'Functional Components in Peanuts

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Critical Reviews in Food Science and Nutrition
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Functional Components in Peanuts
Maria Leonora D. L. Franciscoa; A. V. A. Resurrecciona a Department of Food Science and Technology, The University of Georgia, Griffin, GA, USA
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Critical Reviews in Food Science and Nutrition, 48:715746 (2008) Copyright C Taylor and Francis Group, LLC ISSN: 1040-8398 DOI: 10.1080/10408390701640718
Functional Components in Peanuts

MARIA LEONORA D.L. FRANCISCO and A.V.A. RESURRECCION
Department of Food Science and Technology, The University of Georgia, Grifn 30223 GA USA
Downloaded By: [Consortium for e-Resources in Agriculture] At: 10:06 3 March 2011
Peanut is one of the most widely used legumes due to its nutrition and taste. The fact that is has been recognized recently as a functional food, its evaluation for its role in a heart-healthy diet has received tremendous attention. Functional compounds have been isolated, identied, quantied, and even enhanced to maximize the amount for adequate health benets. The peanut industrys byproducts such as peanut hulls and shells, skins, and even leaves and roots have also been identied as possible sources of bioactive compounds. New uses for these underutilized renewable sources can create new market opportunities and increase the value of agricultural residues. Keywords peanuts, Arachis hypogaea, functional foods, avonoids, phenolic acids, plant sterols, stilbenes, antioxidants
INTRODUCTION The relation between diet and health has increased the demand of consumers for more information about functional foods. Scientic research conducted during the past several years indicates that many potential health benets from food components beyond basic nutrition exist (IFIC, 2004). The benecial compounds in functional foods have been called by various terms such as phytochemicals, functional, and bioactive components. These substances exert their effects in human health by acting as antioxidants (Chun et al., 2005), activating liver detoxication enzymes (Percival, 1997), blocking the activity of bacterial and viral toxins (Moure et al., 2001), reducing cholesterol absorption (Kris Etherton et al., 2002) or inhibiting platelet aggregation (Pignatelli; et al., 2000). At least 120 naturally occurring foods have been identied as containing functional components (Pennington, 2002) and this number is expected to increase as the search for new or alternative food sources have become a major research interest. Peanuts have recently attracted attention as a functional food. In the past, peanuts were perceived as an unhealthy food because of their high fat content, as much as 50% w/w. At present, peanuts shifted their image from being an energy dense food to a benecial food for long-term health as evidenced by the numerous benecial components found in peanuts such as vitamin E, copper, magnesium, avonoids, and others. The evaluation of their role in a heart-healthy diet has increased in the last decade (Kris Etherton et al., 1999). Clinical studies on the consumption of peanuts and tree nuts demonstrated benecial effects on
Address correspondence to A.V.A. Resurreccion, Department of Food Science and Technology, 1109 Experiment street Grifn, GA 30223 1797 Tel: 770 412 4736 Fax: 770 412 4748. E-mail: aresurr@uga.edu
plasma lipids and lipoproteins such as reduced total cholesterol and low density lipoprotein cholesterol and triglycerides without reducing high density lipoprotein cholesterol. The health benets associated with peanuts are a reection of their nutritional prole (Griel et al., 2004) including their nutrient density, fatty acid prole, and the presence of bioactive compounds. It has been proven that peanuts and tree nuts are low in saturated fatty acids and high in monounsaturated and polyunsaturated fatty acids. The presence of bioactive compounds in peanuts and nuts that elicit positive healthful effects have been identied as plant proteins, dietary ber, micronutrients, plant sterols, and phytochemicals (Kris Etherton et al., 1999). A listing of these compounds is given in Table 1. There are about ve large epidemiological studies that looked at the effect of frequent nut consumption (nuts are dened as almonds, Brazil nuts, cashews, hazelnuts, macadamia nuts, pecans, pistachios, walnuts, and legume peanuts) on the risk of coronary and ischemic heart disease. These studies were the Adventist Health study, the Iowa Womens Health study, the Nurses Health Study, the Cholesterol and Recurrent Events study and the Physicians Health study (Kris Etherton et al., 2001). The Adventist Health study (Fraser et al., 1992) showed that subjects who consumed nuts more than four times a week experienced substantially fewer denite fatal coronary heart disease events and denite non-fatal myocardial infarctions. The Nurses Health study showed that women who ate more than ve units of nuts (one unit = 1 oz of nuts) a week had a signicantly lower risk of total coronary heart disease than women who never ate nuts or who ate less than one unit a month (Hu et al., 1998). Similarly, the Physicians Health study suggests that nut consumption is associated with a reduced risk of total and sudden cardiac death (Albert et al., 2002). Studies conrming that nuts contain several cardio-protective constituents are lacking.
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M.L.D.L. FRANCISCO AND A.V.A. RESURRECCION
Table 1 Benecial components present in peanuts (value per 100 g peanuts) (USDA Nutrient Database for standard reference, Release 19; Awad et al., 2000; Gu et al., 2004; Talcott et al., 2005a; Sobolev and Cole, 1999; USDA Database for the avonoid content of selected foods, Release 2.1; Chukwumah et al., 2007). Component Dietary ber Total monounsaturated fatty acids Total polyunsaturated fatty acids Vitamin E (-tocopherol) Folate Magnesium Potassium Calcium Total phytosterols -sitosterol Campesterol Stigmasterol Total proanthocyanidins p-Coumaric acid (-)-Epigallocatechin trans-Resveratrol Biochanin A Daidzein Genistein Product description All types, roasted, no salt Unit g g g mg mcg mg mg mg mg mg mg mg mg mg mg mcg mg mg mg Amount 8.00 24.64 15.69 6.93 145.00 176.00 658.00 54.00 60.70 47.20 5.80 7.70 15.60 8.82 0.66 5.50 0.13 1.75 0.23
Runner, dry roasted
Roasted Georgia Green, raw, normal-oleic All types, oil-roasted, with salt Florunner, roasted Runner, raw, defatted
More studies are needed to conrm the presence of these compounds and quantify the amounts needed to achieve benecial effects. Nevertheless, available data show that peanuts and nuts have the potential to contribute signicantly to human health (Higgs, 2003). Several bioactive compounds function as antioxidants. Antioxidants are only one of the food components that help prevent the production of undesirable or unstable compounds that cause cellular damage. Some bioactive components, but not all, function as antioxidants. Growing knowledge about the health promoting impact of antioxidants in everyday foods, combined with the assumption that a number of common synthetic preservatives may have hazardous effects, has led to multiple investigations in the eld of natural antioxidants (Peschel et al., 2006). Because of the growing concern for the potential health hazards of synthetic antioxidants such as butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and propyl gallate (PG), several authors are researching the risk of these antioxidants to humans when used in foods. Thus, there is renewed interest in the increased use of naturally occurring antioxidants (Nepote et al., 2004b). The replacement of synthetic antioxidants by natural ones may have benets due to health implications and functionality, however, some of them such as those from spices and herbs have limited applications despite their high antioxidant activity, as they impart a characteristic herb avor to the food. Plant phenolics have primary antioxidant activity. Primary antioxidants terminate the free radical chain reaction by donating
hydrogen or electrons to free radicals and converting them to more stable products (Rajalakshmi and Narsimhan, 1996) and are a potential source of natural antioxidants. The commercial development of plants as sources of antioxidants can be used to enhance the properties of foods for both nutritional purposes and for preservation. Crude extracts of fruits, herbs, vegetables, cereals, nuts, and other plant materials rich in phenolics are increasingly of interest in the food industry (Rice-Evans et al., 1997; Sang et al., 2002) for their antioxidant activity. Within the antioxidant literature, studies dealing with residual sources have been augmented considerably, which is caused by a value adding recycling interest of the agro- and food industry (Peschel et al., 2006). Recycling of by-products has been supported by the fact that polyphenols have been located specically in the peels, seeds, and hulls (Lee et al., 2003; Duh and Yen, 1997; Lu and Foo, 1999; Yamaguchi et al., 1999). Seeds of plants usually contain effective antioxidants in or around their germs to retain germination ability for long-term preservation. While the leaves and barks are usually exposed to sunlight and oxygen, so they are also potential sources of antioxidants (Namiki et al., 1993). The volume and diversity of agricultural byproducts represent an enormous and underutilized renewable resource, which can create an adverse impact in the economy and environment through disposal. Byproducts may contain numerous bioactive compounds such as vitamins, phenolics, antioxidants, carotenes, glucosinolates, soluble ber, and other components benecial to human and animal health, as well as materials potentially useful for manufacturing bio-based products (USDA ARS, 2003). The aim of this review is to present general aspects on bioactive components isolated and determined from peanuts, peanut products, and byproducts. The paper will focus on the present knowledge on the different compounds, their chemical structure, and natural occurrence in peanuts and comparable sources of functional components, and the evidence for a protective effect against diseases and functionality as a food ingredient. Additional information on extraction and analysis, processing effects, and food product application are also included.
FLAVONOIDS Chemistry and Properties Flavonoids are a class of secondary plant phenolics, ubiquitously distributed in the leaves, seeds, bark, and owers of plants. They constitute a relatively diverse family of aromatic molecules that are derived from phenylalanine (Havsteen, 2002) as shown in Fig. 1. It takes different, but related courses, depending on the kind of avonoid that is required. Over 4,000 avonoids have been identied to date. These compounds play many different roles in the ecology of plants. Due to their attractive colors, they may act as visual signals for pollinating insects. Because of their astringency, the avonoids can represent a defense system
FUNCTIONAL COMPONENTS IN PEANUTS
717
O NH2
Phenylalanine to Chalcone
O
Isoflavanone derivatives Naringenin chalcone Naringenin derivatives

OH O
OH
Vitexin derivatives
OH O
Apigenin derivatives
Naringenin (flavanones)
HO O
Apigenin (flavone)
OH
Kaempferol biosynthesis
HO
OH
OH O
+
OH
OH
Aromadendrin dihydrokaemfero
OH
Leucopelargonidin (flavan-3, 4-diol)

OH HO O OH OH
OH
Anthocyanidins
OH OH HO O
Myricetin biosynthesis
OH
OH
Taxifolin dihydroquercetin
OH
Quercetin (flavonols)
Quercetin catabolism
OH
HO
OH OH HO O
Leucocyanidin (flavan-3, 4-diol)

