All of the sulphur dioxide is purged from the wine by entrainment at high temperature. Total phenol Index was determined by both most used methods: by recording absorbance at 280 nm (Commission Regulation (EEC) No. 2676/90) and Folin Ciocalteu method (Waterhouse, 2001). Results are expressed as absorbance units (a.u.) and as mg/L of gallic acid equivalents respectively. The equipment used was UVeVIS spectrophotometer Perkin Elmer Lambda 20 with Colvin Perkin Elmer software v.1.0. Total anthocyanins (TA) were determined by measuring the absorbance at 520 nm (Zoecklein, Fugelsang, Gump, & Nury, 1995). Absorbance (A) was measured at 520 nm in 1M HCL and sodium metabisulfite solution (20% wt/vol) buffers using the following equation: TA ¼ 20 (AHCl(520nm)(5/3)ASO2(520nm)),the 5/3 correction factor is used to get a more accurate measure of monomeric anthocyanin in wine. Results are expressed as mg/L of maldivine3-O-glucoside. Free anthocyanins (FA) expresses as mg/L of maldivine-3-Oglucoside is calculated by: FA ¼ 20 (A(520nm)ASO2(520nm)), were A(520nm) is the absorbance at 520 nm of a wine dilution of 200 mL of wine in 10 mL of deionised water. The equipment used to measure total anthocyanins was UVeVIS spectrophotometer Perkin Elmer Lambda 20 with Colvin Perkin Elmer software v.1.0. 2.11. Statistical analysis Statistical software (Statsoft, 2001) was used to test significant differences (t-test; p < 0.05). Rered wine; Wewhite wine; RSerosé wine. a no detected.
ea ea ea ea ea ea 13.5 0.5 ea ea ea 2.75 0.02 ea 6.77 0.06 ea ea ea ea ea ea 8.9 0.7 R1 R2 R3 R4 R5 W1 W2 W3 RS1 RS2
1802 2460 828 2487 2451 1105 528 2360 218 701
30.5 55.2 282 221 51.4 32.1 52.9 119 14.1 14.1
28.0 1.5 34.93 0.00 43.9 0.3 72.43 0.10 36.65 0.20 4.88 0.00 5,1 0,3 ea 3.6 0.3 16.01 0.06
ea 11.76 0.07 ea 10.7 0.3 12.8 0.6 ea ea ea ea ea
28.00 118.6 46.69 190.4 43.88 342.9 96.63 183.1 49.45 190.2 7.63 64.50 11.87 29.44 0.00 19.46 3.60 34.56 24.91 117.07
3.7 0.3 11.6 0.3 0.3 0.03 0.02 0.01 0.15 0.11
14.22 0.19 ea ea 18.19 0.01 16.80 0.00 ea 2.12 0.01 1.88 0.01 1.15 0.00 ea
()Epicatechin (þ)Catechin
Flavanols (mg/L)
p-Coumaric Total Acid Caffeic Acid
Cinnamic acids (mg/L)
Total Caftaric Acid Ellagic acid Vanillic acid Syringic acid Gallic Acid
Benzoic acids (mg/L) Sample TPI (mg/L)
Table 2 Total phenolic index (mg/L of GAE), antioxidant activity and concentration of phenolic compounds (mg/L) detected in commercial dealcoholised wine.
