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The anthocyanin in blue flowers of Centaurea cyanus
Abstract
The anthocyanin in the blue cornflower (Centaurea cyanus) has been known for many years to be cyanidin 3,5-diglucoside, namely cyanin. However, in the course of this study, it became
evident that the major anthocyanin in the blue cornflower is not cyanin but cyanidin 3-succinyl glucoside 5-glucoside. This
anthocyanin has not been reported in the literature and is tentatively called “centaurocyanin”. Centaurocyanin is chromatographically
identical with the anthocyanin contained in crystalline protocyanin, the blue pigment from the cornflower. thus, there seems
no doubt that this anthocyanin, but not cyanin, forms the blue complex pigment protocyanin.
... 13 C NMR spectral data of anthocyanins in DMSO-d 6 :TFA (9:1) (150 MHz). ...
... . Complete and mild acid hydrolysis and alkaline hydrolysis were basically performed according to Takeda and Tominaga [13]. The LC-MS were measured on a Shimadzu LC-MS system using a Shim-pak VP-ODS column (I.D. ...
... ( Table 1. 13 C NMR: Table 2. ...
Six new acylated cyanidin glycosides, cyanidin 3-O-beta-(2''-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-galactopyranoside (1), cyanidin 3-O-beta-(2''-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-(6''-malonylgalactopyranoside) (2), cyanidin 3-O-beta-(2''-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-(6''-succinylgalactopyranoside) (3), cyanidin 3-O-beta-(2''-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-galactopyranoside-3''- O-beta-glucuronopyranoside (4), cyanidin 3-O-beta-(2''-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-(6''-malonylgalactopyranoside)-3'-O-beta-glucuronopyranoside (5), and cyanidin 3-O-beta-(2'-E-feruloylglucopyranosyl)-(1 --> 2)-O-beta-(6''-malonylgalactoside)-3' -O-beta-glucuronopyranoside (6), were isolated from the red flowers of two Clematis cultivars, 'Niobe'and 'Madame Julia Correvon'. The chemical structures of the isolated anthocyanins were determined by UV, LC-MS, HPLC, TLC, characterization of hydrolysates, and 1H and 13C NMR spectroscopy, including H-H COSY, C-H COSY, HMBC, HMQC and NOESY. The last three anthocyanins were widely distributed in 37 red flower Clematis cultivars. On the other hand, the first three compounds were found only in two cultivars. Five known flavonol glycosides, kaempferol 3-O-glucoside, kaempferol 3-O-rutinoside, quercetin 3-O-galactoside, quercetin 3-O-glucoside and quercetin 3-O-rutinoside, were isolated from the flowers of'Madame Julia Correvon'.
... Regular consumption of anthocyanins prevents the angiogenesis and cardiovascular diseases (Rechner and Kroner, 2005;Roy et al., 2002;Matsunaga et al., 2010). Commercially, anthocyanins are extracted from the flower petals of Centaurea cyanus, Clitorea ternatea, Hibiscus rosa-sinensis, Rosa x hybrida, Thymus moroderi etc. (Takeda and Tominaga, 1983;Vankar and Srivastava, 2010;Vankar and Shukla, 2011;DíazÀGarcía et al., 2015;Kumari et al., 2017;Escher et al., 2018). The genotypes of China aster flower petals contains good amount of anthocyanins, which can be used as a potential source of natural pelargonidin (Matsumoto Red), cyanidin and delphinidin (Arka Violet Cushion) based colorants in food and pharmaceutical formulations. ...
Anthocyanins are bio colorants which have gained momentum owing to their extensive range of colors and antioxidant activity which has great potential in food, pharmaceutical, textile and cosmetic industries. China aster became popular among the consumers due to its myriad colors. To find out the pigment composition responsible for flower color, fifteen genotypes of China aster were studied using liquid chromatography- mass spectrometry (LC-MS/MS). The flower color analysis indicated that the 15 genotypes of China aster grouped into seven groups viz., red purple, red, purple, purple violet, violet, white and yellow. Flower petals were evaluated for color through Royal Horticultural Society Color Chart (RHSCC) and calorimeter that resulted in most of the genotypes were categorized under red purple group. The flower color in China aster is due to the presence of three primary anthocyanidins namely cyanidin, pelargonidin and delphinidin. A total of 4 anthocyanins namely cyanidin, pelargonidin, delphinidin and malvidin were identified and quantified. The genotype Arka Violet Cushion was the richest source of anthocyanins (469.36 mg/100 g FW) and IIHRJ22, the poorest (1.17 mg/100 g FW). Genotype Arka Violet Cushion recorded highest for both the cyanidin and delphinidin, however, pelargonidin was recorded highest in Matsumoto Red. The genotype Arka Violet Cushion has been identified with highest anthocyanin can be exploited commercially for bio-color synthesis. The trend of decreased L* value of Color Reader with increased total anthocyanin content was observed in red purple and purple group. The correlation between L* value and total anthocyanin content was not observed in white and violet group. The results revealed that the white and yellow group has very low anthocyanin content which indicates the presence of co-pigmentation in China aster. Arka Violet Cushion recorded 2–3 times higher anthocyanin content than the commercial sources viz., Clitorea ternatea, Centaurea cyanus and Hibiscus rosa-sinensis, which can be exploited commercially for bio-color synthesis.
