nutraceuticals and functional foods: whole versus processed foods

12
Review Nutraceuticals and functional foods: whole versus processed foods Fereidoon Shahidi Department of Biochemistry, Memorial University of Newfoundland, St. John’s, NL, Canada A1B 3X9 (e-mail: [email protected]) The importance of functional foods, nutraceuticals and other natural health products has been well recognized in connec- tion with health promotion, disease risk reduction and reduc- tion in health care costs. Whole foods such as whole grains as well as skins and processing by-products of foods often serve as a concentrated source of components with health beneficial effects. In most cases, processing negatively affects the bioac- tive components of functional foods and nutraceuticals. There- fore, minimally processed products better serve the health conscious consumers. Introduction It is well known that consumption of plant-based foods, including fruits, vegetables and whole grains, cereals and nuts as well as intake of marine foods and their long-chain u3 fatty acids is instrumental in health promotion and dis- ease risk reduction. Therefore, there has been a growing in- terest in research, development and commercialization of functional food ingredients, nutraceuticals and dietary sup- plements around the globe. In addition, it is believed that certain unprocessed or minimally processed foods might have superior health benefits compared to their processed counterparts; however, this assumption may not hold when considering certain phytochemicals like lycopene in tomato. This overview provides a cursory account of the topic of nutraceuticals and functional foods with emphasis on the use of whole foods versus their processed and minimally processed counterparts. Functional foods, nutraceuticals and natural health products Health Canada defines functional foods as products that resemble traditional foods but possess demonstrated physi- ological benefits. However, nutraceuticals are commodities derived from foods, but are used in the medicinal form of pills, capsules, potions and liquids and again render demon- strated physiological benefits. The latter group has now been amalgamated in a new category under natural health prod- ucts that promote health. Thus, natural health products not only include nutraceuticals, but encompass herbal and other natural products. In certain countries, functional foods and nutraceuticals are used interchangeably; however, in all cases, the main focus is on improving health and reducing disease risk through, mainly, prevention. The importance of this approach on health care cost is enormous as has been examined by Holub (2006). It has been stated that a minimum intake of selenium per day or u3 fatty acids from marine oils would reduce the burden on health care tremendously as nearly one third of all diseases are life-style related (Table 1). Therefore, the short-term goal of func- tional foods, nutraceuticals and dietary supplements is to improve the quality of life and enhance health status while its long-term goal is to increase lifespan while maintaining health. However, a major problem facing affluent societies as well as the rest of the world is reduced activity and lack of exercise by most of the public which may lead to obesity with the consequence of a host of diseases and the so-called ‘‘metabolic syndrome’’ (Moebus & Stang, 2007). Changing of eating habits and consumption of fast foods as well as environmental factors may adversely affect the health status and these concerns must be adequately addressed. Whole versus processed foods Traditionally, consumption of whole grains, cereals and nuts has been encouraged. The early reason for use of whole unprocessed products was their high fiber contents which rendered health benefits. However, more recent studies in our laboratories and elsewhere have demonstrated that the phytochemicals and phenolics/polyphenols in wheat, barley and beans are primarily located in the outermost layers and/ or skin and thus their removal would lead to products that are less beneficial to health. Liyana-Pathirana and Shahidi (2007a, 2007b) reported that among different milling fractions (bran, flour, shorts and feed flour) of two wheat 0924-2244/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.tifs.2008.08.004 Trends in Food Science & Technology 20 (2009) 376e387

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Page 1: Nutraceuticals and functional foods: Whole versus processed foods

Trends in Food Science & Technology 20 (2009) 376e387

Review

0924-2244/$ - see front matter � 2008 Elsevier Ltd. All rights reserved.doi:10.1016/j.tifs.2008.08.004

Nutraceuticals and

functional foods:

whole versus

processed foods

Fereidoon Shahidi

Department of Biochemistry, Memorial University of

Newfoundland, St. John’s, NL, Canada A1B 3X9

(e-mail: [email protected])

The importance of functional foods, nutraceuticals and other

natural health products has been well recognized in connec-

tion with health promotion, disease risk reduction and reduc-

tion in health care costs. Whole foods such as whole grains as

well as skins and processing by-products of foods often serve

as a concentrated source of components with health beneficial

effects. In most cases, processing negatively affects the bioac-

tive components of functional foods and nutraceuticals. There-

fore, minimally processed products better serve the health

conscious consumers.

IntroductionIt is well known that consumption of plant-based foods,

including fruits, vegetables and whole grains, cereals andnuts as well as intake of marine foods and their long-chainu3 fatty acids is instrumental in health promotion and dis-ease risk reduction. Therefore, there has been a growing in-terest in research, development and commercialization offunctional food ingredients, nutraceuticals and dietary sup-plements around the globe. In addition, it is believed thatcertain unprocessed or minimally processed foods mighthave superior health benefits compared to their processedcounterparts; however, this assumption may not holdwhen considering certain phytochemicals like lycopene intomato. This overview provides a cursory account of thetopic of nutraceuticals and functional foods with emphasison the use of whole foods versus their processed andminimally processed counterparts.

