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Phenolic Composition of Grape and Winemaking By-Products of Brazilian Hybrid Cultivars BRS Violeta and BRS Lorena

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Phenolic Composition of Grape and Winemaking By-Products of Brazilian Hybrid Cultivars BRS Violeta and BRS Lorena Food Chemistry 159 (2014) 95–105 Contents lists available at ScienceDirect Food Chemistry journal homepage: www.elsevier.com/locate/foodchem Phenolic composition of grape and winemaking by-products of Brazilian hybrid cultivars BRS Violeta and BRS Lorena Milene Teixeira Barcia a, Paula Becker Pertuzatti a, Sergio Gómez-Alonso b,c, Helena Teixeira Godoy a, ⇑ Isidro Hermosín-Gutiérrez c, a Universidade Estadual de Campinas (UNICAMP), Depto. Ciência de Alimentos, Faculdade de Engenharia de Alimentos, Cidade Universitária ‘‘Zeferino Vaz’’, S/N, CEP 13083862 Campinas, São Paulo, Brazil b Fundación Parque Científico y Tecnológico de Albacete, Paseo de la Innovación, 1, 02006 Albacete, Spain c Instituto Regional de Investigación Científica Aplicada, Universidad de Castilla-La Mancha, Campus Universitario s/n, 13071 Ciudad Real, Spain article info abstract Article history: The phenolic composition of grapes and winemaking by-products (skins from grape marc, and lees) from Received 19 September 2013 Brazilian hybrid cultivars BRS Violeta (red) and BRS Lorena (white) was studied. Two vintages, five classes Received in revised form 1 February 2014 of phenolic compounds, and recovery yields using three dehydration techniques were considered: oven- Accepted 27 February 2014 drying at 50 °C (D50); spray-drying (SD); and freeze-drying (FD). Recovery yields were higher using FD, Available online 12 March 2014 although less expensive SD was a good alternative for Violeta lees. D50 caused great recovery reduction in Violeta but yielded similar results for Lorena. Violeta winemaking by-products were excellent sources of Keywords: anthocyanins (mainly non-acylated and p-coumaroylated diglucosides), flavonols (mainly myricetin- Anthocyanins based) and hydroxycinnamic derivatives (mainly caffeic-based). Lorena winemaking by-products con- Pyranoanthocyanins Phenolic acids tained lesser amounts of phenolic compounds, around a tenth of the values found in Violeta grapes for Flavonols flavonols (mainly quercetin-based), hydroxycinnamic derivatives (mainly caffeic-based) and condensed Condensed tannins tannins. Lorena cultivar contained small amounts of trans-resveratrol and its 3-glucoside, which were Grape marc missing in Violeta cultivar. Lees Ó 2014 Elsevier Ltd. All rights reserved. Non-vinifera grape 1. Introduction ing the previously crushed grapes, in white wine production tech- nology, or after the maceration phase concurrent with The polyphenolic compounds present in the grape transfer to fermentation step, in red wine production technology. After must the wine during the maceration step of its elaboration until reach- fermentation, a decanting process takes place when the superna- ing equilibrium conditions that depend on the characteristics of tant wine is separated from the lees (mainly constituted by thin the winemaking process (e.g., maceration time, temperature, particle grape residues and death yeasts) (Maragkoudakis et al., intensity and duration of pressing, using of macerating enzymes, 2013; Paradelo, Moldes, & Barral, 2010). yeast strain, and used SO2 doses). As the major part of grape poly- Wine lees are mainly composed of microorganisms (mainly phenols comes from the solid grape parts, a high proportion of autolysed yeast cells), tartaric acid, inorganic matter and phenolic polyphenols still remains in the solid winemaking by-products or compounds (Pérez-Serradilla & Luque de Castro, 2008). The scarce grape marc (Gallego, García-Carpintero, Sánchez-Palomo, Viñas, & literature dealing with this topic has revealed the adsorption Hermosín-Gutiérrez, 2012). capacity of yeast cell wall with regards to anthocyanins and other Grape marc (a mixture of mainly grape skin and seeds) is one of phenolic compounds, like flavonols or hydroxycinnamic acids the most abundant by-products of the winemaking process, and (Morata, Gómez-Cordovés, Colomo, & Suárez, 2005; Pérez-Serradil- this presents problems of storage, transformation, or elimination, la & Luque de Castro, 2008; Pérez-Serradilla & Luque de Castro, from both ecological and economical points of view. However, it 2011). It is well known that grape residue from winemaking can be considered as a low-cost source of natural antioxidants (seeds, skins) contain a high amount of secondary metabolites (Shojaee-Aliabadi et al., 2013). Grape marc is produced after press- including phenolic acids, flavan-3-ols and anthocyanins (Makris, Boskou, & Andrikopoulos, 2007). However, many studies have been focused on winemaking by-products from Vitis vinifera varieties ⇑ Corresponding author. Tel.: +34 926295300. but little is known about the polyphenol potential of non-vinifera E-mail address: [email protected] (I. Hermosín-Gutiérrez). grape varieties (Sant’Anna, Brandelli, Marczak, & Tessaro, 2012). http://dx.doi.org/10.1016/j.foodchem.2014.02.163 0308-8146/Ó 2014 Elsevier Ltd. All rights reserved. 