Anthocyanins acylated

Advances in analytical procedures resulted in several reports on anthocyanins acy-lated with hydroxycinnamic acids (p-coumaric, caffeic, ferulic, sinapic, and 3,5-dihydroxycinnamic acids), hydroxybenzoic acids (p-hydroxybenzoic and gallic acids), and aliphatic acids (malonic, acetic, malic, oxalic, succinic and tartaric acids). However, not all of them were found in anthocyanins isolated from foods. Among the 44 fruits listed in Table 4.3.1, 15 presented acylated anthocyanins as did 12 of 13 vegetables shown in Table 4.3.3 and 2 of the 9 grains cited in Table 4.3.4. On the other hand, acylated anthocyanins were found in all grapes from Vitis species, although at different abundance levels, as can be seen in Table 4.3.2. A higher... 

Goda, Y. et al.. Two acylated anthocyanins from purple sweet potato. Phytochemistry, 40, 1809, 1995. 

Saito, N. and Osawa, Y., Platyconin, a new acylated anthocyanin in Chinese bell flower, Platycodon grandflorum. Phytochemistry, 10, 445, 1971. 

Idaka, E. et al., Strnctnre of zebrinin, a novel acylated anthocyanin isolated from Zebrina pendula. Tetrahedron Lett., 28, 1901, 1987. 

A biphasic solvent system composed of tert-butyl methyl ether, -butanol, acetonitrile, and water (2 2 1 5) acidified with triflnoroacetic acid has been applied to fractionate anthocyanins. The npper (organic) phase acts as the stationary phase and the lower (aqneons) as the mobile phase. HSCCC has been applied to obtain several anthocyanin fractions from wine, red cabbage, black cnrrants, chokeber-ries, " bilberries (Vaccinium myrtillus) acylated anthocyanins, and also isolate individnal anthocyanins from wine. ... 

CZE is particularly useful for separating anthocyanin dimers or polymeric anthocyanins. Calvo et al. (2004)" separated 13 anthocyanins by CZE including acylated and non-acylated anthocyanins, pyranoanthocyanins, and flavonol derivatives in wine. Saenz-Lopez et al. (2004)" applied CZE to analyze wine aging (1 to 14 yr) as related to monomeric anthocyanins, anthocyanin derivatives, tannins, and fla-vonols. Bicard et al. (1999)" reported the improved detection sensitivity of anthocyanin chemical degradation analysis by CZE. 

Giusti, M.M. and Wrolstad, R.E., Acylated anthocyanins from edible sources and their applications in food systems, Biochem. Eng. 14, 217, 2003. 

Tamura, H. and Yagami, A., Antioxidative activity of mono-acylated anthocyanins isolated from Muscat Bailey A grape, J. Agric. Food Chem., 42, 1612, 1994. 

Tomoyuki, O. et al., Determination of acylated anthocyanin in human urine after ingesting a purple-fleshed sweet potato beverage with various contents of anthocyanin by LC-ESI-MS/MS, Biosci. Biotechnol Biochem., 70, 2540, 2006. 

Goto, T., Takase, S., and Kondo, T., PMR spectra of natural acylated anthocyanins determination of stereostructure of awobanin, shisonin and violanin (Commelina communis, Viola tricolor, Perilla orimoides). Tetrahedron Lett, 27, 2413, 1978. Agrawal, P.K., NMR spectroscopy in the structural elucidation of ohgosaccharides and glycosides, Phytochemistry, 31, 3307, 1992. 

Nakatani, Nobuji, Kikuzaki, Hiroe, Hikida, Junko, Ohba, Mayumi, Inami, Osamu and Tamura, Itaru. "Acylated Anthocyanins from Fruits of Sambucus Ca31nadensis," Phytochemistry, Volume 38, Number 3, pages 755757, 1995. 

Fig. 2.103. Structures of all the compounds found in fraction B (a) anthocyanins and acylated anthocyanins direct condensation products between flavanols and anthocyanins (c) dimers resulting from the condensation mediated by acetaldehyde between anthocyanins and flavanols. Reprinted with permission from C. Alcalde-Eon el al. [236].

