Anthocyanin

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Anthocyanins are glucosides of anthocyanidins, the basic chemical structure of which is shown here.
Anthocyanins are glucosides of anthocyanidins, the basic chemical structure of which is shown here.
Anthocyanin gives these pansies their dark purple pigmentation.
Anthocyanin gives these pansies their dark purple pigmentation.

Not to be confused with Anthocyanidin, their sugar free counterparts.

Anthocyanins (from Greek: ἀνθός (anthos) = flower + κυανός (kyanos) = blue) are water-soluble vacuolar pigments that may appear red, purple, or blue, according to pH. The pigment belongs to a class of molecules called flavonoids, which are synthesized via the phenylpropanoid pathway. Anthocyanins are synthesized by organisms in the plant kingdom, and have been observed to occur in all tissues of higher plants, including leaves, stems, roots, flowers, and fruits. Anthoxanthins are their clear, white to yellow plant pigment counterparts.

Contents

[edit] Function

Red color in Fuji apples
Red color in Fuji apples
Anthocyanin is the purple color of the vertical stripes on stem of this Jalapeño cultivar.
Anthocyanin is the purple color of the vertical stripes on stem of this Jalapeño cultivar.

In flowers, bright reds and purples are adaptive for attracting pollinators. In fruits, the colorful skins also attract the attention of animals, which may eat the fruits and disperse the seeds. In photosynthetic tissues (such as leaves and sometimes stems), anthocyanins have been shown to act as a "sunscreen", protecting cells from high-light damage by absorbing blue-green and UV light, thereby protecting the tissues from photoinhibition, or high-light stress. This has been shown to occur in red juvenile leaves, autumn leaves, and broad-leaved evergreen leaves that turn red during the winter. It has also been proposed that red coloration of leaves may camouflage leaves from herbivores blind to red wavelengths, or signal unpalatability, since anthocyanin synthesis often coincides with synthesis of unpalatable phenolic compounds.

In addition to their role as light-attenuators, anthocyanins also act as powerful antioxidants. However, it is not clear whether anthocyanins can significantly contribute to scavenging of free-radicals produced through metabolic processes in leaves, since they are located in the vacuole, and thus, spatially separated from metabolic reactive oxygen species.

[edit] Occurrence

Juvenile anthocyanin in new rose growth. The reddish hue disappears as the new leaves mature.
Juvenile anthocyanin in new rose growth. The reddish hue disappears as the new leaves mature.
Food source Anthocyanin content
in mg per 100 g
açaí 320
blackcurrant 190-270
chokeberry 1,480[1]
eggplant 750
orange ~200
Marion blackberry 317[2]
black raspberry 589[3]
raspberry 365
wild blueberry 558[4]
cherry 350-400
redcurrant 80-420
red grape 888[5]
red wine 24-35

Anatomically, anthocyanins are found in the cell vacuole, mostly in flowers and fruits but also in leaves, stems, and roots. In these parts they are found predominantly in outer cell layers such as the epidermis and peripheral mesophyll cells.

Most frequent in nature are the glycosides of cyanidin, delphinidin, malvidin, pelargonidin, peonidin and petunidin. Roughly 2% of all hydrocarbons fixated in photosynthesis are converted into flavonoids and their derivatives such as the anthocyanins. There is no less than 109 tons of anthocyanins produced in nature per year.[citation needed] Not all land plants contain anthocyanin; in the Caryophyllales (including cactus, beets, and amaranth), they are replaced by betalains.

Plants rich in anthocyanins are Vaccinium species, such as blueberry, cranberry and bilberry, black raspberry, blackberry, blackcurrant, chokeberry, cherry, eggplant, black rice (forbidden rice), purple grape, red wine, red cabbage and violet petals. One hundred grams of ripe Marion blackberry, for example, contains 317 mg of anthocyanins (table). Anthocyanins are less abundant in banana, asparagus, pea, fennel, pear and potato.

The highest recorded amount appears to be specifically in the seed coat of black soybean (Glycine max L. Merr.) containing some 2,000 mg per 100 g[6] and in skins and pulp of black chokeberry (Aronia melanocarpa L.) (table). However, the Amazonian palmberry, açaí, having about 320 mg per 100 g[7] (of which cyanidin-3-glucoside is the most prevalent individual anthocyanin (approximately 10 mg per 100 g),[8] is also a high-content source for which only a small fraction of total anthocyanins has been determined to date.

Nature and food science have produced various uncommon crops containing anthocyanins, including blue- or red-fleshed potatoes and purple or red broccoli, cabbage, cauliflower, carrots and corn. Anthocyanins can also be found in naturally ripened olives, and are partly responsible for the purple color seen in Kalamata and Alfonso olives, although no studies to date have have quantified their amount.

