Physico-Chemical Characteristics, Fatty Acid, Composition of Grape Seed Oil and Phenolic Compounds of Whole Seeds, Seeds and Leaves of Red Grape in Libya

Home , Grape seed oil, Iodine value, Saponification value, Seed oil

International Journal of Applied Science and Mathematics Volume 2, Issue 5, ISSN (Online): 2394-2894

Physico-chemical Characteristics, Fatty Acid, Composition of Grape Seed Oil and Phenolic Compounds of Whole Seeds, Seeds and Leaves of Red Grape in Libya

Sultana Hussein Salem Abdrabba Food Technology Department, Faculty of Agriculture, Chemistry Department, Faculty of Science, Omar Al-Mukhtar University, AL-Bayda, P.O. 919, Libya Omar Al-Mukhtar University, AL-Bayda, P.O. 919, Libya * Email: [email protected]

Abstract – This research was carried out on grape by- important commercial fruit crops worldwide. There are product of grape cultivar namely (Sultana) obtained from El- more than 70 grape species and a large number of grape Bieda city, (El-Jabal-El-Akhder region) in Libya, harvested cultivars growing all over the world [2]. at the optimum maturity to throw the light on the physico- Grape are one of the major fruit crops and about 80% of chemical characteristics, fatty acid composition of grape seed the harvest is used by the wine-making industry, which oil and phenolic compounds of whole seeds, seeds and leaves of grape. The oil yield from the seeds of grape was 16.63%. leads to the generation of large quantities of wastes and The physicochemical characteristics namely specific gravity, serious environmental problem for disposal. Therefore, a refractive index, free fatty acid, peroxide value, new commercial industry considering reutilizing the wate Thiobarbituric acid, ρ-anisidine, totox value, iodine number, by-products is emerging within the wine industry [3].The saponification number which were determined and the vilification by-products are traditionally used either as tocopherols content (as α-tocopherol), was 44.50 mg/100g. It animal food or as source of various products such as could be observed that the fatty acid composition for the ethanol, alcoholic beverages, tartaric and citric acid, grape seeds of red grape had high content of polyunsaturated fatty seed oil, and dietary fiber ([4],that constitute processes of acid especially linoleic \acid (55.30%) followed by oleic acid limited economical interest. (25.81%) while palmitic acid was the dominant saturated fatty acid (11.87%). Furthermore the phenolic compounds of Vinification industry wastes, which consist mainly of whole seeds, seeds consist of eleven of polyphenol compounds solid by-products, include marcs, pomace and stems, and with different ratio were identified in all parts including may account on average for almost 30% (w/w) of the vanillic acid, catechin, protocachoic acid, coumarin, gallic grapes used for wine production. All these by-products acid, ferulic acid, catechol, chlorogenic acid, synergic acid, may bear a considerable burden of phenolic compounds pyrogallol and caffiec acid. [5],depending on the type of grape (white or red), the part of the tissue (skin, seed, etc.), as well as the processing Keywords – Fatty Acid, Phenolic Compounds, Sultana conditions (e, g., pomace contact). Grape seed represents Grape. about 2 – 3% of the whole grape berry. Grape are

