Phenolics, Aroma Profile, and In Vitro Antioxidant Activity of Italian Dessert Passito Wine from Saracena (Italy)
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Phenolics, Aroma Profile, and In Vitro
Antioxidant Activity of Italian Dessert
Passito Wine from Saracena (Italy)
Monica R. Loizzo, Marco Bonesi, Giuseppe Di Lecce, Emanuele Boselli, Rosa Tundis, Alessandro Pugliese, Francesco Menichini,
C: Food Chemistry
and Natale Giuseppe Frega
Abstract: A traditional sweet dessert wine from Saracena (Italy), made with nonmacerated local white grapes (Guar-
naccia, Malvasia and Moscato), was analyzed for phenolics and aroma profile and antioxidant activities. The most
abundant classes of phenols identified by high-performance liquid chromatography were hydroxybenzoic acids and
flavan-3-ols, where gallic acid showed the highest content (376.5 mg/L). The analysis by solid phase microextraction-gas
chromatography-mass spectrometry revealed the presence of superior alcohols (from iso-butanol and iso-amyl alcohol up
to 2-phenylethanol) and their ethyl esters, terpenes (such as linalool), furfuryl compounds, and free fatty acids (up to
palmitic acid) as the key odorants of this wine. The antioxidant activity, evaluated by different in vitro assays 2,2-diphenyl-1-
picrylhydrazyl (DPPH), 2,2 -azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS), and β-carotene bleaching test),
showed that passito wine had a radical scavenging activity (IC50 value of 0.03 v/v against DPPH·) and inhibited linoleic
acid oxidation with an IC50 value of 0.4 v/v after 30 min of incubation.
Keywords: aroma, antioxidant activity, dessert wine, phenolics, HPLC tandem MS, SPME-GC-MS
Practical Application: It is well known that moderate consumption of wine is actually recommended since it appears
associated with a decreased incidence of several diseases. Passito of Saracena, a well-appreciated Italian dessert wine,
demonstrated an interesting antioxidant activity. Moreover, the aroma profile contributed and defined the chemical
markers of the quality of this wine and their quantitative ranges, which are needed to assess the authenticity of local niche
production claiming a quality designation.
Introduction 2000). In Italy, 3 different categories of dessert wine are pro-
According to our new report entitled “US Wine Market Fore- duced: passito wines (Passito di Pantelleria and Vinsanto); Port-
cast to 2012” (2010), the U.S. wine market is one of the fastest like wine (Marsala), and sparkling sweet wines (Brachetto d’Acqui
growing markets in the world that at present accounts for around or Vernaccia di Serrapetrona). These wines are consumed also
12% of the global wine consumption. This market is expected as aperitif, to accompany aged cheese and blue cheese, and in
to grow about 3% during 2010 to 2013. The market is domi- cooking.
nated by table or still wine, which accounts for nearly 90% of The traditional way to produce passito in Calabria (Italy) in-
the market while dessert and sparkling wine together hold just volves picking grape bunches and place them on a cannizza and
over 10% market share. However, some experts believe that there allowing grapes to dry in the sun for 10 to 15 d but covered dur-
is potential for expanding this category market by re-educating ing the night. This process called appassimento (raisining) generally
and re-introducing consumers to high-quality products. Dessert increases the sugar content up to 30% to 40%. Some grape juice is
wines are distributed worldwide and some of the most impor- also left out in a jar for a few days. Then the dried grapes are placed
tant dessert wines are Beerenauslesen and Trockenbeerenauslesen in a jar for a few days and pressed. This sweet, slightly fermented
(Germany), Banyuls, Sauternes, Monbazillac, Jurancon, Maury, liquid is mixed with the juice that was also exposed to the sun.
and Rivesaltes (France), Sherry (Spain), Porto and Madeira (Por- The entire mixture is then closed in a jar and allowed to ferment
tugal). Leaving Europe for North America Canadian and Up- for 3 to 4 wk.