Functional foods, nutraceuticals and natural healthproducts

Health Canada defines functional foods as products thatresemble traditional foods but possess demonstrated physi-ological benefits. However, nutraceuticals are commoditiesderived from foods, but are used in the medicinal form ofpills, capsules, potions and liquids and again render demon-strated physiological benefits. The latter group has now beenamalgamated in a new category under natural health prod-ucts that promote health. Thus, natural health products notonly include nutraceuticals, but encompass herbal and othernatural products. In certain countries, functional foods andnutraceuticals are used interchangeably; however, in allcases, the main focus is on improving health and reducingdisease risk through, mainly, prevention. The importanceof this approach on health care cost is enormous as hasbeen examined by Holub (2006). It has been stated thata minimum intake of selenium per day or u3 fatty acidsfrom marine oils would reduce the burden on health caretremendously as nearly one third of all diseases are life-stylerelated (Table 1). Therefore, the short-term goal of func-tional foods, nutraceuticals and dietary supplements is toimprove the quality of life and enhance health status whileits long-term goal is to increase lifespan while maintaininghealth. However, a major problem facing affluent societiesas well as the rest of the world is reduced activity andlack of exercise by most of the public which may lead toobesity with the consequence of a host of diseases and theso-called ‘‘metabolic syndrome’’ (Moebus & Stang,2007). Changing of eating habits and consumption of fastfoods as well as environmental factors may adversely affectthe health status and these concerns must be adequatelyaddressed.

Whole versus processed foodsTraditionally, consumption of whole grains, cereals and

nuts has been encouraged. The early reason for use of wholeunprocessed products was their high fiber contents whichrendered health benefits. However, more recent studies inour laboratories and elsewhere have demonstrated that thephytochemicals and phenolics/polyphenols in wheat, barleyand beans are primarily located in the outermost layers and/or skin and thus their removal would lead to products thatare less beneficial to health. Liyana-Pathirana and Shahidi(2007a, 2007b) reported that among different millingfractions (bran, flour, shorts and feed flour) of two wheat

Page 2: Nutraceuticals and functional foods: Whole versus processed foods

Table 2. Total phenolic content and total antioxidant activity ofwheat, barley and bean fractions

Commodity Total phenoliccontenta

Total antioxidantactivityb

Soft winter wheatBran 66.9 55.8Flour 24.1 27.1

Barley (Falcon)Outermost layer 6.26 59.7Innermost layer 0.51 0.45

Red beanHull 223.5 46.7Whole bean 93.6 8.84

AlmondBrown skin 88 52.9Whole seed 8 4.21

Adapted from Liyana-Pathirana and Shahidi (2006a), Madhujithet al. (2006), Madhujith and Shahidi (2005), and Siriwardhanaand Shahidi (2002).

a Total phenolic content: mg ferulic acid eq./g crude extract forwheat; mg ferulic acid eq./g defatted material for barley; mg cate-chin eq./g extract for bean; and mg quercetin eq./g extract foralmond.

b Total antioxidant activity (measured as TEAC): mmol Trolox eq./L for wheat; mmol Trolox eq./g defatted material for barley; times aseffective as Trolox for bean and almond.

Table 1. Examples of life-style related diseases and health care costin Canada

Cardiovascular diseases(coronary heart disease, hypertension, etc.)

$13 billion/year

Type 2 diabetes $10 billion/yearCancers (colon, prostate, breast, etc.) $20 billion/yearInflammations (arthritis, bowel, etc.) $10 billion/yearDiet-related disorders $30 billion/yearOthers (osteoporosis, kidney disorders,psychiatric disorders, etc.)

Adapted from Holub (2006).

377F. Shahidi / Trends in Food Science & Technology 20 (2009) 376e387

cultivars Triticum turgidum L. var. drum and Triticum aesti-vum L., bran had the highest phenolic content while endo-sperm possessed the lowest, and this was also reflected infree radical and reactive oxygen species (ROS) scavengingcapacity, reducing power and iron (II) chelation capacityof products. The same trend was observed for oxygen radi-cal antioxidant capacity (ORAC; Fig. 1), photochemilumi-nescence, Rancimat, inhibition of low-density lipoprotein(LDL)-cholesterol oxidation, in which wheat bran extractshowed the highest antioxidant activity while endospermextract exhibited the lowest (Liyana-Pathirana & Shahidi,2007b). Various phenolic contents were found, as shownin Table 2. The major phenolic compounds, namely vanillic,p-coumaric, ferulic and sinapic acids were present at higherlevels in bran than in flour (Liyana-Pathirana & Shahidi,2007b). Another study on the same wheat cultivars revealedthat unprocessed whole grains possessed the highest antiox-idant capacity among grains and that the by-products alwaysexhibited higher antioxidant capacity compared to thepearled grains (Fig. 2; Liyana-Pathirana et al., 2006). Theconcentration of grain antioxidants is drastically reducedduring the refining process (Fig. 3), suggesting that phenoliccompounds are concentrated in the outermost layers. Incommercial soft and hard winter wheats Tr. aestivum L.,

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Fig. 1. Oxygen radical absorbance capacity (ORAC, mmol/g) of wholegrains and milling fractions of two wheat varieties, CWAD and CWRS.AeF represent whole grains, bran, flour, shorts, feed flour, and semo-lina, respectively. CWRS variety does not yield a semolina fraction

(adapted from Liyana-Pathirana & Shahidi, 2007b).

the whole grain contained a higher total phenolic content,total antioxidant activity, 1,1-diphenyl-2-picrylhydrazyl(DPPH) scavenging capacity, b-caroteneelinoleate bleach-ing capacity and inhibitory activity for cupric ion-inducedLDL-cholesterol oxidation than the flour (Liyana-Pathirana& Shahidi, 2006a). An overview of the antioxidant proper-ties of wheat and its fractions has recently appeared (Shahidi& Liyana-pathirana, 2008). Similar to wheat, barley whole

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Fig. 2. Total antioxidant capacity (mmol Trolox equivalents/g) ofpearled grain- and by-products of two wheat varieties CWAD (Cana-dian Western Amber Durum) and CWRS (Canadian Western RedSpring). A and B represent grain- and by-products of CWAD variety,respectively, while C and D represent the corresponding values for

CWRS variety (adapted from Liyana-Pathirana et al., 2006).