approximately 25% (w/w) dry pomace, of which about I. INTRODUCTION 38% (w/w) is seed [6]. Grape seed is a complex matrix containing approximately 40% fiber, 16%oil, 14%, and The food and agricultural products processing industries 7% complex phenols besides sugar, minerals, salts etc [7]. generate substantial quantities of phenolics-rich by- Reference [8] reported that red grape seed contained products, which could be valuable natural sources of 14.34% oil whereas white grape seed contained 14.72% antioxidants. Some of these by-products have been the oil. subject of investigations and have proven to be effective Grape seeds are also a source of healthy fatty acids and sources of phenolic antioxidants. When tested in edible dietary fibers [9].Some unsaturated fatty acids contained oils, and in fish, meat and poultry products. Reference [1] in grape seed oil, such as -linolenic acid (ω-3) and γ- found that using natural antioxidants to enhance the linolenic acid (ω -6), are considered essential fatty acids oxidative stability of food lipids has received special because they cannot be produced by humans [10]. attention because of the global trend to avoid the use of Consumption of unsaturated fatty acids has been synthetic food additives. Such a trend has resulted in an correlated to a reduction of cardiovascular disease, cancer, increased demand for natural antioxidants. Nevertheless, hypertension, and autoimmune disorders [11]. some natural antioxidants currently available, such as Additionally, dietary fiber makes up a considerable tocopherol and herb extracts, have limited uses due to high portion of grape seeds and peels— about 80% of their dry cost and particular flavour and colour attributes. weight- and has been linked with lower risks of heart Therefore, developing new types of antioxidants from disease, obesity, diabetes, and colon cancer [12]. nature source may be a strategy to resolve problems The addition of grape seeds to a staple food may caused by lipid oxidation. However, many strains of increase the quantity of fiber in the diet. Oil content of antioxidant producing modules have been isolated from grape seed strongly depends on grape variety, though the various foods. The grape (Vitis L.), which has a long usual range is 10-16% of dry weight. It consists mainly of history of cultivation and utilization, is one of the most triglycerides and the fatty acids composition is adjusted to Copyright © 2015 IJASM, All right reserved 175 International Journal of Applied Science and Mathematics Volume 2, Issue 5, ISSN (Online): 2394-2894