state New York ice wine were produced (Brooke 1987; Jackson The effect of dehydration by sun exposure on Pedro Ximénez
grapes that are used to obtain a famous Andalusia sweet wine was
investigated by Peinado and others (2009) and Lopez de Lerma and
MS 20121784 Submitted 12/27/2012, Accepted 02/18/2013. Authors Loizzo,
Bonesi, Tundis, Pugliese, and Menichini are with Dept. of Pharmacy, Health Sciences others (2012). Grapes subjected to this process undergo significant
and Nutrition, Univ. of Calabria, 87036 Rende (CS), Italy. Authors Lecce, Boselli, modifications in terms of higher sugar concentration, change in
and Frega are with Dept. of Agricultural, Food and Environmental Sciences, Marche volatile and phenolics profile, and enzymatic activity. In partic-
Polytechnic Univ., via Brecce Bianche, 60131 Ancona, Italy. Direct inquiries to author ular, sun drying enriches musts in phenolics thus increasing the
Loizzo (E-mail: monica_rosa.loizzo@unical.it).
antioxidant activity.
This work is dedicated to the memory of Professor Francesco Orlandi (1927 In Europe, this production is enforced by the Commission
to 2012), who was an inspiration to scientists and played a key role in alcohol Regulation (EC) No 606/2009 and its subsequent modifica-
research, not only in Italy, but also in the international arena. tions. Passito of Saracena (Italy) has often been awarded as a
C 2013 Institute of Food Technologists
R
doi: 10.1111/1750-3841.12110 Vol. 78, Nr. 5, 2013 r Journal of Food Science C703
Further reproduction without permission is prohibitedPassito chemistry and bioactivity . . .
high-quality Italian dessert wine. The must is obtained by crush- Wine samples
ing autochthonous Malvasia and Guarnaccia overripe grapes. The The survey was carried out on Passito of Saracena wine (5
special aroma and taste also derive from Moscato grapes, which samples) aged from 1 to 4 y. All samples were acquired directly
are collected and dried a few weeks before harvest. The Moscato from the wineries. All bottles were stored in the dark (10 ◦ C) and
grape berries are dried, selected, crushed, and then manually analyzed immediately after opening. A sample aliquot (50 mL)
added to the first-pressing must. After a long and slow fermenta- was taken and mixed with equal aliquots of the others to obtain a
tion, a wine with sweet amber and golden reflections, intense single sample for analysis.
C: Food Chemistry
aroma, and the taste of honey, dried figs, and exotic fruits is
obtained. Passito wine analyses
The aroma profile of wine, also called bouquet, is determined by The chemical parameters (pH, total acidity, volatile acidity, re-
alcohols, aldehydes, esters, acids, monoterpenes, and other minor ducing sugars, alcohol percentage, ash, dry extract, sulfates, and
components such as sulfur and nitrogen compounds which are chloride) were determined according to the Commission Reg-
already present in the grapes or are formed during the fermen- ulation (EEC) No 2676/90. Sugars (glucose and fructose) were
tation process and storage, and participate to the overall pleasant quantified by HPLC (Thermo Electron Corp., Waltham, Mass.,
flavor perceived on drinking. The aroma profile is influenced by U.S.A.) equipped with a UV100 set to 210 nm and a RI-150. The
environment, ripeness, and grape variety, as well as winemaking analyses were performed isocratically at 0.8 mL/min and 65 ◦ C
procedures (Verzera and others 2008). Recently, solid phase mi- with a 300 mm × 7.8 mm i.d. cation-exchange column (Aminex
croextraction (SPME), which allows to determine the low-level HPX-87H) and a Cation H+ Microguard cartridge (Bio-Rad Lab-
components in complex mixtures, has been used to study the wine oratories, Hercules, Calif., U.S.A.) using 0.003 N H2 SO4 as mo-
aroma compositions (Verzera and others 2008). bile phase (Gerbi and Tortia 1991). The total phenolic content was
Several phenolic compounds are present in wine and their con- evaluated by using the Folin–Ciocalteu method (Menichini and
centrations depend on grape variety, climatic conditions, and, others 2009) and expressed as mg/L (+)-catechin, while proan-
of course, viticultural and winemaking techniques. These com- thocyanidins were spectrophotometrically determined according
pounds are responsible for wine color and also flavor and astrin- to Di Stefano and others (1989). Moreover, color density, poly-
gent taste (Lesschaeve and Noble 2005). Also, they manifest a meric color, and percent of polymeric color were determined
wide range of beneficial health effects including antioxidant activ- according to the methodology previously reported by Giusti and
ity (Boselli and others 2009). Pellegrini and others (2003) stated Wrolstad (2001).