OH
OH
Anthocyanidins
OH OH
(+)-catechin (flavan-3-ol)
Figure 1 Schematic diagram of the major branch pathways of avonoid biosynthesis.
against harmful insects. Other relevant roles of avonoids in plants are listed in Table 2. Flavonoids are benzo- -pyrone derivatives (Heim et al., 2002) consisting of three phenolic rings A, B, and C (Fig. 2). The benzene ring A is condensed with a six-member ring C, which carries a phenyl benzene ring B as a substituent in the 2-position. Ring C may be a heterocyclic pyran or pyrone (Aherne and O Brien, 2002). Flavonoids can be categorized into several classes based on the saturation level and pattern of substitution of the C ring. These are: anthocyanidins, anthocyanides,
avonols, isoavonols, avones, isoavones, avanones, isoavanones, avanols, isoavanols, avanes, isoavones, aurones and, coumarins (Havsteen, 2002). Individual compounds within a class differ in the pattern of substitution of the A and B rings (Pietta, 2000). Figure 3 shows some of the avonoids with their structures. The chemical nature of the avonoids depends on the structural class, degree of hydroxylation, degree of methoxylation, other substitutions such as glycosidic side groups, and conjugations between the A and B rings. Hydroxyl groups are involved
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Table 2 Role of avonoids in plants (Havsteen, 2002; Heim et al., 2002; Pietta, 2000; Drewnowski and Gomez-Carneros, 2000). Characteristic Antioxidant Natural pesticide Antimicrobial agent Catalyst Visual attractor Feeding repellant Light screen Growth inhibitor Mechanism of Action Scavenge reactive oxygen species produced by the photosynthetic electron transport chain Protects plants against parasites and predators Inhibits/kills bacteria, pathogenic protozoans Hastens light phase photosynthesis; regulates iron channels involved in phosphorylation Attracts pollinating insects Inherent astringent compounds defend plants against harmful insects Screens UV radiation of sun and scavenge UV-generated reactive oxygen species Inhibits exocytosis of auxin indolyl acetic acid; induces gene expression
during metabolism, transformed either as methylated, sulfated, or glucuronidated. In foods, avonoids exist primarily as 3O-glycosides and polymers. The common glycosidic units are glucose, galactose, arabinose, rhamnose, and glucorhamnose. Several types of higher structure exist, and polymers comprise a substantial fraction of dietary avonoid intake (Heim et al., 2002). In plants, avonoids are relatively resistant to heat, oxygen, dryness, and moderate degrees of acidity, but can be modied by light. The nature of the hydroxyl group attached to the C-3 of ring C affects the photostability of the avonoid molecule (Aherne and OBrien, 2002). Flavonoids exhibit a wide range of properties such as pigments and avor compounds, depending on their particular structures. Some compounds are extremely potent odorants (e.g. vanillin and eugenol), but the major avors associated with avonoids are bitterness and astringency (Cheynier, 2005). Astringency, dened as a drying or puckering mouth feel detectable throughout the oral cavity, is due to a complexing reaction between dietary polyphenols and proteins of the mouth and saliva (Drewnowski and Gomez Carneros, 2000). Flavanols Flavanols are also referred to as avan-3-ols or catechins. Based on structure (Fig. 3), they lack the 2,3-double bond and the 4-one structure (RiceEvans et al., 1997). The predominating avanols are (+)-catechin and (+)-gallocatechin, ()-epicatechin, (+)-epicatechin, ()-epigallocatechin, and the following gallic esters: ()-epicatechin gallate and ()epigallocatechin gallate (Fig. 4). Oligomers or polymers of avan-3-ols, also called as proanthocyanidins or condensed tannins, are the second most abun3 2 8 7 1 4
dant natural phenolics. The size of the proanthocyanidin molecule is described by the degree of polymerization (DP). The units are linked mainly through C4C8 bond, but the C4C6 linkage also exists. These linkages are called B-type linkages. An A-type linkage also exists where an additional ether bond between C2C7 results in double linkage of the avan-3-ol units (Rasmussen et al., 2005). Proanthocyanidins consisting exclusively of (epi)-catechin are designated as procyanidins while those containing (epi)-afzelecin or (epi)-gallocatechin as subunits are named propelargonidin or prodelphinidin, respectively. Procyanidins exist most widely in plants. Propelargonidin and prodelphinidin are less common in nature (Gu et al., 2003). Structures of proanthocyanidins are presented in Fig. 5. Flavones and Flavonols Flavones and avonols have similar C-ring structures with a double bond at the 2-3 position, with the former lacking a hydroxyl group at the 3-position (Hollman and Arts, 2000). Major avones in plants are luteolin and apigenin while major avonols are quercetin, kaempferol, myricetin, and isorhamnetin (Fig. 6). Flavanones and Flavanonols Flavanones and avanonols are minor avonoids having a saturated C-ring. Naturally occurring avanones have the 2S conguration while the avanonols are usually 2R:3R, with a few having the 2S:3S or 2R:3S stereochemistry. Flavanones are slightly soluble, easily converted to isomeric chalcones in alkaline media, and have the tendency to separate rst in fractional crystallization and are easily precipitated at low pH and low temperature. These precipitates remain insoluble in water, methanol, ethanol, or acetone and mixtures thereof (Tomas-Barberan and Clifford, 2000b). Major avanones are eriodictyol, hesperitin, and naringenin (Fig. 7). The most popular avanonol is taxifolin. Isoavones/Isoavonoids Isoavones are intrinsic plant compounds having a 1,2diarylpropane structure. Structurally, they are well dened and to date, over 60 members of the class have been identied. Isoavones are present in plant foods either as the aglycone
1 2 3
B
5 6
A
6 5
Figure 2
C
4
Nuclear structure of avonoids.
719
3 2 8 7 6 5 4 4 8 5 2 3 6 6 7 1
3 2 1 2 3 5 6 4 5 7 6 5
O
3 8 2 1 2
OH
4 5 6
OH
O
Flavone 3 2 4 5 6 7 6 5 8
Flavanol
Flavonol 3
8 7 6 5
1 2 3
O
2 2 3 7 6
2 8
4 5 6
O
2
O
Flavanone
Figure 3
O
Isoflavone
5 6 5 4
OH O
Flavanonol
Chemical structures of the avonoid family.
OH
Catechins
OH O R OH
(+)-Catechin (+)-Gallocatechin
Substitution pattern
R=H R = OH
HO
OH
OH
Epicatechins
OH
Substitution pattern
Epicatechin R = H R2 = H Epigallocatehin R = OH R2 = H Epicatechin-3-gallate R = H R2 = Gallate Epigallocatechin-3-gallate R = OH R2 = Gallate
HO
O R R2 OH
O
Gallate H3C
OH
OH OH
Figure 4 Basic structure of catechins, epicatechins, and gallate.
720
R1 R2 H HO O R4 R5 OH
HO O O
Flavan-3-ols
R3
OH OH
OH
B-type
H
OH
OH
OH
HO
O R1 R2 OH HO O R3 R4 OH
Figure 5 Basic structures of proanthocyanidins.
O OH
OH
OH OH H
HO H H HO
A-type
(genistein or daidzein) or as different glycosides, including acetyl and malonyl glycosides and the -glucosides of genistein and daidzein (Fig. 8). Among the avonoids, isoavones are considered phytoestrogens or plant derived estrogens. These are structurally similar to the mammalian oestrogen oestradiol-17 and exhibit oestrogenicity. The overall structure of isoavone phytoestrogens is relatively rigid, with rotation possible only around the phenolic isoavone bond (Cassidy et al., 2000).
Dietary Sources Flavonoids in food are generally responsible for color, taste, prevention of fat oxidation, and protection of vitamins and enzymes (Yao et al., 2004). Existence of avonoids in foods is highly variable both qualitatively and quantitatively. Some avonoids are ubiquitous, whereas others are restricted to specic plant families or species. Within a single species, large variations may also occur, as a result of genetic differences, environmental conditions, and growth or
3 2 8 7 4
O
C
2 3
1 6
Flavone 5 Apigenin Luteolin Substitution pattern 5, 7, 4 - OH 5, 7, 3, 4 - OH ,
R1 R2
B
A
6 5
O
O
3
A
4
R3
C
Flavonol 8 Substitution pattern Quercetin 5, 7, 3, 4 - OH , Kaempferol 5, 7, 4 - OH Myricetin 5, 7, 3, 4, 5 - OH , 7 6 5
O
C
2
1 6
O
Flavanones Substitution pattern R1, R2 OH; R3 - H R1 OH; R2 OMe; R3 - H R1 H; R2 OH; R3 - H
OH O
Eriodictyol Hesperitin Naringenin
Figure 6
Basic structures of avones and avonols.
Figure 7
Basic structure of avanone.
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HO
HO
O OH
Daidzein
OH
O OH
Genistein
HO
HO
O OCH3
Formononetin
the homogenous B-type procyanidins (Rasmussen et al., 2005). A-type proanthocyanidins was determined in curry, cinnamon, cranberry, peanut, plums, and avocado (Gu et al., 2003). The amount of A-type proanthocyanidins was determined to be very high in these foods. Curry and cinnamon had 8490% of the total amount of proanthocyanidins as A-type, cranberry and peanuts about 5165%, and plums and avocado about 29% as A-type proanthocyanidins. Vegetables, citrus fruits, rice, and corn are not an important source of proanthocyanidins (Rasmussen et al., 2005). Soybeans are the most signicant source of isoavones, primarily genistein and daidzein (Yang et al., 2001). Occurrence in Peanuts Studies showing that peanuts may reduce the risk of cardiovascular diseases have led to the investigation of avonoids present in peanuts. These avonoids are currently under investigation in a bid to determine their biological and pharmacological effect on human physiology (Chukwumah et al., 2005). Total avonoid contents (both soluble and bound forms) of ten nuts including legume peanuts commonly consumed in the United States were determined by Yang et al. (2005) Walnuts had the highest avonoid content (745 93 mg/100 g), followed by pecans, peanuts, pistachios, cashews, almonds, Brazil nuts, pine nuts, macadamia nuts, and hazelnuts. Prior and Gu (2005) further investigated the proanthocyanidin content of these nuts in terms of interavan linkage, DP, and percentage of polymers present, as shown in Table 4. Mazur et al. (1998) and Mazur (1998) were able to analyze the isoavonoid content of food legumes, with genistein having the most amount of isoavone present in peanuts (Table 5). Surprisingly, the seeds are not the only source of avonoids. Outer layers such as peel, shell, and hull contain a large amount of polyphenolic compounds to protect the seed. About 50 million tons of nutshells and other assorted agricultural wastes are generated each year. For pecans alone, the industry generates about 59,500 tons of shells from its harvest. The commercial
OH
O OCH 3
Biochanin A
Figure 8
Structure of isoavones.
maturation stages. Variations in concentration may also occur from shells/peels/skins, to seeds and to the esh (Cheynier, 2005). Of the fourteen classes of avonoids enumerated in the previous section, comprehensive data on their contents in foods are available only for the avanols (quercetin, kaempferol, and myricetin), avones (apigenin and luteolin), catechins, and proanthocyanidins (Arts and Hollman, 2005). The main dietary sources of avonoids are fruits, beverages (fruit juice, wine, tea, coffee, chocolate, and beer) and, to a lesser extent, vegetables, dry legumes, and cereals (Kroon and Williamson, 2005). Flavonoids found in animals are considered to originate from the plants that animals feed rather than being synthesized in situ (Yao, et al., 2004). Main sources of dietary avonoids for each sub-group are given in Table 3. Quercetin is the main avonol in the human diet, abundantly found in onions and tea (Yang et al., 2001). Catechins and epicatechins are the principal components in all types of teas, thus sometimes they are called tea catechins. Proanthocyanidins on the other hand are widely present in fruits and berries, nuts, beans, barley, sorghum, curry, cinnamon, wine, and beers. Most of these plant-based foods contained exclusively
Table 3 Subclasses and dietary sources of avonoids (Aherne and O Brien, 2002; Rasmussen et al., 2005; Hollman And Arts, 2000; Tomas-Barberan and clifford, 2000; Cassidy et al., 2000; Gu et al., 2004; Manach et al., 2004; Cornwell et al., 2004; Chukwumah et al., 2007). Flavonoid sub-group Flavonols Representative avonoids Kaempferol, Myricetin, Quercetin, Rutin Major food sources (amount, mg/kg or mg/L) Onions (300), Apples (50), Broccoli (100), Tomato (430), Tea (30), Red wine (16), Kale (450) Parsley (1850), Celery (140) Soya beans (2210), Chick peas (36), Peanuts (211) Apples (17), Red wine (208), Green tea (800), Black tea (500), Peanuts (160), Peanut butter (130) Citrus peel (1000), Grapefruit (650), Lemon (300) Aubergine (7500), Blueberry (5000), Blackberry (4000)
Flavones Isoavones Flavanols
Apigenin, Chrysin, Luteolin Daidzein, Genistein, Glycitein, Formononetin Catechin, Gallocatechin, Proanthocyanidins
Flavanones/Flavanonols Anthocyanins
Eriodictyol, Hesperitin, Naringenin, Taxifolin Malvidin, Pelargonidin
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Table 4 Interavan linkages, constituent units, DP, and concentrations of proanthocyanidins in nuts, peanuts, and peanut by-products (Prior and Gu, 2005; Yu et al., 2006; Gu et al., 2004). Items Hazelnut Pecan Pistachios Almond Walnut Peanut Cashew Peanut butter Peanut skins: Raw Roasted Interavan linkagea B B B B B A, B B A A, B A, B Constituent unitsb C ,G C , G C , G Af, C C C C No data No data No data DP range (Average)c 1-P (10.8) 1-P (8.2) 1-P (9.1) 1-P (8.5) 1-7, P(7.8) 1-5 (2.6) 12 13 No data No data Total content of proanthocyanidinsd 501 494 237 184 67 16 9 13 645e 514e % of polymerse 64.4 45.1 51.6 43.6 29.7 0.0 0.0 0.0 No data No data
aA
denotes A-type linkage between polymers; B denotes B-type linkage between polymers. b Af, C and GC represent constituent units (epi)afzelechin, (epi)catechin, and (epi)gallocatechin. Denotes the presence of 3-O-gallate. c The 1-5 or 1-P in column DP values indicated that monomers through pentamers or polymers were detected. The average DP determined by thiolysis for selected foods is presented in parentheses. d Expressed as mg/100 g on the basis of wet weight. e Proportion of the polymers calculated based upon weight. f Expressed as mg/100 g dry sample.
value of shells alone is a measly $2.00 a ton (Suszkiw, 1999). But a growing number of studies have been looking at shells as possible source of antioxidants. One of the earliest studies on shells was done by Pendse et al. (1973) The report highlighted the isolation of 5,7dihydroxychromone from peanut shells, but eriodictyol and luteolin were also eluted from the acetone extract of powdered peanut shells. Daigle et al. (1988) also found that during the immature stage of peanut shells, eriodictyol was the predominant avonoid, while luteolin was the most predominant in shells from mature peanuts. The antioxidative properties of peanut hulls were extensively studied only in the 1990s (Duh and Yen, 1995; 1997; Yen and Duh, 1993; 1994; Yen et al., 1993). Luteolin was the principal antioxidative component from the methanolic extracts of peanut hulls. Further studies showed that the concentration of total phenolics and luteolin increased as maturity of peanut hulls increased (Yen et al., 1993). Peanut testae (skins, seed coats) are an extremely low value by-product of peanut blanching operations. Their commercial value is $12 to $20 per ton and their limited use is only as a minor component of cattle feed. Based on world in-shell peanut production of 29.1 million tons in 19992000 and an average skin content of 2.6%, world production of peanut skins can be estimated at over 750,000 tons annually (Sobolev and Cole, 2003). Peanut skins have a pink-red color and carry an astringent taste.
Table 5
They are typically removed before peanut consumption or inclusion in confectionary and snack products. In the early 1940s, these were initially thought to be toxic. But after a thorough examination by Dr. Jack Masquelier, then a doctoral candidate at the Faculty of Medicine and Pharmacy, University of Bordeaux, in France, peanut skin was found to be nontoxic, and protects and strengthens blood vessels (Louis, 1999). The colorless extract obtained was named OPC, oligomer proanthocyanidins. Current research demonstrates peanut skins to contain benecial avanols and potentially other health promoting compounds (Yu et al., 2005). Karchesy and Hemingway (1986) reported that mature, red peanut skins contain about 17% by weight of procyanidins, nearly 50% of which are low molecular weight oligomers. Lou et al. (1999; 2001; 2004) made a comprehensive analysis of the water-soluble phenolic extract from peanut skins, resulting in six A-type proanthocyanidins, including procyanidins A1 and A2 (Fig. 9), and three newly found epicatechin oligomers (Lou et al., 1999) (Fig. 9). They isolated ten compounds from the water-soluble fraction of peanut skins (Fig. 10), including eight avonoids and two novel indole alkaloids, reported for the rst time from a natural source (Lou et al., 2001). In 2004, they isolated ve oligomeric proanthocyanidins, B2 , B3 , and B4 (Fig. 11) from the water-soluble fraction and two new polyphenols, epicatechin-(2--O-7,4--6)-[epicatechin-(4--
Isoavonoid content of food legumes (g/100 g) (Mazur et al., 1978; Mazur, 1998). Coumestrol 2.4 0.0 tra 5.0 0.0 ndb Formononetin 4.4 0.0 0.0 215.0 6.8 nd Biochanin A 2.6 11.7 0.0 838.0 6.5 nd Daidzein 28.2 11.4 30.3 11.4 49.7 58.0 Genistein 158.0 18.2 55.7 76.3 82.6 64.0
Food description Kidney beans White kidney beans Black-eyed peas Chickpeas Peanuts Peanuts
a tr b nd
present in trace amounts not detected
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OH OH HO O
O 2
D F
3
OH
B E
HO
A
OH
C
OH O
OH
OH
Procyanidin A 2
D
O
F
3
OH
O
D
2
E
HO OH
F
3
OH
OH
OH
E
HO OH
Procyanidin A 1
Epicatechin-(2 -O-7,4 -8)-ent-epicatechin
OH
HO
D
O
OH HO O
F
3
OH
E
OH OH
A
OH
C
OH O
Epicatechin-(2 -O-7,4 -6)-ent-catechin D

HO O
F
3
OH
E
OH OH
D
HO O
F
3
OH
Epicatechin-(2 -O-7,4 -6)-catechin
E
OH OH
Epicatechin-(2 -O-7,4 -6)-ent-epicatechin