Procyanidin Total B2
ORAC (mM)
DPPH FRAP (mmolFe2þ/L) (mM)
M. Bogianchini et al. / LWT - Food Science and Technology 44 (2011) 1369e1375
Antioxidant Activity
1372
3. Results and discussion 3.1. Phenolic composition and antioxidant activity of commercial dealcoholised wines Table 2 shows the phenolic content of the different types of commercial dealcoholised wines. A total of 10 phenolic compounds were identified, caftaric acid being the most abundant compound, followed by procyanidin B2, (þ)-catechin and gallic acid (Table 2). Their concentrations were found to be similar to those described for normal French (Landrault et al., 2001) and Spanish wines (Guerrero, García-Parrilla, Puertas, & Cantos-Villar, 2009). The
M. Bogianchini et al. / LWT - Food Science and Technology 44 (2011) 1369e1375
1373
Table 3 Concentration (mg/L) of phenolic acids and antioxidant activity determination of commercial dealcoholised wines (Sa and Sb) during the storage of bottles (T1 - T30). Wine
Benzoic acids (mg/L) Gallic Acid
SaT1 SaT7 SaT15 SaT30 SbT1 SbT15 SbT30
85.0 93.10 66.70 72.42 50.6 52.15 48.1
0.3b 0.03c 0.08d 0.02e 1.7b 0.09b 0.3b
Cinnamic acids (mg/L)
Vanillic acid
Ellagic acid
17.0 1.4b 21.40 0.09b 12.91 0.07b 15.01 0.07b ea ea ea
7.11 4.73 5.23 4.07 4.6 4.23 3.31
Total
Caftaric Acid
0.02b 109.07 228.30 7.22b 0.09c 119.26 225.7 1.9b 0.16c 84.84 165.1 13.7c 0.11c 91.50 171.1 0.5c 0.3b 55.18 397.4 2.6b 0.02b 56.38 364.9 1.4b 0.00c 51.43 315.8 1.3c
Antioxidant Activity
Caffeic Acid
Ferulic Acid
Total
ORAC (mM)
26.8 0.3b 20.53 0.02c 15.46 0.19d eae ea ea ea
ea ea ea ea 0.89 0.02b 0.8 0.3b eab
255.07 246.18 180.57 171.10 398.27 365.68 315.84
13378 17942 14026 8990 15590 15848 9964
3647b 1807b 1090b 2284b 1343b 1571b 665c
FRAP (mmolFe2þ/L) DPPH (mM) 2.99 2.55 2.39 1.39 3.34 2.74 2.20
0.17b 0.18b 0.07b 0.07c 0.16b 0.18b 0.51b
17.4 22.3 14.1 10.72 12.0 10.42 5.7
0.4b 0.6c 0.4d 1.02e 0.3b 0.21b 0.4c
Different superscript letters within the same sample indicate significant differences among the different times of storage (p < 0.05). a no detected; T e time in days.
alcohol lost in the medium does not lead to precipitation of these compounds and can therefore be considered a source of bioactive compounds. Certain process to dealcoholise wines involves heating to evaporate ethanol and therefore 5-hydroxymethylfurfural (5-HMF) could be present in commercial samples. This compound, like other furfuryl alcohol derivatives, was studied by the Scientific Panel on Food Additives, Flavouring, Processing Aids and Materials in Contact with Food (EFSA, 2005) to evaluate the implication of these substances for human health. The Scientific Panel concluded that 5-HMF and four other furfuryl alcohol derivatives, insofar as their metabolism includes the formation of furfural, a known reactive hepatotoxic aldehyde, cannot be predicted to be metabolised to innocuous or endogenous products. 5-HMF has been shown to be bioactivated in vitro to reactive genotoxic intermediates by sulfotransferases (EFSA, 2005). However, 5-HMF is present only at low concentrations (0.02e4.6 mg/L) similar to the concentrations found in orange juices, normal white or red wines (Yuan & Chen, 1999). The concentration of 5-HMF is important for producers as they must guarantee their products are safe. The AA of commercial dealcoholised wines is shown in Table 2. As expected, dealcoholised red wines showed higher AA values for the ORAC, DPPH and FRAP assays than dealcoholised rosé and white wines. These results are coherent with reported data for red wines (Fernández-Pachón, Villano, García-Parrilla, & Troncoso, 2004). However, most of these commercial dealcoholised wines presented an ORAC AA value three times higher than reported values for wines (Fernández-Pachón et al., 2004; Granato, Katayama, & Castro, 2010). Because the concentration of polyphenolic compounds (Table 2) is within the same range of French and Spanish wines (Guerrero et al., 2009; Landrault et al., 2001), this high AA value may be caused by the addition of ascorbic acid (90 mg/L) for product stability purpose. The label on these products states that ascorbic acid (90 mg/L) is added. We tested whether this concentration of ascorbic acid might explain