The anthocyanin composition of flowers has also been frequently investigated by chromatographic methods. Acylated anthocyanins and flavonols have been extracted from the flowers of Dendrobium cv. Pompadour and separated by TLC and RP-HPLC techniques. Fresh flowers (approximately. 1 kg) were extracted with 101 of methanol-acetic acid-water (4 1 5, v/v), and the extract was concentrated and analysed by preparative and analytical RP-HPLC using ODS columns (150 X 19 mm i.d. and 250 X 4.6 mm i.d.) at 40°C. The gradient consisted of methanol-water-acetic acid in various volume ratios. Flow rates were 4 and 1 ml/min for preparative and analytical separations, respectively. Cyanidin 3- (6-malonylglucoside)-7,3 -di(6-synapilglucoside) and the demalonyl derivative were detected in the flowers [261],... 

The anthocyanin profile of the flowers of Vanda (Orchidaceae) was investigated with a similar technique. Flowers (2 kg) were extracted with 101 of methanol-acetic acid-water (9 l 10,v/v) at ambient temperature for 24 h. The extract was purified by column chromatography, paper chromatography, TLC and preparative RP-HPLC. Analytical HPLC was carried out in an ODS column (250 X 4.6 mm, i.d.) at 40°C. Gradient conditions were from 40 per cent to 85 per cent B in 30 min (solvent A 1.5 per cent H3P04 in water solvent B 1.5 per cent H3P04, 20 per cent acetic acid and 25 per cent ACN in water). The flow rate was 1 ml/min and analytes were detected at 530 nm. The chemical structures of acylated anthocyanins present in the flowers are compiled in Table 2.90. The relative concentrations of anthocyanins in the flower extracts are listed in Table 2.91. It can be concluded from the results that the complex separation and identification methods (TLC, HPLC, UV-vis and II NMR spectroscopy, FAB-MS) allow the separation, quantitative determination and identification of anthocyanins in orchid flowers [262],... 

C.A. Williams, J. Greenham, J.B. Harborn, J.-M. Kong, L.- S. Chia, N.-K. Goh, N. Saito, K. Toki and F. Tatsuzawa, Acylated anthocyanins and flavonols from purple flowers of Dendrobium cv. Pompadour . Biochem. Syst. Ecol. 30 (2002) 667-675. 

F. Tatsuzawa, N. Saito, H. Seki, M. Yokoi, T. Yukawa, K. Shnoda and T. Honda, Acylated anthocyanins in the flowers of Vanda (Orchidaceae). Biochem. Syst. Ecol. 32 (2004) 651-664. 

Goto T, Takase S, Kondo T (1978) PMR spectra of natural acylated anthocyanins. Determination of the stereo structure of awobanin, shisonin and violanin. Tetrahedron Lett 27 2413-2416... 

Maccarone E, Maccarone A, Rapisarda P (1985) Acylated anthocyanins from orange. Ann Chim 75 79-86... 

Grapevine MATE-type proteins act as vacuolar H+-dependent acylated anthocyanin transporters. Plant Physiol 150 402-415. 

Pale, E. et al., Acylated anthocyanins from the flowers of Ipomoea asarifolia, Phytochemistry, 48, 1433, 1998. 

Slimestad, R., Aaberg, A., and Andersen, 0.M., Acylated anthocyanins from petunia flowers. Phytochemistry, 50, 1081, 1999. 

Hosokawa, K. et al., Seven acylated anthocyanins in the blue flowers of Hyacinthus orientalis. Phytochemistry, 38, 1293, 1995. 

Oszmianski, J., Bakowska, A., and Piacente, S., Thermodynamic characteristics of copigmentation reaction of acylated anthocyanin isolated from blue flowers of Scutellaria baicalensis Georgi with copigments, J. Sci. Food Agric., 84, 1500, 2004. 

Mateus, N. et al.. Isolation and structural characterization of new acylated anthocyanin-vinyl-flavanol pigments occurring in aging red wines. J. Agric. Food Chem. 51, 211, 2003. 

Harada, K., Kano, M., Takayanagi, T., Yamakawa, O., and Ishikawa, F., Absorption of acylated anthocyanins in rats and humans after ingesting an extract of Ipomoea batatas purple sweet potato tuber, Biosci. Biotechnol. Biochem., 68, 1500, 2004. 

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