that to correctly investigate antioxidant activity several methods
must be applied. HPLC-UV and mass spectrometry conditions
This study was designed to gain knowledge of an Italian Passito The determination of low molecular weight phenolics in pas-
wine produced in the area of Saracena (Calabria, Italy). For this sito wine was carried out using RP-HPLC–diode array detector
purpose, the high-performance liquid chromatography (HPLC) (DAD). The HPLC ternary pump was a mod. 9010 from Var-
phenolics profile, SPME-gas chromatography-mass spectrometry ian (Middelburg, the Netherlands). A Chrompack (Middelburg)
(SPME-GC-MS) of the volatile fraction, and determination of 25 cm × 4.6 mm i.d. column packed with Chromosphere C18
antioxidant activity through different in vitro assays (2,2-diphenyl- (5 μm particle size) was used. The separation of phenolic com-
1-picrylhydrazyl [DPPH], ABTS, and β-carotene bleaching test) pounds was carried out in 45 min under the following conditions:
were performed. The experimental results derived from this inves- at 0 min, mobile phase A (formic acid 4.5% v/v) was pumped
tigation are the premise to assess the commercial value and health isocratically for 5 min; then B (acetonitrile at a flow rate of 0.7
quality of this rather neglected dessert wine. The data will con- mL/min) was increased from 0% to 15% in 35 min; successively,
tribute to the preservation of traditional and local agro-food pro- the mobile phase B reached 40% in 25 min and was held for 20
duction method and protection against the cheaper mass-produced min. The HPLC system was coupled to a Varian Prostar 330 DAD
industrial sweet wines. and a LCQ-DUO ion-trap mass spectrometer (Thermoquest, San
José, Calif., U.S.A.). The chromatograms were monitored at 3
Materials and Methods wavelengths (280, 320, and 365 nm) to analyze each group of
compounds. Each wavelength was suitable for a peculiar class of
Chemicals compounds: 280 nm was used for hydroxybenzoic acids, flavan-
ABTS solution, acetate buffer, β-carotene, caffeic acid, 3-ols and procyanidin, 320 nm for hydroxycinnamic acids and
(+)-catechin, chlorogenic acid, p-coumaric acid, DPPH, their tartaric esters, and 365 nm for flavonols. Mass spectra were
EDTA, (–)-epicatechin, ferulic acid, ferrozine, gallic acid, obtained using electro-spray negative and positive ionization in a
homovanillic acid, kaempferol-3-O-glucoside, L-ascorbic acid, range of m/z 100 to 800 and the tandem mass experiments were
linoleic acid, 2-nonanone, propyl gallate, protocatechuic acid, carried out with relative collision energy of 30% to 40%. All the
quercetin, quercetin-3-O-glucoside, tripyridyltriazine, trans- data were acquired with the Excalibur software ver. 1.2 by Finni-
resveratrol, Trolox, butylated hydroxytoluene, Tween 20 and gan. Individual compounds were quantified using a calibration
vanillic acid, were purchased from Sigma-Aldrich (Milan, Italy). curve of the corresponding standard compound. When reference
cis-Resveratrol was obtained after exposure of the trans-isomer compounds were not available, the calibration of structurally re-
standard to UV light (Cvejic and others 2010). SPME poly- lated substances was used. The data are reported as the averages
dimethylsiloxane (PDMS) 100 μm fiber (model 57300-U) and of 3 determinations (Santos-Buelga and Williamson 2003; Boselli
sealed 15 mL vials were purchased by SUPELCO (Bellefonte, Pa., and others 2006, 2008).