Figure 9 A-type proanthocyanidins isolated from the water-soluble fraction of peanut skins.
8)]-catechin and epicatechin-(2--O-7,4--8)-[epicatechin-(4-8)]-catechin-(4-)-epicatechin, based on their spectral data (Lou et al., 2004). Catechins, A-type and B-type procyanidins dimers, trimers, and tetramers were also detected by Yu et al. (2006) in chemically puried peanut skin aqueous and ethanol extracts. Furthermore, higher concentrations of compounds mentioned were observed in raw peanut skins than roasted peanut skins. Total catechins, procyanidins dimers, trimers, and tetramers in directly peeled peanut skin were 16.1, 111.29, 221.33, and 296.07
mg/100 g, respectively versus 8.79, 143.48, 157.53, and 203.91 mg/100 g, respectively in roasted dry skin (Yu et al., 2006). A complete list of polyphenols obtained from peanuts, peanut products, and by-products by various authors is presented in Table 6. Daily Consumption and Bioavailability The level of intake of avonoids from the diet is considerably high, as compared to those of vitamin C, E, and carotenoids
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Figure 10
Flavonoids and alkaloids isolated from the water-soluble fraction of peanut skins.
(Pietta, 2000). The reports available for daily consumption of avonoids differ in values, basically due to differences in the methods used for quantifying, limitation of compounds identied, and the confusion of total phenolics with total avonoids by investigators (Chun et al., 2005). The rst reported average daily intake of avonoids in the USA in 1976 is one g/day by spectrophotometric assay. This consisted of 16% avonols, avones, and avanones; 17% anthocyanins, 20% catechins, and 45% biavones. As recently established, the estimated daily intake of polyphenols is 1 g/day, (Kroon and Williamson, 2005; Scalbert and Williamson, 2000; Scalbert et al., 2005) where avonoids account for two-thirds of the total intake of polyphenols in the diet. The average individual intakes of avonols in a number of epidemiological prospective cohort studies published so far are 20 mg/day in middle-aged to older American males, 26 mg/day in elderly Dutch men, 4 mg/day in Finnish middle-aged men and women, and 26 mg/day in Welsh middle-aged men (Hollman
and Arts, 2000). Mean avonol and avone intake of US Health Professionals was estimated at 20 to 22 mg/day, where quercetin contributed almost 75% for both men and women (Sampson et al., 2002). The American daily intake of avonoids from 14 fruits and 20 vegetables commonly consumed is 103 mg catechin equivalents (Chun et al., 2005). Dietary intake of proanthocyanidins before was largely unknown because of lack of reliable values for their content in foods. But the recent development of an analytical method for proanthocyanidins has allowed the quantication of individual oligomers and polymers which the USDA National Food and Nutrition Analysis Program have employed. Based on the database and food consumption data (USDA Database for the Proanthocyanidin Content of Selected Foods, 2004), it has been shown that proanthocyanidins account for a major fraction of avonoids ingested in the US diet. Infants, children, and older people appear to ingest more proanthocyanidins than adults
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OH HO O
B
OH
2
A
3
Procyanidin B2
OH
OH O
2 3 OH
OH
E
OH
D
OH
H3C
2 3
OH OH O
2 3
HO
E
OH OH
H3C
2 3
OH O
OH
HO
E
2 3
OH OH
D
OH
D
OH
Procyanidin B3
Procyanidin B4
OH
OH OH HO O OH
HO O
OH
B
OH O OH OH OH OH
B G
HO OH O
A I
OH O OH
OH
C D
O
A
OH
D
HO
H
OH
HO
H
OH OH O O
K
OH
F
OH
F
OH
E E
OH OH
HO
I
HO OH
L
OH
G
HO
Epicatechin-(2 -O-7,4 -6)[epicatechin-(4 -8)]-catechin

Figure 11
Epicatechin-(2 -O-7,4 -8)epicatechin-(4 -8)-catechin-(4 -8)epicatechin
Oligomeric proanthocyanidins isolated from the water-soluble fraction of peanut skins.
on the basis of body weight. The 2- to 5-yr old age group consumes more proanthocyanidins daily than other groups because they consume more fruit. Gu et al. (2004) estimated that the daily intake of proanthocyanidins in the US was about 53 mg/day excluding the monomers, and 57.7 mg/day including the monomers. The distribution between the intake of monomers, dimers, and trimers was found to be almost equal with an intake of 4.16.4 mg/day for each group, whereas the intake of oligomers (410-mers) and polymers (>10-mers) was both around 20 mg/day. Thus, of the estimated total daily intake of proanthocyanidins, about 73% had a DP>3. One of the objectives of bioavailability studies is to determine, among the hundreds of dietary polyphenols, which are bet-
ter absorbed and which lead to the formation of active metabolites. With the occurrence of over 4,000 avonoids, bioavailability differs greatly between the various avonoids, and the most abundant avonoids in the diet are not necessarily those that have the best bioavailability prole (Manach et al., 2005). A review of 97 bioavailability studies of polyphenols in humans shows that among the avonoids, isoavones are the most well-absorbed, followed by catechins, avanones, and quercetin glucosides, but with different kinetics. The least well-absorbed polyphenols are the proanthocyanidins, the galloylated tea catechins, and the anthocyanins (Manach et al., 2005). The proanthocyanidins found in food cover a wide range of DP as shown in Table 4. The concentration of monomers,
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Table 6

