Anthocyanidins identified

Debromination with ageing has been observed in the indigoid components of purple [171,172], and photochemical breakdown patterns of the three anthocyanidins contained in Arrabidaea chica red dye, produced by Andean Indian cultures in the tenth to fifteenth centuries, have been hypothesized [173]. Although identifying dye sources in ancient artefacts is quite difficult, it is helped considerably by understanding the fading and degradation mechanisms. 

IDENTIFIED ANTHOCYANINS AND ANTHOCYANIDINS AND THEIR OCCURRENCE IN VARIOUS RED FRUIT JUICE... 

Flavonol synthase (FLS E.C.l.14.11.23) catalyzes the committed step in the production of fiavonols by introduction of a double bond between C2 and C3 of the corresponding dihydroflavonols. Like E3H, ELS has been described as a 2-oxoglutatarate-dependent dioxygenase based on its cofactor requirements for 2-oxoglutarate, Fe, and ascorbate. FLS was initially identified in enzyme preparations from illuminated parsley cell suspension cultures [67]. Subsequently, FLS was characterized from the flower buds of Matthiola incana and carnation (Dianthus caryophyllus L.), and it was suggested that there was regulation between flavonol and anthocyanidin biosynthesis [83, 84]. 

Dihydroflavonol 4-reductase (DFR EC 1.1.1.219) is a member of the short-chain dehydrogenase/reductase family and catalyzes the stereospecific conversion of (+)-(2R,3R)-dihydroflavonols to the corresponding (2R,3S,4S) flavan-3,4-cw-diols (leucoanthocyanidins), with NADPH as a required cofactor. The enzyme activity was first identified in cell suspension cultures of Douglas fir (Pseudotsuga menziesii) and was shown to be related to the accumulation of flavan-3-ols and proanthocyanidins [96]. Leucoanthocyanidins and DFR were later shown to be required for anthocyanidin formation by complementation of Matthiola incana mutants blocked between dihydroflavonol and anthocyanidin biosynthesis [97, 98], DFR has been purified to apparent homogeneity and biochemically analyzed from flower buds of Dahlia variabilis [99]. DFR was shown to accept different substrates depending on the plant species from which it was isolated (reviewed in 100). 

Flavanone 3 -hydroxylase (F3 H ECl.14.13.21 CYP75B) activity was initially identified in microsomal preparations of golden weed (Haplopappus gracilis) [110]. E3 H from irradiated parsley cell cultures was later biochemically analyzed and characterized as a cytochrome P450 having an absolute requirement for NADPH and molecular oxygen as cofactors [111]. The enzyme has been shown to have activity with flavanones, flavones, dihydroflavonols, and flavonols, but does not appear to have activity with anthocyanidins [111]. The first cDNA clone for E3 H was isolated from Petunia [112]. It has been suggested that E3 H may serve as an anchor for the proposed flavonoid multi-enzyme complex on the cytosolic surface of the endoplasmic reticulum [44]. 

Two classes of dimeric anthocyanins isolated from plants (section 10.2.6) have been identified in plants for the first time. One class includes pigments where an anthocyanin and a flavone or flavonol are linked to each end of a dicarboxylic acyl unit. The other class includes four different catechins linked covalently to pelargonidin 3-glucoside. During the last decade, seven new desoxyanthocyanidins and a novel type of anthocyanidin called P)Tanoanthocyanidins have been reported (Section 10.2.2). Toward the end of the 20th century, several color-stable 4-substituted anthocyanins, pyranoanthocyanins, were discovered in small amounts in red wine and grape pomace.Recently, similar compounds have been isolated from extracts of petals of Rosa hybrida cv. M me Violet, scales of red onion, and strawberries. About 94% of the new anthocyanins in the period of this review are based on only six anthocyanidins (Table 10.2). 