U.S.A.). Spectrophotometric determinations were carried out us-
ing a UV-vis Jenway 6003 spectrophotometer (Carlo Erba, Milan, Solid phase microextraction
Italy) with cuvettes of 1 cm length. Solvents were HPLC-grade A SPME PDMS 100 μm fiber (model 57300-U, Supelco) was
and were purchased from VWR Intl. (Milan, Italy). employed for the extraction of volatiles from the passito wine
C704 Journal of Food Science r Vol. 78, Nr. 5, 2013Passito chemistry and bioactivity . . .
headspace according to the modified methodology previously de- Table 1–Chemical and chromatic parameters of Passito wine.
scribed by Rodrı´guez-Bencomo and others (2003). In brief, each Parameters Mean ± standard deviation
wine sample was sealed into a 15 mL vial (Supelco) and heated for
10 min at 60 ◦ C. Then the SPME fiber was inserted into the vial Alcoholic percentage (ethanol, % vol) 14.2 ± 0.6
Total acidity (g/L as tartaric acid) 6.9 ± 0.3
for 60 min at 60 ◦ C. Afterwards the fiber was inserted into the gas
Volatile acidity (g/L as acetic acid) 0.9 ± 0.07
chromatograph injector (15 min at 250 ◦ C). Reducing sugars (g/L) 116 ± 4.5
Ashes (g/L) 2.1 ± 0.8
C: Food Chemistry
Total dry extract 151 ± 2.8
GC-MS analysis Dry extract without sugar 35.3 ± 0.8
A Hewlett-Packard 6890 gas chromatograph equipped with a Sulfates (as K2 SO4 ) 0.2 ± 0.05
±
DB-WAX capillary column (30 m length, 0.25 mm i.d., 0.25 μm Chloride (as NaCl) 0.06 0.008
pH 3.8 ± 0.03
film thickness) (Agilent Technologies, Palo Alto, Calif., U.S.A.) Total polyphenols (mg/L as (+)-catechin ) 249 ± 5.8
and interfaced with a Hewlett Packard 5973 was used for analysis. Proanthocyanidins (mg/L as cyaniding chloride) 76.8 ± 1.9
Mass selective ionization of the sample components was performed Color density 3.06 ± 0.09
in electron impact mode (EI, 70 eV) using a m/z range of 30 to Polymeric color 2.63 ± 0.07
% Polymeric color 86.1 ± 2.4
400 and a scan time of 3.89 s, with a flux of 0.8 mL/min of helium.
The sample was injected by placing the SPME fiber into the GC
inlet for 15 min in the splitless mode. The oven temperature
program started with an isothermal step of 5 min at 45 ◦ C. Then,
the temperature was raised to 220 ◦ C at a rate of 4 ◦ C/min and Results and Discussion
kept at 220 ◦ C for 20 min. The injector temperature was set at Physico chemical analyses
250 ◦ C and the detector at 280 ◦ C. Analyses were carried out Mean values and SDs for each chemical parameter determined
in triplicate. GC retention times were used for identification of on passito wine are reported in Table 1. Passito wine showed a total
the compounds using the Wiley 138, Wiley 275, or NIST 98 acidity of 6.9 g/L as tartaric acid and a volatile acidity of 0.9 g/L;
libraries. 2-Nonanone was used as internal standard to quantify these results are quite similar to other Passito wine values reported
the individual compounds. in the literature. In fact, Giordano and others (2009) investigated
3 different protected designation of origin (PDO) passito wines
Antioxidant activity namely Caluso Passito, Cinque Terre Sciacchetrà, and Passito from
DPPH radical-scavenging activity assay. Radical- Pantelleria and found a total acidity ranging from 5.4 to 7.3 g/L
scavenging activity was investigated using the technique reported as tartaric acid and a volatile acidity of 1.0 to 1.2 g/L. Our sam-
by Blois (1958) with some modifications. An aliquot of 1.2 mL ples are characterized by a lower content of reducing sugar (116
of 1 × 10−4 M DPPH solution in ethanol and 300 μL of wine at g/L) and ash (2.1 g/L). These parameters may vary according to
different dilutions in water (not diluted, 1/2, 1/3, 1/4, 1/5) were the origin and processing technology of wines (Frias and others
mixed. The bleaching of DPPH was determined by measuring 2003). Other passito wines, such as Greco di Bianco DOC and
the absorbance at λ = 517 nm. Mantonico DOC, both produced with Calabrian autochthonous
Greco di Bianco and Mantonico grapes, exhibited a total acidity
Antioxidant capacity determined by radical cation
of 6.49 and 9.90 g/L as tartaric acid, respectively. The content of
(ABTS+ ). ABTS assay was based on the method of Re and others
reducing sugar was 98 and 82 g/L for Greco di Bianco and Man-
(1996). After addition of 25 μL of samples at different dilutions
tonico wines, respectively, and was therefore lower with respect to
in water (not diluted, 1/2, 1/3, 1/4, 1/5) or Trolox standard to
our passito wine. This fact could be explained considering that the
diluted ABTS+ solution, absorbance at λ = 734 nm was measured.