Polyphenols isolated from peanuts and peanut products. Compound Resveratrol Dihydroquercetin p-Hydroxybenzoic acid p-Coumaric acid Luteolin Eriodictyol 5,7-dihydroxychromone p-Hydroxybenzoic acid trans-p-Coumaric acid trans-Ferulic acid trans-Caffeic acid trans-Sinapic acid Trans-resveratrol Procyanidin dimer A1 Procyanidin dimer A2 Procyanidin trimer A Epicatechin-(2 O7,4 6)-catechin Epicatechin-(2 O7,4 6)-ent-catechin Epicatechin-(2 O7,4 6)-ent-epicatechin Proanthocyanidin A1 Proanthocyanidin A2 Epicatechin-(2 O7,4 8)-ent-epicatechin Isorhamnetin 3-O-[2-O--glucopyranosyl-6-O--rhamnopyranosyl]--glucopyranoside Isorhamnetin 3-O-[2-O--xylopyranosyl-6-O--rhamnopyranosyl]--glucopyranoside Quercetin-3-O-[2-O--xylopyranosyl-6-O--rhamnopyranosyl]--glucopyranoside 3,5,7-trihydroxyisoavone-4-methoxy-3O--glucopyranoside Epicatechin-(2 O7,4 6)-[epicatechin-(4 8)]-catechin Epicatechin-(2 O7,4 8)-epicatechin-(4 8)-catechin-(4 8)-epicatechin Procyanidin B2 Procyanidin B3 Procyanidin B4 Ethyl protocatechuate Epicatechin-(2 O7,4 8)-catechin Epicatechin-(2 O7,4 8)-epicatechin Epicatechin-(4 8)-catechin Chlorogenic acid Caffeic acid Coumaric acid Ferulic acid Epigallocatechin Epicatechin Catechin gallate Epicatechin gallate Resveratrol Procyanidins (trimers, tetramers, pentamers, hexamers, heptamers, octamers) Procyanidin monomers A-type procyanidin dimers B-type procyanidin dimers A-type procyanidin trimers B-type procyanidin trimers A-type procyanidin tetramers B-type procyanidin tetramers Resveratrol Reference Rudolf and Resurreccion, 2006; 2007 Pratt and Miller, 1984 Talcott et al., 2005a Yen et al., 1993; Daigle et al., 1988; Pendse et al., 1973 Daigle et al., 1988; Pendse et al., 1973 Pendse et al., 1973 Dabrowski and Sosulski, 1984
Raw material Peanut kernels
Peanut hulls
Peanut our
Peanut skins
Nepote et al., 2004b Verstraeten et al., 2005
Lou et al., 1999
Lou et al., 2001
Lou et al., 2004
Yen et al., 2005 Karchesy and Hemingway, 1986
Yu et al., 2005
Lazarus et al., 1999 Yu et al., 2006
Peanut roots, leaves
Chen et al., 2002; Chung et al., 2003
dimers, and trimers in foods is by far exceeded by the higher polymerized proanthocyanidins. Recent studies suggest, however, that only the low-molecular-weight oligomers (those having a DP 3) are entirely absorbed in the gastrointestinal tract. The permeability of a proanthocyanidin polymer with a mean DP of 6 was approximately 10 times lower, suggesting that only
monomers, dimers, and trimers are absorbed and the polymers are not. So despite their high abundance in foods, dietary proanthocyanidins are very poorly absorbed by the body and may only exert local effects in the gastrointestinal tract or effects mediated mainly by the monomeric forms (Rasmussen et al., 2005).
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Health Benets Flavonoids are nontoxic substances that manifest a diverse range of benecial biological activities. The action of avonoids in health is controlled by its chemical structure. Since these compounds are based on the avan nucleus, the number, positions, and types of substitutions inuence avonoid actions. The multiple hydroxyl groups of avonoids are responsible for their substantial antioxidant, chelating, and prooxidant activities. While methoxy groups introduce unfavorable steric effects and increase lipophilicity and membrane partitioning. A double bond and carbonyl function in the heterocyclic or polymerization of the nuclear structure increases activity by giving a more stable avonoid radical through conjugation and electron delocalization (Heim et al., 2002). The degree of polymerization also affects the biological action of avonoids since, and as mentioned in the case of proanthocyanidins, their biological effects will only make sense at low DPs. Dietary avonoids have been implicated with prevention of age-related diseases including cardiovascular disease and cancer. Many epidemiological studies have provided mixed results. A review of studies relating to the role of avonoids as healthpromoting agents is discussed below. Antioxidant Effects Highly reactive oxygen species, such as singlet oxygen, 1 O2 , the superoxide anion radical O2 , the hydroperoxyl radical OH , the nitrogenoxide radical NO , and alkyl peroxyl free radicals, are regularly produced in animals and humans under physiological and pathological conditions (Fang et al., 2002). Accumulation of free radicals in the body may cause several conditions including the development of atherosclerosis, cancer, and cataract and destruction of B-cells and impairment of insulin action leading to diabetes (Knekt et al., 2002). Endogenous antioxidant defenses of the human body such as superoxide dismutase are capable of scavenging free radicals and repairing oxidative damages. Polyphenols acting as exogenous antioxidant defenses are also capable of scavenging reactive oxygen species through electron-donating properties, generating a relatively stable phenoxyl radical (Rasmussen et al., 2005). They scavenge superoxide anion, singlet oxygen, lipid peroxy-radicals, and/or stabilizing free radicals involved in oxidative processes through hydrogenation or complexing with oxidizing species (Ren et al., 2003). Another antioxidant mechanism as mentioned is the chelation of metals such as iron and copper ions, which prevent their participation in Fenton-type reactions and the generation of highly reactive hydroxyl radicals. This ability to react with metal ions, however, also enabled polyphenols to act as pro-oxidants (Yang et al., 2001). There is a hierarchy of avonoid and isoavonoid antioxidant activities that is dependent on structure and denes the relative abilities of the compounds to scavenge free radicals as shown in Table 7. Based on the table, most of the dietary sources
Table 7 Relative total antioxidant activities of avonoids and antioxidant vitamins (Rice-Evans et al., 1997; Kim and Lee, 2004). Antioxidant1 Antioxidant activity TEAC2 Vitamins Vitamin C Vitamin E Flavonoids Quercetin Kaempferol Myricetin Rutin Luteolin Chrysin Apigenin (+)-Catechin (-)-Epicatechin Epigallocatechin Epigallocatechin gallate Epicatechin gallate Taxifolin Naringenin Hesperidin Eriodictyol Genistein Genistin Biochanin A Daidzein Daidzin Formononetin Procyanidin B2 Procyanidin B1
1 Compounds 2 Measured
VCEAC3 100.00 24.00 229.40 114.60 261.80 65.80 178.30 24.90 89.80 215.70 245.50 264.40 234.90 221.40 213.50 135.10 12.30 n.d. 128.00 32.80 25.60 71.80 31.30 n.d. n.d. n.d.
1.00 1.00 4.70 1.30 3.10 2.40 2.10 1.40 1.50 2.40 2.50 3.80 4.80 4.90 1.90 1.50 1.00 1.80 2.90 1.20 1.20 1.30 1.20 0.10 7.58 6.55
highlighted are present in peanuts. as the TEAC (Trolox equivalent antioxidant activity) the concentration of Trolox with the equivalent antioxidant activity of a 1 mM concentration of the experimental substance. 3 Antioxidant activity expressed as VCEAC (Vitamin C equivalent antioxidant capacity) the ABTS radical scavenging activity expressed as mg/L vitamin C equivalents at 10 min; nd - no data.
of avonoids have higher antioxidant activities than the well known antioxidants such as vitamins C and E. The activity of an antioxidant is also determined by its reactivity as a hydrogen or electron-donating agent; the fate of the resulting antioxidantderived radical, which is governed by its ability to stabilize and delocalize the unpaired electron, its reactivity with other antioxidants, and the transition metal-chelating potential (Rice-Evans et al., 1997). Studies on the free radical-scavenging properties of avonoids have permitted the characterization of the major phenolic components of naturally occurring phytochemicals as antioxidants. The half peak reduction potential (Ep/2) has been attributed as a suitable parameter for representing the scavenging activity of avonoids. Table 8 reveals the avonoids with efcient scavenging properties with their corresponding half peak reduction potential. A avonoid with a low value for half peak reduction potential (i.e. < 0.2 mV) is readily oxidizable and therefore a good scavenger. Note that the avonoids with the highest scavenging activities include those with the o-dihydroxy structure in the B ring (Rice-Evans et al., 1997).
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Table 8 Hierarchy of avonoid antioxidant activities and the relationship with reduction potentials (Rice-Evans et al., 1997; Heim et al., 2000; Pietta, 2000). Flavonoid1 Quercetin Rutin Catechin Luteolin Taxifolin Naringenin Galangin Apigenin Chrysin Hesperitin Kaempferol
1
Antioxidant activity (mM)2 4.7 2.4 2.4 2.1 1.9 1.5 1.5 1.5 1.4 1.4 1.3
Half peak reduction potential3 (mV) 0.06 0.18 0.16 0.18 0.15 0.60 0.32 >1.00 >1.00 0.40 0.12
2
avonoid intake and the risk of coronary artery disease (CAD) and ve cohort studies on the risk of stroke have been published. Seven of these prospective studies found the protective effects of avonols and avones or of catechins with respect to fatal or nonfatal CAD, and reductions of mortality risk were up to 65%. These studies were as follows: the Zutphen Elderly Study, the Finnish Mobile Clinic Health Examination Survey, the Iowa Womens Health Study, the Alpha Tocopherol, Beta Carotene Cancer Prevention Study, the Dutch Zutphen Elderly Study, and the Rotterdam Study, in the Netherlands (Arts and Hollman, 2005). Anticancer Promoting Agents Knekt et al. (2002) estimated avonoid intakes of 10,054 men and women mainly on the basis of the avonoid concentrations in Finnish foods with a dietary history method. They found that men with higher quercetin intakes had a lower lung cancer incidence (P = 0.001), and men with higher myricetin intakes had a lower prostate cancer risk (P = 0.002). The role of dietary avonoids in cancer prevention is widely discussed in the literature. A growing number of epidemiological studies suggest that high avonoid intake may be correlated with a decreased risk of cancer. The mechanism of action of avonoids against cancer have been identied including the modulation of metabolism and disposition of carcinogens; inhibition of cancer cell proliferation, angiogenesis and activity of P-glycoproteins, disturbance of normal cell cycle progression, and induction of apoptosis, differentiation between normal and abnormal cells, and detoxication enzymes (Ren et al., 2003). In vitro studies of specic avonoids (i.e. cucurmin, genistein, and quercetin) show that they affect signal transduction pathways, leading to inhibition of cell growth and transformation, enhance apoptosis, reduced invasive behavior, and slower angiogenesis (Lambert et al., 2005). Inhibition of Platelet Aggregation Platelet aggregation is a central mechanism in the pathogenesis of acute coronary syndromes, including myocardial infarction and unstable angina. Platelet aggregation contributes to the development of atherosclerosis by several mechanisms and the inhibition of platelet aggregation is thus regarded as benecial. There is also extensive evidence that antiplatelet therapy reduces CVD (Rasmussen et al., 2005; Vita, 2005). The benecial effects appeared to be related to reduced activation of protein kinase C, as reported by Freedman et al. (2001) when they examined the effects of grape juice on platelet function. Several in vitro studies showed that avonoids such as quercetin and catechin inhibit platelet aggregation. Pignatelli et al. (2000) also showed that catechin and quercetin inhibited collagen-induced platelet aggregation and platelet adhesion to collagen. These data indicate that avonoids inhibit platelet function by blunting hydrogen peroxide production and, in turn, phospholipase C activation. In addition, specic avonoids were found to have the ability to compete for binding to the thromboxane A2 receptors, therefore,
Compounds highlighted are present in peanuts. Measured as the TEAC (Trolox equivalent antioxidant activity) the concentration of Trolox with the equivalent antioxidant activity of a 1 mM concentration of the experimental substance. 3 Designated Ep/2. An Ep/2 of < 0.2 indicates a chemical that is readily oxidized and therefore an efcient free radical scavenger.
Inhibition of Low Density Lipoprotein Oxidation and Atherosclerosis Researchers have shown that atherosclerosis has an intimate relation with oxidative modication of low density lipoprotein (LDL). When oxidized LDL is formed, macrophage receptor scavenges the oxidized LDL and then forms foam cells. Over time, cholesterol, lipoprotein, hematoblasts, connective tissues, and calcium may deposit and form plaque in arteries. Plaque makes arteries thicker and narrower, which may lead to atherosclerosis. The best way to prevent the formation of a fatty streak of atherosclerosis at the initial stage is to suppress LDL oxidation and use of drugs to decrease hyperlipidermia (Yen, and Hsieh, 2002). LDL oxidative modication may be suppressed by supplementing antioxidants, such as vitamin E. It was suggested that the availability of avonoids at the oxidative site on LDL may block oxidative attack and prevent LDL oxidation in vivo (Birt et al., 2001). The antioxidant primarily inhibits LDL peroxidation by scavenging free radicals and chelating metal ions (Yen and Hsieh, 2002). Protection Against Cardiovascular Diseases (CVD) The formation of stable phenoxyl radical by avonoids through its scavenging properties protects the body against oxidation and limits the risk of developing CVD (Rasmussen et al., 2005). Of the few prospective studies in humans that have predicted the effects of avonoids on CVD risk, some showed an inverse association, whereas others showed no association. But overall, the evidence suggests that individuals with the highest avonoid intake have modestly reduced risks of CVD (Vita, 2005) A recent review by Arts and Hollman (2005) on clinical studies conducted as of 2005 showed that 12 cohort studies on
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antagonism of this receptor may represent an additional mechanism for the inhibitory effect of avonoids in platelet function (Guerrero et al., 2005). There are quite a few studies involving the biological effect of bioactive compounds isolated from peanuts. Moreno et al. (2006) assessed the effects of peanut shell extract on lipid metabolic enzymes and evaluated its potential development for the treatment of obesity. Animal studies showed that the action of peanut shell extract may in part be attributed to the inhibition of fat absorption in the digestive tract, the activation of lipid metabolism in the liver, and the reduction of the adipocyte lipolysis. The bioactivity of the extract may be caused by the potentiating action of several compounds such as coumarin derivatives and avonoid glycosides, making the extract a potential multifunctional botanical therapeutic for weight control. Verstaeten et al. (2005) investigated the antioxidant action and membrane disruption protection of procyanidin dimers and trimers isolated from peanut skins. Results indicated positive interaction between the dimers and trimers with lipid membranes and thus can modulate membrane uidity, affecting numerous cellular processes, the functionality of membrane-associated enzymes and certain intracellular transport mechanisms and membrane receptors. A reduction in the ability of oxidants and other disturbing molecules to damage cell membranes is expected upon absorption of procyanidins-rich foods. PHENOLIC ACIDS Chemistry and Properties Two classes of phenolic acids can be distinguished: derivatives of benzoic acid and derivatives of cinnamic acid (Fig. 12). The hydroxybenzoic acid derivatives are phenolic metabolites with a general structure C6C1 (Tomas-Barberan and Clifford, 2000a). Hydroxybenzoic acids in both free and esteried forms are found only in a few plants eaten by humans, thus, they have not been extensively studied and are not currently considered to be of great nutritional interest (Manach et al., 2004). Cinnamic acids are a series of trans-phenyl-3-propenoic acids differing in their ring substitution (Clifford, 2000). The hydroxycinnamic acids, p-coumaric, caffeic, ferulic, and sinapic acids are more common than hydroxybenzoic acids. These acids are rarely found in the free form, except in processed food that had undergone freezing, sterilization, or fermentation (Manach et al.,
O O
2004). Hydrocinnamic acids occur in most tissues in a variety of conjugates in esters and amide forms, whereas conjugated glycoside rarely occurs (Karakaya, 2004). The best known conjugate is 5-caffeolyquinic acid (chlorogenic acid), formed between trans-cinnamic acids and quinic acid (Clifford, 2000). Phenolic acids are potent antioxidants just like the avonoids due to the reactivity of the phenol moiety, the primary mode of which is radical scavenging via hydrogen atom donation (Robbins, 2003). Dietary Sources Phenolic acids and its derivatives are abundant in food and may account for about one third of the phenolic compounds in the diet (Table 9). These compounds are found as esters which are either soluble or insoluble. The most frequently encountered hydroxycinnamic acids are caffeic acid and ferulic acid. Derivatives of hydroxycinnamic acid are found in almost every plant (Yang et al., 2001). Caffeic acid, both free and esteried, is generally the most abundant phenolic acid and represents between 75% and 100% of the total hydroxycinnamic content of most fruit. While ferulic acid is the most abundant phenolic acid found in cereal grains, which constitute its main dietary source. Occurrence in Peanuts The polyphenolic content of raw and dry roasted peanut samples containing varying levels of oleic acid (normal, mid, and high) were recently determined by Talcott et al. (2005a; 2005b) Normal oleic acid peanuts had higher concentrations of individual polyphenolics than mid- and high-oleic peanuts. Free p-coumaric acid, three esteried derivatives of p-coumaric, and two esteried derivatives of hydrobenzoic acid were identied as the predominant polyphenolics. Whole raw peanuts had a mean of 25 mg/kg of p-coumaric acid (from a range of 8 to 66 mg/kg among cultivars) and the value increased to an average of 69 mg/kg when peanuts were roasted at 175 C for 10 min. Differences in concentration among cultivars only show that background genetics, disease resistance, growth conditions, post-harvest handling, or response to roasting conditions greatly affects the occurrence of polyphenols. p-coumaric acid was also previously identied to be present in defatted peanut our at a concentration of 4068% of the total phenolics (Seo and Morr, 1985). Huang et al. (2003) isolated and identied the ethanolic extract fraction from peanut seed testa that showed the highest yield and marked antioxidant activity. Thin layer chromatographic separation of this fraction allowed the isolation of the antioxidant component in peanut seed testa which was identied as ethyl protocatechuate (3,4-dihydroxybenzoic acid ethyl ester). Daily Consumption and Bioavailability
R1
OH
R1
R2 R3
Hydroxybenzoic acid
R2
Hydroxycinnamic acid
Figure 12
Structures of phenolic acids.
The American daily intake of phenolics from 14 fruits and 20 vegetables commonly consumed is 450 mg gallic acid equivalent
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Table 9 Dietary sources of phenolic acids (Manach et al., 2004; Talcott et al., 2005; 2005; Dabrowski and Sosulski, 1984). Phenolic acid Hydroxybenzoic acids Representative Protocatechuic acid Gallic acid p-Hydroxybenzoic acid Caffeic acid Chlorogenic acid Coumaric acid Ferulic acid Sinapic acid Sources (amount, mg/kg or mg/L) Blackberry (270), Raspberry (100), Black currant (130), Strawberry (90), Roasted peanuts (142) Blueberry (2200), Kiwi (1000), Cherry (1150), Plum (1150), Aubergine (660), Apple (600), Pear (600), Potato (190), Corn our (310), Cider (500), Coffee (1750), Roasted peanuts (266), defatted peanut our (173)
Hydroxycinnamic acids
(Chun et al., 2005). A German study estimated daily consumption of hydrocinnamic acids, hydrobenzoic acids and caffeic acid at 211, 11, and 206 mg/day, respectively (Manach et al., 2004). Benzoic acid may be obtained from foods or as an antimicrobial additive. Based on the World Health Organizations Joint Expert Committee on Food Additives (JECFA), an acceptable lifetime daily intake (ADI) of benzoic acid of up to 5 mg/kg body weight was approved (Tomas-Barberan and Clifford, 2000a). Intake of hydrocinnamic acid varies widely but may be very high, up to 800 mg/day among coffee drinkers (Manach et al., 2004). Very few studies have addressed the bioavailability of hydroxycinnamic acids compared with other polyphenols. For hydroxybenzoic acids, very little is known about its absorption and metabolism. However, the few studies addressing the bioavailability of gallic acid in humans revealed that this compound is extremely well absorbed, compared with other polyphenols (Manach et al., 2005).
PLANT STEROLS Chemistry and Properties Plant sterols are an essential component of the membranes of all eukaryotic organisms. They are either synthesized de novo or taken up from the environment. Plant sterols are called phytosterols which covers plant sterols and plant stanols. Over 250 different sterols and related compounds in various plant and marine materials have been reported. Beta-sitosterol, campesterol, and stigmasterol are the most common plant sterols. Chemical structures of these sterols are similar to cholesterol, differing in the side chain. For example, sitosterol and stigmasterol have an ethyl group at C-24, and campesterol a methyl group at the same position (Piironen et al., 2000; Ohr, 2003). They inhibit the absorption of cholesterol in the gut, while not being absorbed themselves in signicant amounts. Sterols in plants exist in the free form or esteried to fatty acids or as steryl glycosides (EU-SCF, 2002). Hydrogenation of the plant sterols results in the formation of plant stanols. They are saturated phytosterols that are less abundant in nature but they can be produced by 5-alpha hydrogenation of the corresponding phytosterols (e.g. sitostanol and campestanol). Plant sterols are categorized into three: (a) 4-desmethylsterols (no methyl groups); (b) 4-monomethylsterols (one methyl group) and; (c) 4,4-dimethylsterols (two methyl groups) (IFST, 2005). The most common plant sterols belong to the 4-desmethylsterols, which are structurally similar to cholesterol as shown in Fig. 13. Dietary Sources The commonly consumed plant sterols are sitosterol, stigmasterol, and campesterol which are predominantly supplied by vegetable oils. Minimal amounts can be sourced from cereals, nuts, and vegetables (Piironen et al., 2000). Phytosterols are natural components of vegetable oils such as sunower seed oil and tall oil, the latter derived from the process of paper production from wood. The proportion of plant stanols is higher in tall oil than
Health Benets In animal studies, dietary gallic and ellagic acids have shown hepatoprotective activity against carbon tetrachloride toxicity, but the doses given are well above those that might be expected from normal human diets. The safety of ellagic acid at high doses however, remains controversial (Tomas-Barberan and Clifford, 2000a). The same is true for caffeic acids. Caffeic acid at a level of 2% in diet (which is extremely high compared to the normal dietary levels) induced forestomach and kidney tumors in rats and mice (Hagiwara et al., 1991). Protocatechuic acid at a concentration of 10 g/ml showed a stronger inhibitory effect against LDL oxidative modication induced by Cu2+ than ascorbic acid at the same concentration (Yen and Hsieh, 2002). Yen et al.s (2005) review also showed that protocatechuic acid was an efcacious agent in different tissues such as diethylnitrosamine in the liver, 4,-nitroquinoline-1-oxide in the oral cavity, azoxymethane in the colon, N-methyl-N-nitroso urea in glandular stomach tissue, and N-butyl-N-(4-hydroxybutyl) nitrosamine in the bladder.
731
Beta-sitosterol
-Avenasterol
HO
HO
Stigmasterol
Campesterol
HO
HO
-Avenasterol
HO
Figure 13
Structural formulae of 4-desmethylsterols.
vegetable oils. Normal rening of edible oils results in partial extraction of plant sterols together with some tocopherols. It is estimated that 2500 tons of vegetable oil needs to be rened to produce one ton of plant sterols (IFST, 2005). Thus, phytosterols are by-products of vegetable oil rening. Phytosterols are isolated from conventional edible oils (soya, maize, sunower, and rapeseed). The conventional caustic rening procedure involves degumming, neutralization, bleaching, and deodorization. The last step, a mass-transfer process, by which substances are evaporated from the oil under reduced pressure (210 mbar) and elevated temperature (230270 C), leads to the formation of a distillate making around 0.10.3% of oil mass and containing 820 % sterols (EU-SCF, 2000). The main sources of phytosterols in the basic diet are cooking oils and margarines. Bread and cereals can also contribute signicantly to total phytosterol intake. Reduced-fat health spreads available in the market contain about 0.30.4% phytosterols, corn oil margarines are highest in phytosterols (0.5%). Vegetables and fruits contain < 0.05% (based on the edible portions), except seedlings of barley, beans, peas which contain 0.10.2% phytosterols. Sunower and sesame seeds are also rich sources,
containing about 0.50.7% and legumes can contain 0.22% phytosterols (EU-SCF, 2000). Occurrence in Peanuts Peanuts as a source of phytosterol has been getting a lot of attention with new research ndings identifying beta-sitosterol in peanuts and peanut products as cancer growth inhibitors, as well as protectors against heart diseases (PI, 2000). Awad et al. (2000) studied the phytosterol contents of peanuts and peanut products (Table 10). Results show that among the four cultivars studied, the Valencia peanuts in raw, dry roasted, and oil roasted, contained the highest phytosterol concentration; regular and natural peanut butter contain signicant amounts of phytosterols as well as peanut our; the peanut oil rening process, however, decreases the amount of phytosterols in peanut oil. Rened peanut oil contains 38% more phytosterol than rened (pure) olive oil. Commercial peanut oil analyzed by Ye et al. (2000) contained more than 200 mg total sterols/100 g. This gure is within the reported value of the USDA Nutrient Database of 207 43 mg/100 g of peanut oil (USDA, 2007).
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Table 10