In addition to the 18 anthocyanidins listed previously, Table 10.1 contains seven new desoxyanthocyanidins and a novel type of anthocyanidin called pyranoanthocyanidins. While 31 monomeric anthocyanidins have been properly identified, most of the anthocyanins are based on cyanidin (30%i), delphinidin (22%i), and pelargonidin (18%), respectively (Figure 10.2). Altogether 20%i of the anthocyanins are based on the three common anthocyanidins (peonidin, malvidin, and petunidin) that are methylated. Around 3, 3, and 2% of the anthocyanins or anthocyanidins are labeled as 3-desoxyanthocyanidins, rare methylated anthocyanidins, and 6-hydroxyanthocyanidins, respectively. 

Each anthocyanidin is involved in a series of equilibria giving rise to different forms, which exhibit their own properties including color. One- and two-dimensional NMR have been used to characterize the various forms of malvidin 3,5-diglucoside present in aqueous solution in the pH range 0.3 to 4.5 and to determine their molar fractions as a function of pH. In addition to the flavylium cation, two hemiacetal forms and both the cis and trans forms of chalcone were firmly identified. In a reexamination, the intricate pH-dependent set of chemical reactions involving synthetic flavylium compounds (e.g., 4 -hydroxyflavylium) was confirmed to be basically identical to those of natural anthocyanins (e.g., malvidin 3,5-diglucoside) in... 

Finally, Weinges et al. (31, 33) postulated the formation of dimers such as 27 or 28, 29 or 30 directly from catechins without involving 3,4-flavandiols (leucoanthocyanidins). This process has never been demonstrated in fruits directly and specifically not in grapes. Only the proanthocyanin dimers have been positively identified through the formation of catechins and anthocyanidins during acid hydrolysis. Dimer formation proceeds by enzymatic oxidation of two molecules of catechin... 

Introduction to 2-D NMR experiments The purpose of the standard 1-D H NMR experiment is to achieve structure-related information about sample protons (i.e., chemical shifts, spin-spin couplings, and integration data) describing the relative number of protons. Applied to anthocyanins, this information may help to identify the aglycone (anthocyanidin), number of monosaccharides present, and anomeric configuration of the monosaccharides. However, for most anthocyanins, the information gained by a standard 1 -D H NMR experiment is insufficient for complete structure elucidation. In recent years, various 2-D NMR experiments have evolved as the most powerful tools for complete structure elucidation of anthocyanins. 

Anthocyanidin synthase (ANS) is the enzyme that dehydrates the leucoanthocyanidins (Figure 3-8). While this enzyme had been postulated to exist, and cDNA s encoding the putative ANS had been identified (e.g. A2 in... 

Anthocyanins are composed of anthocyanidines and their sugar molecules. Anthocyanins are one of the most typical phy to chemicals in the pigments of the plant kingdom with various colors such as carotenoids. Surprisingly, the anthocyanins of over 150 flavonoids are highly antioxidative. To date, it is thought that more than 4000 flavonoids have been identified [7]. 

The polyphenols such as anthocyanidins might have a protective effect on atherosclerosis. This concept suggests that the Recommended Optimal Intake (ROI) is a more important factor for the antioxidation than the Recommended Dietary Allowance (RDA). Now, considering the absence of the appropriate methodology to identify anthocyanidins in the plasma, the analysis of the plasma antioxidant capacity might be a suitable index to define the optimal nutritional intake [95]. 

Piovan et al. [80] reported the characterization of anthocyanins in both flower material and in vitro cnltmes of Catharanthus roseus. The anthocyanidins malvidin, petunidin, and hirsntidin were identified from both sonrces. Next to known aglycones, three 3-0-glycosides as well as three 3-0-(6-0-/)-coumaroyl)glycosides... 

The MS analysis can be performed either by ESI-direct injection of the sample or LC separation. Table 6.18 reports the anthocyanidin C4 derivatives identified by ESI/MS of fraction 4 (point m in Fig. 6.25) of a red wine and a grape marc extract. 

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