wine samples of passito had lower acidity and higher sugar content
Antioxidant activity by β-carotene bleaching test. An- due to the different state of ripeness of the grapes. Growing area,
tioxidant activity was determined using the β-carotene bleach- climate conditions (temperature and humidity can vary very sig-
ing test previously described by Conforti and others (2007). The nificantly according to the light exposure and height above sea and
bleaching of β-carotene was measured and expressed as antioxidant date of harvest are crucial factors determining the sugar content
activity (AA): and total acidity of the grapes. Usually, a higher sugar content is
always associated with a lower total acidity, as it was the case of the
AA = [1 − (A0 − At )/(A◦0 − A◦t )] × 100 passito wine of Saracena.
Winemaking techniques including maceration, modalities of
where A0 and A◦ 0 are the absorbance values measured at the fermentation, and aging can influence the content of total
incubation t = 0 min for samples and control, respectively, while polyphenols significantly (Zeppa and others 2001). Saracena pas-
At and A◦ t are the absorbance values measured in the samples and sito wine had a total phenolics content of 249 mg/L as (+)-
control, respectively, at t = 30 min and t = 60 min. catechin. This value is similar to the total polyphenols content
of Calluso Passito wine (251.3 mg/L as (+)-catechin) produced
in the north of Italy from Erbaluce grapes (Giordano and others
Statistical analysis 2009) and is similar to the total phenolics content of white wines of
All experiments were carried out in triplicate. Data were ex- good quality. Fuda and others (2007) had analyzed several passito
pressed as means ± standard deviation (SD). Prism GraphPad wines produced in Calabria (Italy) and reported a high content
Prism version 4.0 for Windows (GraphPad Software, San Diego, of (+)-catechin (7.5 to 33.1 ppm) for Mantonico DOC sweet
Calif., U.S.A.) was used for plotting the concentration-response wine, whereas a lower content of apigenin was found in Greco
curve and one-way ANOVA test followed by multicomparison di Bianco 2004 (4.2 to 17.3 mg/L). A total phenolics content of
Dunnet’s test. 450 mg/L as gallic acid equivalent was found in Muscat of Samos,
Vol. 78, Nr. 5, 2013 r Journal of Food Science C705Passito chemistry and bioactivity . . .
Table 2–Principal phenolic components of Passito wine. Table 3–The major volatile compounds identified in Passito wine
after SPME extraction.
