Comparison of extracts prepared from plant by-products Using different solvents and extraction time Abstract By-products obtained

after red fruit processing still contain large amounts of polyphenols, especially anthocyanins which act as antioxidants. The effect of solvent and extraction time on the yield of extracted antioxidants from grape, black and red currant by- products (marc) was investigated. Ethanol and methanol extracts of red and black currant contain twice more anthocyanins and polyphenols than water extracts, extracts made from grape marc had seven times higher values than water extracts. In water extracts the yields of polyphenols decreased, while in methanol and ethanol extracts their content increased with the time of extraction. The highest antioxidant activity was in extracts made from black currant marc, the lowest was in extracts made from red currant marc. Grape extracts had high antioxidant activity due to its high content of polyphenols. Antioxidants from grape stalks and marc: Influence of extraction procedure on yield, purity and antioxidant power of the extracts This study was aimed to assess the feasibility of extracting antioxidant compounds from wine-making wastes (grape stalks and marc) by solvent extraction. Together with the type of raw material it was also investigated the influence of some process parameters on final antioxidants yields and extract purity: a degreasing pre-treatment, type of solvent (ethanol or a mixture ethylacetate:water/9:1), temperature (28 or 60 C) and length of maceration (5 or 24 h). Solvent and temperature were statistically influent (p < 0.05), and the yields were higher with ethanol (but with lower purities) and at 60 C. Antioxidant power of the extracts was evaluated by different analytical methods. An accurate comparison of our data with many literature works about antioxidants recovery from different natural sources showed similar results and highlighted a general great variability in the extraction procedures. Extraction of anthocyanins from grape skins assisted by high hydrostatic pressure The effect of different parameters such as high hydrostatic pressure (HHP) (200, 400, 600 MPa), ethanol concentration (20100%), time (3090 min) and temperature (2070 C) was studied for the optimal anthocyanin extraction from red grape skins. Extracts obtained at an ethanol concentration of 50%, at 70 C and 600 MPa possessed the highest antioxidant capacity lmol TROLOX equivalents TE g1 DM and the extraction yields were three-fold greater than control extractions. The antioxidant capacity of the extracts was not

directly correlated to the highest amount of anthocyanins, which were optimal extracted with the set of conditions 100% ethanol, 50 C and 600 MPa achieving extraction yields about 23% higher than under control conditions. Anthocyanin recovery under HHP was selective and increased according to the glucoside moiety linked to the flavylium nucleus; p-coumaroylglucoside anthocyanins were more favourably extracted than mono- and acetylglucosides. Therefore, a higher extraction rate was related to the higher number of methoxyl and hydroxyl groups linked to the C3 and C5 of the flavylium nucleus, hence extraction of malvidin > peonidin > petunidin > delphinidin > cyanidin. Comparison of chromatic properties, stability and antioxidant capacity of anthocyanin-based aqueous extracts from grape pomace obtained from different vinification methods The chromatic properties of anthocyanin-based aqueous extracts obtained from grape pomace from different vinifications meth- ods (one rose vinification, 6 h of skin contact time and three red wine vinifications, with 4, 8 and 12 days of skin contact time) have been studied. Differences due to the vinification method from which the pomace was obtained were clearly observed. Extracts from rose vinifications had the highest content of anthocyanin compounds (measured both spectrophotometrically and by HPLC methods) although the total phenol content did not differ significantly between the different pomace extracts. As regards the stability of the different aqueous extracts under different pH, temperature and light conditions, only small differences were observed. Also, the antioxidant capacity of the extracts was evaluated and no significant differences were found between them; a better correlation being found between antioxidant capacity and estimated total phenol content than with anthocyanin content. Microwave assisted extraction of anthocyanins from grape skins A new method for the analysis of anthocyanins in grapes based on a systematic study of the extractability of eleven anthocyanins from grapes has been developed. Microwave assisted extraction was applied as a prior stage to the chromatographic determination of anthocyanins in the extracts. The stability of anthocyanins under the extraction conditions was checked using a standardised extract from grape skins. Temperatures from 50 C up to 150 C were evaluated. A fractional factorial experimental design was developed to analyse the influence on the extraction process of six different extraction variables: solvent (mixtures of methanol and water), stirring, extraction temperature, extraction time, microwave power and extraction volume. The extraction solvent was the most important variable for the recovery of most anthocyanins from grapes. Finally, the influence of the extraction time was also studied. With

