The addition of a metal ion helps stabilization of carbinol pseudo-base structures in the equilibrium mixture of delphinidin at appropriate pH values and provides a blue hue [ 25 ]. Also, color changes of flower anthocyanins are due to the copigmentation of anthocyanidins with flavonoids, which increases the color intensity of the flower [ 3 ]. In addition, glycosylation and acylation increase the color strength of anthocyanin.
Anthocyanins are less stable at higher solution temperatures. In contrast, heat treatment of an anthocyanin-rich extract solution may not cause a degradation of anthocyanin pigments. This is because the extract commonly contains phenolic compounds that are enzymatically degraded by polyphenol oxidase. Therefore, mild heat treatment of raw materials, such as blanching, in the food processing industry can prevent oxidation of anthocyanins by polyphenol oxidase. The use of natural colorant and additives in processed foods and beverages is important for increasing consumer acceptability of these products.
Anthocyanins are some of the natural colored pigments extracted from plants, which have an attractive hue. Anthocyanins extracted from plants are red, blue, and purple pigments. These pigments are the natural colorants with low to no toxicity. Natural colorants are somehow safe to be consumed even at higher doses compared to synthetic colorants.
Anthocyanins, as natural colorants, have value-added properties [ 29 ]. These properties are antioxidants, as nutraceutical and many health benefits, such as an antimicrobial effect and prevention of chronic diseases. Anthocyanins occur as flavylium ions in grapes and wines. During digestion, the flavylium ion is converting to carbinol pseudo-base, quinoidal-base, or the chalcone at increasing pH before being absorbed into the blood system [ 30 ].
As mentioned earlier, anthocyanin pigment appears to be red in acidic conditions and blue to purple in alkaline solutions. These colored pigments are commonly extracted from flowers, berries, blackcurrant, and purple-colored fruits and vegetables. Also, water is the typical extraction medium for isolation of anthocyanin pigments. Moreover, some food processing factories use alcoholic solutions to extract anthocyanin pigments.
It is because anthocyanins are soluble in both water and most of the organic solvents.
Password Forgot My Password. This review focuses on the advances in the last 15 years, and cites references. Snedecore and W. Totani, M. Khanna and M.
On the contrary, anthocyanin is not soluble in the apolar organic solvent. It is also not stable in alkaline or neutral solutions. At a lower pH or in an acidic condition, anthocyanidins such as cyanidin is highly soluble in water due to the formation of flavylium cation which appears as red [ 19 ]. Acidic conditions maintain the stability of flavylium ion and increase the intensity of the red hue of the anthocyanin pigment.
This characteristic makes it a good candidate as a colorant, where the red anthocyanin pigment is highly stable in acidic aqueous solutions. It is best used as a colorant for red-colored beverages. Deprotonation of the flavylium ion occurs at increasing pH, where the quinoidal bases favor alcoholic solution [ 16 ].
For example, the colors of red wine can be visualized as purplish red at lower pH or bluish-violet at higher pH. The typical range of pH in red wine is 2. In an alcoholic solution, the red flavylium cation substantially converts to blue quinonoidal species which makes the red wine looks bluish-violet.
Selected Natural Colorants in Foods and Beverages. Jennifer M. Ames and Thomas Hofmann. Chapter 1, pp It includes reviews of the chemistry and physiology of food colorants, carotenoids, anthocyanins and the oxidative transformation of tea.
Anthocyanin aglycone has higher solubility in alcohol than its glucoside, whereas glycosylated anthocyanin is highly soluble in water [ 31 ]. The polyphenolic structure of anthocyanin adds a hydrophobic characteristic to it, and makes it soluble in organic solvents, such as ethanol and methanol. Besides the flavylium cation, the solubility of anthocyanidin in water could be due to the 3-hydroxyl group in the C-ring of anthocyanidin that always linked to sugar s , which forms a stable anthocyanin in water.
Among the anthocyanidins, delphinidin is the most soluble in methanol, followed by water, ethanol, and acetone [ 32 ]. As compared to delphinidin, cyanidin has lower solubility in methanol. It is because a low yield of cyanidin has been extracted from grape skins using methanol [ 33 ]. Also, delphinidin has higher solubility in water compared to malvidin because malvidin has lower polarity than delphinidin [ 34 ].