Phytosterol contents of pecans, peanuts and peanut products. Total phytosterols (mg/100g EP) 64125 100 >200 7595 95.8 63.3 126.9 55.1 105.2 60.7 113.5 75.9 89.2 61.4 103.8 61.7 206.8 189.2 139.1 137.9 143.5 156.7 54.5 59.7 Reference Koehler and Song, 2002 Ye et al., 2000 Ye et al., 2000 Ye et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000 Awad et al., 2000
Product Raw, shelled, Georgia green Raw, shelled peanut Commercial peanut oil Pecans Raw, shelled, air-dried Red peanuts Runner peanuts Valencia peanuts Virginia peanuts Dry roasted Red peanuts Runner peanuts Valencia peanuts Virginia peanuts Oil roasted Red peanuts Runner peanuts Valencia peanuts Virginia peanuts Peanut oil Unrened Rened Deodorized Hydrogenated Peanut Butter Natural Regular Peanut Flour Dark roast Light roast
tion from 991.2 to 2071.7 g/g oil (Maguire et al., 2004). Betasitosterol was also the major sterol found in pecans. The amount from seven cultivars ranged from 75 to 95 mg total sterols per 100 g, which is about 90% of the total. The remaining 10% consisted of campesterol, brassicasterol, and stigmasterol (Ye et al., 2000).
Daily Consumption and Bioavailability Average dietary intakes of plant sterols in Western diets are between 200400 mg/day. Major sources of plant sterols in typical Western diets are cooking oils, margarines, peanut butter, legumes, and some seeds (sunower and sesame) (IFST, 2005). Asians and vegetarians on the other hand consume 345400 mg/day (Awad et al., 2000). Approximately 250 mg of phytosterols per day ( 4 mg/kg bw/d) is consumed in a typical US diet. In the adult Finnish population, the average intake is about 300 mg/d ( 5 mg/kg bw/d) with an upper limit of 680 mg/d ( 10 mg/kg bw/d) (EUSCF, 2000). In the Netherlands, the total mean intake of betasitosterol, campestanol, and beta-sitostanol was 285 97 mg/d (Normen et al., 2001). Generally the intake of adult vegetarians and their children is higher (up to 40%) than the average for the population as a whole. Infant formulae based on cows milk contain 0.080.20 mmol/L -sitosterol, 0.030.10 mmol/L campesterol and around 0.02 mmol/L stigmasterol, while human milk is not a signicant source of phytosterol (EU-SCF, 2000). Health Benets
Changes in the phytosterol composition of the Georgia Green peanut were investigated by Koehler and Song (2002). Beta-sitosterol, campesterol, stigmasterol, and avenasterol were found in all samples of the Georgia Green peanuts at various maturities. The content of beta-sitosterol and stigmasterol both increased signicantly at each degree of maturity, while campesterol levels remain unchanged. Avenasterol levels increased only to the third maturity level, then declined slightly. Phytosterol levels in Georgia Green peanuts were found not to be dependent on the number of days between planting to harvest but are dependent on the maturity level of the harvested peanut kernels. Mature kernels (at the orange and brown/black maturity stages), contain signicantly more total phytosterols. Grosso and Guzman (1995) and Grosso et al. (1997; 2000) studied the sterol composition of aboriginal peanut seeds from Peru, Bolivia, and some wild peanut species native to South America. Seven 4-desmethylsterols were detected namely: cholesterol, campesterol, stigmasterol, Beta-sitosterol, 5 -avenasterol, 7 -stigmasterol, and 7 -avenasterol. Betasitosterol was the prominent sterol in the composition of all samples from various sources followed by campesterol, stigmasterol, and 5 -avenasterol. Other nuts also contain substantial amounts of phytosterols. Oil extracted from freshly ground walnuts, almonds, hazelnuts, and macadamia nuts contain -sitosterol, ranging in concentra-
Plant sterol and plant stanols appear to be without hazard to health, having been shown without adverse effects in a large number of human studies. Their low abundance in human tissues can be explained by the fact that they are poorly absorbed, and are excreted faster from the liver than cholesterol (Kris-Etherton, 2002). They show no evidence of toxicity even at high dose levels since gastro-intestinal absorption is low (IFST, 2005). Furthermore, the European Union through the Scientic Committee on Food concluded that the use of phytosterol-esters in yellow fat spreads (maximum level of 8% free phytosterols) is safe for human use (EU-SCF, 2000). More recently, the European Food Safety Authority (EFSA) through its Scientic Panel on Dietetic Products, Nutrition, and Allergies, has recommended that sterol-containing foodstuffs should not be consumed in amounts resulting in total phytosterol intakes exceeding 3 g/day (EFSA, 2003). In the USA plant sterol esters in plant oil-based spreads at levels up to 20% are generally recognized as safe (EU-SCF, 2000). The USFDA in 2000 authorized the use of labeling health claims in certain foods about the role of plant sterol or stanol in reducing the risk of coronary heart disease. They work by blocking the absorption of cholesterol from the diet (Ohr, 2003). Studies with sitosterol or mixtures of plant sterols have shown that they reduce serum cholesterol levels in humans by
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approximately 10%. This discovery has resulted in subsequent research to evaluate the effects of sitosterol derivatives on cholesterol absorption and serum cholesterol levels. The reduction in total and LDL cholesterol is the result of a decrease in cholesterol absorption and an alteration of enzymes involved in cholesterol metabolism and excretion (Kris-Etherton et al., 2002). In vivo studies have shown that the consumption of phytosterol inhibits the development of chemically induced colon cancer. In addition, phytosterol consumption normalized the hyperproliferative state of rat and mouse colonocytes, where hyperproliferation of colonic mucosa is considered to be a risk factor in the development of colon cancer. In vitro studies have shown that beta-sitosterol, identied in peanuts and peanut products, inhibits HT-29 human colon cancer cell growth, induces apoptosis in LNCaP human prostate cancer cell, inhibits apoptosis in MDA-MB-231 human breast cancer cells, and testosteronemetabolizing enzymes in normal rat tissues (Awad et al., 2000; 1998). The relation between plant sterol intakes and colorectal cancer risk in the Netherlands, however, showed no clear association between the intake of any of the plant sterols and colon and colorectal cancer risk for men and women, respectively (Normen et al., 2001). Based on extensive toxicological testing of phytosterol preparations in a 13-week feeding study with rats, in a two-generation feeding study with rats, in studies on oestrogenic potential, and in tests on genotoxicity, no safety concerns were apparent (EU-SCF, 2000).
HO
1
OH HO
HO
OH
Figure 14
OH
Resveratrol isomers, 1, trans-resveratrol and 2, cis-resveratrol.
than white wines since resveratrol is found in the skin (Cornwell et al., 2004).
Occurrence in Peanuts Stilbene phytoalexins are produced by the peanut plant as a defense mechanism against exogenous stimuli like fungal invasion. Stilbenoids found in peanut include resveratrol, 3isopentadienyl resveratrol, and various arachidins (Ku et al., 2005). Resveratrol is present in peanuts to protect the plant from plant pathogens (Higgs, 2003). The amount, however, is low compared to those of grapes. Resveratrol was found to be present in substantial amounts in the leaves, roots, and shells of peanuts, but very little was found in developing seeds and seed coats of eld-grown peanuts (Chung et al., 2003). The phytoalexin content of peanuts, however, increases during germination and is enhanced by microbial infection, postharvest induction procedures such as soaking and drying; wounding (slicing and incubation); UV light exposure, among others. Raw peanuts soaked in water for about 20 hours and dried for 66 hours increased the resveratrol content between 45 and 65 times after the soaking treatment (Seo et al., 2005). Germination of peanut kernels (25 C, 95% relative humidity, 9 days in the dark) increased the resveratrol signicantly from the range of 2.3 to 4.5 g/g up to the range of 11.7 to 25.7 g/g (Wang et al., 2005). Rudolf and Resurreccion (2006) were also able to increase the resveratrol content of peanut kernels by application of abiotic stresses. Slicing (2 mm), ultrasound exposure for 4 min at 25 C, and incubation for 36 h increased the resveratrol content from 0.48 g/g in untreated peanuts to 3.96 g/g in treated peanuts. Boiled peanuts contain more resveratrol than peanut butter and roasted peanuts. The maturity of peanuts is also a factor where smaller peanuts have higher levels than more mature peanuts (Sobolev and Cole, 1999). The resveratrol contents of peanut butter also vary with blended peanut butters (those containing vegetable oils) containing more resveratrol than natural peanut butters (Ibern-Gomez et al., 2000). Unequal distribution of resveratrol is found where higher levels are present in the seed-coat than the kernel. Seed coats from
STILBENES Chemistry and Properties Stilbenes contain two phenyl compounds connected by a 2carbon methylene bridge. They occur in nature in a rather restricted distribution. Stilbenes like isoavonoids, are also classied as phytoestrogens. Most stilbenes in plants act as antifungal phytoalexins, compounds that are usually synthesized only in response to infection or injury. Phytoalexins possess antifungal activity against Aspergillus, Penicillium, and Cladosporium species. The most extensively studied stilbene is resveratrol (3,5,4 -trihydroxystilbene) (Yang et al., 2001; Sobolev and Horn, 2003). Resveratrol occurs in the cis- and trans- isomers (Fig. 14). Only the trans- isomer was reported as estrogenic (Cornwell et al., 2004).
Dietary Sources The major dietary source of phytoestrogenic stilbene is resveratrol. Resveratrol is one of the major stilbene phytoalexin compounds produced by grape berries and peanuts in response to stress like fungal infection, the presence of heavy metal ions, or ultra-violet (UV) irradiation (Seo et al., 2005). The type of postharvest processing affects the nal concentration of resveratrol in the product. For example, red wines have more resveratrol
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runner and Virginia types contained approximately 0.65 g/g of seed coat, which is equivalent to < 0.04 g/seed (Sanders et al., 2000). Ethanolic extract prepared from defatted peanut skins even showed higher resveratrol contents. The ethanolic extract contained 91.4 g/g while the dry peanut skins contain 9.07 g/g (Nepote et al., 2004a). Pistachios were also found to contain resveratrol. The formation of the cis-isomer in pistachios was found to be higher than in peanuts according to Tokusoglu et al. (2005) Trans-resveratrol content and of peanuts and peanut products is shown in Table 11. Another stilbenoid can be found in peanuts. Piceatannol (3,4,3 ,5 -tetrahydroxy-trans-stilbene), like resveratrol, are also synthesized as phytoalexins. Its concentration in peanuts is lower than resveratrol. However, in a study conducted by Ku et al. (2005) on the production of stilbenoids from the calluses of peanuts, showed that the concentration increased from 2.17 to 5.31 g/g after exposure to UV irradiation for 18 hours under static culture. Daily Consumption and Bioavailability No report has been published regarding daily intake of resveratrol by consumers. It can be assumed, however, that red wine drinkers would have more resveratrol intake than non-drinkers. Resveratrol has high bioavailability and physiological levels can be obtained through drinking red wine (Cornwell et al., 2004). Health Benets Resveratrol has been associated with reduced CVD and reduced cancer risk. Resveratrol has been shown from in vitro, ex vivo, and animal studies to have many attributes that may provide protection from atherosclerosis, antiproliferative, and proapoptotic properties against breast, colon, prostatic, and leukemia cells (Higgs, 2003).
Table 11 Trans-resveratrol content in peanuts and peanut products. Trans-resveratrol content (g/g) 0.0180.080 0.1480.504 1.7797.092 0.0231.792 0.0480.306 0.0390.069 0.2650.671 0.5340.753 0.1000.250 0.0900.300 0.2700.700 3.0004.920 1.0501.380 2.3907.840 Reference Sobolev and Cole, 1999 Sobolev and Cole, 1999 Sobolev and Cole, 1999 Sanders et al., 2000 Sanders et al., 2000 Sanders et al., 2000 Ibern-Gomez et al., 2000 Ibern-Gomez et al., 2000 Lee et al., 2004 Lee et al., 2004 Lee et al., 2004 Rudolf and Resurreccion, 2006 Rudolf and Resurreccion, 2007 Chukwumah et al., 2007
There is evidence to suggest that resveratrol inhibits LDL oxidative susceptibility in vitro and platelet aggregation. Olas and Wachowicz (2002) reported that resveratrol had a protective effect against reactive oxygen species production in resting and activated blood plates. Moreover, resveratrol also reduced the different step of platelet activation (platelet adhesion to collagen and brinogen, aggregation, secretion and eicosanoid synthesis). Resveratrol has also been shown to inhibit the expression of the tissue factor gene; tissue factor protein initiates the coagulation cascade resulting in thrombus formation. The evidence suggests that resveratrol may decrease CVD risk by multiple mechanisms (Kris-Etherton et al., 2002). Stilbenes inhibit cellular events associated with tumor initiation, promotion, and progression. They inhibit free radical formation, which will inhibit tumor initiation. They act as an antimutagen since they induce the quinine reductase enzyme capable of detoxifying carcinogens. Moreover, they exhibit antiinammatory activity and inhibit the hydroperoxidase activity of cyclooxygenase, thus inhibiting the arachidonic pathway leading to the formation of prostaglandins that stimulate tumor cell growth and can activate carcinogenesis (Cassidy et al., 2000). Resveratrols estrogenic activity has led investigations of its potential use as a chemotherapeutic agent in breast cancers. A study conducted on human breast xenografts in vivo induced transcription via both ER and ER, resulting in lower tumor growth, decreased angiogenesis, and increased apoptosis (Garvin et al., 2006). Induction of peanuts to synthesize bioactive stilbenoids exhibited potent antioxidant and anti-inammatory activities as shown by Chang et al. (2006). All peanut stilbenoids at 15M (arachidin-1, arachidin-3, isopentadienylresveratrol) showed varied potencies in suppressing lipopolysaccharide-induced inammation of mouse macrophage cells as affected by the number and position of other hydroxyl groups and isopentyl or isopentadienyl moiety. Production of prostaglandin and nitric oxide was signicantly inhibited by arachidin-1 (p < 0.001), resveratrol (p < 0.001), and arachidin-3 (p < 0.01), ANALYSIS OF BIOACTIVE COMPONENTS IN PEANUTS Extraction Methods It has been stated that there are more than 4,000 phenolic compounds and the number is still increasing. Most of the compounds that have been proven to be potent antioxidants are from plant materials. Extraction procedures would play a big role in getting these bioactive components since extracting solvent, isolation procedures, purity of active compounds, as well as the test system and substrate to be protected by the antioxidant affects its function (Moure et al., 2001). Solvent Extraction Solvent extraction is more frequently used for isolation of antioxidants and both the extraction yield and the antioxidant
Product Roasted peanuts Peanut butter Boiled peanuts Spanish, raw Virginia, raw Runner, raw Peanut butter, blended Peanut butter, natural Virginia, raw Spanish, raw Peanut butter Runner, raw, treated1 Runner, raw, treated2 Runner, raw
1 Raw
peanuts were sliced to 2 mm, exposed to ultrasound for 4 min at 25 C, and incubated for 36 h at 25 C. 2 Raw peanuts were stressed by slicing and ultrasound and incubated at 25 C.
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activity of extracts are strongly dependent on the solvent, due to the different antioxidant potential of compounds with different polarity (Moure et al., 2001). The extraction of polyphenols is dependent on two events, the dissolution of each polyphenolic compound at the cellular level in the plant material matrix, and their diffusion in the external solvent medium (Shi et al., 2005). A list of extraction solvents used for polyphenolics is given below. Extraction by hot water. Water is a natural solvent, which does not leave any harmful residue behind. Infusion and decoction are simple methods for extraction with water. The former involves addition of boiling water to the material, while the latter requires boiling the material for about 15 min in water (Silva et al., 1998). For optimal extraction, the temperature of the water ranges from 80 to 100 C. Temperatures over 100 C are detrimental to polyphenols, which can cause denaturation. (Shi et al., 2005). Extraction by water and ethanol solvent. The most common type of extraction is done with alcohol-water solutions. Ethanol and water are the most widely employed solvents for hygienic and abundance reasons, respectively (Moure et al., 2001). Ethanol is a safe solvent that can be used for extraction purposes, where even if it is found in the nal extract, it is safe for human consumption (Shi et al., 2005). Alcoholic solvents efciently penetrate cell membranes, permitting the extraction of high amounts of endocellular material (Silva et al., 1998). Extraction by water and methanol solvent. This process is carried out at low temperatures to avoid oxidation. Methanol provides as good results as ethanol. Hydrocinnamic derivatives, avonols, and catechins are extracted using this solvent mixture (Shi et al., 2005). Extraction by ethyl acetate and water solvent. Ethyl acetate is a good solvent for polyphenols. It has a low polarity, thus capable of extracting polyphenols that are dissolved in the lipid fraction of the food. The advantage lies in the fact that it has a low boiling point, which makes it easy to remove and reuse (Shi et al., 2005). The efciencies of the various solvents mentioned were tested by several authors. Duh et al. (1992) found that among the organic solvents, the methanolic extract from peanut hulls produced a higher yield, and the antioxidant component identied from this extract was equal to the commercial antioxidant BHT and stronger than alpha-tocopherol. Nepote et al. (2002) extracted antioxidant components from defatted and nondefatted peanut skins using methanol, ethanol, acetone, and water. The high content of total phenolics was detected in the methanolic and ethanolic extracts from defatted peanut skins. Huang et al. (2003) also compared the yield and antioxidant activity of peanut seed testa extracted using various solvents namely: methanol, ethanol, acetone, hexane, and ethyl acetate. Among the solvent extracts, ethanol extracts produced the highest yield and antioxidant activity, showing that polar solvents
were more efcient than less polar solvents in terms of extraction of antioxidative components. It was also evident that the antioxidant activity of polar solvent extracts was markedly stronger than that of less polar solvent extracts, which showed hardly any antioxidant activity. In terms of the concentration of ethanol for extraction, Nepote et al. (2005) found that both 50 and 70% (v/v) ethanol in water are the best solvents to extract a high yield of total phenolic and antioxidant compounds in peanut skins. However, when considering the evaporation time and cost, the preferred solvent mixture was 70% (v/v) ethanol in water. Yu et al. (2005) on the other hand used ethyl acetate and water in isolating phenolics also from peanut skins. Their study revealed that the water extract fraction from puried peanut skin extract shows higher total phenolics concentration than the ethyl acetate portion. Based on the polarity of water and ethyl acetate, phenolic compounds in the water layer are more polar than those that would preferentially dissolve in ethyl acetate. Thus, water would favorably dissolve more polar plant polyphenols with higher antioxidant activity. Higher polarity means more hydroxyl groups on the ring of polyphenols and based on the conclusion of Cao et al., (1997) the more hydroxyl substitutions, the stronger the antioxidant and prooxidant activities. This nding is encouraging with the fact that functional ingredients used in the formulation of health promoting foods and dietary supplements need to be water soluble for optimal physiological benets (Yu et al., 2005). The best conditions for the extraction of antioxidative compounds from peanut skins were established by Nepote et al. (2005) as follows: 70% ethanol as solvent, non-crushed peanut skins, ratio of solvent/solid of 20 ml/g, at 10 minutes shaking and three extractions. At these conditions, the phenolic compounds obtained were 118 mg/g. While the study of Yu et al. (2005) obtained high yield of phenolic compounds using peanut skins from peanut kernels roasted at 175 C for 5 min and extracted using ethanol (80%) as recovery method. Ultrasound-assisted Extraction High-frequency ultrasound is a powerful technique that is being applied to material analysis research and food product development. The mechanical effects of ultrasound provide greater forced penetration of solvent into cellular materials; improves mass transfer to and from interfaces; and facilitates the release of contents by disrupting the biological cell walls on the surface and within the raw material (Mason, 1998). A cavitation phenomenon is produced during ultrasonication when acoustic power inputs are sufciently high to allow the multiple productions of microbubbles that collapse and create shock waves that cause cells to disintegrate into very ne cell debris particles (Chukwumah et al., 2005). The ultrasound waves produce an increase in temperature and pressure, giving rise to advantageous increases in transport phenomena and in the displacement of the partitioning equilibrium (Waksmundzka-Hajnos et al., 2004). Advantages of ultrasound-assisted extraction include shorter extraction time, lower extraction temperature, and less bioactive compound loss (Liu et al., 2005).
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A high-frequency ultrasonication method was used in extracting selected phytochemicals from peanuts. The results showed that the amount of biochanin, genistein, and resveratrol increased with increasing extraction time and that the highest amount of biochanin and resveratrol was obtained at 150 min and 180 min for genistein (Chukwumah et al., 2005).
X + H3 O+ XH + H2 O M(III) + AH AH+ + M(II)
(4) (5)
Measuring Bioactive Components with Antioxidative Properties Within a biological system, there are at least four general sources of antioxidants: (1) enzymes (e.g. catalase, superoxide dismutase); (2) large molecules (e.g. albumin); (3) small molecules (e.g. ascorbic acid, tocopherol, polyphenols) and (4) some hormones (e.g. estrogen) (Prior et al., 2005). In measuring the total antioxidant capacity of a biological sample, several methods are usually conducted because of the possibility of interaction among different antioxidants in vivo may make the measurement of any individual antioxidant less representative of the overall antioxidant status (Prior and Cao, 1999). An increase in concentrations of antioxidants does not necessarily mean that there has been an increase in reactive species. At the same time, a decrease in antioxidant levels could be the result of either an increase in reactive species that react with the antioxidants or a response to lower production of reactive species. Because of the complex interactions within cells, one test is normally not enough to understand precisely what is going on within the cell (Grifn and Bhagooli, 2004). The chemistry behind the antioxidant capacity assays are classied into two: assays based on hydrogen atom transfer (HAT) reactions and assays based on single electron transfer (SET). HAT-based methods measure the classical ability of an antioxidant to quench free radicals by hydrogen donation (AH = any H donor) X + AH XH + X (1)
SET reactions are usually slow and can require long times to reach completion. SET methods are very sensitive to ascorbic acid and uric acid. While trace components and contaminants like metals also interferes with the method, accounting for high variability and poor reproducibility and consistency (Prior et al., 2005). In foods, separating each antioxidant is costly and inefcient, thus, researchers develop methods to evaluate the total antioxidant capacity of a given good, where total antioxidant capacity means the integrated effects of all the antioxidants and if any, the synergistic effects of them (Wu et al., 2004a). A brief description of some of the different antioxidant capacity methods are discussed briey and a summary is presented in Table 12. The First International Congress on Antioxidant Methods was convened in 2004 for the purpose of discussing the chemical methods for antioxidant content and activity in model systems and foods, measurement of antioxidant capacity in food and biological systems, and the in vitro and in vivo methods used to estimate effectiveness in animals and man (Finley, 2005). From the evaluation of data presented in the Congress and in the literature, it was proposed that three assays be considered for standardization: the Folin-Ciocalteu method, the oxygen radical absorbance capacity assay, and the Trolox equivalent antioxidant capacity assay (Prior et al., 2005). Folin-Ciocalteu Procedure This method was derived from the Folin-Denis colorimetry method introduced in 1912. This method is also based on the chemical oxidation of the reduced molecules by a mixture of the two strong inorganic oxidants, phosphotungstic and phosphomolybdic acids. But unlike the ofcial method for total phenolics, the Folin-Denis colorimetry is subject to precipitations that interfere with colorimetry. The method, proposed by Otto Folin and Vintila Ciocalteu in 1927 is convenient, simple, requires only common equipment, and has produced a large body of comparable data. The assay is inclusive of monophenols and gives a predictable reaction with the types of phenols found in nature. With the diverse nature of phenols, the degree of reaction is wide, such that the expression of the results as a single number such as milligrams per liter gallic acid equivalence is necessarily arbitrary. Also, since the reaction is independent, quantitative, and predictable, an analysis of a mixture of phenols can be recalculated in terms of any other standard (Singleton et al., 1999). The Folin-Ciocalteu method has also some setbacks. Since the total phenolic content is determined based on nonspecic reduction-oxidation reactions, the analysis is affected by other nonphenolic reducing molecules present in the samples such as ascorbate, citrate, and sulte. Also, high sugars can form reactive reductones (endiols) in the nal solution, and aromatic
Antioxidant capacity measurements are based on competition kinetics and the quantitation is derived from kinetic curves. HAT reactions are solvent and pH independent and are usually quite rapid. HAT-based methods generally are composed of a synthetic free radical generator, an oxidizable molecular probe, and an antioxidant. The presence of reducing agents, including metals, interferes with HAT assays and therefore may lead to erroneously high apparent reactivity (Prior et al., 2005). The SET-based methods detect the ability of a potential antioxidant to transfer one electron to reduce any compound, including metals, carbonyls, and radicals. X + AH X + AH+ AH+ A + H3 O+ (2) (3)