this new method, anthocyanins can be extracted from grapes in 5 min, using 100 C as extraction temperature and 40% methanol in water as the extraction solvent. Repeatability and reproducibility were also checked, the resulting RSDs (n = 9) were lower than 7% for glucosides, the main components, and lower than 9% for the acyl derivatives, the compounds found in the lowest concentrations. Semi-batch extraction of anthocyanins from red grape pomace in packed beds: experimental results and process modelling A semi-batch extraction process of anthocyanins was studied in a packed bed. Methanol was used as solvent and the raw material studied consisted of skins of the tempranillo grape, which was obtained from the pomace from red wine vini cation. The results show large di usional e ects due to strong control from the mass transfer. The best results were obtained using a high temperature and a high flow rate. A penetration model is proposed in terms of a bed of spherical particles. The model provides a value for the diffusion coefficient of the solute within the solid matrix. It can be seen that the adjustment of the model is satisfactory and that it is able to predict, to a reasonable extent, the yield of the extraction process. Upgrading of grape skins: Significance of plant cell-wall structural components and extraction techniques for phenol release In order to accomplish a major specificity and efficiency in the extraction process of phenols from grape skin, a combination of knowledge of distribution and linkage of these compounds and techniques used to extract them is necessary. Degradation of the cell-wall polysaccharide structures is a fundamental step in the phenol release from grape skins, notably those phenols that are linked to the CW, but also those contained or associated with cell vacuoles. Ferulic acid linkages are known to play a fundamental role in maintaining the sugar structure in grape skin CW and minimization of the effect of the ferulate cross-links, or enzyme catalysed breakage of these cross-links, could be a first step in order to increase the phenolic yield during the extraction process. A detailed study about the effects of the phenolic compounds of interest both on the sensory properties of wine and on the human health would also help to discern what kind of compounds are the most suitable to be extracted. Extraction and formulation of anthocyanin-concentrates from grape residues Abstract

The interest in natural food colorants shows an increasing tendency due to the strictening rules and consumers concerns over synthetic additives. One of natural pigments with high potential are anthocyanins, which are providing colours from yellow to blue in berries, flowers and vegetables. However the use of anthocyanins as food colorants is still limited because of their relatively low stability during processing, formulation and storage. In this work extraction of anthocyanins from grape marc was investigated with different concentrations of acetone (50 wt%, 70 wt% and 100 wt%) at 20 C and at 60 C temperatures. Pilot-scale extraction of grape marc was performed upon the results obtained from laboratory scale experiments. High-pressure concentrated powder form (CPF) technique was applied in order to formulate the obtained extracts in powderous form. Carrier materials, such as starch and silica were tested. Colorimetric properties (lightness, chroma and hue angle) of powderous products were measured and compared with synthetic colorants. Colour stability was monitored during storage at different conditions (light/dark and ambient temperature/refrigerator). The results were compared with the non-formulated extracts, which were stored at same conditions. Product formulation with CPF improved the colour stability of anthocyanin extracts, while for the nonformulated extracts degradation of colour rapidly occurred. The results show that formulated anthocyanin extracts have potential use as natural colorants. However, the major difference compared to synthetic colorants is still in the saturation of the colour. Differences in Anthocyanin Extractability from Grapes to Wines According to Variety Abstract The anthocyanin concentration of Vitis vinifera L. cvs. Cabernet Sauvignon, Merlot, Syrah, and Monastrell grape skins was determined together with anthocyanin extractability at the exact time of harvest (measured by an extractability assay based on the comparison of the anthocyanin concentration of two different solutions obtained after macerating the grapes for four hours at two different pH values). These data were compared with the anthocyanin concentration and chromatic characteristics of the resulting wines. Monastrell grapes from the Jumilla area had the highest anthocyanin concentration (whether expressed as g/g or mg/kg of berries), but the extractability assay indicated the difficulty of their extraction. The extractability assay for Cabernet Sauvignon, Merlot, and Syrah indicated that their anthocyanins could be extracted easily, which was confirmed by the chromatic analysis of the resulting wines. Cabernet Sauvignon and Syrah wines presented the highest wine color intensity, although their anthocyanin concentration in the grapes was lower than that of Monastrell grapes. Results indicated that the above extractability assay could be useful for predicting some important chromatic wine parameters and