the AA values by dealcoholising the wine in the laboratory (rotavapor set at 38 C and operating under vacuum) and adding ascorbic acid afterwards. The ORAC value of the wine was 13672 2108 mM Trolox equivalents initially and 26137 4824 mM Trolox equivalents after ascorbic acid had been added, which explains the increase in AA. The phenolic composition and AA of commercial dealcoholised wines was monitored over time to check their stability. Commercial dealcoholised wines lost 33e54% of AA e as determined by ORAC, FRAP and DPPH e after 30 days of storage (Table 3). The lesser solubility of certain phenolic compounds in a medium without ethanol can explain this fact. Indeed, in most of the commercial dealcoholised wines, phenolic compounds significantly decreased after 30 days of storage. Specifically, caffeic acid disappeared, while the concentrations of caftaric acid and ellagic acid decreased by around 25% and 43%, respectively (Table 3). It does not have the allergic effects associated with SO2, which is an advantage in terms
of health. However, the data in Table 3 show that the phenolic concentration is not stable. Recent research studies report that ascorbic acid has a pro-oxidant effect on model wine matrix containing (þ)-catechin (Bradshaw, Cheynier, Scollary, & Prenzler, 2003). Our results agree with these latest findings. 3.2. Effects of RO on dealcoholised wines 3.2.1. Effects of RO on enological parameters Table 1 shows the analytical characteristics of the original red wine and of the dealcoholised products following RO. As can be seen, the retention of glucose, the main organic acids and glycerol was higher than 90% for both retentates at 4% and 2% (v/v). The total acidity increased in the first stage and fell in the second one, while the volatile acidity increased in both stages. On the other hand, RO did not affect the analysed parameters as the pH, fructose, and tartaric acid content of dealcoholised wines (4% and 2% alcoholic degree), which remained the same as in the original wine. The treatment caused the free and total sulphur dioxide content to fall by around 25% and 75% for the retentate of 4% and 2% (v/v), respectively. This fall must be controlled during the treatment to avoid any wine oxidation. Astringency (expressed as the gelatine index), on the other hand, increased slightly during the first stage of the treatment and decreased during the second stage. However, the values of the index of gelatin obtained (50e60%), and the concentration of tannins (around 1.5 g/L) in wine indicates that wines are slightly astringent. These values have not a relevant impact on astringency (Goldner & Zamora, 2010; Llaudy et al., 2004). The modified colour intensity increased by around 20% in both stages dealcoholised wines and the tonality diminishes around 15%. This could have been due to the reduction in sulphur dioxide, which is known to produce a reversible reaction that affects the colour (Zoecklein et al., 1995). All absorbances at 420 nm (yellow), 520 nm (red), and 620 nm (blue) increased, but the absolute increase was higher for 420 and 520 nm than for 620 nm, resulting in a higher red and yellow component and therefore a more purple colour. Nevertheless, this increase could be affected by the lower alcohol content, since Somers and Evans (1979) observed an increase in colour at both 420 and 520 nm when the concentration of alcohol was reduced. The CIELAB parameters were lower when the alcoholic strength was reduced. The decrease in the red/green value (a*) led to a greener colour and the decrease in the blue/yellow value (b*) led to a more blueness colour. All these changes in colour parameters can be easily explained by the effect of ethanol on copigmentation phenomena. It is knew that ethanol decrease the anthocyanin copigmentation (Boulton, 2001). Consequently, a decrease in ethanol content implies a greater proportion of flavilium form of anthocyanins which must increase the colour intensity and decrease the hue. The consequence is an increase of the blueness
44b 132b 59b 155b 231b 193b 153b 223b 301b
hue which characterises the colour of young wines. All this data is confirmed by the changes observed in CIELAB coordinates.