the following value: 0-0.2% myristic acid (C14:0), 7-13% II. PROCEDURE FOR ANALYSIS palmitic acid (C16:0), 3-6% stearic acid (C18:0), 0-0.9% , palmitoleic acid (C16:1), 14-25%; oleic acid (C18:1), 61-73% Sample preparation: Red grapes (Sultana cultivar) linoleic acid (C18:2), 0-0.6% linolenic acid (C18:3). The high were harvested at the optimum maturity and collected content in unsaturated fatty acids (around 85-90%) makes randomly from local farms at El-Gabal-Al-Akhader region it high quality nutritional oil [13]. from EL-Bieda city, Libya during August/2012. Grape phenolics, including flavonoids and related The grape fruits were washed with distilled water then Polyphenols from grape, wine, and grape seeds, have purified the samples from impurities and wounded fruits. generated remarkable interest based on positive reports of After manual removal of seeds from the whole berries, their antioxidant properties and ability to serve as free grape leaves were removed by hand. Grape seeds and radical scavengers. The beneficial effects of grape seed leaves were dried under vacuum at 40 ºC for 6 hrs in an polyphenols are due to their free radical scavenging oven dryer. The dried grape seeds and leaves were ground capability, but the antioxidant activity of grape seed in a grinder for 2 min (Moulinex- France. Type 643). The polyphenols is superior to other well-known antioxidants, grinding process was stopped every 15 second intervals to such as vitamin C, vitamin E, and β-carotene. Some avoid heating the sample. The grape seeds, and leaves clinical data have shown that procyanidin oligomers from powders were stored in polyethylene bags and kept frozen grape seeds are 20 times more potent than vitamin C and until used for further analysis. 50 times more potent than vitamin E as antioxidant [14]. Oil content: were determined after soxhlet extraction Besides their antioxidant activity, grape seed polyphenols with petroleum ether at 70-80 ºC as solvent for 6 hrs. also inhibit some enzymes that catalyze the release of Physical Methods: The physical and chemical histamine, which is responsible for inflammation and properties (Refractive index and specific gravity, Free allergies. Most antioxidants found in grape seed extracts fatty acid (F.F.A) (as % Oleic acid); Peroxide value (meq. are polyphenolics [15]. The key types of phenolics present active O /kg oil), Thiobarbituric acid (TBA) (TBA) (mg in grapes and grape seeds are proanthocyanidins, 2 alonaldehyde/kg) , saponification number, iodine value anthocyanins, and resveratrol [16]- [18]. were analyzed according to [29], [30]. Studies have shown that proanthocyanidins have preventative effects against cancer, heart disease, and p-Anisidine value. p- Anisidine value of oils was aging by inhibiting malignant cell growth, delaying heart determined by the reaction of aldehydic compounds in oil cell death, and maintaining membrane integrity as cells and the p-anisidine, and absorbance measured at 350 nm, age [19]- [21]. Anthocyanins are the pigments which give according to standard methods [31]. grapes and grape seeds their red and purple color. Totox value: Anthocyanins have been reported to exhibit health- Totox value was calculated according [32]. using the PV promoting properties, including antinflammation of blood conjuction with the Anisidine value using the following vessels and reduction of platelet coagulability, which may equation: reduce risks of developing atherosclerosis, an initial step Totox value = 2 PV + An V in cardiovascular disease [22]. Where: PV = peroxide value PV = peroxide value. Studies have shown that resveratrol, as well as Total tocopherol content: Total tocopherol was anthocyanins, may positively affect heart health by determined coloromitecally as described by [33]. The modulating proteins regulating immune responses, resultant solution was measured at 470 nm using a including inflammation of the vascular system [23], spectrophotometer model Safas Monaco 1900. [24].Overall, polyphenolics appear to be potentially Total lipid extraction: Dried grape seeds (50g) were capable of preventing cancer and cardiovascular diseases. blended with 500 ml of methanol – chloroform (1:2, v/v) Grape seed extract has become popular in recent years as a at 4 ºC in Warring blender. The extraction was carried out nutritional supplement that possesses antioxidant activity twice and the combined extracts were dried in a rotary [25]. evaporator at 40 ºC. The solution was washed with water Grape seeds are used as a dietary supplement and and dried over anhydrous sodium sulphate. The lipid nutritional food additive in the USA, Australia, Japan and extracts were filtered through lipid–free filter paper, Korea and in many European countries. There has been an solvent was removed from filtrates with a rotary increasing consumer demand this product due to its evaporator under reduced pressure to obtain total lipids. powerful on antioxidant properties and other beneficial The extracted lipids were redissolved in 10 ml of biological activities [26], [27]. . The distribution and methanol–chloroform (1:2 v/v ) and stored in 25 ml absolute content of antioxidant (e. g. polyphenols) in grape volumetric flask under nitrogen in the dark at (-25 ºC ) seed extracts principally depends on the raw materials until for further analysis. used, but they can be changed and/or modified by the Methylation of fatty acids: Fatty acid compositions of procedure due to extract them. Phenolics have a number of the oils samples were determined according to the important roles to play in viticulture and enology procedure of [34]. A sample of oil (50 mg) was including UV protection, disease resistance, pollination, transferred into screw-cap vial. Benzene (2 ml) and 1% color and defence against predation in plants [28]. H2SO4 (10 ml) in absolute methanol were added. The vial was covered under a stream of nitrogen gas before heating in an oven at 90˚C for 90 min. Distilled water (10 ml) was