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Fig. 3. Total phenolic contents (mg ferulic acid equivalents/g) of pearledgrain- and by-products of two wheat varieties CWAD (Canadian West-ern Amber Durum) and CWRS (Canadian Western Red Spring). A andB represent grain- and by-products of CWAD variety, respectively,while C and D represent the corresponding values for CWRS variety

(adapted from Liyana-Pathirana et al., 2006).

Table 3. Major phenolic compounds identified in wheat, barleyand almond

Phenolics

Wheat Vanillic acid, p-coumaric acid, ferulic acid,sinapic acid, caffeic acid, tyrosine, hydroquinone,kaempferol, coumarin, flavone, anthocyanin

Barley Vanillic acid, caffeic acid, p-coumaric acid,ferulic acid, sinapic acid, syringic acid,protocatechuic acid, gallic acid, catechin,epicatechin

Almond Caffeic acid, ferulic acid, p-coumaric acid,sinapic acid, quercetin, isorhamnetin, quercitrin,kaempferol 3-O-rutinoside, isorhamnetin3-O-glucoside, and morin

Adapted from: Sharma, Anand, Sankhalkar, and Shetye (1998), Go-goi et al. (2001); Liyana-Pathirana and Shahidi (2007a, 2007b),Zhao et al. (2006), Madhujith et al. (2006), Wijeratne et al.(2006), and Sang et al. (2003).

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Fig. 4. Effects of processing on the distribution of free, esterified, andinsoluble-bound phenolic acids in canola meal. {A e hexane ex-tracted; B e extracted with 10% ammonia in methanol and hexane;C e extracted with 10% ammonia in methanol containing 5% water

and hexane (adapted from Naczk & Shahidi, 1989).}.

378 F. Shahidi / Trends in Food Science & Technology 20 (2009) 376e387

grain was also rich in antioxidant constituents. Phenolic ex-tracts from whole barley kernel possessed high antioxidant,antiradical and antiproliferative potentials (Madhujith &Shahidi, 2007). Among all barley fractions obtained duringpearling, the outermost layer yielded the highest phenoliccontent and exhibited the highest Trolox equivalent antiox-idant capacity (TEAC), DPPH and superoxide radicalscavenging capacities (Madhujith, Izydorczyk, & Shahidi,2006). Barley husks, extracted with ethyl acetate after hy-drolysis, showed an antioxidant activity comparable tosynthetic antioxidants such as butylated hydroxyanisole(BHA) and butylated hydroxytoluene (BHT; Garrote,Cruz, Dominguez, & Parajo, 2008). In beans, a higher levelof phenolics was detected in the hulls (6.7e270 mg/gextracts as catechin equivalents) than in whole seeds(4.9e93.6/g extracts; Madhujith & Shahidi, 2005). Majorphenolic acids present in bean hulls included vanillic,caffeic, p-coumaric, ferulic and sinapic acids. Flavonoidssuch as delphinidin, cyanidin and procyanidins B2, C1, C2and X were also identified in red, brown and black beanhull extracts (Madhujith, Amarowicz, & Shahidi, 2004).Therefore, dominance of phenolics with their beneficialeffects provides another main reason for use of whole grainsand seeds instead of starchy endosperms of cereals anddehulled products. Table 2 shows clearly that both totalphenolics and antioxidant potential associated with suchproducts are dominant in their ‘‘hulls’’ and or ‘‘husk/bran’’components. The phenolic compounds present in wheat,barley and almond are listed in Table 3.

It is noteworthy to pay attention to different forms inwhich phenolics/polyphenols occur in plant food products.Phenolics occur in the free, soluble ester and insolublebound forms. Therefore, it is essential that the insoluble-bound phenolics be released in such determinations as theseproducts are hydrolyzed in the gastrointestinal tract or co-lon and would then render their beneficial effects. Most

phytochemicals in fruits and vegetables are in the free orsoluble conjugate forms of glucosides. However, phenoliccompounds in grains and oilseeds exist mostly in the insol-uble bound form associated with cell wall polyssacharides(Naczk & Shahidi, 1989). It has been shown that colonicfermentation of such material, which survives gastrointesti-nal digestion, may lead to the release of some of the boundphenolics and hence exert their unique health benefits in thecolon after absorption. Therefore, to relate any in vivo stud-ies or certain in vitro studies, it is essential to correctly andappropriately assess their concentration. Naczk and Shahidi(1989) reported that insoluble-bound phenolics contributedsome 6e20% to the total phenolics in canola meal (Fig. 4).More recent studies in our laboratories showed that bothwheat and barley had large proportions of bound phenolics,which are the major components responsible for the antiox-idant activity of these products (Figs. 5 and 6). These

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Fig. 5. Free, esterified and bound phenolic contents (mg ferulic acidequivalents/g) of whole grains, flour and bran of a hard wheat variety

(adapted from Liyana-Pathirana & Shahidi, 2006b).

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Fig. 7. Total phenolic contents (mmol/g) in whole grains of corn, wheat,oats and rice (adapted from Adom & Liu, 2002).

379F. Shahidi / Trends in Food Science & Technology 20 (2009) 376e387

findings lend further support to the findings of Adom andLiu (2002) (Fig. 7) and Nordkvist et al. (2006).

