Analysis and Antioxidant Capacity of Anthocyanin Part I

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Critical Reviews in Analytical Chemistry

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Analysis and Antioxidant Capacity of Anthocyanin Pigments. Part I: General Considerations Concerning Polyphenols and Flavonoids
Julia Martn Bueno , Fernando Ramos-Escudero , Purificacin Sez-Plaza , Ana Mara Muoz , Mara Jos Navas & Agustin G. Asuero
a c b b a b b
Department of Analytical Chemistry , Higher Polytechnic School, The University of Seville , Seville , Spain
b c
Department of Analytical Chemistry , The University of Seville , Seville , Spain
Centro de Bioqumica y Nutricin, Facultad de Medicina, Universidad San Martin de Porres , Lima , Per Published online: 23 Mar 2012.
To cite this article: Julia Martn Bueno , Fernando Ramos-Escudero , Purificacin Sez-Plaza , Ana Mara Muoz , Mara Jos Navas & Agustin G. Asuero (2012) Analysis and Antioxidant Capacity of Anthocyanin Pigments. Part I: General Considerations Concerning Polyphenols and Flavonoids, Critical Reviews in Analytical Chemistry, 42:2, 102-125, DOI: 10.1080/10408347.2011.632312 To link to this article: http://dx.doi.org/10.1080/10408347.2011.632312
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Critical Reviews in Analytical Chemistry, 42:102125, 2012 Copyright c Taylor and Francis Group, LLC ISSN: 1040-8347 print / 1547-6510 online DOI: 10.1080/10408347.2011.632312
Analysis and Antioxidant Capacity of Anthocyanin Pigments. Part I: General Considerations Concerning Polyphenols and Flavonoids
Julia Mart n Bueno,1 Fernando Ramos-Escudero,2 Puricaci on S aez-Plaza,2 3 Mar Ana Mar a Munoz, a Jos e Navas,2 and Agustin G. Asuero2
1 2
Department of Analytical Chemistry, Higher Polytechnic School, The University of Seville, Seville, Spain Department of Analytical Chemistry, The University of Seville, Seville, Spain 3 Centro de Bioqu mica y Nutrici on, Facultad de Medicina, Universidad San Martin de Porres, Lima, Per u
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Many epidemiological studies have shown the benets of a diet rich in fruit and vegetables to human health and for the prevention of various diseases associated with oxidative stress, such as cancer and cardiovascular diseases. Anthocyanins, natural pigments belonging to the group of avonoids, are common components of the human diet, as they are present in many foods, fruits, and vegetables, especially in berries. Their use as colorants has considerable interest because of their coloring properties. Moreover, they have an antioxidant activity. Various adverse effects on health have frequently been attributed to synthetic antioxidants. For these reasons, currently, there is a trend towards relying on antioxidants derived from natural products. The efcacy of anthocyanins as antioxidants depends, to a large extent, upon their chemical structure. They act as antioxidants both in the foodstuffs in which they are found and in the organism after intake of these foods. With this in mind, an introduction to polyphenols is made with emphasis on their role as secondary metabolites, classication, and health relevance. Flavonoid intake, biological activities, databases, classication and structure, distribution, and dietary sources are then considered. Aspects of anthocyanin concerning its early history and chemical structure, color, and intake are dealt with in the second part of the series. The extraction and analysis of anthocyanin pigments and their antioxidant power, paying special attention to the oxidation process, will be the subject of the third part. Bioavailability and metabolism of anthocyanic pigments, the methods used for measuring the antioxidant activity of anthocyanins, and the inuence of anthocyanins on the antioxidant activity of wine will nally be covered in the fourth part. The present review intends to reect the interdisciplinary nature of the research that is currently carried out in this prolic area. Key research articles and reviews are mainly referenced, and we apologize to those researchers whose work is not cited directly by us. Keywords polyphenols, avonoids, secondary metabolites, classication, health relevance, dietary intake, databases
INTRODUCTION Fruits, vegetables, cereals, nuts, seeds, owers, bark, propolis, olives, oil, and beverages such as wine (white and red), coffee, tea (green and black), chocolates and other cacao products, and manufactured foods supply a number of micronutrients, such as minerals, bers, and vitamins, as well as a whole series of compounds called phytochemicals (Cicerale et al., 2010; Gonz alez-Gallego et al., 2010; Jaganathan and Mandal, 2009; Sharma and Rao, 2009; Heneman and Zidenberg-Cherr,
Address correspondence to Agustin G. Asuero, Dept. of Analytical Chemistry, Faculty of Pharmacy, The University of Seville, 41012 Seville, Spain. E-mail: asuero@us.es
2008; Han et al., 2007) (Figure 1). Although phytochemicals may be dened in the strictest sense as chemical produced by plants, this term is actually used to denote chemicals from plants that may have an inuence on health, but are not essential (El Gharras, 2009). Advances in separation science, biology, and chemistry have boosted the interdisciplinary elds of pharmacognosy and natural products chemistry research, yielding a wealth of information about many classes of naturally occurring dietary phytochemicals (Bohlim et al., 2010; Dai and Mumper, 2010; Garc a-Salas et al., 2010; Kelm et al., 2005; Schreier, 2005). Analytical chemistry has in this context a vital role, as has been stressed several times in this journal (Escudero, 2011; Biesaga and Pyrzynska, 2009; Chrzaski, 2009; Peckova
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FIG. 1. Types of phytochemicals. et al., 2009; Pohl et al., 2009; Zima et al., 2009; Harnly et al., 2007; Marszall and Kaliszan, 2007; Schoefs, 2004; Escarpa and Gonz alez, 2001; Antolovich et al., 2000). Special attention has been paid to analytical methodologies involved in the isolation, determination, and characterization of bioactive polyphenols in plants, fruits and vegetables, herbal drugs, medicinal plants, and wines (Corradini et al., 2011; Ignat c et al., 2009; van Beek et al., 2009; et al., 2011; Medi c-Sari Stobiecki and Kachlicki, 2006; Rijke, 2005; Robards, 2003; Robards and Antolovich, 1997), including sample-handling strategies (Gonz alez and Gonz alez, 2010; Tura and Robards, 2002), a feature of analysis often ignored. As examples of applications we have chromatographic techniques (Marston, 2007; Sun et al., 2005), i.e., high-performance liquid chro c et al., 2011; Raczkowska matography (HPLC) (Medi c-Sari et al., 2011) and thin-layer and high-performance thin-layer chromatography (Cimpoiu, 2006), capillary electroseparation methods (electrophoresis, electrochromatography) (Gotti, 2011; Ganzera and Nischang, 2010; Hurtado-Fern andez et al., 2010), mass spectrometry (MS) (Vukics and Guttman, 2010; Cuyckens and Claeys, 2004; Stobiecki, 2000), HPLC/MS (Steinmann and Ganzera, 2011), nuclear magnetic resonance (NMR) (Eisenreich and Bacher, 2007), LC/NMR (Wolfender et al., 2001), and spectrophotometry (Raczkowska et al., 2011; Harnafy and Amrani, 2008). SECONDARY METABOLITES Among these phytochemical compounds are the widespread redox-active secondary metabolites of a phenolic nature, called polyphenols (Ferrazzano et al., 2011; Burton-Freeman, 2010; Chong et al., 2010; Crozier et al., 2009, 2010; Martin and Appel, 2010; Pereira et al., 2009; Boudet, 2007; Whiting, 2001), although this term should be restricted to rather complex molecules, also referred to as tannins (Quideau et al., 2011; Tarascou et al., 2010). Polyphenols, some of which are ubiquitous in plants while others are restricted to particular families, species, or organs, together with terpenic or isoprenoids (carotenoids, monoterpenes, phytosterols, essential oils, squalene), sulfur-containing compounds (glucosinolates of the Brassicaceae family, Alliaceae family derivatives), and nitrogen-containing compounds (alkaloids and heterocyclic aromatics) are the main secondary metabolites in plants (Cartea et al., 2011; Maiani et al., 2009; Verkerk et al., 2009; Hartmann, 2007; Crozier et al., 2006; Juarez et al., 2005). Secondary metabolites are distinct from the components of intermediary (primary) metabolism (carbohydrates, proteins, amino acids, and lipids) in that they are nonessential for the basic metabolic processes of growth and development of the plant. In spite of this, they are indeed crucial for many important functional aspects of plant life (Kroymann, 2011; Fraga et al., 2010; Lattanzio et al., 2009; Korkina, 2007; Duthie et al., 2003). The phenomenon of secondary metabolism and its differentiation from basic primary metabolism was already recognized in the second half of the 19th century, by Julius Sachs (1873), one of the great pioneers of plant physiology (Neumann et al., 2009; Hartmann, 2007). Nevertheless, only recently has the worth of secondary metabolites come to be appreciated. Secondary metabolites have structural roles in differing supporting or protective tissues, involvement in defense strategies, i.e., against predators and pathogens (viruses, mycoplasma, bacteria, and fungi), and signaling properties, particularly in the interactions between plants and their environment (Li et al., 2010; Crozier et al., 2009; Lattanzio et al., 2009). When introduced into the environment they have signicant effects on soil composition and the microenvironments that plants inhabit (Cohen and Kennedy, 2010; Shirley, 1996). In addition, secondary metabolites, in addition to providing plants with unique survival or adaptive strategies (Michalak, 2006) are of commercial signicance to humankind.