Table 12 Comparison of methods for assessing antioxidant capacity (Prior et al, 2005; Prior and Cao, 1999). Simplicity
c
737
Antioxidant Assaya ORAC TRAP FRAP CUPRAC TEAC DPPH TOSC LDL oxidation PHOTOCHEM Cyclic voltammetry
a ORACOxygen
Biological relevance Yes Yes No No No Yes Yes Yes No
Mechanismd HAT HAT SET SET SET SET HAT HAT ? HAT
Endpoint Fixed time Lag phase Time, varies Time Time IC50 IC50 Lag phase Fixed time Anodic wave
Quantitation AUC IC50 lag time OD xed time OD xed time OD xed time OD xed time AUC Lag time Lag time or AUCe Peak potential
Coefcient of variationf (%) n.d. 4.6 n.d. n.d. 3.66.1 n.d. 6.0 n.d. 2.0 n.d.
Lipophilic & Hydrophilic AOC +++ +++ +++
++b
+++ +++ + + + +
radical absorbance capacity; TRAPTotal radical trapping parameter assay; FRAPFerric reducing antioxidant power; CUPRACcopper reduction assay; TEACTrolox equivalent antioxidant capacity assay; TOSCTotal oxidant scavenging capacity; PHOTOCHEMPhotochemiluminescence b +, ++, + + + = desirable to highly desired characteristic c , , = less desirable to highly undesirable based upon this characteristic d HAT = hydrogen atom transfer; SET = single electron transfer e The lipophilic assay is quantied by AUC measured over a dened measuring time, and the hydrophilic assay is quantied based upon the lag phase. f Interassay coefcient of variation.
amines react, as phenols. These substances increase the absorbance value by reacting with the Folin reagent and, if not correctly subtracted, can give an overestimated total phenolic value (Singleton, 1985; Stevanato et al., 2004). ORAC Assay The oxygen radical absorbance capacity (ORAC) method uses phycoerythrin as an oxidizable protein substrate and AAPH as a peroxyl radical generator or Cu2+ -H2 O2 as a hydroxyl radical generator (Prior and Cao, 1999). AAPH undergoes spontaneous decomposition and produces peroxyl radicals, with a rate primarily determined by temperature. The antioxidant samples are not likely to affect this rate, particularly when the chemical structure of AAPH and the very high molar ratio of AAPH to an antioxidant sample are considered. Therefore, the ORAC assay has high specicity; it measures the capacity of an antioxidant to directly quench free radicals. The area under-curve technique combines both inhibition percentage and the length of inhibition time of free radical action by an antioxidant into a single quantity, which makes it superior to similar methods that use either an inhibition percentage at a xed time or a length of inhibition time at a xed inhibition percentage (Cao and Prior, 1998). Because peroxyl radicals are the most common radicals found in the human body, ORAC measurements is more biologically relevant (Wu et al., 2004a; Wang et al., 2004). However, the ORAC assay requires about 70 minutes to quantitate results (Prior and Cao, 1999). Since the early version developed by Cao et al. (1993) was time-consuming and labor-intensive, an automated procedure was developed and modications were also incorporated such as the adoption of uorescein as the new probe instead of phycoerythrin. Phycoerythrin was found to lose 3050% of its intensity in the absence of free radicals due to photobleaching and it was also observed to cause nonspecic protein bind-
ing with the analyzed compounds, in particular with avonoids (Huang et al., 2002). The developed ORACFL , according to the authors, has the ability to obtain a measure of total antioxidant capacity in the protein free plasma, using the same peroxyl radical generator for both lipophilic and hydrophilic antioxidants (Wu et al., 2004a; Prior et al., 2003; Wu et al., 2004b). ABTS Assay or TEAC Procedure The assay is based on the ability of compounds to scavenge the long-lived stable radical cation chromophore of 2,2 azinobis-(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS+ ). The radical is usually generated by oxidizing ABTS with metmyoglobin and hydrogen peroxide. The method, however, has been criticized on the basis that the faster reacting antioxidants may also contribute to the reduction of the ferryl myoglobin radical. An improved method was proposed and it utilizes potassium persulfate for the direct production of the ABTS radical (Re et al., 1999). This preformed ABTS radical is stable for at least two days when stored in the dark at room temperature (Prior and Cao, 1999). The relative ability of hydrogendonating antioxidants to scavenge ABTS+ generated in the aqueous phase, can be measured spectrophotometrically in the near-infrared region showing maxima at 660, 734 and 820 nm. At these wavelengths, the interference from other absorbing components and from sample turbidity is minimized. The results are expressed by comparison with standard amounts of the synthetic antioxidant Trolox (6-hydroxy-2,5,7,8-tetramethylchroman-2carboxylic acid), to give rise to the TEAC (Trolox equivalent antioxidant capacity) in molar units. Trolox, a vitamin E analogue, is not a natural compound found in foods. A TEAC value can be assigned to all compounds by comparing their scavenging capacity to that of Trolox. Thus, some authors refer this method as TEAC assay (Antolovich et al., 2002; Obon et al.,
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2005; Kim and Lee, 2004; Arts et al., 2003). The ABTS+ assay as demonstrated by several authors, can be used to measure the antioxidant activity of a broad diversity of substances such as L-ascorbic acid, glutathione, uric acid, albumin, bilirubin, cysteine, BHT, -tocopherol, phenolic acids, avonoids, and catechins (Cano et al., 1998). Other modications of the TEAC assay exist: TEAC I (metmyoglobin) measures hydrophilic antioxidants; TEAC II (manganese dioxide) measures lipophilic antioxidants, while TEAC III (potassium persulfate) may be applied for both. The three procedures vary on how the ABTS radical was generated (Aruoma, 2003). Other Methods
ing the reaction. During an induction period, this oxidation is inhibited by the antioxidants in the plasma. The length of the induction period (lag phase) is compared to that of an internal standard, Trolox, and then quantitatively related to the antioxidant capacity of the plasma (Prior and Cao, 1999). Antioxidant Capacity of Peanuts There are quite a few studies on the antioxidant capacity (AOC) of peanuts found in the literature. Hwang et al. (2001) observed that the antioxidative activities of roasted defatted peanut kernels at 180 C for 60 min displayed the most remarkable AOCs on linoleic acid in emulsions where the induction period was determined to be about 200 hr in Tween 20 emulsion and 350 hr in Tween 80 emulsion, compared to the control, raw, defatted peanuts of 12 hr. Wu et al. (2004a) examined the lipophilic and hydrophilic antioxidant capacities of common foods in the United States including nuts and nut products. Using the ORAC assay, the hydrophilic ORAC values among different nuts was quite large, ranging from 4.43 to 175.2 mol of Trolox equivalents (TE) per gram for pine nuts and pecans, respectively. Peanuts had a lipophilic and hydrophilic ORAC of 2.73 and 28.93 mol TE per gram, respectively, for a total antioxidant capacity of 899 mol TEs per serving (serving size = 28.4 g). Peanut butter had a total of 34.32 mol TE per gram. The AOC of normal and high oleic acid peanuts were found to be relatively high in raw and roasted peanuts and increased by 22% on average following roasting (Talcott et al., 2005b). However, no meaningful differences in AOC were observed between high and normal oleic acid peanuts, but differences were present among cultivars (Talcott et al., 2005b). Total phenolics in 10 different nut types were analyzed by Kornsteiner et al. (2006) and the mean content of total phenolics ranged from 32 mg GAE/100 g (pine nuts) and 1,625 mg (walnuts). Raw peanuts with skin had a mean of 420 mg GAE/100 fresh weight. The use of defatted peanut skin as raw material was explored by Nepote et al. (2004). They found that the methanolic and ethanolic defatted peanut skin extract contains about 158.6 mg/g and 144.1 mg/g total phenolics, respectively. The radical scavenging activities were 32.59% in methanolic extract and 31.5% in ethanolic extract at a concentration of 1 g/ml. Yen et al. (2005) found that the AOC of the ethanolics and the isolated antioxidative component from the extract of peanut seed testa, ethyl protocatechuate, revealed 92.6% and 84.6% scavenging effect, respectively, on ,-diphenyl--picrylhydrazyl (DPPH) radical. The hydroxyl radical scavenging effect of ethanolic extract and ethyl protocatechuate were 70.6% and 67.7%, respectively. The total AOC of the water and ethanol extracts of peanut skins were compared with the water and ethanol extract of green tea, the latter known to have high AOC. Under identical extraction and analytical conditions, Yu et al. (2005) reported that extracts from peanuts skins showed higher AOC than green tea. The antioxidant capacities of water and ethanol extracts of raw peanut skins were 3.39 and 4.10 (mM Trolox/mM phenolics) respectively. Roasted peanut skins had 3.30 and 3.72
The ABTS assay as well as other methods like ORAC uses Trolox equivalents to express antioxidant activity. But Trolox is not a familiar compound to chemists. Furthermore, total antioxidant capacity results expressed on a molar basis are difcult to understand. Vitamin C on the other hand, is commonly recognized as a leading natural nutrient and antioxidant. Thus, the description of antioxidant potential using vitamin C equivalent antioxidant capacity (VCEAC) calculated on a weight basis was proposed. The VCEAC assay also uses ABTS radicals, like the TEAC. The ABTS radical scavenging activity of selected chemical compounds at the level of 100 mg/L is expressed as mg/L vitamin C equivalents (mg VCEAC/L) at 10 min (Kim and Lee, 2004). The DPPH method is representative of the methods employing model radicals in the evaluation of radical scavengers. It is not discriminative with respect to the radical species but gives a general idea about the radical quenching ability. The antiradical activity is dened as the amount of antioxidant necessary to decrease the initial DPPH concentration by 50% (efcient concentration = EC50 [(mol/l)AO/(mol/l)DPPH]. A direct relation is observed where the larger the antiradical power is, the more efcient the antioxidative action is. The method is rapid, a sample analysis takes approximately 15 min in total and little manpower, and no expensive reagents or sophisticated instrumentation is required (Aruoma, 2003; Koleva et al., 2002). The ferric reducing antioxidant power (FRAP) assay involves the reduction of a ferroin analog, the Fe3+ complex of tripyridyltriazine Fe(TPTZ)3+ , to the intensely blue colored Fe2+ complex Fe(TPTZ)2+ by antioxidants in acidic medium, pH of about 3.6. Results are obtained as absorbance increases at 593 nm and can be expressed as micromolar Fe2+ equivalents or relative to an antioxidant standard (Antolovich et al., 2002; Aruoma et al., 2003). The total radical trapping parameter (TRAP) assay was the most widely used method for measuring the total antioxidant capacity of plasma or serum. The TRAP assay uses peroxyl radicals generated from an azo-compound, 2,2 -azobis(2amidinopropane)dihydrochloride (ABAP), and peroxidizable materials contained in plasma or other biological uids. After adding ABAP to the plasma, the oxidation of the oxidizable material is monitored by measuring the oxygen consumed dur-
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(mM Trolox/mM phenolics) for water and ethanol extracts, respectively. While green tea had 1.91 and 2.46 (mM Trolox/mM phenolics) of the water and ethanol extract, respectively. Results also show that one gram of peanut skin contains 90 to 125 mg total phenolics, the amount of which is comparable with grape skin and grape seeds. A follow up study by Yu et al. (2006) revealed that the water and ethanol extracts from peanut skin showed higher free radical scavenging activity as compared to Trolox and Vitamin C. The antioxidant and membrane effects of procyanidin dimers (dim) and trimers (tri) isolated from peanut skins were examined and compared with those of the procyanidins found in cocoa. Procyanidins of the B- and C- bonded types were isolated from cocoa whereas the A-type procyanidins were isolated from peanut skins. All types were evaluated in protecting phosphatidyl choline liposomes from Triton X-100-mediated disruption. The magnitude of the protection was strongest for the A-types than B and C-types (dim A1 > dim A2 > dim B and trim C > tri A (Verstraeten et al., 2005). A summary of AOC of peanuts and peanut by-products are listed in Table 13. The antioxidant activities of other nutshells like pistachio, walnut, and almond have also been determined. The vitamin C equivalent antioxidant capacity (VCEAC) of the ten com-
monly consumed nuts in the US showed walnuts (4581 11 M VCE/g), followed by pecans and peanuts as the top three commodities with high VCEAC values (Yang et al., 2005). Whereas the study of Wu et al. (2004a) revealed pecans, walnuts, and hazelnuts as the top three nuts with high total antioxidant capacity using the ORAC assay. Pistachio hull extract was effective in retarding oil deterioration at 60 C, with increasing activity at concentrations between 0.020.06%. The study also shows that pistachio hull extract was comparable to BHA and BHT (Goli et al., 2005). The corresponding scavenging activity of the superoxide radical of the almond seed, skin and shell cover was 75.5, 88.9, and 97.4% at 100 ppm, respectively, while the reduction of hydrogen peroxide concentration at 100 ppm was 59.8, 62.6, and 65.6 for seed, skin, and shell cover, respectively (Siriwardhana and Shahidi, 2002). Total antioxidant capacity of the ethanolic extracts of almond skin was also evaluated to be 13 times greater than that of the whole seed extract at the same concentration. Free radical scavenging activity of the brown skin was recorded to be 100% for DPPH and hydroxyl radical at 200 and 100 ppm, respectively (Siriwardhana and Shahidi, 2002). Two out of nine compounds isolated from almond skin showed very strong radical scavenging activity against DPPH (Sang et al., 2002).
Table 13