In associated studies, we found that nuts such as almondand hazelnut hulls and by-products were important sourcesof phenolics and compounds with antioxidant activity. Thebrown skin extract of almond showed a TEAC that was 13times greater than that of the whole seed extract. The freeradical scavenging activity of brown skin extract also ex-ceeded that of the whole seed (Siriwardhana & Shahidi,2002). In a cooked comminuted pork model system, almondbrown skin extract inhibited the formation of thiobarbituricacid reactive substances (TBARS), hexanal and totalvolatiles more effectively than did the whole seed extract(Wijeratne, Amarowicz, & Shahidi, 2006). The brownskin of almond contained higher concentrations of caffeic,ferulic, p-coumaric and snapic acids, which are the majorphenolic acids in almond, than whole seed (Wijeratneet al., 2006). Quercetin, isorhamnetin, quercitrin, kaemp-ferol 3-O-rutinoside, isorhamnetin 3-O-glucoside, andmorin were also identified in both almond skin and shell

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Fig. 6. Total antioxidant capacity (mmol Trolox equivalents/g) of free,esterified and bound phenolic fractions of whole grains, flour andbran of a hard wheat variety (adapted from Liyana-Pathirana & Shahidi,

2006b).

extracts (Wijeratne, Abou-Zaid, & Shahidi, 2005). Similarto almond, extracts of hazelnut skin also showed superiorantioxidant efficacy and higher phenol content comparedto kernel extracts (Shahidi, Alasalvar, & Liyana-Pathirana,2007). Other research on pistachio (Vahabzadeh, Mehra-nian, & Mofarrah, 2004) and peanuts (Van Ha, Pokorny,& Sakurai, 2007) also reported high antioxidant activityof their by-products. Therefore, consumption of wholefoods and potential of by-products from agricultural bio-products may serve as important sources of raw materialthat could be used as functional food ingredients andnutraceuticals.

Processing effects on phytochemicalsProcessing of foods and food ingredients often exerts

a major effect on their constituents, including bioactives.Thus, processing of soybeans in the production of proteinconcentrates and isolates may lead to a substantial decreasein their isoflavone content. Similarly products such as tofumay contain only a fraction of the isoflavones originallypresent in soybean (Jackson et al., 2002). In addition, fer-mentation processes such as those used in the productionof fermented soybean foods may lead to the formation offree isoflavones that may render activities different fromthose of their original glycosylated forms (Chiou & Cheng,2001). Thus, processing may have a negative effect on thecontent of certain bioactives such as isoflavones in food andnutraceutical products.

In processing of tomatoes, however, and in the produc-tion of ketchup, tomato paste and other canned or driedproducts, there may be a positive effect on their lycopeneactivity. Lycopene occurs in all-trans form in fresh toma-toes; however, processing may lead to the formation ofa cis configured double bond in the products. The cis config-ured product is more bioavailable and hence this exampledemonstrates a positive effect of processing on bioactivesin tomato, as reviewed by Rao and Ali (2007).

Treatment of canola/rapeseed or sesame seeds by roast-ing has also been shown to render a positive effect on thestability of polyunsaturated fatty acids (PUFA) in the

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380 F. Shahidi / Trends in Food Science & Technology 20 (2009) 376e387

products and retention of their activity because of the for-mation of Maillard reaction products that possess antioxi-dant potential (Jeong et al., 2004; Shahidi, Amarowicz,Abou-Gharbia, Shehata, & Adel, 1997). Furthermore, pro-cessing may lead to the formation of conjugated fatty acids.This is similar to the rumen fermentation that leads to theformation of conjugated linoleic acid with beneficial healtheffects (Buccioni et al., 2006) and provides an examplewhere a trans fatty acid may render a desirable effect.

Other processed and fermented productsFermentation is generally referred to the chemical con-

version of carbohydrates into ethanol or acids driven bymicroorganisms. Fermentation process of food materialcan alter the chemical nature and sensory quality of thefood as well as the efficacy of some bioactive constituents.Among the most popular fermented food products arealcoholic beverages such as beer and wine, and variousvinegars. Other fermented food includes yogurt, pickles,soy sauce and a variety of fermented bean products, amongothers. On the other hand, tea processing, in the productionof black and oolong tea, which involves oxidation of tealeaves, is also referred to as fermentation in the tea industry,although no real fermentation occurs since this process isnot driven by microorganisms. Black tea, a fermented prod-uct from tea leaves, is the most widely consumed non-alcoholic beverage. Theaflavins and thearubigins are thegroups of polyphenols formed during fermentation thataccount for the quality characteristics of black tea such ascolor, mouthfeel, and extent of tea cream formation (Lewis,Davis, Cai, Wilkins, & Pennington, 1998). Catechins andtheir esters, the major phenolics in tea leaves and substratefor fermentation, including catechin, epicatechin (EC),epicatechin gallate (ECG), epigallocatechin (EGC), andepigallocathin gallate (EGCG), are oxidized by polyphenoloxidase and peroxidase to form theaflavins and thearubiginsduring fermentation (Lakshminarayanan & Ramaswamy,1978). Simultaneously, volatile aroma aglycones of pheno-lic glycosides are released by various glycosidases and pos-sibly contribute to the typical flavor of black tea (Halder &Bhaduri, 1998). Numerous studies have indicated that blacktea possesses antioxidant, antimicrobial, anti-inflammatory,and anticancer activities, among others (Chou, Lin, &Chung, 1999; Huang et al., 2006; Pasha & Reddy, 2005).More recently, improvement of black tea in terms of itsnutritive and therapeutic values by yeast fermentation hasbeen proposed (Pasha & Reddy, 2005).

