Approximately 1500 colored compounds, also known as natural food pigments, have been isolated from foodstuffs.

On the basis of their chemical structure, these food pigments can be grouped in the following six classes: heme pigments, chlorophylls, carotenoids, flavonoids, betalains, and miscellaneous pigments.

1. Heme Pigments Heme (from the Greek for blood) is responsible for the red color of two important animal pigments: hemoglobin, the red pigment of blood, and myoglobin, the red pigment of muscles. Practically all the red color of red meat is due to myoglobin. Other colored muscle compounds (cytochromes, vitamin Bi2, flavoproteins) do not contribute significantly to the color of red meat.

FIGURE 1 Structure of heme. The myoglobin in meat is subject to chemical and color changes. Freshly cut meat looks purplish. On exposure to air, the surface of the meat acquires a more pleasing red hue (blooming

of the cut). The color change is due to the oxygenation of myoglobin. Severe oxidative deterioration may result in the formation of green pigments (sulfmyoglobin, chole-myoglobin). When meat is cooked, the protein moiety (globin) of myoglobin is denatured and the heme is converted chiefly to nicotinamide hemichrome, the entire pigment acquiring a brown hue. In cured meats, in which nitrite is used, many reactions occur, some of which lead to color changes. Among the established reactions are the following: (1) the nitrite salt is converted to nitric oxide (NO), nitrate, and water; (2) the NO replaces the H2O attached to the iron of heme and forms nitrosyl myoglobin, which is reddish; (3) on heating, the nitrosyl myoglobin is transformed to nitrosyl hemochrome, which has the familiar pink color of cured meats; and (4) any metmyoglobin present in the cured meat is similarly nitrosylated, reduced, and finally converted to nitrosyl hemochrome.

2. Chlorophylls Several chlorophylls have been described. Two of them, chlorophyll a and chlorophyll b, are of particular interest in food coloration because they are common in green plant tissues, in which they are present in the approximate ratio 3:1, respectively. Their structures resemble that of heme since they are all derivatives of tetrapyrrole. As food pigments, chlorophylls impart their green color to many leafy (spinach, lettuce, etc.) and nonleafy (green beans and peas, asparagus, etc.) vegetables and to unripe fruits. They are not very stable pigments. Ethylene, a gaseous plant hormone, destroys chlorophylls, and it is occasionally used to degreen fruits.

3. Carotenoids Many of the yellow, orange, and red colors of plants and animals are due to carotenoids, pigments similar to those of carrots. The basic structure of carotenoids is a chain of eight isoprenoid units. Some carotenoids are hydrocarbons and are known as carotenes, while others contain oxygen and are called xanthophylls. The carotenoids of foods, however, are usually in the all-trans form. Carotenoids occur free or as esters of fatty acids or as complexes with proteins and carbohydrates; for example, in paprika, capsanthin is esterified with lauric acid. In live lobster, astaxanthin is complexed with protein; the astaxanthin-protein complex is blue-gray, the color of live lobster, but on heating, the complex is broken and the freed astaxanthin imparts its red color to the cooked lobster.

Carotenoids are present in a large variety of foods, from yeast and mushrooms, to fruits and vegetables, to eggs, to fats and oils, to fish and shellfish. As fat-soluble substances, carotenoids tend to concentrate in tissues or products rich in lipids, such as egg yolk and skin fat, vegetable oils, and fish oils.

Types of Carotenoids and Their Natural Sources

Name and source

f-Carotene (carrot, egg, orange, chicken fat)

Xanthophyll (vegetables, egg, chicken fat)

Zeaxanthin (yellow corn, egg, liver)

Cryptoxanthin (egg, yellow corn, orange)

Physalien (asparagus, berries)

Bixin (annatto seeds)

Lycopene (tomato, pink grapefuit, palm oil)

Capsanthin (paprika)

Astaxanthin (lobster, shrimp, salmon)

Torularhodin (Rhod otorula yeast)

Canthaxanthin (mushrooms)

f -Apo-8-carotenal (spinach, orange)

Additional information (not necessary to right)

