Anthocyanins - Anthocyanin Color Source Anthocyanins are one of the most abundant natural pigments available.

Anthocyanins are the vacuolar pigments found in almost every part of higher plants. The word "anthocyanin" is derived from two Greek words, anthos (flower) and kyanos (blue). There are six types of anthocyanins all exhibiting different stability profile based on their structure, supporting compounds, process and chemicals used for extraction and food processing. Anthocyanin pigments change their color with the change in the pH. So based on the pH, anthocyanins can be red, blue or purple. Because of this property of changing anthocyanin color, this pigment is also used as a pH indicator. Anthocyanin pigments change from blue in bases and red from acids. Anthocyanin pigments are odorless and flavourless. You can find anthocyanin pigments in every part of the higher plants like stems, roots,

leaves, fruits and flowers. Till 2006 more than 550 anthocyanins had been discovered. Anthocyanin pigments are responsible for the red, purple, and blue colors of many fruits, vegetables, cereal grains, and flowers. These pigments undergo reversible structural transformations with a change in pH manifested by strikingly different absorbance spectra. Anthocyanins being natural colorant appear in the exempt from certification in the FDA list but permits restricted use. They are not used in drugs and cosmetics. They are used in beverages, fruit fillings, snacks, dairy products and confectionery. Anthocyanin Pigment Properties Red, Purple and Blue Red Cabbage, Source Strawberries, Grape Skin, Blueberries, Raspberries Cyanidin, Color Pigments Delphinidin, Malvidin, Peonidin, Color

Petunidin, Pelargonidin Solubility Soluble in aqueous solutions Stability Each pigment has different stability Brighter in lower pH range Becomes blue at higher pH Antimicrobial Other Properties Properties Antioxidant properties Anti-cancer properties International Coding Cyanidin CAS# 52858-5 Delphinidin CAS# 52853-0 Malvidin CAS# 643-

84-5 Peonidin CAS# 13401-0 Petunidin CAS# 142930-7 Pelargonidin CAS# 13404-3 E163 Anthocyanin as Food Additive Natural anthocyanin pigments act as a secondary metabolites and anthocyanins are food additives with e number 163. All anthocyanins have great antioxidant properties in vitro but scientists are not sure whether this antioxidant property is conserved after consuming the plant carrying it or not. Types of Anthocyanins

sugar-free anthocyanidin aglycones anthocyanin glycosides

Sources and Usesof Anthocyanins Berries are the rich source of anthocyanin color and natural anthocyanin pigments. Also you can get it from grapes, black carrots and other fruits and vegetables. The anthocyanin color is water

soluble so chiefly used as a coloring agent in different kinds of food. Anthocyanin color is used in jams, sugar confectioneries, jellies, soft drinks and frozen products. ANTHOCYANINS AND ANTHOXANTHINS. The term anthocyanin has been employed by botanists to denote all the water-soluble pigments of flowers and blossoms, but with new knowledge of the chemical nature of these colouring matters a more exact classification has become possible and the expression is now applied to particular substances which are responsible for the red, blue, mauve, purple and violet colours of flowers. The anthoxanthins are a chemically related class of water-soluble yellow or orange pigments possessing relatively feeble tinctorial power. The bright yellow, orange and green colours are usually due to the presence of one or other of the plastid pigments (xanthophyll, carotin, chlorophyll etc.), insoluble in watery media but soluble in fats and oils. These do not occur, as do the antho cyanins, in the cell-sap, and there is no visible chemical link con necting the plastid and anthocyanin pigments.

One of the most interesting and obvious properties of the anthocyanins is the change of colour which they exhibit when treated with acids or alkalis. It is said that Yorkshire children turn bluebells red by placing them in ant-hills; the formic acid produced by the insects is responsible for this curious result. In 1664 Robert Boyle wrote "Take good Syrrup of Violets, Impraeg nated with the Tincture of the flowers, drop a little of it upon a White paper . . . and on this Liquor let fall two or three drops of Spirit either of Salt or Vinegar, or almost any other eminently Acid Liquor and upon the Mixture of these you shall find the Syrrup immediately turn'd Red.... But to improve the Experi ment, let me add what has not been hitherto observ'd, namely, that if instead of Spirit of Salt, or that of Vinegar, you drop upon the Syrrup of Violets a little Oyl of Tartar per Deliquiurn or the like quantity of Solution of Potashes, and rubb them to gether with your finger, you shall find the Blew Colour of the Syrrup turn'd in a moment into a perfect green." It is probable that the green colour resulted from the produc tion of a bright yellow colour by the action of the alkali on an anthoxanthin in solution, the anthocyanin retaining its blue colour. Many colourless flowers, for example jasmine and Antirrhinum, develop bright yellow colorations in