There has been a universal argument concerning the im-pact of alcohol consumption on our body. While the harmfuleffects of alcohol have been acknowledged, favorable im-pacts by moderate consumption of alcoholic beverageshave also been proposed. Moderate consumption of redwine has been associated with decreased risk of developingcoronary heart disease (Klatsky, Armstrong, & Friedman,1992; Maclure, 1993; Moore & Pearson, 1986; Verschuren,1993). Alcohol is believed to increase serum HDL-

cholesterol concentration and therefore decrease its accu-mulation in blood vessels (Hulley & Gordon, 1981; Thorn-ton, Symes, & Heaton, 1983). In addition, it positivelyaffects platelet aggregation and clotting/fibrinolysis (Kluft,Veestra, Schaafsma, & Pikaar, 1990; Renaud, Beswick, Feh-ily, Sharp, & Elwood, 1992; Ridker, Vaugham, Stampfer,Glynn, & Hennekens, 1994), and hence reduces the risk ofcoronary heart disease. However, components in wine otherthan alcohol are major contributors to its protective roleagainst cardiovascular diseases. It has been demonstratedthat the health benefits of red wine against many diseasesare mainly attributed to the occurrence of phenoliccompounds with antioxidants activity. Red wine is rich inpolyphenols such as catechins, stilbenes, anthocyanins,proathocyanidins and other phenolics, which determinethe color, bitterness, astringency, chemical stability andhealth effect of the wine (Dell’Agli, Busciala, & Bosisio,2004). Phenolic compounds in red wine possess many bio-activities including antioxidant/antiradical activity, modula-tion of lipid metabolism, vasorelaxation/blood pressuremodulation, inhibition of smooth muscle cell migrationand proliferation, and inhibition of platelet aggregation,etc., and therefore render a protective effect against athero-genesis (Dell’Agli et al., 2004). Resveratrol, a naturally oc-curring polyphenol mostly found in grapes and productsthereof, is thought to possess chemopreventive properties.Its cancer preventive effectiveness has been reported bothin vitro and in vivo (Jang et al., 1997). Resveratrol is presentin white, rose and red wines, but occurs at the highest levelin red wines (Pervaiz, 2003). As most of these polyphenolsare present in the skin and seeds of grapes, consumption ofextracts of grape seeds and skin has led to the production ofa variety of natural health products that are commerciallyavailable and their beneficial health effects often exceedthose of red wine. However, others argue that polyphenolsin wine are present in the soluble state and hence aremore biologically available, whereas in the source materialsthey are strongly bonded and may not be readily absorbed(Alonso, Castro, Rodriguez, Guillen, & Barroso, 2004).Beer, another popular alcoholic beverage, has also beendemonstrated to show positive impacts on health. Beer isthought to make a substantial contribution to the diet interms of antioxidants, mainly phenolics, certain B vitamins,minerals such as selenium, and perhaps soluble fiber(Bamforth, 2002). It also serves as a good source of folicacid, leading to decreased homocysteine content in theblood (Mayer, Simon, & Roslova, 2001). Beer also containsan array of health-promoting isoflavonoids (phytoestrogens;Lapcik, Hill, Hampl, Wahala, & Adlercreutz, 1998). How-ever, despite all the health benefits of alcoholic beverages,it should be noted that excessive alcohol consumption hasclear detrimental effects causing mortality.

Further fermentation of ethanol yields acetic acid, thekey ingredient of vinegar. Historically, vinegar has beenused as a preservative and condiment, but more recentlyit has also been considered as a potential functional food

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381F. Shahidi / Trends in Food Science & Technology 20 (2009) 376e387

ingredient owing to the presence of phytochemicals. Vine-gars are generally produced from various types of agricul-tural raw materials containing sugar or starch, such asmalt, cider, fruits, and in some Mediterranean countrieswine as raw material (Adams, 1985). The phytochemicalspresent in the final products depend on the source material,which dictates their type, quantity and quality. Whilemaintaining a good portion of the phytochemicals presentin the source materials, bacterial fermentation impartsnovel components to vinegars (Shahidi, 2007). In additionto acetic acid and other organic acids, vinegars are rich inpolysaccharides, protein, and phenolic compounds (Xuet al., 2007). Various types of vinegars have proven tobe advantageous for human health promotion. They havebeen found effective in promoting recovery from exhaus-tion (Fushimi et al., 2001), improving digestion (Liljeberg& Bjorck, 1998), regulating blood glucose level (Ebihara& Nakajima, 1988), stimulating appetite and promotingcalcium absorption (Kishi et al., 1999), as well as prevent-ing hypertension (Kondo, Tayama, Tsukamoto, Ikeda, &Yamori, 2001; Sugiyama, Saitoh, Takahata, Satoh, &Hashimoto, 2003).

Soybeans are also used as the substrate for fermenta-tion, especially in Asian countries. Fermented soybeanproducts include miso (in Japan), sufu (in China), and tem-peh (in Indonesia; Chang, Ding, Tai, & Wu, 2007). Duringthe fermentation of soybean by fungi, isoflavone glyco-sides are hydrolyzed to release free isoflavone aglyconeby fungal b-glucosidase (Chiou & Cheng, 2001), andtherefore render health benefits to fermented soybean prod-ucts. Isoflavones are believed to play an important role inpreventing certain hormone-dependent and other diseasessuch as cardiovascular diseases and various cancers(Messina, 2000).