Antioxidant activities of peanuts, peanut butter, and peanut by-products. Antioxidant activity assay Oxygen radical absorbance capacity Oxygen radical absorbance capacity Linoleic acid oxidation DPPH radical scavenging Activity (conc. antioxidant)1 L-ORACFL , 2.73 mol Trolox/g H-ORACFL , 28.93 mol Trolox/g TEAC, 26.9 M Trolox equi/g (raw); 32.3 M Trolox equi/g (roasted) OS (Tween 20, 20 mg/ml), 200 h OS (Tween 80, 20 mg/ml), 350 h I (extract 1.5 mg/ml), 89.3% I (BHA 240 M), 92.6% I (catechin 8 M), 89.3% AA (9.6 mg), 96.196.8% OS (0.48%), 194 h OS (1.20%), 292 h OS (0.01% BHA), 143 h OS (control), 107 h IC50 (10 l), 111 ppm I (extract 300 mg/10ml), 48.83% A (extract 300 mg/10ml), 0.910 I (extract 100 mg/l), 92.6% I (extract 200 mg/l), 70.6% I (methanol, 1 g/l), 32.59% I (ethanol, 1g/l), 31.5% OS (extract 0.5 g equiv), 30 h OS (BHT 10 mg), 20 h L-ORACFL , 3.05 mol Trolox/g H-ORACFL , 31.27 mol Trolox/g Reference Wu et al., 2004
Sample (solvent) Peanut kernels (hexane/ dichloromethane; acetone/ water/acetic acid) Peanut kernel, Ga. Green (methanol) Peanut kernels, roasted, defatted (water) Peanut hulls (methanol)
Talcott et al., 2005b
Hwang et al., 2001 Yen and Duh, 1994
Peanut hulls (methanol) Peanut hulls (methanol)
Linoleic acid oxidation Soybean and peanut oil oxidation
Yen and Duh, 1995 Duh and Yen, 1997
Peanut hulls (methanol) Peanut hulls, irradiated (water) Peanut skin (ethanol) Peanut skin (methanol and ethanol) Peanut leaves (methanol) Peanut butter (hexane/ dichloromethane; acetone/ water/acetic acid)
1 AA,
Linoleic acid oxidation DPPH and reducing power DPPH and hydroxyl radical scavenging DPPH radical scavenging Oxidative stability index Oxygen radical absorbance capacity
Kuo et al., 1999 Lee et al., 2006 Yen et al., 2005 Nepote et al., 2002 Green and Sanders, 2004 Wu et al., 2004
Antioxidant activity (thiocyanate method), calculated as percentage of inhibition of peroxidation of linoleic acid; BHA, butylated hydroxyanisole; BHT, butylated hydroxytoluene; DDPH, ,-diphenyl--picrylhydrazyl; IC50 , Inhibitory concentration for 50% inhibition in the reduction of oxidation; L-ORACFL , Lipophilic ORAC assay with uorescein; H-ORACFL , Hydrophilic ORAC assay with uorescein; OS, Oxidative stability; I, percent inhibition; A, absorbance, for measuring reducing power; TEAC, Trolox equivalent antioxidant activity.
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EFFECTIVE PROCESSING METHODS TO INCREASE THE CONCENTRATION OF BIOACTIVE COMPOUNDS IN PEANUTS Many antioxidative phenolic compounds in plants are present as a covalently bound form with insoluble polymer. To obtain natural antioxidants from plants, it is necessary to nd an effective processing method to liberate them. Several methods such as heat treatment and far-infrared radiation have been studied to liberate and activate low molecular weight natural antioxidants (Jeong et al., 2004a; 2004b). Secondary sources of antioxidants like Maillard reaction products will also be discussed.
Heat Treatment Most of the phenolic compounds found in the outer layers of plants such as peel, shell, and hull are high in concentration to protect inner materials such as the seed. A number of phenolic acids, however, are covalently bound with insoluble polymers and other cell wall components such as arabinoxylans and proteins (Jeong et al., 2004a; Lee et al., 2006). Simple heat treatment can liberate the low molecular antioxidant compounds from the repeating subunits of high molecular weight polymers (Jeong et al., 2004a). However, an effective processing step for liberating antioxidant compounds from different plant species may not be the same. For example, simple heat treatment could not cleave covalently bound phenolic compounds from rice hulls (Lee et al., 2003) but in grape seeds, several low-molecular weight phenolic compounds were newly formed in heat treated grape seeds at 150 C for 40 min (Kim et al., 2006). Talcott et al. (2005b) also reported an increase in the level of p-coumaric acid was obtained when normal and high oleic acid peanuts were roasted at 175 C for 10 min. Free and bound forms of p-coumaric acid were obtained previously, and thus, the increase in concentration may be due to the release of free p-coumaric acids by heat-catalyzed hydrolytic reactions from its native esteried or bound forms. Simple heat treatment of peanut hulls at 150 C for 60 min also increased the total phenol contents, the radical scavenging activity, and the reducing power of the water extract from peanut hulls. The results showed that the phenol content increased from 72.9 to 90.3 M, the scavenging activity increased from 1.90% to 23.69% and the reducing power increased from 0.471 to 0.718, compared to the untreated controls (Lee et al., 2006). Polyphenols exist naturally in foods, serving as a primary source of antioxidants. During food processing and storage, degradation of natural antioxidants may occur. On the other hand, chemical reactions among food components may lead to the formation of secondary antioxidants. Important candidates for secondary food antioxidants are Maillard reaction products (Dittrich et al., 2003). During processing, cooking, or storage of foods, many complex physical and chemical changes in foods occur. The major compositional changes occurring are decreases in protein, amino acids, reducing sugars, water, and the formation of melanoidins. Many of these changes are due to Maillard
reaction. The rst stage of Maillard reaction is the formation of Amadori rearrangement products that may be further degraded upon storage or easily formed at high temperature conditions such as baking and roasting. Exposure to high temperature, however, may have some limitations on the production of Maillard reaction products (MRP) since based on a study using model solutions heated at 120 C for 10 to 30 min resulted in a decrease in radical scavenging activity of the MRP as time of exposure increases, possibly due to the degradation of the antioxidant MRP (Yilmaz and Toledo, 2005). Maillard reaction products formed in foods are reported to possess various types of antioxidant activity such as metal chelators and even pro-oxidant properties, and since then antioxidant activities of Maillard products have been extensively studied (Rajalakshmi and Narasimhan, 1996; Dittrich et al., 2003; Del Castillo et al., 2002; Mastrocola and Munari, 2000). The predominant antioxidants appeared to be the low molecular weight fraction of MRPs containing compounds such as reductones and maltol (Alfawaz et al., 1994). Dittrich et al. (2003) conrmed in their study that Maillard products, particularly those with amino reductone structure, have a strong potential to inhibit LDL oxidation. In addition to reducing sugars, other carbonyl compounds including lipid peroxidation products are also able to react with amino groups, producing brown macromolecular pigments with properties similar to those of melanoidins (Hidalgo et al., 1999). The antioxidative effect of the products formed by the reaction of oxidized lipids with amino acids and protein in a preheated model system was studied by Mastrocola and Munari (2000). They found out that the MRPs had the ability to retard peroxide formation and that the antioxidant activity developed with increased browning of the samples. The effect of roasting conditions on the AOC of various raw materials have been investigated and the results indicate a significant increase in total phenolic content, radical scavenging activity, reducing powers, and AOC as a function of roasting time and temperature (Jeong et al., 2004a; 2004b; Yanagimoto et al., 2002; Yen and Chuang, 2000; Lee et al., 2006). Long roasting times have been observed the result in increased oxidative stability in peanuts. In general, the longer the roasting time, the more extensive are the browning reactions, with resultant decreases in free amino acids and soluble carbohydrates (Chiou, 1992).
Irradiation Far-infrared (FIR) rays are dened as electromagnetic waves having a wavelength of longer than 4 m but shorter than microwaves ( > 0.1 cm). FIR rays are biologically active and transfer heat to the center of materials evenly, without degrading the constituent molecules of the surface (Lee et al., 2003). Reports show that FIR radiation liberates and activates lowmolecular-weighted natural antioxidants in plants. FIR may have the capability to cleave covalent bonds and liberate antioxidants such as avonoids, carotene, tannin, ascorbate, avoprotein, or polyphenols from repeating polymers (Lee et al., 2006).
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The antioxidant activities of peanut hull extracts were evaluated after FIR radiation for 5 to 60 min by Lee et al. (2006). They found that the total phenolic content, radical scavenging activity, and reducing power of the peanut hull extract increased as the time of exposure to FIR increased. Total phenolic content of water extracts of peanut hulls increased from 72.9 to 141.6 M, radical scavenging activity increased from 2.34% to 48.83%, and reducing power increased from 0.473 to 0.910, respectively, compared to the untreated controls (Lee et al., 2006). Harrison and Were (2006) used gamma irradiation to increase the phenolic content and antioxidant capacity of almond skin ethanolic extracts. Almond skin extracts irradiated at 4 kGy (trial 1) or 12.7 kGy (trial 2) exhibited higher phenolic content than the control (0 kGy) as well as greater scavenging ability compared to non-irradiated extract as determined by TEAC. In addition, phenolic extracts from 16.3 8 kGy irradiated skins had signicantly lower conjugated dienes values than the control and Trolox samples after 24 hours of storage. Peroxide values were likewise lower for irradiated extracts compared to the control.
FUNCTIONALITY EFFECTS OF PHYTOCHEMICALS FROM PEANUTS IN FOODS Antioxidants The antioxidative effect of extracts obtained from peanut skin and hulls on various products were studied (Nepote et al., 2004; Duh, and Yen, 1997; Rehman, 2003; OKeefe et al., 2003). Methanolic extracts of peanut hulls and BHA in soybean and peanut oils were compared after accelerated oxidation at 60 C. Samples containing the peanut hull extract showed lower peroxide values and acid values compared with the untreated controls. Moreover, the methanolic extract of peanut hulls was signicantly better than BHA-treated samples in reducing oxidation of both oils (Duh and Yen, 1997). Rehman (2003) conducted a study on the antioxidant activity of methanolic extract of peanut hulls for fried potato chips by adding the extracts to sunower oil at 800, 1200, and 1600 ppm, to be used for frying the potato chips. The extract exhibited very strong antioxidant activities, almost equal to synthetic antioxidants like BHA and BHT. They found acceptable ratings, lower values of free fatty acids, and peroxide values in potato chips treated with 1200 and 1600 ppm of extract stored at 45 C for six months, compared to the control samples. Color, avor, taste, and overall acceptability scores were signicantly higher for treated potato chips than the control, fried in oil without antioxidants, while no signicant difference was obtained between samples with peanut hull extract and samples treated with synthetic antioxidants. Methanol and ethanol extracts of peanut hulls were also evaluated in peanut pastes and cooked minced chicken by OKeefe et al. (2003) Peanut pastes were spiked with peanut hull extracts and stored at 40 C for 710 days, while cooked minced chicken was stored at 8 C for 4 days. Results show signicant AOC in the foods
investigated and that signicant differences in activity of peanut hull extracts exist between methanol and ethanol but the authors did not indicate what the differences are. The antioxidant activity of peanut skin extract in muscle foods was investigated by OKeefe and Wang (2006). The most significant reduction in oxidation (TBARS) was obtained in ground beef at 14 days of storage, and in ground beef samples with additional salt. No changes were observed in terms of color, although the extract added a slight red color to the sample. Sensory aroma and cooking loss were not affected by the addition of extract, as well as the microbial growth in fresh ground beef. Methanolic extracts from defatted and non-defatted peanut skins were evaluated in sunower oil stored at 60 C to induce oxidation (Nepote et al., 2000). Samples containing the two extracts individually had lower peroxide value in comparison with untreated controls. However, the antioxidant activity of both peanut skin extracts was lower than of the commercial BHT. Another study by Nepote et al. (2004b) involved honey roasted peanuts with 0.02% (w/w) peanut skin extract. Peroxide and TBARS increased across the storage time for all samples for 126 days, as did oxidized and cardboard avors. However, the roasted peanutty avor decreased. The addition of natural antioxidants from peanut skins did not affect the acceptance of the product by consumers. Peanut skin extract protected the peanuts against lipid oxidation, however, to a lesser extent compared with BHT. Antimicrobial Agents The effect of peanut tannins on the growth of A. parasiticus was investigated by Sanders and Mixon (1979) and Azaizeh et al. (1990) Seed coat tannin, methanol-extracted, water-soluble material from the peanut seed coats was tested in vitro, and the results showed that as the concentration of tannins increased to 7.5%, inhibition of fungal growth increased linearly to 88% (Sanders and Mixon, 1979). Similarly, when some of the methanol-extracted and water soluble tannin extracts were incorporated in yeast extract sucrose liquid medium, the growth of A. parasiticus was signicantly inhibited and the levels of aatoxin reduced (Azaizeh et al., 1990). The antimicrobial effect of phenolic compounds is probably related to the inhibition of bacterial enzymes, alterations in cell wall permeability, an increase in the hydrogen ion activity of the microbial environment, a reduction in the surface and/or interfacial tension, and chelation of essential minerals, particularly iron (OConnell and Fox, 2001). CONCLUSION Peanuts, peanut products, and its byproductsroots, leaves, hulls, skins, and kernels are a highly potential source of functional and benecial components that exhibit wide biological and practical applications that are of great interest to the food industry. There is substantial evidence that peanuts are packed
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with bioactive compounds, therefore, it would be worthwhile to further embark on experimentation and investigation on the functionality of this valuable agricultural crop.
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Critical Reviews in Food Science and Nutrition