0.01b
0.03b 0.00b 0.08b
0.11b 0.06b 0.02b 0.4b 0.00b 0.8b 0.02b 0.06b 0.01b
3.29 3.53 3.60 3.25 3.45 3.3 3.26 2.82 3.25
0.04b 0.03b 0.12b 0.06b 0.05b 0.3b 0.03b 0.07b 0.12b
0.38 eab eab 0.88 0.68 1.01 eab eab 0.19
0.01b
9.70 9.83 9.91 8.7 8.3 8.05 9.76 9.71 9.73
0.15b 0.23b 0.12b 0.4b 0.3b 0.14b 0.03b 0.13b 0.05b
20496 20335 20433 19619 19845 19838 18835 19336 19055
3.2.2. Effects of RO on phenolic composition and AA Table 4 shows the phenolic composition, furfuryl alcohol and AA of a red wine and of the products resulting from RO. The resulting products were dealcoholised wines with 4% and 2% (v/v) alcoholic degree. Total anthocyanins were 286.00 2.00 mg/L for the original wine and 289.00 3.00 mg/L for the dealcoholised 2% (v/v) wine. Therefore, no significant differences were observed as a result of this process. As Table 4 shows, RO did not significantly affect any phenolic acid, irrespective of their chemical structure (benzoic acids, cinnamic acids). However, flavanols are affected in some extent. Concerning the stability of these products, the concentration for phenolic compounds of the wines dealcoholised by RO did not significantly change after 7 months of storage (Table 4). Their AA did not change significantly either. It is important to bear in mind that samples were stabilised by sulphurous dioxide, which is commonly used in winemaking. The results show that the RO method does not alter the phenolic profile and antioxidant properties of the final product, enabling a healthy product to be obtained with a low-alcohol content (2% v/v) and stable bioactive compounds that are similar to those found in normal wine.
0.01b 0.04b
0.00b 0.00b 0.00b 0.07b
4. Conclusions Wewine; DWedealcoholised wine; Tetime in months. Different superscript letters within the same sample indicate significant differences among the different times of storage (p < 0.05). a no detected.
12.67 14.49 14.46 13.3 13.70 12.9 12.89 11.50 13.10 0.8b 0.20b 0.6b 0.08b 0.13b 2.23b 2.5b 0.22b 0.13b 50.4 41.76 41.3 34.86 49.10 47.10 38.5 31.55 47.97 0.4b 0.07b 0.12c 0.12b 0.3c 0.5c 0.03b 0.4b 0.3b 12.0 11.10 7.95 7.81 15.0 12.7 8.70 9.3 8.8 21.5 0.3b 16.7 0.15c 14.9 0.5c 13.8 0.8b 16.9 0.4b eac 13.60 0.03b 10.71 0.06b 9.80 0.15b ea ea ea eab 32.4 0.5c 29.23 1.19c eab 18.8 0.6c 19.1 0.5c eab eab 1.12 1.11 1.00 0.97 eab 0.87 0.95 0.16b 0.01b 0.07b 0.03b 0.06b 0.24b 0.09b 0.02b 0.14b 3.04 2.71 3.12 2.68 2.53 3.30 3.37 2.21 3.26 2.9b 0.8b 0.3b 0.5b 1.4b 5.9b 1.9b 0.3b 0.4b 84.3 83.4 88.4 82.5 82.9 83.3 86.9 73.7 87.6 W 12 T0 W 12 T2 W 12 T7 DW 4 T0 DW 4 T2 DW 4 T7 DW 1 T0 DW 1 T2 DW 1 T7
Furfural derived Antioxidant activity Cinnamic acids Stilben Flavanols
Protocatechuic acid 3-O-Methylgallic acid (þ)-Catechin ()-Epicatechin Procianidin B2 Procianidin B1 Caftaric acid Gallic acid
Benzoic acids Samples
Resveratrol glucoside Furfuryl alcohol DPPH (mM) FRAP (mmolFe2þ/L)
M. Bogianchini et al. / LWT - Food Science and Technology 44 (2011) 1369e1375
Table 4 Concentration (mg/L) of phenolic compounds, furfuryl alcohol and antioxidant activity of dealcoholised wines obtained by reverse osmosis during the storage of bottles (T0 - T7).