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Secondary metabolites have been used as dyes, bers, glues, oils, waxes, avoring agents, traditional medicine, drugs, UV screens, cosmetics, and perfumes and are viewed as potential sources of new natural drugs, antibiotics, insecticides, and herbicides (Jaganatath and Crozier, 2010; Epstein, 2009; Gruenwald, 2009; Arct and Pytkowska, 2008; Korkina, 2007). Note that at least one-fourth of all prescribed pharmaceuticals in industrialized countries contain compounds that are directly or indirectly, via semi-synthesis, derived from plants. However, many of them are still in use today, and often no useful synthetic substitutes have been found that possess similar efcacy and pharmacological specicity (Neumann et al., 2009). In addition, 11% of the 252 basic and essential drugs considered by the World Health Organization, are exclusively derived from owering plants (Rates, 2001). POLYPHENOLS A large variety of plant phenols exist, being the most abundant and the most widely represented class of plant natural products. However, most polyphenols share a common origin: the amino acids phenylalanine (derived from the shikimic acid pathway) or tyrosine, which are deaminated to cinnamic acids entering the phenylpropanoid pathway (Vogt, 2010; Emiliani et al., 2009; Gould et al., 2009; Pourcel et al., 2007). The ability of plants to produce such an abundance of phenolic compounds is based upon the continuous evolution of new genes brought about by gene duplication and mutation and subsequent recruitment and adaptation to specic functions (Boudet, 2007). Phenolics are characterized by having at least one aromatic ring with one or more hydroxyl groups attached (Tsao, 2010; Crozier et al., 2009; Pereira et al., 2009), ranging from single low molecular weight, single aromatic-ring compounds to the large and complex (highly polymerized) tannins and derived polyphenols. Research into natural organic compounds. including phenols, was initiated by C. W. Scheele and L. N. Vauquelin, who were the rst to isolate gallic acid and simple organic acids (Vacek et al., 2010). Tannin-containing plant extracts have been used to process animal skin into leather since ancient times (Quideau et al., 2011; Serrano et al., 2009). The term tannin was rst introduced in 1796 and came from the use of these compounds in tanneries. The rst descriptions of vegetable tannins were by Emil Fischer in the early 1900s, and further distinction between hydrolyzable and non-hydrolyzable tanning (condensed tannins) was later established by his disciple Freudenberg in 1920 (Tarascou et al., 2010; Haslam, 2007). Polyphenols belong to four main classes (Figure 1): avonoids, phenolic acids (hydroxyderivatives of benzoic acid and cinnamic acid, i.e., p-hydroxybenzoic, protocatechuic, vanillic, and syringic acids) and their esters (chlorogenic, caftaric, coutaric, and fertaric acids), stilbenes (resveratrol, pterostilbene, piceatannol), characterized by a double bond (1,2-diarylethene) connecting the phenolic rings, and lignans (pinoresinol, podophyllotoxin, steganacin), characterized by a 1,4-diarylbutane structure, i.e., having 2-phenylpropane units.
Flavonoids and phenolic acids account for 60% and 30% respectively of total dietary polyphenols (Nichenametla et al., 2006). Phenolic molecules not attached to sugar moieties are referred to as the aglycone form; phenolic molecules existing in a conjugated form with one or more sugar residues are called glycosides. Most phenolics are found in nature associated with mono- or polysaccharides or functional derivatives such as esters or methyl esters, varying widely in their hydroxylation pattern and can be glycosylated or acylated (Kren, 2008; Lin and Harnly, 2007). POLYPHENOL HISTORY: A SHORT PRIMER Phenolic compounds have attracted the attention of researchers for decades. Three British scientists managed to open the door to both basic and applied knowledge of plant polyphenols today: E. C. Bate-Smith, Tony Swain, and Jeffrey B. Harbone (Quideau et al., 2011; Grayer and Williams, 2007; Cooper-Driver, 2001; Harborne, 1988, 1989; Anonymous, 1988; Jones, 1988). These researchers were leading lights in the separation, structural elucidation, and taxonomical distribution of phenolic compounds (Robins et al., 2007). They founded the Plant Phenolic Group, the forerunner of the Phytochemical Society of Europe (Lewis et al., 2003). In 1961 they cofounded the journal Phytochemistry, which in September 1980 was designated as the ofcial organ of the Phytochemical Society (Robins et al., 2007). Jeffrey Harborne, who came from the eld of organic chemistry, became an academic leader in the biochemistry of secondary metabolites, particularly avonoids and other plant phenols (Prebble, 2010; Hanson, 2002), working at the interface between chemistry and traditional areas of plant science, systematics, and ecology, particularly as related to the complex chemical language between plants, microbes, and animals (Harborne, 2001). In the 1950s Bate-Smith and Swain gave the lead into totally new ways of looking at these substances (Haslam, 2007); they conrmed that leucoanthocyanidins, a term that was nally replaced with proanthocyanidins (oligomers of the monomeric avan-3-ols), were identical with condensed tannins (BateSmith, 1954; Bate-Smith and Swain, 1953). In 1962 they came up with their own proposal for a denition of plant polyphenols, later rened at the molecular level by Edwin Haslam, a British physical organic chemistry at the University of Shefeld (Quideau et al., 2011). Other outstanding contributions in the tannins eld were made in the following decades by the groups of Weinges, in Germany, of Haslam, in the UK, of Porter, in New Zealand, and of Hemingway, in the USA (Tarascou et al., 2010). Proposals about the formation of secondary metabolites in plants, in the rst half of the 20th century, were based mainly on analogy with reactions of organic chemistry and on comparison of structures rather than on biochemical evidence (Hartman, 2007). With the advantages of paper chromatography and UV spectroscopy (Santos-Buelga and Williamson, 2003),
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it was possible around 1960 to recognize the widespread occurrence of many plant molecules thought to be rare. Tracer techniques with radioactively labeled nuclides developed by Melvin Calvin allowed us for the rst time to solve the mysteries of the biosynthesis of polyphenols and other secondary metabolites (Hartmann, 2007; Harborne, 2001), changing the scene dramatically. In the late 1970s, it was widely recognized that tannins, and specially protanthocyanidins, were widespread and extremely abundant in numerous plant families, could be found in any plant organ, and also that only part of them could be extracted by usual solvents, a large proportion remaining insoluble (Haslam, 2007). MS and NMR techniques saw a variety of instrumental developments and improvements from the 1970s on (Eisenreich and Bacher, 2007; Hartmann, 2007), allowing efcient application of precursors and intermediates labeled with stable nuclides, and thus chemical degradation was no longer necessary. New advanced methods in sensitivity, combined with high resolution separation techniques with mass spectrometry detection like gas chromatography (GC-MS) and liquid chromatography (LC-MS), gave fresh impetus to the chemical analysis of the compounds (Corradini et al., 2011; Vukics and Guttman, 2010; Van Beek et al., 2009; Andersen, 2008; Daayf and Lattanzio, 2008; Eisenreich and Bacher, 2007; Hartmann, 2007; Cuyckens and Claeys, 2004). While other more sophisticated techniques such as those mentioned above are becoming more popular as research tools, the relatively high capital costs are still an impediment to their routine use in enforcement laboratories, a fact that must be taken into consideration (Scotter, 2011). POLYPHENOLS: NOW AND THEN Traditionally, interest in polyphenols has mainly been related to their organoleptical properties such as color, astringency (tannins), bitterness (avonols), and taste (Haslam, 2007; Cheynier, 2005; Tom as-Barber an and Esp n, 2001), as well as to their physiological importance to plants because they play an important role in plants as defense and signaling compounds in reproduction, pathogenesis, and symbiosis (involved in response mechanisms against stress) (Grotewold, 2006a; Manetas, 2006; Michalak, 2006; Schaefer and Rolshause, 2006; Treutter, 2006; Mazza et al., 2000). It is well known that phenolic compounds play an important role in red wine color, bitterness, and astringency, as well as a range of other tactile or mouth feel characteristics (Mateus, 2009; Oberholster, 2008; Birse, 2007; Lesschaeve and Noble, 2005; Zimman et al., 2004). Despite the fact that most of the literature on plant phenolics focuses mainly on those in fruits, vegetables, wines, and teas, many phenolic compounds present in fruits and vegetables (phenolic acids and avonoids) are also found in cereals (Dykes and Rooney, 2007; Lieberman, 2007; Naczk and Shadidi, 2006; Escribano-Bail on et al., 2004). More recently polyphenols are increasingly being recognized by their nutritional value, since they may help reduce the risk of chronic diseases (Ruel and Couillard, 2007; Willcox et al.,
