Chemical structures of anthocyanins

The magnitude of the copigmentation is influenced by pH value, pigment and copigment concentrations, chemical structure of anthocyanin, temperature, and ionic strength of the medium. As to the effect of the solvent, the important issue is the hydrogen-bonded molecular structure of the liquid water, not the polarity of the medium. ... 

Brouillard, R., Chemical structure of anthocyanins, m Anthocyanins as Food Colors, Markakis, R, Ed., Academic Press, New York, 1982. 

Novel pyranoanthocyanins have also been isolated and identified in blackcurrant (Ribes nigrum) seed using HPLC, 2D NMR and ES-MS. Blackcurrant seeds were extracted with acetone-water (70 30, v/v) and the components of the extract were separated in a polyamide column followed by HPLC-DAD. The new pigments were finally separated in an MCI-HP20 column. The chemical structures of anthocyanins 1-2 and the novel pyranoanthocyanins 3-6 with the pyrano[4,3,2-de]-l-bcn/opyrylium core structure are shown in Fig. 2.110. It was stated that the analytical method developed separated well the novel pyranoanthocyanins [245],... 

Fig. 2.110. Chemical structures of anthocyanins 1-2 and the novel pyranoanthocyanins 3-6. Reprinted with permission from Y. Lu et al. [245],...

Brouillard R (1982) Chemical structure of anthocyanins. In Markakis P (ed) Anthocyanins as food colors. Academic, New York, pp 1-40... 

Figure 3. Chemical structures of anthocyanins at different pH values.

Research into the copigmentation of anthocyanins started as early as 1913 when Willstatter and Everest determined the chemical structure of cyanidin 3-glucoside isolated from blue cornflowers and red roses, and attributed the color changes to different pH levels in cell saps. This theory, however, was questioned and in 1916, Willstatter and Zollinger,revising the previous work, proposed a new theory according to which the colors of the anthocyanins varied significantly by the effects... 

Another problem is that the anthocyanin mixtures may be very complicated and not all absorptivity coefficients may be known. Even when they are known, it is necessary to first evaluate whether the objective is the estimation of total anthocyanin content or the determination of individual pigments, and then to decide which absorption coefficient(s) to use. The absorptivity is dependent on both the chemical structure of the pigment and also on the solvent used, and preferably the coefficient used should be one obtained in the same solvent system as the one used in the experiment. If the identity of the pigment is unknown, it has been suggested that it could be expressed as cyanidin-3-glucoside since that is the most abundant anthocyanin in nature. 

Fig. 2.94. Chemical structures of the main anthocyanins found in the petals of Delphinium cultivars. Reprinted with permission from K. Honda et al. [226].

The chemical structures of the main anthocyanins are shown in Fig. 2.94. The results illustrated that TLC can also be used for taxonomical studies [226],... 

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],... 

Besides the great pigment classes such as carotenoids, flavonoids, anthocyanins and chlorophylls a wide variety of other pigments have been separated, quantitated and identified by different liquid chromatograpchic techniques. The chemical structures of these pigments show high diversity. Unfortunately, in the majority of cases the biological activity of these... 

Odake, K. et al.. Chemical structures of two anthocyanins from purple sweet potato, Ipomoea batatas. Phytochemistry, 31, 2127, 1992. 

The basic chemical structure of anthocyanidins (aglycone) is shown in Figure 5.1. Over 600 naturally occurring anthocyanins have been... 

Figure 4.1 Chemical structures of the principal classes of polyphenols. The examples shown are of polyphenols with hydroxyl groups in the 7- and 4"-positions. Anthocyanins may also be found in oligomeric forms. The coumestane is coumestrol, The isoflavone (daidzein) differs from the flavonoid h the substitution of the phenolic group. For the flavonoid it is in the 2-position, whereas it is in the 3-position in the isoflavone.

Among the worldwide total of 30000 known natural products, about 80% stems from plant resources. The number of known chemical structures of plant secondary metabolites is four times the number of known microbial secondary metabolites. Plant secondary metabolites are widely used as valuable medicines (such as paclitaxel, vinblastine, camptothecin, ginsenosides, and artemisinin), food additives, flavors, spices (such as rose oil, vanillin), pigments (such as Sin red and anthocyanins), cosmetics (such as aloe polysaccharides), and bio-pesticides (such as pyrethrins). Currently, a quarter of all prescribed pharmaceuticals compounds in industrialized countries are directly or indirectly derived from plants, or via semi-synthesis. Furthermore, 11% of the 252 drugs considered as basic and essential by the WHO are exclusively derived from plants. According to their biosynthetic pathways, secondary metabolites are usually classified into three large molecule families phenolics, terpenes, and steroids. Some known plant-derived pharmaceuticals are shown in Table 6.1. 

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