The stability of carotenoids in foods varies greatly, from severe loss to actual gain in carotenoid content during storage. Carotenoid losses amounting to 20 or 30% have been observed in dehydrated vegetables (e.g., carrots, sweet potatoes) stored in air. These losses are minimized when the dry product is stored in vacuum or inert gas (e.g., nitrogen), at low temperatures, and protected from light. The main degradative reaction of carotenoids is oxidation. Oxygen may act either directly on the double bonds or through the hydroperoxides formed during lipid autoxidation. Hydroperoxides formed during enzymatic lipid oxidation can also bleach carotenoids by a coupled lipid-carotenoid oxidation mechanism. On the other hand, certain vegetables, such as squash and sweet potatoes, in which carotenoid biosynthesis continues after harvesting, may manifest an increase in carotenoid content during storage

4. Flavonoid Pigments Hundreds of flavone-like pigments are widely distributed among plants. The basic structure of all these compounds comprises two benzene rings, A and B, connected by a heterocycle. The classification of flavonoids is based on the nature of the heterocycle. Most of these pigments are yellow (Latin, flavus). One important exception is the anthocyanins, which display a great variety of red and blue hues. a) Anthocyanins The name of these pigments was originally coined to designate the blue (kyanos) pigments of flowers (anthos). It is now known that not only the blue color, but also the purple, violet, magenta, and most of the red hues of flowers, fruits, leaves, stems, and roots are attributable to pigments chemically similar to the original "flower blues." Two exceptions are notable: tomatoes owe their red color to lycopene and red beets owe theirs to betanin, pigments not belonging to the anthocyanin group. Anthocyanins are glycosides of anthocyanidins, the latter being polyhydroxyl and methoxyl derivatives of flavylium. The color of anthocyanins is influenced not only by structural features (hydroxylation, methoxylation, glyco-sylation, acylation), but also by the pH of the solution in which they are present, copigmentation, metal complexa-tion and self-association. The pH affects both the color and the structure of an-thocyanins. In very acidic solution, anthocyanins are red, but as the pH rises the redness diminishes. In freshly prepared alkaline or neutral solution, anthocyanins are blue or violet, but (with the exception of certain multiacylated anthocyanins) they fade within hours or minutes.

Major Classes of Flavonoids Class Structure Example (source)

Flavones

Apigenin (chamomile)

Flavan-3-ols (catechins)

()-Epicatechin (cocoa)

Flavan-3, 4-diols

Leucocyanidin (peanut)

Flavanones

Naringenin, hesperidin (citrus fruits)

Flavonols

Quercetin (apples, grapes)

Flavanonols

Taxifolin (Prunus)

Isofiavones

Genistein (soybeans)

Anthocyanidins

Pelargonidin, cyanidin, delphinidin (berries, red apples, red grapes)

Chalcones

Butein (Butea)

Aurones

Aureusidin (Oxalis)

FIGURE 4 Six anthocyanidins common in foods. The electric charge shown at position 1 is delocalized over the entire structure by resonance.

Generally, the attractive color of anthocyanin-pigmented foods is not very stable. Canning of red cherries or berries results in products with considerable bleaching. Strawberry preserves lose one-half of their anthocyanin content after a few weeks on the shelf, although the browning reaction may mask the loss. And red grape juice is subject to extensive color deterioration during storage. Sulfur dioxide, which is used for the preservation of some fruit products (pulps, musts), bleaches anthocyanin pigments, but on heating of the fruit prduct in vacuum the SO2 is removed and the anthocyanin color reappears. Large concentrations of SO2, combined with lime, decolorize anthocyanins irreversibly and are used in the preparation of maraschino cherries. Anthocyanins act as anodic and cathodic depolarizers and thereby accelerate the internal corrosion of tin cans. It is therefore necessary to pack anthocyanin-colored products in cans lined with special enamel. In aging red wines anthocyanins condense with other flavonoids and form polymeric redbrown pigments. On continued polymerization these pigments become insoluble and form sediments in bottled red wines.