2004) and, in general, have a positive effect on health, because of their free radical scavenging capacity, which, among other biological effects, increases antioxidant activity and prevents cellular oxidation (Quideau et al., 2011; Jaganatah and Crozier, 2010; Neveu et al., 2010; Terry et al., 2001). The capacity of phenolic compounds to trap free radicals depends upon their structure, in particular of the hydrogen atoms of the aromatic group that can be transferred to the free radicals (Leopoldini et al., 2011; Heim et al., 2002), and of the capacity of the aromatic compound to cope with the uncoupling of electrons as a result of the surrounding displacement of the electron- system (Quideau et al., 2011; Min and Boff, 2002; Parr and Bolwell, 2000; Cao et al., 1997). Acid dissociation constants (Asuero and Michalowski, 2011; Asuero, 2007; Herrador et al., 1987; Asuero et al., 1986a, 1986b) are important physicochemical parameters that describe the extent of ionization of functional groups as a function of pH (Dufor and Dangles, 2005; Mielczarek, 2005; Amic et al., 1999). The antiradical properties, i.e., the ability to react quickly and efciently with electron-decient radicals, depend on the acidity of phenolic hydroxyl groups and on the stability of the formed radical (Musialik et al., 2009). The polyphenol eld is gaining attention, and its fertility is reected by the frequency of recently published relevant reviews (Table 1). However, the physiological mechanisms linking the antioxidant chemical characteristics of polyphenols with their health effects are still the subject of discussion (Halliwell, 2005, 2011; DArchivio et al., 2010; Gutteridge and Halliwell, 2010; Moiseeva and Manson, 2009; Lotito and Frei, 2006; Cheynier, 2005; Williams et al., 2004). It should be pointed out that the bioavailability of polyphenols in humans and experimental animals remains largely unknown (Crozier et al., 2010; Halliwell, 2007; Karakaya, 2004). The percentage of absorbed natural polyphenols is usually quite low. Instead, researchers have seen a large quantity of metabolites of polyphenols in the form of simple phenolic acids in the blood (Wang et al., 2010a; Forester and Waterhouse, 2009; Galvano et al., 2008). The amount and form in which plant phenolic substances are administered inuence greatly the physiological effects connected with their consumption (Vacek et al., 2010). Nonetheless, the physiological activity of these molecules has been related to their structure and geometry (Aparicio, 2010; Amic et al., 2007; Sakata et al., 2006; Rackova et al., 2005; Rasulev et al., 2005; Rice-Evans et al., 1996; Van Acker et al., 1996). During the past two decades the interest in polyphenols has increased considerably, especially among food scientists, nutritionists, the agricultural industry, and consumers (Neveu et al., 2010). The French have high smoking rates and a diet rich in fats, but reduced rates of coronary heart disease in comparison with people from northern European countries. This observation, called the French Paradox, has been ascribed to the consumption of red wines rich in phenolic compounds and has awaked a growing interest in polyphenol research (Lippi et al., 2010; De Leiris et al.; 2008; De Lange, 2007; Simoni,
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TABLE 1 Some recently published reviews on polyphenols Content Emerging ndings on the anti-cariogenic properties of polyphenols, which have been obtained from several in vitro studies investigating the effects of these bioactive molecules against Streptococcus mutans, as well as in vivo studies Overview of recent reports on the inuence of dietary polyphenols on gut microbiota to summarize the main interactions between dietary polyphenols and benecial and pathogenic intestinal bacteria Overview of the research carried out in the eld of antioxidant polyphenolic compounds, employing theoretical and computational methods. Mechanism of avonoids and polyphenols as antioxidants Chemical properties, biological activities, and synthesis of polyphenols. The state of the art and the most signicant advances in the eld of polyphenol research Effect of fruits and their inherent phenolic compounds in human subjects on postrandial lipaemia, glycaemia/insulinaemia, and associated events, such as oxidative stress and inammation Bioavailability and biological activities of olive oil phenolic compounds The effects of fruit polypenols on four risk factors of CVD: platelet function, blood pressure, vascular function, and blood lipids Phenolic extraction, purication, analysis, and quantication as well as its antioxidant properties Bioavailability and evidence of protective effects of berry avonoids and phenolics Bioavailability of dietary phenolic compounds in humans, the difculties and the controversies surrounding the studies aimed at determining the bioavailability of these compounds Focuses on the encapsulation of the more widely used polyphenols, discussing their effectiveness, variations, developments, and trends The most important mechanisms proposed for the actions of polyphenols in animal settings The effects of fruit and tea avonoid and its metabolites on inammation and immunity. Mechanisms of the effects, including those on enzyme function and regulation of gene and protein expression The effects of berry polyphenolics on vision physiology and their bioavailability in ocular tissues Effects of dietary polyphenols on specic epigenetic alterations: effective chemopreventive strategies for reducing the health burden of cancer and other diseases in humans Polyphenols as dietary supplements Polyphenols in cardiovascular protection Dynamic capacity of polyphenols to protect against age-associated disorders through a variety of important mechanisms Plant phenolic composition; analytical methods The chemistry and biochemistry of polyphenols as related to classication, extraction, separation, and analytical methods, their occurrence and biosynthesis in plants, and the biological activities and implications in human health Polyphenols in the diet: classication and sources, antioxidant hypothesis, bioaccessibility, bioavailability, and effects on health Biological activity and effects on health of polyphenols Dietary polyphenols: chemistry, bioavailability, and effects on health Cosmeceuticals and polyphenols: need to develop adequate physiological models supporting antioxidant activity of polyphenols The known metabolism of each major class of wine and grape phenolics, the means to measure them, and ideas for future investigations Reference Ferrazzano et al., 2011
Hervert-Hern andez and Go ni, 2011 Leopoldini et al., 2011
Quideau et al., 2011 Burton-Freeman, 2010
Cicerale et al., 2010 Chong et al., 2010 Dai and Mumper, 2010 Del Rio et al., 2010a DArchivio et al., 2010
Fang and Bhandari, 2010 Fraga et al., 2010 Gonz alez-Gallego et al., 2010
Hanneken et al., 2010 Link et al., 2010 Martin and Appel, 2010 Morand, 2010 Queen and Tollefsbol, 2010 Tarascou et al., 2010 Tsao, 2010
Weichselbaum and Buttriss, 2010 Williamson and Clifford, 2010 Crozier et al., 2009 Epstein, 2009 Forester and Waterhouse, 2009
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TABLE 1 Some recently published reviews on polyphenols (Continued) Content Polyphenols: the main organoleptic attributes and biological properties related to health benets of red wine Benecial, toxicological, and/or optionally endocrine disrupting activities of phenolics. Immunochemical detection and/or isolation method development Biological effects of plant polyphenols in the context of relevance to human health Several aspects related to phenolic chemistry. The increasing interest in phenolic biological activities Preventive polyphenol activity against oral diseases The history and progress of the polyphenolic chemistry of tea and coffee, as well as their stability and the trapping activity of reactive oxygen species and reactive carbonyl species In vitro antioxidant activity of foods, emphasizing the main role of phenolic compounds. Biological signicance of these values and the biological signicance of in vivo measurements Polyphenols as antioxidants or pro-oxidants. Effects in cell culture Dietary polyphenols in connection with cancer prevention The role of polyphenols from fruits, vegetables, and beverages in neuroprotection and particularly in Alzheimers disease and the research challenges in this area The problems associated with polyphenol-intake predictions: strengths, limitations, and application in nutritional research The potential health benets of dietary polyphenols from the point of view of bioavailability Dietary polyphenol. Phenolic compounds to protect the gastrointestinal tract against damage by reactive species present in foods or generated within the stomach and intestines Biological mechanisms of action and protective effects of dietary polyphenols Phenolics, inammation, and nutrigenomics. Mechanism of action of food derived-components playing an active role in prevention of inammation Research on grape and wine phenolics. Justication for continued research Effects and mechanism of bioactive polyphenolic compounds commonly found in many fruits and vegetables on cancer The reaction mechanisms involving polyphenols and the structures of the resulting products. Effects on organoleptic and nutritional quality Studies on the prevention of cardiovascular diseases by polyphenols The antioxidant effects of polyphenols and their relevance for health. The experimental evidence supporting a protective role of polyphenols against the main degenerative diseases Bioavailability of phenolic compounds. The importance of antioxidant activities of phenolic compounds and their possible usage in processed foods as natural antioxidants Absorption, metabolism, and bioavailability of phenolic compounds The nature and contents of the various polyphenols present in food sources and the inuence of agricultural practices and industrial processes Activity and mechanism of action of polyphenols Overview of the kinetic, structural, and mechanistic properties of the various polyphenolic antioxidants and their respective radicals Polyphenolic compounds: physiological effects. Antioxidant activity Polyphenolic compounds: structure and classication. Bioavailability and metabolism Knowledge and methodology of natural phenolics chemistry Plant polyphenols: antioxidant activity and anticarcinogenic and anti-atherogenic effects The functions of phenolics both in plants and in human beings. Biosynthesis of phenolics in plants, identication and isolation of the genes coding for phenolic biosynthetic enzymes or regulatory proteins Polyphenols: dietary intake, amounts consumed, bioavailability, and the factors controlling their bioavailability Reference Mateus, 2009 Meulenberg, 2009 Pandey and Rizvi, 2009 Pereira et al., 2009 Petti and Scully, 2009 Wang and Ho, 2009 Fern andez-Pach on et al., 2008