Copyright © 2015 IJASM, All right reserved 176 International Journal of Applied Science and Mathematics Volume 2, Issue 5, ISSN (Online): 2394-2894 added to the cooled vial. The methyl esters in each vial Grape seeds are composed of 10-20% oil, along with fiber, were extracted with 5 ml of petroleum ether for three protein, and other components, including phenolic times. The three petroleum ether extracts were combined antioxidants. Each oil variety has different amounts of and concentrated to the minimum volume using a stream vitamin E by [39], [40], grape seed oil is one of the major of nitrogen. sources of vitamin E and contain relatively high quantities Analysis of fatty acid methyl esters: of tocopherols and tocotrienols in the range of 1-53.06 mg Analysis of fatty acids was carried out using a gas of vitamin E/100 g of oil [41]- [43], Among the different chromatography (Shimadzu GC-4CM-PFE) equipped with tocopherol species in foods, tocopherol has the highest stainless steel column packed with 3% diethylene glycol vitamin E antioxidant activity [39]. succinate on chromosorb W 80/100 and flame ionization Physical properties detector (FID). The oven and detector temperatures were With respect for the physical properties of the grape 180˚C isothermal and 270˚C, respectively. N2 was used as seed oil as illustrated in table (1). It could be observed that a carrier gas at a flow rate of 20 ml/min. the refractive index and specific gravity at 20°C were Extraction of phenolic compounds: (1.4731 and 0.8965) respectively. These results are in Methanolic extract: fresh grape fruits were washed and conformity with those of [44] who reported that the freeze-dried immediately, while seeds and leaves were refractive index and specific gravity of melon seed oil dried at 60ºC, then the dry materials were ground , the were (1.4733 and 0.914) respectively. powder were macerated in methanol 80% (1:3 w/v) for Chemical properties 24hr. The methanolic extract were filtered and evaporated The chemical characteristics of edible fats and oils are under vacuum up to dryness, the residue was named crude play an important role in assessing their quality assurance, extract. The crude extract were dissolved in distilled water palatability and consumer acceptability, as well as they are and then partitioned with ethyl acetate (6 x times x related with the healthy safe quality of these fats and oils 200ml). The ethyl acetate layers dehydrated with Na2SO4 by using them. Therefore, the chemical quality assurance and evaporated to dryness. The residue were named ethyl criteria, including the acidity (free fatty acid as % oleic acetate fraction. The remaining water layer then was acid), peroxide value (meq/kg oil), thiobarbituric acid partitioned with n-butanol (6 x times x 200ml). The (TBA) value (mg malonaldehyde/kg oil), ρ-Anisidine, butanol layers dehydrated with Na2SO4 and evaporated to iodine value (g/100g oil), and Saponification value (mg dryness. The residues were named butanol fraction [35]. KOH/g oil) were determined. As illustrated in the HPLC analysis: Identification and quantification of obtained results of Table (1), it could be indicated that the phenolic compounds of all extracts was determined as grape seed oil was found to have free fatty acid% of 2.65, described by [36]. The samples were performed in national Acid value was reported to be an industrially qualitative research center, Cairo by HPLC (HP) equipped with a parameter for selective seed oils applications. [45]. The Hewlet-Packered 1050 photodiode array detector (Agilent peroxide value is very useful criteria for indicating the Tchnologies 1200 or palo HI to. Calif (USA). with deterioration of oils. Peroxide value was determined to be Hewlet-Packered HPLC chem station of software and auto 0.95 meqO2/kg oil, while the TBA was 3.54 mg sampler using a PDS-Column C18-5 micron (150 mm x 4- malonaldehyde / kg oil, ρ-Anisidine was 3.11, and totox 6mm). Operated at 45 ºC. The solvent system used was value was 5.01, the low peroxide value (10.00 meq/g) gradient of A (acetic 2.5%) B (acetic 8%) and C indicates that the oil is stable. The iodine value is also (acacetonitrile). The solvent flow rates was 1m/min used as an index for evaluating the ability of oil to go ingection volume 50 ml. phenolic compounds were rancid [46], [47]. assayed by external standard calibration at 280 nm. Iodine number was 165.5 g/100g and finally saponification number was 192.21mg KOH/g oil as shown III. RESULTS AND DISCUSSION in table (1). Grape seed oil can be categorized as an drying oil because drying oils have an iodine value above 100 Grapes have a long and abundant history. During the g/100g. This nondrying attribute means the oil can be used ancient Greek and Roman civilizations, grapes were effectively in the paint industry [48]. revered for their use in winemaking [37]. Grape fruit The value of saponification of our study was compatible contains various nutrient elements, such as vitamins, with those obtained by reference [49]. who found that the minerals, carbohydrates, edible fibers and phytochemicals. saponification value of grape seed oil was 194. Grape seeds are waste products of the winery and grape Tocopherols are collectively known as vitamin E, and juice industry. These seeds contain lipid, protein, represent an important class of phenolic antioxidants that carbohydrates, and 5–8% polyphenols depending on the occur naturally in vegetable oils and function to maintain variety [15]. oil quality by terminating free radicals [50], α-, β-, γ- and Oil yield δ- are the four homologue forms of tocopherols that Oil content of grape seed strongly depends on grape generally exist in oil as minor ingredients. variety, though the usual range is 10-16%^ of dry weight. The current results indicated that tocopherol content of The results showed that the grape seeds obtained from red grape seed oil was (44.50) mg/100g. Grape seed oil these residuesas shown in table (1). The yield of the grape has the following nutritional properties: cholesterol free, seed oil was found to be about 16.63%, These result are low in saturated fats, contain linoleic acid and high density compatible with those obtained by [7], [38]. who found lipoprotein, and rich in vitamin E and antioxidants Copyright © 2015 IJASM, All right reserved 177 International Journal of Applied Science and Mathematics Volume 2, Issue 5, ISSN (Online): 2394-2894