1374
We determined the AA and the phenolic composition of dealcoholised wines and the results led us to conclude that the dealcoholised wines provide a good source of polyphenols without the disadvantages of alcohol intake. We tested the influence of bottle storage on the polyphenolic composition and AA in commercial dealcoholised wines and observed a significant decrease in these two parameters after 30 days of storage. This may prove important for labelling the optimum time of consumption in terms of AA for consumers who want to drink wine with antioxidant properties. RO is a process suitable for obtaining dealcoholised wines that maintain their phenolic compounds and AA. The bioactive composition of dealcoholised wines obtained in this way is more stable than in dealcoholised wines obtained by other methods. Acknowledgements The authors are grateful to the University of Milan for Michele Bogianchini’s fellowship and to the Spanish Ministry of Science and Innovation for its financial support (Research project AGL 200764622). References Belisario-Sánchez, Y. Y., Taboada-Rodríguez, A., Marín-Iniesta, F., & López-Góméz, A. (2009). Dealcoholised wines by spinning cone column distillation: phenolic compounds and antioxidant activity measured by the 1.1-diphenyl-2-picrylhydrazyl method. Journal of Agriculture and Food Chemistry, 57(15), 6770e6778. Benzie, I. F., & Strain, J. J. (1996). The ferric reducing ability of plasma (FRAP) as a measure of “antioxidant power”: the FRAP assay. Analytical Biochemistry, 239, 70e76. Betes-Saura, C., Andres-Lacueva, C., & Lamuela-Raventos, R. M. (1996). Phenolics in white free run juices and wines from Pened’es by high-performance liquid chromatography: changes during vinification. Journal of Agricultural and Food Chemistry, 44(10), 3040e3046. Boulton, R. (2001). The copigmentation of anthocyanins and its role in the color of red wine: a critical review. American Journal of Enology and Viticulture, 52(2), 67e87. Bradshaw, M. P., Cheynier, V., Scollary, G. R., & Prenzler, P. D. (2003). Defining the ascorbic acid crossover from anti-oxidant to pro-oxidant in a model wine matrix containing (þ)-catechin. Journal of Agriculture and Food Chemistry, 51(14), 4126e4132. Commission Regulation (EEC) No. 2676/90. (October 3 1990). Commission regulation (EEC) No. 2676/90 determining community methods for the analysis of wines. Official Journal, L272, 1e192. EFSA. (2005). Opinion of the scientific panel on food additives, flavourings, processing aids and materials in contact with food (afc) on a request from the
M. Bogianchini et al. / LWT - Food Science and Technology 44 (2011) 1369e1375 commission related to flavouring group evaluation 13: furfuryl and furan derivatives with and without additional side-chain substituents and heteroatoms from chemical group 14. Question number EFSA-Q-2003-156. Adopted on 27 April 2005. The EFSA Journal, 215, 1e73. Fernández-Pachón, M. S., Villano, D., García-Parrilla, M. C., & Troncoso, A. M. (2004). Antioxidant activity of wines and relation with their polyphenolic composition. Analitica Chimica Acta, 513(1), 113e118. Goldner, M. C., & Zamora, M. C. (2010). Effect of polyphenol concentrations on astringency perception and its correlation with gelatine index of red wine. Journal of Sensory Studies, 25(5), 761e777. Granato, D., Katayama, F. C. U., & Castro, I. A. (2010). Assesing the association between phenolic compounds and the antioxidant activity of Brazilian red wines using chemometrics. LWT- Food Science and Technology, 43, 