Halliwell, 2008 Ramos, 2008 Singh et al., 2008 Spencer et al., 2008 Yang et al., 2008 Halliwell, 2007 Han et al., 2007 Evans et al., 2006 Kennedy et al., 2006 Nichenametla et al., 2006 Cheynier, 2005 Manach et al., 2005 Scalbert et al., 2005 Vita, 2005 Karakaya, 2004 Manach et al., 2004 Duthie et al., 2003 Bors and Michel, 2002 S anchez Moreno, 2002a S anchez Moreno, 2002b Whiting, 2001 Duthie et al., 2000 Parr and Bolwell, 2000
Scalbert and Williamson, 2000
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2000; Renaud and Lorgeril, 1992). A need for dietary compositional information on polyphenols has been generated to facilitate epidemiological and intervention studies with human subjects (Spencer et al., 2008; Duthie et al., 2003). POLYPHENOL DATABASE AND INTAKE Several thousand polyphenols have been characterized in plants and several hundreds of them are found in food plants. Dietary polyphenols differ widely in their physicochemical properties, bioavailability, biological properties, and health effects (Darvesh et al., 2010; Martin and Appel, 2010; Crozier et al., 2009; Pandey and Rizvi, 2009; Scalbert el al., 2005; Williamson and Manach, 2005; Parr and Bolwell, 2000). About 1 g of polyphenols per day is commonly ingested with foods, which is signicant when compared with the estimated daily consumption of other phytonutrients such as carotenoids, vitamin E, and vitamin C, estimated at 5, 12, and 90 mg/d, respectively (Wallace, 2011). Polyphenols are therefore the most abundant antioxidant in the diet (Scalbert et al., 2005; Slanina and Taborska, 2004), i.e., about 10 times higher than the intake of vitamin C and 100 times that of vitamin E. The estimated daily intake of polyphenols in the US was 449.8 mg using per capita consumption data for 34 commonly consumed fresh fruits and vegetables (Chun et al., 2005). The total intake of polyphenols estimated in the Dutch diet is 863 415 mg/day (Ovaskainen et al., 2008). The main daily intake of polyphenols in the Spanish diet was estimated between 2590 and 3016 mg/person/day (Saura-Calixto et al., 2007). The amount of non-extractable polyphenol was almost double that of extractable polyphenols. The main total intake of polyphenols in Finnish adults was 863 415 mg/d (Ovaskainen et al., 2008). Phenolic acids comprised the dominant group of polyphenols (75% of total intake) followed by proanthocyanidins (14%) and other avonoids (10%). However, the risk of toxicity from the food supply, in spite of a high dietary consumption of polyphenols, is relatively low, largely due to poor absorption (Martin and Appel, 2010). Nevertheless, the increasing use of dietary bioactive agents through food base polyphenol enrichment (i.e., with puried agents) could render polyphenol consumption potentially problematic. Interest in food composition and its properties in relation to human health has a long history (Colombani, 2011). The history and applications of food composition databases is given by Black et al. (2011), Church (2005, 2006), and Williamson (2005). In the United States, the Department of Agriculture (USDA) has maintained food composition tables for over 115 years (Haytowitz et al., 2008), since the pioneering work of Atwater and Woods in1892 (Atwater, 1895). Currently, the USDAs Nutrient Databank System incorporates data for approximately 7500 foods and up to 140 nutrient components (Haytowitz et al., 2009). Considerable information on polyphenol content of food is scattered in up to 1000 peer-reviewed publications. The new Phenol-Explorer database was been compiled, managed by the
Institute Nationale de la Recherche Agronomique (Scalbert, n.d.), which covers over 60,000 foods useful to epidemiologists, food scientists, and food manufacturers (Neveu et al., 2010; P erez-Jim enez et al., 2010b). A list of the 100 richest dietary sources of polyphenols was produced with the aid of the Phenol-Explorer database, the content ranging from 15000 mg per 100 g in cloves to 10 mg per 100 mL in rose wine (P erezJim enez et al., 2010a). Another database within the framework of the European Food Information Resources Network, EuroFir, is available (Hollman et al., 2009; Westenbrink et al., 2009). EuroFir is serving as a basis to build national food composition databases in different countries, i.e., Spanish (Burgos et al., 2009) and Irish (Black et al., 2011) databases. However, original food sampling and description uncertainty, complexity of fruit and vegetable phytochemical content across species, cultivar, and growing and processing conditions (heterogeneous sources), diversity and concentration of polyphenols present in foods, and limited systematic approaches to comprehensively characterize and quantify polyphenols in plants food using standardized analytical methods make it difcult to build a complete database (Kay, 2010; Spencer et al., 2008). A database concerning the antioxidant capacities of both the lipophilic and hydrophilic components of foods (Wu et al., 2004) has been built. An algorithm to estimate total antioxidant capacity (TAC) of the U.S. diet (Floegel et al., 2010) has also been developed and validated. FLAVONOIDS Carotenoids (xanthopylls, carotenes), tetrapyrrole derivatives (i.e., chlorophylls), and avonoids are three of the most important natural pigments (Bechtold and Mussak, 2009; DelgadoVargas et al., 2000; Merken and Beecher, 2000). The avonoids constitute the largest group of polyphenols (of low molecular weight) and are considered to be responsible for the color and taste of many fruits and vegetables (Grotewold, 2006a). They are present particularly in the epidermis of leaves and the skin of fruits (Crozier et al., 2009; Onylagha and Grotewold, 2004; Iwashina, 2000). Flavus means yellow in Latin, the collective name of avonoids for this group being applied by Geissman (1949). The avonoids group shows extraordinary diversity and variation, and many of these compounds are yellow in color, as the Latin root suggests. Flavonoids are secondary plant metabolites, which together with other plant phenols share a common origin: the amino acid phenylalanine and the acetate coenzyme A esters (Pourcell et al., 2007; Parr & Bowell, 2000). These compounds are generally biosynthesized by the shikimate pathway, from which they are produced using intermediates of carbohydrate metabolism. Rapid and substantial progress in the research on the phenylpropanoid pathway was carried out from the 1970s to the 1990s, the focus being mainly centered (Shirley, 1996; Koes et al., 1994) on a broad understanding of the metabolic pathway. More recently, efforts were carried out from a biochemical and a molecular point of view (Korkina, 2007;
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Woo et al., 2005), by using a variety of approaches (transposon tagging, positional cloning, coimmuno-precipitation, afnity chromatography, hybrid experiments). In the past few years new information concerning the (transcriptional) regulation of the phenylpropanoid pathway has been obtained, derived from studies in a variety of plant species (Hichri et al., 2011; Jaganatah and Crozier, 2010; Vogt, 2010). The avonoid biosynthesis pathway is probably the most thoroughly studied plant secondary metabolism pathway. New analytical and biophysical methods, such as the implementation and application of nanotechnology to solve biological problems, are currently being developed for new approaches towards resolving a most complex scenario of biological systems (Vogt, 2010). Flavonoids can accumulate in vacuolar compartments, or be secreted, for example, as part of root exudates. Most intriguing is the accumulation of avonoids on the surface of leaves and owers (Onyilagha and Grotewold, 2004). Flavonoids have roles in many facets of plant physiology. One of the most important roles is to inuence the transport of the plant hormone auxin (Buer et al., 2010; Peer and Murphy, 2007). The avonoids of dietary signicance are widely distributed in the plant kingdom (Biesaga and Pyrzinska, 2009), and they are present in edible plants in widely varying combinations; avonols, avanones, avones, avonols (essentially avan-3-ol), isoavones, and anthocyanins are the most relevant for human diet. Since rst identied in the mid-1800s, more than 9,000 avonoid structures have been described, with formulas, references, and