Phenolic compounds Mean ± standard deviation
Compound RTa mg/L
Benzoate Ia 84.9 ± 2.5
Benzoate IIa 88.6 ± 6.4 iso-Butanol 8.50 22.1 ± 0.3
Gallic acida 376 ± 24.5 iso-Amyl acetate 8.80 6.7 ± 0.2
Hydroxytyrosolb 78.3 ± 3.5 Limonene 10.72 1.6 ± 0.08
Protocatechuic acidc 37.3 ± 1.4 iso-Amyl alcohol 12.72 161 ± 3.6
C: Food Chemistry
Caftaric acidd 68.2 ± 5.9 1-Hydroxy-2-propanone 15.68 9.1 ± 0.2
Tyrosolb 148 ± 12.9 1-Hexanol 19.60 23.2 ± 0.7
(+)-Catechine 71.7 ± 4.9 1-Heptanol 19.86 18.9 ± 2.3
cis-Coutaric acidf 7.7 ± 0.4 Ethyl hexanoate 20.01 156 ± 9.7
trans-Coutaric acidf 15.0 ± 0.9 Acetic acid 20.57 75 ± 2.4
2-Furancarboxaldehyde 20.85 6.0 ± 0.3
Caffeic acidd 27.9 ± 1.9
Ethyl octanoate 21.98 6.4 ± 0.1
Fertaric acidg 10.2 ± 0.4
Procyanidin dimere 195 ± 9.5 2,3-Butanediol 23.54 60.6 ± 4
Linalool 23.68 0.6 ± 0.04
p-Coumaric acidf 13.0 ± 0.8
5-Methyl-2-furancarboxaldehyde 24.26 4.1 ± 0.9
Ferulic acidg 11.5 ± 0.9
Ethyl decanoate 26.26 135 ± 12.3
trans-Resveratrolh 4.9 ± 0.1 2-Furanmethanol 27.08 3.7 ± 1.0
Procyanidind 18.8 ± 1.1 Butanedioic acid, diethyl ester 27.41 9.9 ± 0.2
Oligomeric procyanidinse 203 ± 17.5 Ethyl dec-9-enoate 27.78 4.7 ± 0.3
Total phenolic 1460 α-Terpineol 28.04 1.1 ± 0.09
Phenolic compounds quantified as: a mg gallic acid/L; b mg tyrosol/L; c mg
α-Muurolene 28.58 0.5 ± 0.04
protocatechuic acid/L; d mg caffeic acid/L; e mg (+)-catechin/L; f mg p-coumaric acid/L; Isopropyl dodecanoate 31.73 8.5 ± 0.6
g
mg ferulic acid/L; h mg trans-resveratrol/L. Ethyl dodecanoate 31.98 22.9 ± 1.3
Linalyl propinate 33.33 1.3 ± 0.1
2-Phenylethanol 33.77 34.9 ± 1.7
Nerolidol 37.02 0.4 ± 0.03
a dessert wine produced in Greece using Samos Muscat Blanc à Ethyl tetradecanoate 37.21 13.8 ± 1.4
Petits Grains grapes (Roussis and others 2005). Octanoic acid 37.52 5.7 ± 0.7
Ethyl hexadecanoate 42.00 187 ± 7.7
Decanoic acid 42.43 6.3 ± 0.4
Profiling of phenolics in passito wine 1-Hexadecene 44.69 22.8 ± 0.8
The total content of phenolic compounds quantified with Ethyl octadecanoate 46.35 57.8 ± 3.0
HPLC was 1460 mg/L (Table 2). The most abundant classes of Ethyl 9-octadecanoate 46.74 13.2 ± 1.3
phenols were hydroxybenzoic acids and flavan-3-ols, where gal- Dodecanoic acid 46.93 2.1 ± 0.1
5-(Hydroxymethyl)-2-furancarboxaldehyde 47.07 8.2 ± 0.1
lic acid showed the highest content (376.5 mg/L). Four flavanols 1-Octadecene 48.88 5.1 ± 0.2
were tentatively identified; they were monomeric (catechin) and Tetradecanoic acid 51.42 21.4 ± 0.2
dimeric forms (procyanidins). The high content of oligomeric Pentadecanoic acid 54.39 13.5 ± 0.6
procyanidins in a white wine can be due to polymerization of sim- Hexadecanoic acid 58.22 118.1 ± 7.5
9-Hexadecenoic acid 59.73 22.6 ± 1.3
ple flavonoids, such as catechins, during aging. Procyanidins with
a high degree of polymerization were eluted as one peak at the a
Retention time (min) on DB-WAX capillary column. Results are given as means ±
standard deviations of 3 replications in mg/L.
end of the chromatogram as it usually happens with a C18 station-
ary phase (Boselli and others 2006). The content of catechin and
procyanidin dimer was 72 and 195 mg/L. The phenyl ethyl alco-
vineyard climate and soil parameters, cultivation practices, and
hols detected were: 2-phenylethanol, hydroxytyrosol, and tyrosol
the aging time and conditions (Rodriguez-Delgado and others
at concentration of 35, 78, and 148 mg/L. 2-Phenylethanol is well
2002). Based on this consideration, the differences in the chemi-
known for its sensory floral aroma and is derived from the yeast
cal profile among Passito wines of different origin should not be
metabolism of the nonvolatile phenylalanine (Poláŝkova and others
surprising.