[4]Grape seed oil is high quality culinary oil having a high therefore an important factor in oil quality. The ratio of the smoke point, 252 ºC, making a good choice for frying and different fatty acids in the oil influences the stability of the other high temperature food applications. Due to its oil, as well as determining its nutritional value. Some fatty stability and fluidity properties, grape seed oil spreads and acids are considered to be better than others; mixes better with food, requiring 50% les than other oils Table: 2 Fatty acid composition (expressed as %) of grape [4]. seed oil (sultana cultivar) Table 1: Oil content%, physical, chemical properties and Fatty acid Symbol % tocopherol content of grape seed oils Palmitic acid C16:0 11.87 % oil 16.63 Palmitoliec acid C16:1 0.66 Physical properties Stearic acid C18:0 5.78 Refractive index 20ºC 1.4731 Oleic acid C18:1 25.81 3 Specific gravity20ºC (kg/dm ) 0.8965 Linoliec acid C18:2 55.30 Chemical properties arachidonic C20:4 0.35 FFA% 2.65 Gadoliec acid C20:1 0.23 PV (meqO2/kg lipid) 0.95 TSFA 17.65 TBA (mg malonaldehyde/kg oil) 3.54 TMUSFA 26.7 ρ-Anisidine 3.11 TPUSFA 55.65 Totox 5.01 TFA 100 Iodine number (g/100g) 165.5 TSFA= Total saturated fatty acid Saponification number (mg KOH/g oil) 192.21 TMUSFA= Total monounsaturated fatty acid Tocopherol 44.50 TPUSFA=Total polyunsaturated fatty acid TFA= Total fatty acids Fatty acid composition: The fatty acid profile of edible oils plays an important role in their stability and nutritional Phenolic compounds: Grape is a phenol-rich plant, value. Monounsaturates (18:1) and polyunsaturates (18:2) and these phenolics are mainly distributed in the skin, fatty acids have been found to be effective replacements stem, leaf and seed of grape, rather than their juicy middle for saturates as part of cholesterol-lowering diets [51]. sections [56], [57]. The total phenolic content of grape However, it is also known that the oils with substantial skins varied with cultivar, soil composition, climate, amounts of unsaturation, particularly 18:2 fatty acids, are geographic origin, and cultivation practices or exposure to susceptible to oxidation and may produce products that diseases, such as fungal infections. [58]. contribute to arteriosclerosis and carcinogenesis. Some To date, leaves from Vitis vinifera L. constitute the less studies with experimental animals indicate that excessive studied or valorized residue of the grape crops and the amounts of linoleic acid promote carcinogenesis [52]. winery industry. The scarce information available on the Also, from the obtained data in table (2), it could be grapevine leaves composition informs on their content in observed that the linoleic acid (18:2) is the major fatty organic acids, phenolic acids, flavonols, tannins, acid in the 62.2%, and grape seed oil appears to be an procyanidins, anthocyanins, lipids, enzymes, vitamins, excellent source of the linoleic acid (18:2) is the major carotenoids, terpenes, and reducing or non-reducing sugars fatty acid in the 55.30%, and grape seed oil appears to be [59], [60], [61], [37], [62]. . an excellent source of the linoleic acid. The high linoleic The rich and varied chemical composition of these acid value is similar to those found in other oils, such as leaves has led to a considerable interest in this plant sunflower seed oil, linseed and hempseed oils [53]. material as a promising source of compounds with In contrast, oleic acid (18:1) accounted for 25.81%. The nutritional properties and biological potential. Thus, total unsaturated fatty acids level was 82.35%. The total grapevine leaves are employed in the production of food