biological information (Fraga, 2010; He and Giusti, 2010; Motohashi and Motohashi, 2008; Veitch and Grayer, 2008; Andersen and Markham, 2006; Grotewold, 2006b; Williams and Grayer, 2004), and the list is constantly growing. These include over 600 different naturally occurring anthocyanins that are widely distributed among at least 27 families, 73 genera, and innumerable species (Andersen, 2008; Andersen and Jordhein, 2006), and more are continually being isolated. It has been shown that, of the avonoids studied, around 5,000 have antioxidant activity (Motohashi and Sakagami, 2008). Because the number of phytochemicals already identied is only a small part of those that exist in nature, there is considerable interest in new methods of separation, isolation, and characterization of polyphenol structures from foods (Soto et al., 2011; Garc a-Salas et al., 2010; Valls et al., 2009; Liu et al., 2008; Sticher, 2008; Marston, 2007; Yrj onen, 2004; Marston and Hostettmann, 1991). STRUCTURE AND CLASSIFICATION OF FLAVONOIDS Flavonoids have structures consisting of two aromatic rings linked by three carbons in an oxygenated heterocycle (Wolfe and Liu, 2008; Andersen and Markham, 2006; Nichenametla et al., 2006) (Figure 2), i.e., a avan (2-phenyl-benzopyran) nucleus consisting of two benzene rings combined with an oxygen-containing pyran ring, the parent compound bearing a tricyclic (C6-C3-C6) skeleton. The heterocyclic benzopyran
FIG. 2. Top: basic avonoid skeleton; middle: avonol skeleton; bottom: avone skeleton. ring is known as the C ring, the fused aromatic ring as the A ring, and the phenyl constituent as the B ring. The structural differences in each avonoid family result from variations in the number/substitution pattern of the hydroxyl and methoxy groups, as well as different glycosylation patterns (Table 2), and the presence of a C2-C3 double bond in the heterocycle pyran ring (Andersen and Markham, 2006; Nichenametla et al., 2006). These structural variations are responsible for differences in antioxidant activities of avonoids compounds (Galleano et al., 2010; Wolfe and Liu, 2008; Amic et al., 2007; Rasulev et al., 2005; Woodman et al., 2005; Mart nez-Flores et al., 2002; Voskeresensky and Levitsky, 2002). The biological action of avonoids is usually attributed to their ability to exert an antioxidant action by scavenging reactive species, or through their possible inuence on the intracellular redox status. This point of view based on hydrogen-donating antioxidant activity cannot account for the bioactivity of avonoids in vivo, particularly in the brain, where they are found at very low concentrations (Spencer, 2009), and it is an open question. Note that sugar moieties attached to avonoids increase polarity of the molecule for their storage in plant cell vacuoles. The early chemistry of avonoid compounds has been well worked out, largely through the research of Kostanecki, Perkin, Asahina, Willst atter, Robinson, Seshadri, and others (Todd, 1987; Todd and Cornforth, 1976; Geissman, 1949; Robinson and Robinson, 1932). Depending on their structure, avonoids may be classied into about a dozen groups. The following representative modications of the basic skeleton occur in nature (Leopoldini et al., 2011; Han et al., 2007; Andersen and Markham, 2006; Geissman, 1949):
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TABLE 2 Some recently published reviews on avonoids Content Effects of avonoids and related polyphenolic compounds on inammation, with a focus on structural requirements, the mechanisms involved, and pharmacokinetic considerations Flavonoids: anticancer activity and molecular mechanisms, including the treatment of mammary and prostate cancer and some advanced derivatives Overview of avonoids: their classication, structures, and analytical methods for their determination Safety issues surrounding high-dose supplemental avonoid consumption The role of platelets in cardiovascular disease: the potential anti-platelet effect of avonoids, focusing on the various platelet signaling pathways modulated by avonoids, including oxidative stress, protein tyrosine phosphorylation, calcium mobilization, and nitric oxide pathway Overview of neuroprotection by different classes of avonoids on cellular cultures and model animals Effects of avonoids on the CNS Dietary avonoids and human health Current advances on avonoids in food with emphasis on mechanism aspects on the basis of the published literature Advancements on potential cancer preventive effects and mechanical insight on dietary avonoids Recent advances on avonoid research, physiological processes, and approaches to identify the cellular targets of avonoids Human studies on the bioavailability of dietary avonoids and related compounds in which the identication of metabolites, catabolites, and parent compounds in plasma, urine, and ileal uid was based on mass spectrometric methodology Bioavailability and evidence of protective effects of berry avonoids and phenolics Analysis of mechanisms proposed for polyphenol biological actions, especially antioxidant reactions, based on chemical, thermodynamic, and kinetic data Chemical nature, mechanism of action, current status, pharmacodynamic/pharmacokinetic studies, industrial signicance, nutritive values and analysis of avonoids with the recent technology The future of avonoid research: the use of databases as very powerful tools for the design and interpretation of clinical and epidemiological studies Recent advances of patents concerning of natural avonoids and their synthetic analogues in the treatment of cancers, and new synthetic approaches and possible structure-activity relationships of avonoids Mechanisms of anti-inammatory activities of avonoids and their implicated effects on the development of various chronic inammatory diseases Synthetic photochemical transformations of the different classes of avonoids Overview of the status quo of avonoid biosynthesis as related to ower color with genetic engineering modications included Effects of avones and avonols on liposomal membranes consisting of different unsaturated phospholipids and cholesterol Biocatalytic structural modication of avonoids by different kinds of enzymes or microorganisms, the process and possible mechanism Dietary avonoids: phytoestrogens as natural prodrugs in cancer prevention Membrane transport of avonoids, a critical determinant of their bioavailability The potential for avonoids to inuence memory, learning, and neurocognitive performance and attempt to clarify the probable mechanisms that underpin such actions in the brain Reference Ballester et al., 2011 Chahar et al., 2011 Corradini et al., 2011 Egert and Rimbach, 2011 El Haouari and Rosado, 2011
Gutierrez-Merino et al., 2011 Jager and Saabi, 2011 Stoclet and Schini-Kerth, 2011 Xiao et al., 2011 Yao et al., 2011 Buer et al., 2010 Crozier et al., d2010
Del Rio et al., 2010a Galleano, 2010 Gupta et al., 2010
Kay, 2010 Liu et al., 2010
Pan et al., 2010 Sisa et al., 2010 Tanaka et al., 2010 Tsuchiya, 2010 Wang et al., 2010a Arroo et al., 2009 Passamonti et al., 2009 Spencer, 2009
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TABLE 2 Some recently published reviews on avonoids (Continued) Content Bioavailability and biotransformation of avonoids and the mechanisms of activity at the molecular, cellular, organ, and organism levels that may contribute to their anti-inammatory effects The potential of tea and tea avonoids to improve endothelial function and reduce blood pressure, oxidative damage, blood cholesterol concentrations, inammation, and risk of thrombosis Functionality of anthocyanins as alternative medicine Flavonoids as nutraceuticals Neuroprotective actions of avonoids within the brain, including the potential to protect neurons against injury induced by neurotoxins, an ability to suppress neuroinammation, and the potential to promote memory, learning, and cognitive function New examples of naturally occurring avonoids found either as aglycones or glycosides Flavonoid oxidation in plants: from biochemical properties to physiological functions The availability of recombinant avonoids for the rational preparation of pharmaceuticals Biosynthesis, regulation, and contribution to ower coloration of oral pigments Contribution of dietary avonoids to the total antioxidant capacity of plasma in humans Signicance of avonoids in plant resistance The roles that avonoids play in developmental processes of plants, such as auxin transport, pollen germination, and signaling to microorganisms, and their allelopathic and anti-tumor activities Flavonoids: a new role in cell cycle regulation Mechanisms of action of dietary avonoids in their potential role in disease prevention. Absorption, metabolism, and bioavailability Key differences in absorption, metabolism, and pharmacokinetics between the major avonoids present in the diet Associations of dietary avonoid intake with cancer risk The potential of various new avonoid derivatives in hormone replacement therapy Flavonoids: absorption, metabolism, and bioactivity. The impact of membrane transporters as well as metabolic enzymes on the cellular availability New avonoid structures. The biological activity of some of the compounds The current advances in avonoids in food, with emphasis on health aspects Nomenclature, occurrence in foods, and intake of avonoids with emphasis on those prevalent in tea Recent contributions to the role of phenolics, especially avonoids, in different aspects of insect-plant interactions Dietary avonols: chemistry, food sources, dietary intakes, bioavailability, and metabolism The treatment of the effects of avonoids on animal biochemistry from a medical point of view Flavonoid antioxidants: chemistry, metabolism, and structure-activity as central determinants of free radical scavenging, chelation, and prooxidant activity Review of avonoid properties and their antioxidant activities Dietary avonoids: absorption and bioavailability, metabolic and health effects The role of dietary avonoids as antioxidants in vivo Recent research on the biological properties of avonoids Chemical structures of avonoids and their distribution in nature Bioavailability of avonoids and their bioactivity in vivo. Factors inuencing the absorption by the gastrointestinal tract, nature of the conjugates and metabolites in the circulation Reference Gomes et al., 2008