Functional Components in Peanuts

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Functional Components in Peanuts

M.L.D.L. FRANCISCO AND A.V.A. RESURRECCION

Runner, dry roasted

FUNCTIONAL COMPONENTS IN PEANUTS

Isoflavanone derivatives Naringenin chalcone Naringenin derivatives

Leucopelargonidin (flavan-3, 4-diol)

Leucocyanidin (flavan-3, 4-diol)

M.L.D.L. FRANCISCO AND A.V.A. RESURRECCION

Nuclear structure of avonoids.

FUNCTIONAL COMPONENTS IN PEANUTS

Chemical structures of the avonoid family.

M.L.D.L. FRANCISCO AND A.V.A. RESURRECCION

Flavone 5 Apigenin Luteolin Substitution pattern 5, 7, 4 - OH 5, 7, 3, 4 - OH ,

Flavonol 8 Substitution pattern Quercetin 5, 7, 3, 4 - OH , Kaempferol 5, 7, 4 - OH Myricetin 5, 7, 3, 4, 5 - OH , 7 6 5

Eriodictyol Hesperitin Naringenin

Basic structures of avones and avonols.

Basic structure of avanone.

FUNCTIONAL COMPONENTS IN PEANUTS

Flavones Isoavones Flavanols

Eriodictyol, Hesperitin, Naringenin, Taxifolin Malvidin, Pelargonidin

M.L.D.L. FRANCISCO AND A.V.A. RESURRECCION

present in trace amounts not detected

FUNCTIONAL COMPONENTS IN PEANUTS

Epicatechin-(2 -O-7,4 -8)-ent-epicatechin

Epicatechin-(2 -O-7,4 -6)-ent-catechin D

Epicatechin-(2 -O-7,4 -6)-catechin

Epicatechin-(2 -O-7,4 -6)-ent-epicatechin

M.L.D.L. FRANCISCO AND A.V.A. RESURRECCION

FUNCTIONAL COMPONENTS IN PEANUTS

Epicatechin-(2 -O-7,4 -6)[epicatechin-(4 -8)]-catechin

Epicatechin-(2 -O-7,4 -8)epicatechin-(4 -8)-catechin-(4 -8)epicatechin

Oligomeric proanthocyanidins isolated from the water-soluble fraction of peanut skins.

M.L.D.L. FRANCISCO AND A.V.A. RESURRECCION

Raw material Peanut kernels

Nepote et al., 2004b Verstraeten et al., 2005

Lou et al., 1999

Lou et al., 2001

Lou et al., 2004

Yen et al., 2005 Karchesy and Hemingway, 1986

Lazarus et al., 1999 Yu et al., 2006

Peanut roots, leaves

Chen et al., 2002; Chung et al., 2003

FUNCTIONAL COMPONENTS IN PEANUTS

M.L.D.L. FRANCISCO AND A.V.A. RESURRECCION

FUNCTIONAL COMPONENTS IN PEANUTS

Structures of phenolic acids.

M.L.D.L. FRANCISCO AND A.V.A. RESURRECCION

FUNCTIONAL COMPONENTS IN PEANUTS

Structural formulae of 4-desmethylsterols.

M.L.D.L. FRANCISCO AND A.V.A. RESURRECCION

FUNCTIONAL COMPONENTS IN PEANUTS

Resveratrol isomers, 1, trans-resveratrol and 2, cis-resveratrol.

M.L.D.L. FRANCISCO AND A.V.A. RESURRECCION

FUNCTIONAL COMPONENTS IN PEANUTS

M.L.D.L. FRANCISCO AND A.V.A. RESURRECCION

X + H3 O+ XH + H2 O M(III) + AH AH+ + M(II)

FUNCTIONAL COMPONENTS IN PEANUTS

Biological relevance Yes Yes No No No Yes Yes Yes No

Lipophilic & Hydrophilic AOC +++ +++ +++

'Functional Components in Peanuts

'Functional Components in Peanuts