Algal nutraceuticals and u3 fatty acids in marine andother products

Edible marine algae, sometimes referred to as seaweeds,have attracted special interest as good sources of nutrientsincluding protein (Galland-Irmouli et al., 1999), long-chainpolyunsaturated fatty acids (PUFA; Ginzberg, Cohen, Sod-Moriah, Shany, Rosenshtrauch, & Arad, 2000; Kaneda &Andom, 1971), dietary fibers (Han, Lee, & Sung, 1999; Ru-perez & Saura-Calixto, 2001), vitamins (Indergaard & Min-saas, 1991; Le Tutour et al., 1998; Rodriguez-Bernaldo deQuiros, Castro de Ron, Lopez-Hernandez, & Lage-Yusty,2004), and minerals (Indergaard & Minsaas, 1991; van Net-ten, Hoption Cann, Morley, & van Netten, 2000). More re-cently, many researches have focused on marine algae andtheir constituents as nutraceuticals and functional foods fortheir potential health promotion mostly attributed to theiru3 fatty acids, antioxidants, and other bioactives. Theseand other bioactive substances present in products arefound effective in reducing the risk of various diet andage related chronic diseases such as cardiovascular disease(CVD) and cancers (Yuan, 2008).

Although the majority of marine algae have very lowlipid contents, ranging from 0.3% in U. lactuca to 7.2%in Caulerpa lentillifera (Yuan, 2008), algal lipids are richin PUFA such as C20:5u3 (eicosapentaenoic acid, EPA)and C22:6u3 (docosahexaenoic acid, DHA). The propor-tions of EPA and DHA in oils from Skeletonema costatumand Crypthecodinium cohnii were 41% and 37%, respec-tively (Sijtsma & de Swaaf, 2004).

While marine algae are primarily used for production ofsingle-cell oil rich in DHA, and other u3 PUFA (Kyle,2001; Zeller, Barclay, & Abril, 2001), the leftover materialafter processing contains a variety of antioxidative sub-stances that can potentially be utilized as a source of naturalantioxidants. A number of studies evaluating the antioxi-dant activity of marine algae have revealed high antioxidantefficacy of their extracts which is equal to or better thanthat of commercial antioxidants such as butylated hydrox-yanisole (BHA), butylated hydroxytoluene (BHT) and a-to-copherol, and have suggested the use of algal antioxidantsin food formulations (Athukorala, Lee, Choonbok, et al.,2003b; Athukorala, Lee, Shahidi, et al., 2003a; Athukoralaet al., 2005; Park, Shahidi, & Jeon, 2004). Antioxidant ac-tivity of marine algae may arise from pigments such aschlorophylls and carotenoids, vitamins and vitamin precur-sors including a-tocopherol, b-carotene, niacin, thiaminand ascorbic acid, phenolics such as polyphenolics and hy-droquinones and flavonoids, phospholipids particularlyphosphatidylcholine, terpenoids, peptides, and other antiox-idative substances, which directly or indirectly contribute tothe inhibition or suppression of oxidation processes.Among them, phenolics are claimed to be the major activeconstituents that account for the antioxidant potential ofmarine algae. The total phenolic content has been demon-strated to correlate well with the antioxidant potency ofcrude extracts of algae (Duan, Zhang, Li, & Wang, 2006;Siriwardhana, Lee, Kim, Ha, & Jeon, 2003). The phenolicprofile in marine algae varies with the species. Major phe-nolic compounds identified in algal sources include cate-chin in Chlorophyceae Acetabularia ryukyuensis andTydemaniz expeditionis, and most Phaeophyceae and Rho-dophyceae species, epigallocatechin in Halimeda macro-loba and H. opuntia; catechol in Caulerpa serrulata,glycoside rutin in G. elegans and G. texorii, glycoside hes-peridin in most Japanese Chlorophyceae, Pheophyceae, andRhodophyceae species, phlorotannins in Pheophyceae, andbomophenols in Rhodophyceae algae (Chkhikvishvili &Ramazanov, 2000; Takamatsu et al., 2003; Yuan, 2008),among others. Polysaccharides, not only function as dietaryfiber, but they also contribute to the antioxidant activity ofmarine algae. Antioxidant activity of algal polysaccharideshas been reported (Ruperez, Ahrazem, & Leal, 2002; Xue,Tao, & Ao, 2001; Zhang et al., 2003). Polysaccharides inmarine algae are generally in the form of alginates, fucans,lamininarans, cellulose and sulfated galactans such as agarand carrageenans, some of which are characteristicallypresent in marine algae while not found in land plants

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and are believed to possess specific functions (Ruperezet al., 2002). Sulfated polysaccharides are by-products inthe preparation of alginates from edible brown seaweedsand could be used as a good source of natural antioxidantswith potential application in the food industry (Ruperezet al., 2002). Oligosaccharides, the hydrolysis products ofpolysaccharides, also exhibit antioxidant activity. Agar oli-gosaccharides produced by marine bacterial agarase areeffective in inhibiting lipid oxidation and scavenging super-oxide anion and hydroxyl radicals (Wang, Jiang, Mou, &Guan, 2004). Other bioactives in marine algae that mayrender health beneficial effects include sterols (Idler & At-kinson, 1976), vitamin C (McDermid & Stuercke, 2003),tocopherols (Ortiz et al., 2006), carotenoids (Morgan,Wright, & Simpson, 1980), and B vitamins (Watanabe etal., 1999), among others.