ammonia. A typical antho cyanin is bluish-red in acid solution, violet in neutral solution and blue in alkaline solution. blue cornflower, the bordeaux red cornflower, the deep red dahlia, and the red rose contain one and the same anthocyanin, the variation in colour being simply due to the different degrees of acidity and alkalinity of the cell sap. More than one anthocyanin may be present in a flower or blossom, and the colours of many flowers are due to the presence of both anthocyanins and plastid pigments in the tissues. Yellow wallflowers contain a plastid pigment and an anthoxanthin that contributes very little to the total tinctorial effect ; the different shades of red wallflowers are due to varying proportions of antho cyanin and plastid colouring matters. Moreover, very small changes, botanically, in varieties or species may be associated with the development of different anthocyanins. In 1905, Molisch demonstrated the existence of anthocyanin crystals in the living plant, and showed that crystals of these pig ments could be readily prepared on a small scale by simple meth ods. For example, petals of the scarlet pelargonium are flattened and bruised on a glass surface, covered with a few drops of 75% acetic acid and then with a cover-glass and the whole placed under

a clock-glass to ensure slow evaporation. At the edges of the cover-glass or round the petals, crystals gradually maketheir appearance. Grafe, a few years later, carried cut this experiment on a larger scale and for the first tame isolated an anthocyanin pigment in quantity and in a tolerably pure condition. Our knowl edge of the chemistry of the anthocyanins is, however, chiefly due to Willstatter who, in a series of masterly researches, opened and all but completed a new chapter of organic chemistry. In 1913, Willstatter and Everest published an account of an investigation of the pigment of the blue cornflower. They found that the colour ing matter "cyanin" exists in the plant as its blue potassium salt, but that the substance can also combine with acids to red salts and that advantage may be taken of this property in the isola tion of the pure substance. In this case the work involved was difficult, the dried blue cornflower petals contained only 0.75% of their weight of colouring matter. It was later found that dried, deep red dahlia petals contain 2o% of their weight of the same colouring matter and about 5o% of this may be readily isolated in the following manner. The fresh flowers are extracted with acetic acid, methyl-alcoholic hydrochloric acid and 1 volumes of ether being then added. This

precipitates the chloride, which is insoluble in ether, and the salt may then be separated and re crystallized from a solution in 7% hydrochloric acid. It should be added that this process is unusually simple and straightforward owing to the high percentage of colouring matter in the flowers. The work of the florists in developing garden flowers rich in pig ment content has been extraordinarily successful. Cyanin chloride has the composition C2;H31010C1 and, like all the other anthocyanins yet examined, contains sugar in a combined form. This is readily detached by the action of boiling 20% hydro chloric acid, leaving a salt, termed cyanidin chloride, which tinc torially and in many other properties closely resembles cyanin chloride. The sugar so detached is glucose, C,H,208, each molecule of cyanin chloride giving rise to one of cyanidin chloride and two of glucose : Cyanin chloride is thus a diglucoside of cyanidin chloride. Meco cyanin chloride from the poppy (Papaver rhoeas, purple scarlet variety) has the same composition as cyanin chloride and, like it, is degraded to cyanidin chloride and glucose (2 molecules). The solution of cyanin in aqueous sodium carbonate is blue, whereas that of mecocyanin is violet, and there are other diver

gencies. The explanation must be sought in the different mode of the molecular attachment of the cyanidin and glucose com plexes in the two substances. Chrysanthemin, the pigment of the deep red garden chrysanthemum, resembles mecocyanin, but its molecule gives rise to only one molecule of glucose to each mole cule of a cyanidin salt ; it is monoglucosidic. One of the .pig ments of the aster very closely resembles chrysanthemin, whilst the colouring matters of the sweet cherry and of the sloe are apparently allied to mecocyanin, but contain rhamnose as one of the sugar components. Very careful treatment of mecocyanin with hydrochloric acid causes the loss of only one glucose molecule, and the result is chrysanthemin chloride. It will be observed that sev eral anthocyanins may be regarded as derived from cyanidin and that their differences may be traced to the varying nature of the sugars, to the number of sugar molecules attached to one of c} anidin, and to the position of such attachment. The further work of Willstatter and his colleagues brought to light the curious fact that, despite the existence in nature of a range of colour unrivalled by art, the number of fundamental sugar-free pigments of the type of cyanidin chloride, termed anthocyanidins, is very limited.