b) Other Flavonoids Among flavonoids other than anthocyanins, the catechins, flavonols, and leucoanthocyanidins have the widest distribution in foodstuffs, while flavonone glycosides are of special interest in citrus fruits. Catechins, or flavan-3-ols, are present mainly in woody tissues. Among common foods, tea leaves contain at least six catechins representing about 25% of the dry weight of tea leaves. Tea catechins are excellent substrates for the catechol oxidase that is present in tea leaves and participates in the conversion of green tea to black tea. The reddish brown color of tea brew is due to a mixture of pigments known as theaflavins and thearubigins. Anthocyanidins Present as Anthocyanins in Fruits and Vegetables Fruit or vegetable Apple (Malus pumila) Blackberry (Rubus fructicosus) Black currant (Ribes nigrum) Blueberry (lowbush,Vaccinium Anthocyanidin Cyanidin Cyanidin Cyanidin. delphinidin Delphinidin, petunidin,

angustifolium; highbush, V. corymbosum)

malvidin, peonidin, cyanidin

Cherry (sour, Montmorency, Prunus Cyanidin, peonidin cerasus; sweet, Bing, P avium) Cranberry (Vacinnium macrocarpon) Cyanidin, peonidin Elderberry (Sambucus nigra) Fig (Ficus carica) Gooseberry (Ribes grossularia) Grape (red European. Vitis vinifera) Cyanidin Cyanidin Cyanidin Malvidin, peonidin, delphinidin, cyanidin, petunidin, pelargonidin Grape (Concord, Vitis labrusca) Cyanidin, delphinidin, peonidin, malvidin, petunidin Mango (Mangifera indica) Mulberry (Morus nigra) Olive (Olea europea) Orange (Ruby, Citrus sinesis) Passion fruit (Passiflora edulis) Peach (Prunus persica) Pear (Pyrus communis) Peonidin Cyanidin Cyanidin Cyanidin. delphinidin Delphinidin Cyanidin Cyanidin

Plum (Prunus domestica) Pomegranate (Punica granatum) Raspberry (Rubus ideaus) Strawberry (Fragaria chiloensis and F. virginiaca) Beans (red, black; Phaseolus vulgaris) Cabbage (red, Brassica oleracea) Corn (red, Zea mays) Eggplant (Solanum melongena) Onion (Alium cepa) Potato (Solanum tuberosum)

Cyanidin, peonidin Delphinidin, cyanidin Cyanidin Pelargonidin, little cyanidin

Pelargonidin, cyanidin, delphinidin Cyanidin Cyanidin, pelargonidin Delphinidin Cyanidin, peonidin Pelargonidin, cyanidin, delphinidin, petunidin

Radish (Raphanus sativus)

Pelargonidin, cyaniding

Flavonols, like anthocyanidins, exist almost exclusively as glycosides. Flavonol glycosides impart weak yellow hues to apples, apricots, cherries, cranberries, grapes, onions, plums, potatoes, strawberries, tea, tomatoes, and other commodities. The most common leucoanthocyanidins are leu-copelargonidin, leucocyanidin, and leucodelphinidin, which are converted to the corresponding anthocyanidins. This conversion results in the undesirable "pinking" of certain products such as canned pears, canned banana puree, processed brussels sprouts, and beer. On the other hand, polymerization to tannins leads to astringency and the formation of haze in beer (insolubilization of beer proteins).

5. Betalains Betalain is a relatively new term used to describe a class of water-soluble plant pigments exemplified by the red-violet betacyanins and yellow betaxanthins. Betalains owe their name to the red beet (Beta vulgaris), from which they were originally extracted. Other foods containing betalains include chard, pokeberries, and Indian cactus fruits. The major red pigment of red beets is betanin, and their major yellow pigment is vulgaxanthin. Betalains are stable in the pH range 3.5-7.0, which is the pH range of most foods, but they are sensitive to heat, oxidation, and light.

6. Miscellaneous Natural Food Colors There are several hundred additional natural pigments that are not as widely represented in foods. Among them are the quinones and xanthones, which are yellow pigments. An example of a quinone is juglone, which is present in walnuts and pecans. Mangiferin, a representative of xan-thones, is found in mangoes. Tannins include two types of pale yellow to light brown compounds, characterized by their property to convert animal hides to leather. One type consists of condensed tannins, to which reference was made in relation to the leucoanthocyanidins, and the other type comprises hydrolyzable tannins, which are esters of a sugar, usually glucose, with gallic acid, ellagic acid, or both. Corilagin is an example of a gallotannin, in which glucose is esterified with three gallic acid molecules. A yellow pigment that has attracted much attention because of its toxicity to humans and nonruminant animals is gossypol. It is present in cottonseeds, which are used as animal feed and have been considered a potential source of protein for human use. Several biologically very important food constituents are colored, such as phytochrome (yellow), vitamin B2 (riboflavin, orange-yellow), and vitamin B12 (red), although their contribution to food coloration is negligible.