Omega-3 oils, although originating from marine algae,are predominant in marine fish and mammals. Lipidsfrom the body of fatty fish such as mackerel and herring,the liver of white lean fish such as cod and halibut, andthe blubber of marine mammals such as seals and whalesare rich in long-chain u3 fatty acids. The u3 PUFA includethe essential fatty acid a-linolenic acid (C18:3 u3, ALA)and its long-chain metabolites through elongation and desa-turation, EPA, DPA (docosapentaenoic acid, C22:5 u3) andDHA. ALA is abundant from certain plant sources such asflaxseed and to a lesser extent perilla, soybean and canolaas well as walnuts (Shahidi, 2008). EPA and DHA aremainly derived from marine fish (Table 4), shellfish andalgae, while DPA is present in significant amounts onlyin oils from marine mammals such as seal blubber oil.The distribution pattern of fatty acids in triacylglycerols(TAG) differs in fish and marine mammal oils, whichgreatly influence the metabolism, deposition, and potentialhealth benefits (Shahidi, 1998). Long-chain u3 PUFA aremainly located in the sn-2 position of TAG in fish oils,whereas in marine mammal lipids they are predominantlyin the sn-1 and sn-3 positions. More recently, u3 oilsfrom by-products of fishery and fish processing industrieshave attracted special attention. By-products from fish pro-cessing including heads, frames, skin and viscera containconsiderable amounts of u3 PUFA-rich oil and utilizationof marine by-products as good sources of u3 oil are of

Table 4. EPA and DHA content (% of total fatty acids) in variousfish

Fish EPA (%) DHA (%)

Sardine 3 9e3Pacific anchovy 18 11Mackerel 8 8Capelin 9 3Herring 3e5 2e3Freshwater fish 5e13 1e5

Adapted from: Newton and Snyder (1997).

great interest (Venugopal & Shahidi, 1998; Zhong, Madhu-jith, Mafouz, & Shahidi, 2007).

Omega-3 oils, which have proven to play an importantrole in health promotion and prevention/treatment of a num-ber of chronic diseases, may be included in foods such asbakery products, pastas, dairy products, spreads and juice,and may also be used as dietary supplements in liquid orcapsule forms (Shahidi, 2008). In the area of food applica-tion of u3 oils or even as supplement, microencapsulationtechniques have been used to protect the oils from oxida-tion and off-flavor development. Ocean Nutrition Canadahas been a leading company in offering a stable productto the market, prepared by a coacervation process. Themicrocapsules are released in the gastrointestinal tract afterconsumption; hence no adverse effect is noted in the prod-ucts in terms of flavor perception.

Effect of food bioactives on healthThe importance of dietary factors on health status has

been recognized since antiquity. More recently, epidemio-logical and clinical studies have provided fundamentalapproaches for unraveling the chemical and physiologicalmechanisms of the effects of food bioactives on humanhealth. Meanwhile, technologies have been developedfor isolation/purification and identification/characterizationof biologically active components in foods, which are re-sponsible for the efficacy of the food in health promotionand disease prevention. The health benefits of functionalfoods and nutraceuticals are generally focused on severalareas, including prevention and treatment of cardiovascu-lar diseases, various types of cancer, diabetes and inflam-mations, and enhancement of immune response as well asretardation of aging process and extension of a healthylifespan. A variety of bioactive substances from plant oranimal origins have been investigated for their potentialfunctional and physiological properties. Phytochemicals,mainly phenolic compounds, constituent an importantclass of food-derived bioactives acting as antioxidants aswell as by a variety of other mechanisms related to celldifferentiation, deactivation of pro-carcinogenes, mainte-nance of DNA repair, inhibition of N-nitrosamine forma-tion, and change of estrogen metabolism, among others(Shahidi, 2004). Some peptides with hormone-like activi-ties play an important role in metabolism regulation andmodulation. In addition, u3 oils from marine sourcesare known to be cardioprotective and neuroprotective,and are effective in treating a number of diseases andhealth conditions.

Phenolics are among phytochemicals that may rendertheir effects via antioxidant activity and relief from oxida-tive stress and its consequences, among others (Shahidi,2004). The major mechanisms for the antioxidant effectof phenolic compounds in functional foods include freeradical scavenging and metal chelation activities. Forma-tion of free radicals and other ROS such as superoxide, hy-droxyl radical, peroxyl radical, and alkoxy radical, as well

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as hydrogen and other peroxides is one of the main reasonsfor aging process and occurrence of a number of degener-ative diseases, including inflammation, infection, diabetes,cancer, atherosclerosis, shock, radioactive damage, parkin-sonism and ischemia. Simple phenols and their derivativessuch as phenolic acids, flavonoids, stilbenes, tannins, li-gnans, and lignin, can scavenge free radicals and quenchROS and therefore provide effective means for preventingand treating these and other free radical-mediated diseases.Phenolic compounds can prevent oxidation of LDL-choles-terol to an atherogenic form and hence exert a protective ef-fect against heart disease. Anti-platelet aggregation andvasodilatory properties of phenolics also contribute to theircardioprotective role. Phenolic compounds can inhibitgrowth of existing cancer cells by varied mechanisms andhence useful in preventing/treating a number of cancers (In-dap, Radhika, Motiwale, & Rao, 2006; McCann et al.,2007; Yi et al., 2005). Phenolics may also serve as UV fil-ters and signaling agents. In addition to phenolics, otherphytochemicals such as phytates, carotenoids, terpenoids,saponins, enzyme inhibitors, etc. also contribute to thehealth effects of foods usually in a cooperative andsynergistic manner. Generally, the effects rendered bynutraceutical and functional foods are due to a cocktail ofphytochemicals present. A partial summary of phytochem-icals present in foods and their bioactivities is given inTable 5.