saturated acids made up a moderate proportion in 22.6% ingredients and its juice has been also recommended as an of the total fatty acids content of the seed oil. The palmitic antiseptic for eyewash [63], [64]. Polyphenols are the most acid accounted for 11.87% and the stearic acid accounted important phytochemicals in grape because they possess for 5.78% of the total fatty acid content. The promising many biological activities and health-promoting benefits amount of linoleic acid entails disease curing potentials [65]- [67]. and also presents cardiovascular linear option for other For the characterization and quantification of major oils [54]. Similarly, adequate concentration of omega 6 polyphenolic compounds present in whole seeds, seeds, (linoleic acid 55.30%) is also indicating a potentially and leaves extracts of red grape (sultana cultivar), were useful food additive and can be converted to gamma- determined by using HPLC analyzes. As shown in Table linoleic acid that can be used as a dietary increment to (3), eleven of polyphenol compounds were identified of surge the production of anti-inflammatory prostaglandins whole seeds, seeds, and leaves extracts of red grape which play a crucial role in controlling blood thickness (sultana cultivar) including vanillic acid, catechin, and blood pressure, it therefore means having an anti- protocachoic acid, coumarin, gallic acid, ferulic acid, inflammatory effect and is a vital nerve tissue food helping catechol, chlorogenic acid, synergic acid, pyrogallol and in the maintenance of brain and nerve function [55]. caffiec acid. The fatty acid profile of the oil is a measure of the Data revealed the all parts showed considerable proportions of individual fatty acids in the oil, and is percentage protocachoic, catechol and chlorogenic with Copyright © 2015 IJASM, All right reserved 178 International Journal of Applied Science and Mathematics Volume 2, Issue 5, ISSN (Online): 2394-2894 percentage exceed on 4000 mg/100g in order (8729.55, cheap source of antioxidants, which could be industrially 5533.14 and 4039.26 mg/100g) respectively for the whole exploited. seeds, while the high percentage of phenolic compounds in seeds exceed on 1000 mg/100g for chlorogenic acid, gallic REFERENCES acid and catechin with percentage (3903.4, 2823.03 and 1799.29 mg/100g) respectively, on the other hand, the [1] Ishikawa, Y. ˮ Development of new types of antioxidants from leaves had high percentage exceed on 100 mg/100g for microbial origin. ˮ Journal of Agriculture research, 76 : 1992, protocachoic acid, chlorogenic acid and pyrogallol with pp. 261 – 274 ). 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AUTHOR'S PROFILE

Sultana M, Hussein She was born in Tobruk city on the 18 of March 1964. She obtained B.Sc degree in Food Science from Omar El-Mukhtar university, she graduated with M. Sc in oil and fat technology from Alexandria university in 1996, and she graduated Ph. D in fish sea food technology from Alexandria university in 2004. She is a member of food industry society in Alexandria university, El- Mansoura university in Egypt, and member of Society of Arabic plant protection, Lebanon.

Salem Abdrba Mahmoud was born in El-Guba city, El-Jabal-El-Akhder governator, Libya on the 1st of January, 1963. He obtained a B. Sc. Degree in food science from Omar El-Mukhtar University, El-Bayda, Libya in the year 1986. He graduated with M. Sc in food science, Alexandria university, Egypt in 2004. He obtained Ph.D. in food science (food chemistry), Alexandria university, Egypt in 2014. He worked as staff member in chemistry department, faculty of science, Omar El-Mukhtar university from 2014.