2008). In addition, several different forms of hydroxycinnamic acid
and their tartaric esters were detected. These compounds were reg-
istered in considerable amounts; the content of hydroxycinnamic SPME-GC of aroma compounds
acid and derivatives ranged from 10.2 to 68.2 mg/L for fertaric Various compounds are responsible for wine aroma. They are
and caftaric acid, respectively. trans-Resveratrol was found at a classified as follows: primary aroma compounds (originate from
level of 4.9 mg/L. Roussis and others (2005) analyzed the HPLC the grape), secondary aroma compounds (are formed during fer-
phenolic profile of Muscat of Samos and found mainly benzoic mentation), and tertiary aroma compounds (are produced during
acid and cinnamic acid together with unclassified compounds and aging in wood barrels). In recent years, SPME has become the
flavonoids. The phenolic profile of Greco di Bianco and Man- most widely applied sampling procedure for the study of wine
tonico passito wines were reported by Fuda and others (2007) flavor composition (Rocha and others 2001; Torrens and others
who identified apigenin-7-glucoside, caffeic acid, (+)-catechin, 2004; Riu-Aumatell and others 2006). A total of 42 compounds
epicatechin, ferulic acid, gallic acid, p-coumaric acid, rutin, sy- were identified in Saracena passito wine, including alcohols, es-
ringic acid, and vanillic acid as constituents. Among them a high ters, acids, terpenes, aldehydes, and ketones. Many of these com-
content of caffeic acid (38.9 mg/mL for Greco di Bianco and pounds are commonly found in wines (Table 3). Ethyl hexanoate
59.8 mg/L for Mantonico) and gallic acid (30.2 mg/L for Greco di (156 mg/L), ethyl decanoate (135 mg/L), and isoamyl alcohol (161
Bianco and 48.7 mg/L for Mantonico) were found in both wines. mg/L) were determined as the major constituents of passito wine
As previously underlined, the phenolic composition of wine de- and showed concentrations higher than threshold values of 0.005,
pends not only on grape varieties but also on the location of the 0.2, and 30 mg/L, respectively previously reported by Jiang and
C706 Journal of Food Science r Vol. 78, Nr. 5, 2013Passito chemistry and bioactivity . . .
Zhang (2010). Ethyl hexanoate is responsible for the apple peel, Table 4–Antioxidant activities of Passito dessert wine.
and ethyl decanoate for the fruit, oily, and floral odors (Scacco and β-Carotene
others 2010). Other abundant compounds were hexadecanoic acid DPPH ABTS bleaching test
(118 mg/L), acetic acid (75 mg/L), 2,3-butanediol (61 mg/L), assay assay (IC50 v/v)
and ethyl octadecanoate (58 mg/L). The concentrations of ethyl (IC50 v/v) (IC50 v/v) 30 min 60 min
esters of fatty acids, representing the most important group of
Wine sample 0.03 ± 0.005 0.6 ± 0.08 0.4 ± 0.02 0.5 ± 0.04
aroma compounds, depend on several factors including type of
C: Food Chemistry
yeast, fermentation temperature, aeration degree, and sugar con- Data are expressed as mean ± SD (n = 3); DPPH radical scavenging activity assay;
antioxidant capacity determined by radical cation (ABTS+ ); β-carotene bleaching test.
tent (Schreirer 1979). Moreover, ethyl esters are known to have Ascorbic acid was used as positive control in DPPH (IC50 = 5.0 μg/mL) and ABTS
very pleasant fruits, honey, and sweet scents which contribute (IC50 = 1.7 μg/mL); Propyl gallate was used as positive control in β-carotene bleaching
test (IC50 = 1.0 μg/mL at 30 and 60 min incubation).
to the aromatic finesse of wines (Ugliano and Henschke 2009).