[edit] Autumn leaf color

Plants with abnormally high anthocyanin quantities are popular as ornamental plants - here, a selected purple-leaf cultivar of European Beech
Plants with abnormally high anthocyanin quantities are popular as ornamental plants - here, a selected purple-leaf cultivar of European Beech

Many science text books incorrectly state that all autumn coloration (including red) is simply the result of breakdown of green chlorophyll, which unmasks the already-present orange, yellow, and red pigments (carotenoids, xanthophylls, and anthocyanins, respectively). While this is indeed the case for the carotenoids and xanthophylls (orange and yellow pigments), anthocyanins are not present until the leaf begins breaking down the chlorophyll, during which time the plant begins to synthesize the anthocyanin, presumably for photoprotection during nitrogen translocation.

[edit] Structure

[edit] Anthocyanidins: Flavylium cation derivatives

See Anthocyanidins article.

Selected anthocyanidins and their substitutions
Anthocyanidin Basic structure R1 R2 R3 R4 R5 R6 R7
Aurantinidin Basic structure of Anthocyans: The flavio-cation −H −OH −H −OH −OH −OH −OH
Cyanidin −OH −OH −H −OH −OH −H −OH
Delphinidin −OH −OH −OH −OH −OH −H −OH
Europinidin −OCH3 −OH −OH −OH −OCH3 −H −OH
Luteolinidin −OH −OH −H −H −OH −H −OH
Pelargonidin −H −OH −H −OH −OH −H −OH
Malvidin −OCH3 −OH −OCH3 −OH −OH −H −OH
Peonidin −OCH3 −OH −H −OH −OH −H −OH
Petunidin −OH −OH −OCH3 −OH −OH −H −OH
Rosinidin −OCH3 −OH −H −OH −OH −H −OCH3

[edit] Anthocyanins: Glucosides of anthocyanidins

The anthocyanins, anthocyanidins with sugar group, are mostly 3-glucosides of the anthocyanidins. The anthocyanins are subdivided into the sugar-free anthocyanidin aglycones and the anthocyanin glycosides. As of 2003 more than 400 anthocyanins had been reported[9] while more recent literature (early 2006), puts the number at more than 550 different anthocyanins. The difference in chemical structure that occurs in response to changes in pH is the reason why anthocyanins are often used as pH indicator, as they change from red in acids to blue in bases.

[edit] Biosynthesis

Anthocyanins are responsible for the distinctive color of blood oranges, although carotenoids also contribute pigmentation in this fruit.
Anthocyanins are responsible for the distinctive color of blood oranges, although carotenoids also contribute pigmentation in this fruit.
  1. Anthocyanin pigments are assembled like all other flavonoids from two different streams of chemical raw materials in the cell:
  2. These streams meet and are coupled together by the enzyme chalcone synthase (CHS), which forms an intermediate chalcone via a polyketide folding mechanism that is commonly found in plants.
  3. The chalcone is subsequently isomerized by the enzyme chalcone isomerase (CHI) to the prototype pigment naringenin.
  4. Naringenin is subsequently oxidized by enzymes such as flavanone hydroxylase (FHT or F3H), flavonoid 3' hydroxylase and flavonoid 3' 5'-hydroxylase.
  5. These oxidation products are further reduced by the enzyme dihydroflavonol 4-reductase (DFR) to the corresponding leucoanthocyanidins.
  6. It was believed that leucoanthocyanidins are the immediate precursors of the next enzyme, a dioxygenase referred to as anthocyanidin synthase (ANS) or leucoanthocyanidin dioxygenase (LDOX). It was recently shown however that flavan-3-ols, the products of leucoanthocyanidin reductase (LAR), are the true substrates of ANS/LDOX.
  7. The resulting, unstable anthocyanidins are further coupled to sugar molecules by enzymes like UDP-3-O-glucosyl transferase to yield the final relatively stable anthocyanins.

More than five enzymes are thus required to synthesize these pigments, each working in concert. Any even minor disruption in any of the mechanism of these enzymes by either genetic or environmental factors would halt anthocyanin production.

[edit] Potential food value

Anthocyanins are considered secondary metabolites as a food additive with E number 163.

Anthocyanins are powerful antioxidants in vitro. This antioxidant property may be conserved even after the plant which produced the anthocyanin is consumed by another organism, possibly explaining why fruits and vegetables with colorful skins and pulp are considered nutritious. However, it has not yet been scientifically demonstrated that anthocyanins are beneficial to human health.

[edit] Research

Richly concentrated as pigments in berries, anthocyanins were the topics of research presented at a 2007 symposium on health benefits that may result from berry consumption[10]. Scientists provided laboratory evidence for potential health effects against

  • cancer
  • aging and neurological diseases
  • inflammation
  • diabetes
  • bacterial infections

Cancer research on anthocyanins is the most advanced, where black raspberry (Rubus occidentalis L.) preparations were first used to inhibit chemically induced cancer of the rat esophagus by 30-60% and of the colon by up to 80%. Effective at both the initiation and promotion/progression stages of tumor development, black raspberries are a practical research tool and a promising therapeutic source, as they contain the richest contents of anthocyanins among native North American Rubus berries[11].