As noted earlier, omega-3 oils, which are rich in long-chain u3 PUFA, are another important group of bioactivesoriginally mainly from marine sources. Recognition ofhealth benefits from consumption of u3-rich seafoods isone of the most promising developments in human nutri-tion and disease prevention research in the past three de-cades. Long-chain u3 PUFA are of great interest to foodscientists, biochemists, nutritionists, pharmacists and thegeneral public because of their effectiveness in preventionand treatment of coronary heart disease (Schmidt, Skou,

Table 5. Major phytochemicals in foods and their bioactivities

Phytochemicals Food sources

FlavonoidsFlavones Celery, parsley

Flavanones Citrus fruits

Flavonols Onions, tea, green beans, tomatoesFlavan-3-ols Tea, cocoa, apples, berries, certain beansAnthocyanidins Blueberries, blackcurrants, strawberriesIsoflavones SoybeansPhenolic acids Coffee, cereal bran, fruitsLignans Linseed, fruits and vegetablesStilbenes Grapes, peanutsPhytosterols WheatCarotenoids Tomatoes, carrots, bell peppers

Adapted from: Gry et al. (2007).

Christensen, & Dyerberg, 2000), hypertension (Howe,1997), diabetes (Krishna Mohan & Das, 2001), arthritisand other inflammations (Babcock, Helton, & Espat,2000), autoimmune disorders (Kelly, 2001) and cancers(Akihisa et al., 2004; Rose & Connolly, 1999) and areessential for maintenance and development of normalgrowth, especially for the brain and retina (Anderson, Con-nor, & Corliss, 1990). There has been growing evidenceshowing that regular consumption of fish oils containingu3 PUFA can lower the rate of incidence and death fromcardiovascular disease including ischemic heart disease,nonischemic myocardial heart disease, and hypertension(Shahidi, 2008). While the exact biochemical mechanismfor cardioprotective effect of u3 fatty acids is unknown, hy-potheses state that this may be attributed collectively to theirantiarrhythmic, antiatherogenic and anti-thrombotic activi-ties. Long-chain PUFA can lower serum triacylglycerols(Howell, Day, Ellis, & Baynes, 1998), increase membranefluidity and reduce thrombosis by conversion to eicosanoids(Kinsella, 1986). They provide specific physiological func-tions against thrombosis, cholesterol build-up and allergies(Kimoto, Endo, & Fujimoto, 1994).

Omega-3 fatty acids have been shown to have anti-carci-nogenic effects. Epidemiological studies indicated that theymight be protective against prostate cancer (Bhagavathi,Narayanan, Narayanan, Simi, & Reddy, 2003), colon can-cer (Reddy, 1994), and breast cancer (Holmes et al.,2003). Cross-cultural studies among the Inuit and non-Inuitpeople of Canada, Alaska and Greenland from 1969 to1988 showed a significantly lower incidence rate of prostatecancer among the Inuit populations than the non-Inuit pop-ulations (Bhagavathi et al., 2003). It is suggested that die-tary differences between the two populations, inparticular the traditional seafood diet of Inuit people thatare exceptionally rich in u3 fatty acids may account forthe reduced risk of prostate cancer (Bhagavathi et al.,2003). Anti-tumour effect of u3 fatty acids during the

Bioactivities

Antioxidant, antiproliferative, anti-hypertensive, anti-carcinogenicAnti-thrombotic, cell cycle arrest, induction of phase-2 enzymesInhibition of phase-1 enzymes, inhibition of LDL-oxidation,improvement of vascular tone

Anti-inflammatoryEstrogenicAntioxidant, cardioprotective, lifespan extensionCholesterol loweringAntioxidant, anti-inflammatory, anti-carcinogenic

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initiation and post-initiation stages of colon carcinoma hasalso been reported (Reddy, 1994). Studies using in vitro andanimal models also revealed that u3 fatty acids are able tomodulate second messenger systems and cell signaling cas-cades in cancerous breast cells and thus inhibiting breast tu-mor development (Kort, Weijma, Vergroesen, &Westbroek, 1987; Rose, Connolly, Rayburn, & Coleman,1995).

Omega-3 fatty acids exhibit anti-inflammatory activity.In vitro and human studies suggest that u3 fatty acids serveas effective therapeutic agents for the management of in-flammatory arthritic diseases, possibly through modulationof inflammatory cytokine production (Shahidi, 2008). Inaddition, u3 fatty acids play an important role in mentalhealth and neural function such as in visual development,depression and schizophrenia (Shahidi, 2008).

ConclusionsFood bioactives are often effective in promoting health

and leading to disease risk reduction. Whole foods oftencarry the whole complement of bioactives, particularlythose from plant sources, and their skin/hulls is rich inphytochemicals which are often lost during many of thecommonly practiced process and food preparations. There-fore, minimum processing and saturation of phytochemical-rich portions is recommended. In addition, nutriceuticalsfrom marine resources serve as a rich source of health-pro-moting components. Amongst these, u3 fatty acids haveproven to be most effective in alleviating a number ofhealth conditions, including lowering triacylglycerols andreducing the incidences of arrhythmia; hence their inclu-sion into foods and specialty products has been in the fore-front of research and development. Growth in the use ofwhole and health-promoting food is expected to continueto increase.

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