1542e1549. Guerrero, R. F., García-Parrilla, M. C., Puertas, B., & Cantos-Villar, E. (2009). Wine, resveratrol and health: a review. Natural Product of Communications, 4(5), 635e658. International Organisation of Vine and Wine (OIV). (2009) Compendium of international methods of wine and must analysis, vols 1 and 2. Labanda, J., Vichi, S., Llorens, J., & López-Tamames, E. (2009). Membrane separation technology for the reduction of alcoholic degree of a white model wine. LWT - Food Science and Technology, 42, 1390e1395. Landrault, N., Poucheret, P., Ravel, P., Gasc, F., Cros, G., & Teissedre, P. L. (2001). Antioxidant capacities and phenolics levels of French wines from different varieties and vintages. Journal of Agriculture and Food Chemistry, 49(7), 3341e3348. Llaudy, M. C., Canals, R., Canals, J. M., Rozès, N., Arola, L., & Zamora, F. (2004). New method for evaluating astringency in red wine. Journal of Agriculture and Food Chemistry, 52(2), 742e746. López-Tamames, E., Puig-Deu, M. A., Teixeira, E., & Buxaderas, S. M. (1996). Organic acids, sugars, and glycerol content in white winemaking products determined by HPLC: relationship to climate and varietal factors. American Journal of Enology and Viticulture, 47(2), 193e198. Monagas, M., Bartolomé, B., & Gómez-Cordovés, C. (2005). Updated knowledge about the presence of phenolic compounds in wine. Critical Review in Food Science and Nutrition, 45(2), 85e118.
1375
Noble, A. C. (2002). In Astringency and bitterness of flavonoid phenols. ACS Symposium Series, vol. 825 (pp. 192e201). OIV, Oeno Resolution 390/2010. (June, 25th 2010). Guidelines on infrared analyser in oenology. Tbilisi. Ou, B., Hampsch-Woodill, M., & Prior, L. R. (2001). Development and validation of an improved oxygen radical absorbance capacity assay using fluorescein as the fluorescent probe. Journal of Agriculture and Food Chemistry, 49, 4619e4626. Paul, F. (1958). Die alkalimetrische Bestimmung der Freien, gebundenen und gesamten schwefeligen Sw, ure mittels des Apparates von Lieb und Zacherl. Mitt. Rebe u. Wein, Ser. A., Klosterneuberg, 8, 21e7. Ribéreau-Gayon, P., Glories, Y., Maujean, A., & Dubourdieu, D. (1998). In Traité d’œnologie. Chimie du vin, Stabilisation et traitement, Tome 2. France: Dunod. Sánchez-Moreno, C., Larrauri, J. A., & Saura-Calixto, F. (1998). A procedure to measure the antiradical efficiency of polyphenols. Journal of the Science of Food and Agriculture, 76(2), 270e276. Seeram, N. P., Aviram, M., Zhang, Y., Henning, S. M., Feng, L., Dreher, M., et al. (2008). Comparison of antioxidant potency of commonly consumed polyphenol-rich beverages in the United States. Journal of Agriculture and Food Chemistry, 56(4), 1415e1422. Somers, T. C., & Evans, M. E. (1979). Grape pigment phenomena: interpretation of major colour losses during vinification. Journal of the Science of Food and Agriculture, 30, 623e633. Statsoft, Inc.. (2001). STATISTICA for Windows [Computer program manual]. Tulsa, OK: Staftsoft, Inc.. 2300 East 14th Street74104e74442. Waterhouse, A. L. (2001). Determination of total phenolics. In R. E. Wrolstad, T. E. Acree, E. A. Decker, M. H. Penner, D. S. Reid, S. J. Schwartz, C. F. Shoemaker, D. M. Emith, & P. Sporns (Eds.), Handbook of food analytical chemistry (pp. 464e465). New York: Wiley, Unit I1.1. Yuan, J. P., & Chen, F. (1999). Simultaneous separation and determination of sugars, ascorbic acid and furanic compounds by HPLC-dual detection. Food Chemistry, 64(3), 423e427. Zoecklein, B. W., Fugelsang, K. C., Gump, B. H., & Nury, F. S. (1995). Wine analysis and production. New York, NY: Champman & Hall.