96 M.T. Barcia et al. / Food Chemistry 159 (2014) 95–105 The non-vinifera hybrid grape varieties are characterized by Violeta (BRS Rúbea  IAC 1398-21) and BRS Lorena (Malvasia high productivity and high resistance to plant diseases affecting Bianca  Seyval). The samples were randomly collected in tripli- V. vinifera grape varieties (Abe, Mota, Lajolo, & Genovese, 2007). cate (3  500 g) during the harvest of 2011 and 2012 from a winery The Brazilian Agricultural Research Corporation Grape and Wine located in the region of São Roque (São Paulo, Brazil). The grape (Embrapa Uva e Vinho) have launched hybrid grape varieties samples were collected from different batches received at the win- adapted to the specific conditions demanded by the emerging ery, by manual picking of grape berries from different clusters at new grape-growing regions of Brazil. The red grape cultivar BRS different levels (top, medium and bottom parts of the clusters). Violeta is a complex hybrid obtained from the cross between BRS After the processing of the latter grapes, samples of the corre- Rúbea  IAC 1398-21, and maintains the general characteristics sponding winemaking by-products were collected, after their sep- of Vitis labrusca grapes with regards to vine morphology and grape aration from the must (fresh grape marc of Lorena) or wine taste. The BRS Violeta grape was initially launched as an alternative (fermented grape marc of Violeta, and wine lees of Lorena and Viol- to increase quality and competitiveness of table wine and grape eta). Grape berry samples were frozen at À20 °C for 24 h, cut in two juice produced in Brazil, because it is characterized by high levels halves, and further freeze-dried for 48 h. Samples of fermented of sugar concentration and color, and is especially suitable for cul- grape marc from Violeta, fresh grape marc from Lorena, and lees tivation in subtropical climate zones like the state of São Paulo from both grape varieties were frozen at À20 °C for 24 h and then (Camargo, Maia, & Nachtigal, 2005). The white hybrid grape culti- freeze-dried for 48 h. After that, skins were manually separated var BRS Lorena (Malvasia Bianca  Seyval) was developed in 2001 from the samples of dried grape marc. Dried samples of skins from as an alternative for elaboration of white wines, also presenting grape marc and lees were also obtained by oven drying at 50 °C un- high productivity, sugar-rich and relatively acid-rich musts that der forced air flow. Finally, a third drying treatment was applied to are suitable for production of both sparkling and still wines with lees: spray-drying. After drying, the samples of entire grapes and a well-balanced taste (Camargo & Guerra, 2001). skins were crushed and homogenized. All dried samples were The chemical characterization of the phenolic compounds still stored at À18 °C until analyses. present in winemaking by-products (grape marc and lees) consti- tutes basic information for the evaluation of the viability of using 2.3. Extraction of phenolic compounds food by-products in foodstuff, chemical, and pharmaceutical indus- tries. For this reason, the aim of this work was the study of the Dried samples in amounts of 2.5, 1.0, and 0.25 g (grapes, skins occurring phenolics in winemaking by-products (skins from grape and lees of Lorena, respectively) and 2.0, 0.25, and 0.25 g (grapes, marc, and wine lees) generated during the elaboration of red and skins and lees of Violeta, respectively) were extracted with 50 mL white wine from two hybrid grape varieties developed in Brazil (grape and lees) or 75 mL (skins) of a mixture 50:48.5:1.5 (v/v) (BRS Violeta and BRS Lorena). The study was extended over two of CH3OH/H2O/HCOOH, helped by ultrasonic bath, during 2 min vintages and comprised different phenolic classes (anthocyanins and then centrifuged at 5000g at 5 °C for 5 min. A second and third and some pyranoanthocyanins, flavonols, hydroxycinnamic acid extractions of the samples pellets yielded nearly 99% of the sample derivatives, stilbenes, and condensed tannins); in addition, the ef- phenolic content, as confirmed by HPLC of successive extractions fect of three drying techniques applied to the winemaking by- (up to five). The combined supernatants were stored at À18 °C un- products has been considered: freeze-drying, oven-drying at til use. For analysis of non-anthocyanin phenolics, anthocyanin- 50 °C, and spray-drying. free fractions from sample extracts were obtained by solid phase extraction following a previously described method (Lago-Vanzela, Da-Silva, Gomes, García-Romero, & Hermosín-Gutiérrez, 2011a). 2. Materials and methods 2.4. Quantification of condensed tannins by precipitation
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