An amount of 6.7 mg/L was found for iso-amyl acetate, a com-
pound responsible for distinctly banana-like fragrance (Van Wyck Data of antioxidant activity are reported in Table 4. Passito wine
and others 1979). This compound derives from the amino acid scavenged the DPPH with an IC50 of 0.03 v/v, while a value of
metabolism of yeast and its concentration in our sample is in line 0.60 v/v was found using ABTS. Moreover, passito wine showed
with those reported for Caluso passito, Cinque Terre Sciacchetrà, promising inhibition of linoleic acid oxidation (IC50 values of 0.4
and passito from Pantelleria (Giordano and others 2009). The con- and 0.5 v/v at 30 and 60 min of incubation, respectively) that
centration of this ester in Saracena passito wine is higher than its decreased linearly after dilution. Roussis and others (2005) had
flavor threshold (0.03 mg/L) (Jiang and Zhang 2010). Higher alco- reported the scavenging of DPPH radical by Muscat wine from
hols represent the other important group of volatiles identified in Greece founding EC50 values of 314 and 134 γ /(mg/L) at 5 and
wine. The group is composed of aliphatic and aromatic alcohols, 60 min of incubation and correlated the bioactivity to the high
most of which are products of yeast fermentation (Kotseridis and phenolic content. The DPPH and ABTS tests of wines obtained by
others 2000). In Saracena passito wine, iso-butanol, 1-hexanol, Muscat Hamburg grapes revealed that samples ranged from 1402
1-heptanol, 2,3-butanediol, and 2-furanmethanol were identi- to 3410 and from 8841 to 14309 Trolox equivalents, respectively
fied. Among aldehydes, 2-furancarboxaldehyde, and 5-methyl- (Li and others 2009).
2-furancarboxaldehyde were identified. In this passito wine, how-
ever, the bitter almond odor that is characteristic of the presence Conclusion
of benzaldehyde was completely absent, while it is a significantly In conclusion, this work analyzed Saracena passito wine for its
dominant bouquet component of Caluso Passito and Cinque Terre phenolic and aroma profile and potential antioxidant properties.
Sciacchetrà Passito wines (Giordano and others 2009). Numerous This wine is obtained using autochthonous Malvasia and Guar-
studies have shown that the terpenes are critical in determining the naccia grapes with further addition of Muscat grapes. Chemical
bouquet of a wine. Seven terpenes were identified in passito wine. analyses have provided a contribution to define the chemical mark-
They were α-terpinolene (0.5 mg/L), α-terpineol (1.1 mg/L), ers of the quality of this wine, and their quantitative ranges, which
limonene (1.6 mg/L), linalool (0.6 mg/L), nerolidol (0.4 mg/L), are needed to assess the authenticity of local niche production
linalyl propionate (1.3 mg/L), and α-muurolene (0.5 mg/L). Jiang claiming a quality designation (such as PDO). Moreover, passito
and Zhang (2010) reported for linalool and limonene threshold wine demonstrated good antioxidant properties. This bioactiv-
values of 0.0252 and 0.2 mg/L, respectively. In comparison with ity could be related to the presence of flavonoids, anthocyans, and
the other constituents, their concentrations were low according many other polyphenolic compounds, that showed highly positive
to previous studies on other Passito wines. Moreover, these com- effects on human health.
pounds are not influenced by the fermentation process so could
be used as indicators of the grape variety and quality (Begala Acknowledgment
and others 2002). Linalool is the floral representative monoter- This work was supported by European Community POR Cal-
pene alcohol of sweet wine, followed by α-terpineol and nerodiol abria FSE 2007/2013.
(Ribéreau-Gayon and others 2000). In particular, this monoter-
pene compound is related to acacia and honey odor. It has been Conflict of Interest
found also in Greco di Bianco passito wine, but not in Manton- The authors have declared no conflict of interest.
ico passito wine (Fuda and others 2007). The olfactory profile
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