Hodgson, 2008 Motohasi and Sakagami, 2008 Tapas et al., 2008 Vauzour et al., 2008
Veitch and Crayer, 2008 Pourcell et al., 2007 Serrano, 2007 Grotewold, 2006a Lotito and Frei, 2006 Treutter, 2006 Taylor and Grotewold, 2005
Woo et al., 2005 Hollman, 2004 Manach and Donovan, 2004 Neuhouser, 2004 Vaya and Tamir, 2004 Walle, 2004 Williams and Grayer, 2004 Yao et al., 2004 Beecher, 2003 Simmonds, 2003 Aherne and OBrien, 2002 Havsteen, 2002 Heim et al., 2002 Mart nez-Flores et al., 2002 Ross and Kasum, 2002 Rice-Evans, 2001 Harborne and Williams, 2000 Iwashina, 2000 Rice-Evans et al., 2000
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(i) Those in which the C3 fragment of the structure exists in the open-chain form (chalcones, dihydrochalcones). Chalcones are directly or indirectly converted to a range of other avonoids in a pathway of intersecting branches with intermediate compounds being involved in the formation of more than one type of end product (Davies, 2004). (ii) Those in which the C3 fragment is a part of a vemembered heterocyclic ring: benzalcoumaranones, a rare class of oral pigments, extensively studied by Harborne and Geissman, for which Bate-Smith and Geissman (1951) proposed the name of aurone (Grayer and Williams, 2007; Boumendjel, 2003); (iii) Those in which the C3 fragment is present in a six-membered heterocyclic ring, by far the largest class. Differences in the structure of the heterocycle, or C ring, classify them in subgroups including as avonols, avones (catechins), avanones, chalcones, dihydrochalcones and dihidroavonols, anthocyanins, and isoavonoids (isoavones) (Leopoldini et al., 2011; Garc a-Salas et al., 2010; Liu et al., 2008; Wolfe and Liu, 2008; Han et al., 2007), varying in the oxidation state (degree of saturation) of the heterocyclic central pyran ring (Table 2). When unsaturation is present, the geometry of the molecule is planar, as in the case of anthocyanins, avones, and avanols. Flavones are structurally very similar to avonols and differ only in the absence of hydroxylation at the 3 position on the C ring. Flavan-3-ols are structurally the most complex subclass of avonoids, ranging from the simple monomers (+)- catechin and its isomer (-)-epicatechin to the oligomeric and polymeric proanthocyanidins (condensed tannins). Two structural features, the absence of a C2-C3 double bond and the presence of a chiral center at the carbon-2, characterize avanones. Optical activity may also be present in avonoids due to glycosidic substituents. In the majority of naturally occurring avanones, the C ring is attached to the B ring at C2 in the conguration. Unlike other subgroups of avonoids with the same C6C3C6 skeleton, anthocyanins (Figure 3) have a positive charge in their structure at acidic pH. Isoavonoids differ from other avonoid classes in having a basic structural feature where a B ring attaches to C-3 but not C-2. In a few cases, the six-membered heterocyclic C ring occurs in an isomeric open form or is replaced
FIG. 3. Structure of anthocyanins.
by a ve-membered ring, as in the case of chalcone (reductive ring closure of chalcone results in the formation of a avone). Other avonoid groups, which quantitatively are relatively minor dietary components, are dihydroavones, avan-3,4-diols, coumarins, and aurones. Oligomers and polymers of avonoids are called tannins (Haslam, 2007). Condensed tannins, also known as proanthocyanidins or procyanidins, are oligomers of avanols, and their chemical structures are dened by both the kind of monomer and the kind of link between monomers. Hydrolizable tannins are polymers readily hydrolyzed by acids into a central core constituted of a polyol (a sugar, generally D-glucose, or a avonoid, such as catechin) and a phenolic carboxylic acid esterifying partially or totally that core molecule (Quideau et al., 2011; Fraga et al., 2010). The number of different avonoid structures that are theoretically possible is astronomical (William and Grayer, 2004), based on the assumption that ten carbons of the avonoid skeleton can be substituted by a range of different groups (i.e., hydroxyl, methoxyl, methyl, isoprenyl, and benzyl substituents). Flavonoids are often hydroxilated in positions 3, 5, 7, 3 , 4 , and/or 5 . Frequently, one or more of these hydroxyls are methylated, acetylated, prenylated, or sulfated. In biological uids (serum, plasma, and urine) avonoids exist as glucoronide and sulfate conjugates (Rijke et al., 2006). The pattern of conjugation, glycosylation, or methylation can be very complex, can modify the hydrophilicity of the molecule and its biological properties, and can markedly increase the molecular weight of the avonoid. Flavonoids usually occur as glycosides in plants, reecting a biological strategy (Passamonti et al., 2010); the effect of glycosylation renders the avonoid less reactive and more water soluble, increasing the polarity of the molecule, which is necessary for storage in the plant cell vacuoles, decreasing at the same time their propensity to interact with macromolecules (Corradini et al., 2011). However, avan-3-ols (catechins and theaavins) are present in either free form or as gallic acid esters (e.g., in tea) (Holden et al., 2005). The glycosidic linkages appear to be important for the absorption of avonoids (Kren, 2008; Kren and Martinkova, 2001). Flavonoid glycosides are frequently acylated with aliphatic or aromatic acid molecules (Lin and Harnly, 2007). These derivatives are thermally labile and their isolation and further purication without partial degradation is difcult. The analysis of avonoids and their conjugates (Rijke, 2005) is one of the most important areas in the eld of instrumental analytical methods, helping to solve varying problems in biological and medical sciences. MS techniques are the methods of choice in these research areas, mainly the combination of chromatographic systems (CL, LC, or CE) with powerful detectors that enable the identication of simple compounds in complex mixtures (Steinmann and Ganzera, 2011; Vukics and Guttman, 2010; Yang et al., 2009; Stobiecki and Kachlicki, 2006; Cuyckens and Claeys, 2004).
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COLOR AND PHOTOPROTECTIVE EFFECT OF FLAVONOIDS Anthocyanins confer orange, red, magenta, violet, and blue colors. Aurones and chalcones are yellow pigments, while avones and avonols are colorless or very pale yellow, at least to the human eye. Although avonols and avanones by themselves do not have color, they modify coloration by complexation with anthocyanins and/or metallic ions (copigmentation) (Delgado-Vargas et al., 2000). The copigmentation mechanism is unique to the anthocyanin family. The resulting complex palette of color is a key element in various aspects of plant reproduction (Shirley, 1996). The coloration patterns of owers attract insects to anthers (masculine organ) and pistils (feminine organs), and are thus involved in pollen development and germination (Simmonds, 2003). It is well known that many species accumulate avonoids in these organs. The most common avonoids in anthers are anthocyanins, avonols, and chalcones. Animals are attracted by fruit color and after consumption the seeds are dispersed through excrement. One of the most versatile classes of avonoids, the anthocyanins, protect chloroplasts from photodegradation by absorbing high-energy quanta, while scavenging free radicals and reactive oxygen species (ROS) (Fraga, 2010; Sisa et al., 2010; Morganti, 2009; Gould and Lister, 2006). Flavonols provide protection against the damaging effects of UV-B light, and are also involved in promoting the growth of pollen tubes down the style to promote fertilization (Jaganath and Crozier, 2010). Isoavonoids play important defense roles against pathogens and insect attacks and are key signal molecules in the formation of nitrogen-xing root nodules in legumes. Isoavones are also known for their estrogenic activity (Vaya and Tamir, 2004) due to their ability to bind to estrogen receptors and have received much attention due to their putative role in the prevention of breast cancer and osteoporosis (Tarascou et al., 2010; Barnes, 2003). In plants, avonoids are relatively resistant to heat, oxygen, dryness, and moderate degrees of acidity but can be modied by light. Photostability of the avonoid molecule depends on the nature of the hydroxyl group attached to C-3 of the C ring. The absence or glycosylation of this hydroxyl group results in high photostability of the molecule (Sisa et al., 2010; Aherne and OBrien, 2002). BIOLOGICAL ACTIVITIES OF FLAVONOIDS Flavonoids possess a wide range of biological activities (Egert and Rimbach, 2011; Stoclet and Schini-Kerth, 2011; Buer et al., 2010; Liu et al., 2010; Pan et al., 2010; Forester and Waterhouse, 2009; Serrano, 2007; Havsteen, 2002) including antioxidant, antibacterial, antiinammatory, anti-allergic, antitumor, antithombotic, proapoptotic, and vasodilatory action. The wide spectrum of functions explains why recently a number of reviews on the properties of avonoids have been published (Table 3). Many of them are active principles of medical plants and exhibit pharmacological