Malvidin is highly soluble in water compared with methanol and ethanol due to the static dipole moment of malvidin in water being higher than in methanol and ethanol [ 35 ]. Its solubility in water reduces with increasing degrees of acylation [ 12 ]. Although no study compares the solubility of these six anthocyanins in water, a decreasing polarity of anthocyanidins has been reported in the order of delphinidin, cyanidin, petunidin, pelargonidin, peonidin, and malvidin [ 37 ]. In actual fact, malvidin, peonidin, and petunidin are less soluble in water compared to cyanidin, delphinidin, and pelargonidin.
The solubility of anthocyanins in water increases at lower pH values where strong protonation occurs [ 16 ]. The addition of HCl to alcohol increases the solubility of anthocyanins [ 35 ]. Malonylation of anthocyanidin also enhances its solubility in water and stabilizes its structure [ 31 ]. Therefore, malonylation of anthocyanin aglycone preserves its pigment color for the use as food colorant.
Nevertheless, the color of anthocyanin is greatly dependent on the number of hydroxyl groups attached to the B-ring. The use of organic solvents such as methanol and ethanol to extract anthocyanin pigments causes a toxicity issue. Although ethanol is considered as a generally safe extraction medium, isolation of anthocyanins using water-based extraction is consider a greener way.
Subcritical water-based extraction is one of the methods that have been tested for the extraction of anthocyanins from berries. This extraction technique uses acidified water 0.
It is a highly efficient technique for extraction of anthocyanins from fruit. Anthocyanin pigments also can be extracted by the addition of sulfur dioxide to water for stabilizing the anthocyanin structure with an enhanced diffusion coefficient of anthocyanin molecules through the solid [ 39 ]. This increases the solubility of anthocyanins from the plant during extraction with water. Anthocyanins are extracted from plants as a crude mixture.
For that reason, separation or isolation of specific type of anthocyanin is needed for a specific purpose. Separation and identification of anthocyanins can be done by various chromatographic methods. These include thin layer chromatography, high speed countercurrent chromatography, high-performance liquid chromatography, cellulose column chromatography, and reversed-phase ion-pair chromatography, as well as gas chromatography.
In the early days, cellulose column chromatography is used for the separation of anthocyanin mixtures, but difficulties may be encountered in applying this technique in the presence of large amounts of other flavonoid materials. Purification of anthocyanin carried out by countercurrent chromatography is also too expensive to be popular [ 40 ].
Lately, macroporous adsorption resin is used in the purification of phenolic pigments because AB-8 resin is a kind of macroporous resin specially invented for purification of flavonoid [ 41 ]. In addition to separation and identification of anthocyanins, quantification of these compounds is commonly done by various chromatographic methods.
High-performance liquid chromatography is the most used method in quantification of anthocyanins. However, gas chromatography has been applied in the quantification of anthocyanins [ 42 ]. Although gas chromatography is invented specifically for identification and quantification of hydrocarbon, the use of mass spectrometry enables the determination of anthocyanins using gas chromatography. Anthocyanins are found abundant in plants, including red-purplish or red to blue-colored fruits, leaves, flowers, roots, and grains.
Types of anthocyanin and anthocyanidin have been determined in fruits and vegetables. As shown in Table 1 , cyanidinglucoside is the most abundant anthocyanin determined in fruits and vegetables. In plants, cyanidinglucoside is formed as the consequence of low pH [ 54 ].
All berries that contain glycosides of cyanidin probably do so due to the acidic nature of the berries. Malvidin, peonidin, and petunidin are not commonly found in berries. These anthocyanidins are in methylated forms, therefore, the pigments are not commonly found in red berries. A possible reason is that methylated anthocyanidin has lesser reddening effect than the non-methylated structure. Moreover, these anthocyanidins are typically detected in blue-colored fruit. Petunidin is the anthocyanidin formed in most fruits. Other than the fruits and tomato as fruit vegetable, as well as flowers, petunidin is not commonly determined in purple-colored leaves, roots, and grains.
Although most of these purple-colored vegetables contain petunidin and its glycosides, these pigments are not well-known for the potential health benefits.