Work on laboratory cancer models has shown that black raspberry anthocyanins inhibit promotion and progression of tumor cells by

  1. stalling growth of pre-malignant cells
  2. accelerating the rate of cell turnover, called apoptosis, effectively making the cancer cells die faster
  3. reducing inflammatory mediators that initiate tumor onset
  4. inhibiting growth of new blood vessels that nourish tumors, a process called angiogenesis
  5. minimizing cancer-induced DNA damage.

On a molecular level, berry anthocyanins were shown to turn off genes involved with proliferation, apoptosis, inflammation and angiogenesis.[12][13][14]

In 2007, black raspberry studies entered the next pivotal level of research – the human clinical trial – for which several approved studies are underway to examine anti-cancer effects of black raspberries and cranberries on tumors in the esophagus, prostate and colon[15].

[edit] References

  1. ^ Wu X, Gu L, Prior RL, McKay S. Characterization of anthocyanins and proanthocyanidins in some cultivars of Ribes, Aronia, and Sambucus and their antioxidant capacity. J Agric Food Chem. 2004 Dec 29;52(26):7846-56.[1]
  2. ^ Siriwoharn T, Wrolstad RE, Finn CE, Pereira CB. Influence of cultivar, maturity, and sampling on blackberry (Rubus L. Hybrids) anthocyanins, polyphenolics, and antioxidant properties. J Agric Food Chem. 2004 Dec 29;52(26):8021-30.[2]
  3. ^ Wada L, Ou B. Antioxidant activity and phenolic content of Oregon caneberries. J Agric Food Chem. 2002 Jun 5;50(12):3495-500.[3]
  4. ^ Hosseinian FS, Beta T. Saskatoon and wild blueberries have higher anthocyanin contents than other Manitoba berries. J Agric Food Chem. 2007 Dec 26;55(26):10832-8.[4]
  5. ^ Muñoz-Espada AC, Wood KV, Bordelon B, Watkins BA. Anthocyanin quantification and radical scavenging capacity of Concord, Norton, and Marechal Foch grapes and wines. J Agric Food Chem. 2004 Nov 3;52(22):6779-86.[5]
  6. ^ Choung MG, Baek IY, Kang ST, Han WY, Shin DC, Moon HP, Kang KH. Isolation and determination of anthocyanins in seed coats of black soybean (Glycine max (L.) Merr.). J Agric Food Chem. 2001 Dec;49(12):5848-51.[6]
  7. ^ Schauss AG, Wu X, Prior RL, Ou B, Patel D, Huang D, Kababick JP. Phytochemical and nutrient composition of the freeze-dried Amazonian palmberry, Euterpe oleraceae Mart. (acai). J Agric Food Chem. 2006 Nov 1;54(22):8598-603.[7]
  8. ^ Del Pozo-Insfran D, Brenes CH, Talcott ST. Phytochemical composition and pigment stability of Açai (Euterpe oleracea Mart.). J Agric Food Chem. 2004 Mar 24;52(6):1539-45.[8]
  9. ^ Kong J. M., Chia L. S., Goh N. K., Chia T. F., Brouillard R. (2003). "Analysis and biological activities of anthocyanins.". Phytochemistry 64 (5): 923-33. doi:10.1016/S0031-9422(03)00438-2. 
  10. ^ Gross PM (2007). Scientists zero in on health benefits of berry pigments. Natural Products Information Center. Retrieved on 2007-07-27.
  11. ^ Wada L, Ou B (2002). Antioxidant activity and phenolic content of Oregon caneberries.. J Agric Food Chem. Jun 5;50(12):3495-500.. Retrieved on 2007-07-27.
  12. ^ Hou DX. Potential mechanisms of cancer chemoprevention by anthocyanins. Curr Mol Med. 2003 Mar;3(2):149-59. [9]
  13. ^ Karlsen A, Retterstøl L, Laake P, Paur I, Kjølsrud-Bøhn S, Sandvik L, Blomhoff R. Anthocyanins inhibit nuclear factor-kappaB activation in monocytes and reduce plasma concentrations of pro-inflammatory mediators in healthy adults. J Nutr. 2007 Aug;137(8):1951-4.[10]
  14. ^ Neto CC. Cranberry and blueberry: evidence for protective effects against cancer and vascular diseases. Mol Nutr Food Res. 2007 Jun;51(6):652-64.[11]
  15. ^ Stoner GD, Wang LS, Zikri N, Chen T, Hecht SS, Huang C, Sardo C, Lechner JF (2007). Cancer prevention with freeze-dried berries and berry components.. 1: Semin Cancer Biol. May 10;. Retrieved on 2007-07-27.

[edit] External links

v • d • e
Types of Plant Pigments
Flavonoids
Betalains
Carotenoids
Other
v • d • e
Anthocyanins and their glucosides
Anthocyanins
cyanidin-3-rutinoside • Protocyanin
Anthocyanidins
Cyanidin • Delphinidin • Europinidin • Luteolinidin • Pelargonidin • Malvidin • Peonidin • Petunidin • Rosinidin