TABLE 3 Structural differences among avonoid classes (Nichenametla et al., 2006) Carbon involved in double bond on C ring 2nd and 3rd 2nd and 3rd 1st and 2nd 3rd and 4th Functional groups on C ring 3-hydroxy, 3-o-gallate 3-hydroxy, 4-ox 4-oxo 4-oxo 3-hydroxy
Flavonoid class Flavanols Flavonols Flavones Flavanones Anthocyanidins
effects (Tapsell et al., 2006; Havsteen, 2002). The healthpromoting effects of avonoids may relate to interactions with key enzymes, signaling cascades involving cytokines and transcription factors, or antioxidant systems (Buer et al., 2010). Many avonoids in particular are also able to modulate the activity of key human enzymes such as tyrosine kinases (Parr and Bolwell, 2000). The major active nutraceutical ingredients in plants are avonoids (Lobo et al., 2010; Lin and Weng, 2006; Shahidi and Naczk, 2006). Nutraceutical is a term coined in 1979 by Stephen DeFelice (Ahmad et al., 2011). It is dened as a food or parts of food that provide medical or health benets, including the prevention and treatment of disease. Subsequently, several other terms such as medical food, functional food, and nutritional supplements were used. The term functional food was used for the rst time in Japan in the 1980s (Herrero et al., 2005). The work of Espin et al. (2007) may be consulted in order to appreciate the signicance of these terms. Flavonoids are not synthesized in animal cells, thus their detection in animal tissues is indicative of plant ingestion. Once ingested, avonoids undergo extensive metabolism in the small and large intestines, in the liver, and in cells, resulting in very different forms in the body to those found in foods (Spencer, 2009). The chemical diversity, size, three-dimensional shape, and physical and biochemical properties of avonoids allow them to interact with targets in different subcellular locations to inuence biological activity in plants, animal, and microbes (Buer et al., 2010; Peer and Murphy, 2007; Taylor and Grotewold, 2005). Flavonoids appear to have played a major role in successful medical treatments in ancient times and their use has continued up to now (Gutteridge and Halliwell, 2010; Havsteen, 2002). The rst observation concerning their biological activities was made by Rusznyak and Szent-Giorgi (1936); the term vitamin P was proposed for avonoids, although it was later dismissed. Williams and Grayer (2004) have stated: Flavonoids continue to capture the interest of scientists from many different disciplines because of their structural diversity, biological and
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ecological signicance (e.g. the colored pigments in many ower petals), and health promoting and anti-cancer properties. Unlike traditional vitamins, avonoids are not essential for short-term well-being. Nevertheless, modest long-term intake may exhibit potential health benets (Jaganatah and Crozier, 2010). However, the responsible natural chemicals seldom work independently (Lila, 2009). Flavonoid subclasses are simultaneously present in foods or food products of plant origin, thus making it difcult to ascertain which family is responsible for a given potential biological effect (Pascual-Teresa et al., 2010). A complex interplay among the various components accounts for the pharmacological effects of functional foods, nature-derived supplements, and pharmaceuticals, as they modulate biological processes in human metabolism (Lila, 2009).
DIETARY SOURCES Flavonols are the most widespread of the avonoids in plant food. Flavones, unlike avonols, they are not widely distributed, and as a consequence their dietary is very low. Flavan3-ols represent the most common avonoid consumed in the American and, most probably, the Western diet and are regarded as functional ingredients in various beverages, whole and processed foods, herbal remedies, and supplements (Jaganatah and Crozier, 2010). Their presence in food affects quality parame-
ters such as astringency, bitterness, sourness, sweetness, salivary viscosity, aroma, and color formation. Red wines and berries are typically rich in anthocyanins (Birse, 2007; Kuskoski et al., 2006; Zimman, Waterhouse and Kennedy, 2004; Kuskoski et al., 2003). Quercetin, the most common avonol, is abundant in onions, broccoli, and lettuce. Tea leaves, coffee beans, and red wine are rich in avanols. Leguminous species (soybeans) are rich in isoavone, which have a very limited distribution in the plant kingdom. Citrus fruits are rich in avanones, while tropical plants are also rich in avonoids (Passamonti et al., 2010; Liu et al., 2008; Manach and Donovan, 2004). Flavonols and avones occur in food usually as glycosides. Of the major avonoid classes, avonols predominate in fruits in which a variety of glycosides have been identied, whereas in vegetables quercetin glycosides predominate. Flavones are much less common than avanols in fruit and vegetables. The only important edible sources of avones identied to date are parsley and celery (Manach and Donovan, 2004). Flavanones are exclusively found in citrus fruits. Dietary sources of avonoids are compiled in Table 4. FLAVONOID DATABASE The principal weakness in most epidemiological studies in this area lies in the food composition database on avonoids used because data on avonoid composition are scarce (Zamora-Ros
TABLE 4 Dietary sources of avonoids Flavonoid subclass Anthocyanins Chalcones Flavanols Prominent food avonoids Cyanidin Delphynidin Cinnamon methylhydroxychalcone Catechin Epigallocatechin Epigallicatechingallate Taxifolin or dihydroquercetin Aromaderin or dihydrokaempherol Hesperetin Naringenin Eriodiclyol Quercetine Kaempferol Myricetin Apigenin Luteolin Genistein Daidzein Glyatein Mangostin Typical rich food sources Bilberries, black and red currants, blueberries, cherries, chokecherries, grapes, strawberries, pomegranates Apples, pears, strawberries, tomatoes, cinnamon Apples, blueberries, grapes, onions, lettuce, red wine, tea, chocolate, apricots, sour cherries, grape juice, mint Grapes, red onion, ac ai palm Citrus fruits and juices, peppermint
Flavanonols Flavanones
Flavonols
Apples, beans, blueberries, buckwheat, cranberries, endive, leeks, broccoli, lettuce, onions, olives, peppers, tomatoes Citrus fruits, celery, parsley, spinach, rutin, olives, artichokes Soybeans, grape seed/skin, chick-peas, black beans, green peas
Flavones Isoavones
Xanthones
Mangoes, mangosteens, bark of pear, apples, cherries
Sources: Ignat et al., 2011; Han et al., 2007; Naczh and Shadidi, 2006; Manach et al., 2004; Beecher, 2003; Aherne and OBrien, 2002; Duthie et al., 2000; Rice-Evans et al., 2000.
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et al., 2010). However, there has been increasing interest at the international level in assessing the quality of data in food composition databases (Castanheira et al., 2009; Reinivuo et al., 2009). Integrated databases of avonoids for nutrition research, containing information on structural, biological, and physicochemical properties, have been constructed in order to assist chemical and biological research (Kinoshita et al., 2005, 2006). The USDA (United States Department of Agriculture) has maintained tables of food composition for over 120 years, since the pioneering work of Atwater and Woods (Atwater, 1895). The USDA databases are the most complete, updated, and used databases in the estimation of avonoid intake (Zamora-Ros et al., 2010; Haytowiz et al., 2009). The USDA Special Interest Database for avonoid content of selected foods contains 26 of the most abundant compounds within ve predominant subclasses of avonoids: avonols, avones, avanones, avan-3ols, and anthocyanidins (Holden et al., 2005). The Nutrient Data Laboratory (NDL) of USDA conducted a validation study of the USDA Data Quality Evaluation System (DQES) (Bhagwat et al., 2009). The quality of the Brazilian National Flavonoid Databas has also been evaluated following the indications of USDA-DQES (Menezes et al., 2011). There is no doubt that the combination of databases could provide a very powerful tool for the design and interpretation of clinical and epidemiological studies in the future (Kay, 2010). DIETARY INTAKE Considerable effort has been made to establish optimal human dietary consumption levels for avonoids based on their pharmacodynamic effects and to determine avonoid content in assorted dietary sources (Chun et al., 2007). The avonoid content in food ranges from 10 to 104 mg/kg of fresh weight (Manach and Donovan, 2004). Reliable values for avonoids in foods are needed to test the possible relationships of avonoids with cardiovascular diseases and cancer risk reduction, and to adopt potential policies related to these phytochemicals. The World Health Organization recommends a daily intake of at least 400 g of fruits and vegetables, together with physical activity, to prevent cardiovascular diseases, certain cancers, obesity, and diabetes (World Health Organization, 2004). Flavonoids are the most common and the largest plant polyphenolics obtained from the everyday plant-source diet (Chun et al., 2007), and their daily intake, depending on diet, can range from several hundred mg up to 12 g (Pan et al., 2010; Holden et al., 2005; Vries et al., 1997). The U.S. public consumes as much as 250 mg of avonoids per person per day (Manach and Donovan, 2004) in a variety of forms (fruits, vegetables, nuts, drinks, spices, and vitamin and mineral supplements). Intake was estimated at 189.7 11.2 mg, by using USDA databases in the framework of the 19922002 National Health and Nutrition Examination Survey (NHANES), with tea, citrus fruit juices, wine, and citrus fruits being the major dietary sources (Chun et al., 2007). Depending on food choice, this could be even much higher.