for planning the fermentation process according to the characteristics of the grapes at the exact time of harvest and the desired wine. Development of a Stable Extract for Anthocyanins and Flavonols from Grape Skin Abstract The lability of anthocyanins and flavonols extracted from grape (Vitis vinifera L.) skin with commonly used extraction solvents was examined. Results indicate that both anthocyanins and flavonol glycosides are unstable in even mildly acidic extraction solvents and highly labile in 1% hydrochloric acid in methanol, the most commonly used extraction solvent. While lability of anthocyanins has previously been reported, this is the first report of flavonol glycoside stability in these solvents. As a result of these observations, an extraction protocol was developed that maximized anthocyanin (malvidin-3-Oglucoside, malvidin-3-O-acetylglucoside, and malvidin-3-O-p coumaroylglucoside) and flavonol (quercetin-3-O-glucoside and quercetin-3-Oglucuronide) extraction while minimizing degradation in the time between extraction and HPLC analysis. A range of acidified methanol solvents including hydrochloric, formic, acetic, citric, and maleic acids were tested together with acidulated ethanol and several methanol water mixtures ranging from 0% to 100% methanol. The most efficacious solvent system was 50% aqueous methanol, which had the advantage of incorporating both high anthocyanin and flavonol extractability and subsequent stability prior to HPLC analysis. Improvement of anthocyanin yield and shelf-life extension of grape pomace by gamma irradiation Abstract This research investigated the effect of gamma irradiation on anthocyanin extraction from grape pomace, and on inhibition of microbial growth and anthocyanin content during subsequent storage. The combination of four variables was investigated: (1) irradiation at doses from 0 to 9 kGy; (2) packaging under vacuum; (3) addition of a low dose of sodium metabisulfite during irradiation; and (4) extraction in the presence of SO2. Results indicate that the irradiation at 6 kGy, packaging in the presence of 0.1% sodium metabisulfite and extraction in the presence of 2000 ppm of SO2 yielded the highest value of anthocyanins, and improved shelf-life of grape pomace. Extraction of anthocyanins from grape by-products assisted by ultrasonics, high hydrostatic pressure or pulsed electric fields: A comparison

Abstract Extracts from grape by-products contain bioactive substances such as anthocyanins which could be used as natural antioxidants or colourants. The effect of heat treatment at 70 C combined with the effect of different emerging novel technologies such as ultrasonics (35 KHz), high hydrostatic pressure (600 MPa) (HHP) and pulsed electric fields (3 kV cm 1) (PEF) showed a great feasibility and selectivity for extraction purposes. After 1 h extraction, the total phenolic content of samples subjected to novel technologies was 50% higher than in the control samples. Therefore, the application of novel technologies increased the antioxidant activity of the extracts being the extractions carried out with PEF four-fold, with HHP three-fold and with ultrasonics two-fold higher than the control extraction. In addition, the extraction of individual anthocyanins was studied showing a selective extraction based on the glucose moieties linked to the anthocyanidins; anthocyanin monoglucosides were better extracted by PEF, whereas the acylated ones were extracted by HHP. Industrial relevance This study examines the feasibility of different emerging technologies such as high hydrostatic pressure, pulsed electric fields and ultrasonics as potential extraction methods for bioactive substances from grape by-products. Grape byproducts represent a low-cost source of valuable bioactive compounds such as anthocyanins, with great industrial applications as colourants or nutraceuticals. The higher yields obtained in extractions carried out by high hydrostatic pressure and pulsed electric fields are of major interest from an industrial point of view, since solvent amounts were reduced and extraction times shortened. Thus, the combination of emerging technologies for extraction purposes and low-cost raw materials is an economical alternative to traditional extraction methods according to industry demands and a sustainable development.