The daily intake of food avonoids in a group of 45 female Flemish dietitians, determined by using a semi-quantitative food frequency questionnaire, was 166.0 146.6 mg/d, 203.0 243.2 mg/d, and 158.3 151.8 mg/d, respectively, depending on the method (Mullie et al., 2008). The estimated ingestion by the Brazilian population ranged from 60 to 106 mg/day (Arabbi et al., 2004). Estimated dietary avonoid consumption of the Australian population was 351 mg per person per day, of which 75% were avan-3-ols (Johannot and Somerset, 2006). Tea was the major dietary avonoid source in Australia. Great differences in avonoid intake and food sources were observed between a large Mediterranean cohort and non-Mediterranean populations (U.S. and Finland as nonMediterranean countries) (Zamora-Ros et al., 2010). The mean intake for a Spanish population was 313 mg/day (Zamora-Ros et al., 2010). Estimated per capita daily avonoid intake is 182 mg and 177 mg for the UK and Ireland, respectively (Beking and Vieira, 2011). Flavonoids are among the major antioxidant constituents of our diet. The daily intake is almost at the same level as the sum of other antioxidants, including carotene, vitamin C, and vitamin E. CONCLUDING REMARKS The strict relationship between diet and health has been known since ancient times, and recent studies demonstrated the relevance of many food components in modulating health (Gutteridge and Halliwell, 2010; Vitaglioni et al., 2004, Havsteen, 2002). The amount and the type of ingested fats, the intake of dietary ber (Palafox-Carlos et al., 2011), and the consumption of antioxidant compounds have been correlated to various chronic degenerative diseases (Hervert-Hern andez and Go ni, 2011; Crozier et al., 2010; Ramos, 2008; Nichenametla et al., 2006). The explosion of knowledge and interest in polyphenol chemistry in recent decades (i.e., Table 1) attests to its vast potential for practical applications in various elds and for simply gaining a better understanding of the chemistry of life (Ellestad, 2006). A tremendous increase in the number of scientic publications on polyphenols has happened over past 20 years (Quideau et al., 2011). The regular consumption of fruits, seeds, vegetables, and derived foodstuffs and beverages in which polyphenols are present in substantial quantities has been claimed to be benecial for human health, and plant polyphenols nowadays enjoy ever-increasing recognition not only by the scientic community but also, and most remarkably, by the general public (Quideau et al., 2011). Moreover, free radicals are known to take part in lipid peroxidation in foods, which is responsible for rancid odors and avors, which decrease nutritional quality (Leopoldini et al., 2011; Liu, 2010; Shahidi and Zhong, 2010; Scherer and Godoy, 2009; Hounsome et al., 2008). Natural antioxidants have high antioxidant activity and are used in many food applications (Sidani and Makris, 2011; Shoji, 2007). Phenolic compounds, which are widely distributed, have the ability to scavenge free
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radicals by single-electron transfer. The so-called antioxidant property has become the trademark of polyphenols in recent exploitation by the agro-food, cosmetic, and parapharmaceutical industries (although antioxidation is not a property limited to polyphenols) (Quideau et al., 2011). Recently discovered properties of phenolic compounds have been exploited for cosmetics, pharmaceuticals, nutritional supplements, and functional foods (Ahmad et al., 2011; Lobo et al., 2010; Corneli, 2009; Morganti, 2009). The food industry has launched numerous functional products, the health functionality of which is closely connected with their polyphenol content, which is usually higher than its content in traditional products (Valls et al., 2009). Flavonoids can be subdivided into a number of classes: chalcones, dihydrochalcones, aurons, avones, avonols, dihydroavonols, avanones, avanols (catechins), avandioles or leucoanthocyanidins, anthocyanidins (its glycoside is called anthocyanin), and isoavonones (Andersen and Markham, 2006; Grotewold, 2006b). Recent advances in genomics, proteomics, and metabolomics provide new approaches to dening the role of avonoids in plant development and to exploring their potential application in agriculture and medicine (Woo et al., 2005). Protection against oxidative diseases, ability to modulate the activity of various enzymes, and interactions with specic receptors are among the most signicant health benets of avonoids (Jaganatah and Crozier, 2010; Fraga, 2010; Daayf and Lattanzio, 2008; Grotewold, 2006b; Prior et al., 2006; Shahidi and Naczk, 2006). Food composition databases are essential for epidemiological research, public health, nutrition and education, clinical practice, and the food industry (Williamson, 2005), and many national food composition databases exist, the USDA database being the most complete in terms of the estimation of avanoid intake (Haytowitz et al., 2009). Anthocyanins are one of the avonoid groups that have been most widely studied in recent decades (Valls et al., 2009). Anthocyanins usually contain a single glucoside unit, but many anthocyanins contain two, three, or more sugars attached at multiple positions, or occurring as oligosacaride side chains. Intensity and type of the color of anthocyanins is affected by the number of hydroxyl and methoxyl groups: if more hydroxyl groups, then the color goes toward a more bluish shade; if more methoxyl groups, then redness is increased (He and Giusti, 2010; Giusti and Jing, 2008; Heredia et al., 1998). In spite of the increasingly large number of structures they are derived from, only about 30 different anthocyanidins, almost 94% of the new anthocyanins discovered are in fact based on only the six common anthocyanidins: pelargonidin, cyanidin, delphinidin, peonidin, petunidin, and malvidin (Jin and Giusti, 2011; Andersen and Jordhein, 2006). A point of note is that antocyanins are readily distinguished from other avonoids as they undergo rearrangements in response to pH (Crozier et al., 2010). The uniqueness of anthocyanin antioxidants critically depends on their ability
for electron delocalization and to form resonating structures following changes in pH, which does not take place in other popular antioxidants (Zafra-Stone et al, 2007; Prior and Wu, 2006). The topics of anthocyanidin equilibrium forms, biosynthesis, and molecular biology, and anthocyanin localization in plant cells have seen important progress in recent years (Gould et al., 2009; Andersen, 2008). The purpose of this review, which intends to reect the interdisciplinary nature of the research in this prolic area, is to serve as a useful introduction to the study of analysis and antioxidant capacity of anthocyanin pigments, taking into account the general aspects of the topic and considerations concerning polyphenols and avonoids. The following topics will be the subject of future reports: (i) early history, chemical structure, color, and intake of anthocyanins; (ii) the extraction, analysis, and antioxidant power of anthocianin pigments; and (iii) the bioavailability, biological activity, methods used for measuring the antioxidants of anthocyanin, and the inuence of anthocyanins in the antioxidant activity of red wines. ACKNOWLEDGMENTS This work was supported by the Junta de Andaluc a (Spain) through grant excellence research project P06-FQM-02029, for which the authors are grateful. Thanks are due to Professor Ana Troncoso Gonzalez for helping in the discussion and writing of this article. REFERENCES
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This article was downloaded by: [Birla Tech Inst ] On: 30 November 2013, At: 23:03 Publisher: Taylor

Critical Reviews in Analytical Chemistry

Department of Analytical Chemistry , The University of Seville , Seville , Spain

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ANTHOCYANIN PIGMENTS, PART I

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ANTHOCYANIN PIGMENTS, PART I

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Hervert-Hern andez and Go ni, 2011 Leopoldini et al., 2011

Quideau et al., 2011 Burton-Freeman, 2010

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ANTHOCYANIN PIGMENTS, PART I

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Scalbert and Williamson, 2000

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ANTHOCYANIN PIGMENTS, PART I

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Del Rio et al., 2010a Galleano, 2010 Gupta et al., 2010

Kay, 2010 Liu et al., 2010

ANTHOCYANIN PIGMENTS, PART I

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FIG. 3. Structure of anthocyanins.

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ANTHOCYANIN PIGMENTS, PART I

Flavonoid class Flavanols Flavonols Flavones Flavanones Anthocyanidins

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Mangoes, mangosteens, bark of pear, apples, cherries

ANTHOCYANIN PIGMENTS, PART I

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