... Various [67,[73][74][75]. ...
Chemical analysis of different parts of Centaurea cyanus revealed that the plant contained flavonoids, anthocyanins, phenilpropanic compounds, aromatic acids, phenolcarboxylic acids, amino acids, sugars, indole alkaloids, and it was rich in minerals and trace elements. The previous pharmacological studies showed that the plant possessed antibacterial, anti-inflammatory, neural, antioxidant, diuretic, gastro-protective and many other effects. This review will discuss the chemical constituents and pharmacological effects of Centaurea cyanus.
... Various flavonoids were isolated from Centaurea cyanus including apigenin-4'-O-(6-O-malonil-glucoside)-7-O-glucuronide, apigenin-4-O-glucoside, apigenin-7-O-glucoside (cosmosiin), apigenin-7-O apio-glucoside (apiin), methyl-apigenin and methyl-vitexin, cyanidin-3-O-succinyl-glucoside-5-O-glucoside (centaurocyanin) , cyanidin-3,5-diglucoside (cyaniding), 5-methoxy-apigenine (hispidulin), quercetin-3-O-gluco-rhamnoside (rutoside), rhamnetin, isorhamnetin, isorhamnetin-7-O-glucoside, naringenin, kaempferol-glycosides, luteolinglycosides, quercetin, naringin, naringenin-7-O-gluco-rhamnoside, quercetin-3-glucorhamnoside, apigenin-7glucoside, quercetin-7-glucoside, quercetin -3-glucoside, apigenin-8-C-glucoside, aringenine, caffeic, chlorogenic, neochlorogenic acids and umbeliferone (197)(198)(199)(200)(201)(202) . ...
The use of dietary or medicinal plant based natural compounds to disease treatment has become a unique trend in clinical research. Polyphenolic compounds, were classified as flavones, flavanones, catechins and anthocyanins. They were possessed wide range of pharmacological and biochemical effects, such as inhibition of aldose reductase, cycloxygenase, Ca+2-ATPase, xanthine oxidase, phosphodiesterase, lipoxygenase in addition to their antioxidant, antidiabetic, neuroprotective antimicrobial anti-inflammatory, immunomodullatory, gastroprotective, regulatory role on hormones synthesis and releasing…. etc. The current review was design to discuss the medicinal plants contained phenolics and flavonoids, as natural ingredients for many therapeutic purposes.
... Дејство: намалува инфекции на очите, дејствува антиинфламаторно дејство и спречува создавање каменчиња во уринарниот тракт. Има и еменагогно, антиинфламаторно, аперитивно и тонизирачко дејство,а се користи при габични инфекции, треска, кашлица, констипација, нарушувања во функцијата на црниот дроб и жолчката и други состојби (Takeda & Tominaga, 1983;Garbacki et al., 1999). ...
Flora in the Republic of Macedonia comprises about 3200 species in 147 families. According to some sources there are 115 endemic higher plants, of which, 114 belong to gymnosperm. According to other sources, there are 135 species of endemic plants and about 111 of which are local endemic species and 24 are stretched in the border mountains. The exact number has not been determined yet. Eastern part of Macedonia, east of the river Vardar almost poses no endemics, while the rest of the territory, west of the Vardar is very rich in such species. The richest areas with endemic plants are Galicica Mountain, Treska River Gorge and the lowlands surrounding the city of Prilep. Despite the wealth of endemic and relict species, any pharmacognostical data for these plants have not been published yet. Of all these endemic species, 30 could be pharmaconosticly interesting for future investigation of the chemical composition, isolation of potentially active substances and testing biological-pharmacological activity. Modern analytical techniques utilized in the examination of the chemistry of medicinal plants and natural products require a very small amount of material does not pose a risk of endangering endemic species. An additional challenge is the development of an appropriate program for the protection of all endemic, pharmaconosticly interesting species.
... Various [67,[73][74][75]. ...
Chemical analysis of different parts of Centaurea cyanus revealed that the plant contained flavonoids, anthocyanins, phenilpropanic compounds, aromatic acids, phenolcarboxylic acids, amino acids, sugars, indole alkaloids, and it was rich in minerals and trace elements. The previous pharmacological studies showed that the plant possessed antibacterial, anti-inflammatory, neural, antioxidant, diuretic, gastro-protective and many other effects. This review will discuss the chemical constituents and pharmacological effects of Centaurea cyanus.
The region of northeast India boasts sizeable flora of non-native species which has arrived during last few centuries. Whilst several of these species have escaped in wild and naturalized, others have mingled in the flora and remain oblivious. Some species have gained dominance and replaced native flora and these are considered "invasive". This article reports the first record of an herbaceous plant, Centaurea cyanus L. of Asteraceae family from northeast India. The plant was found in the summer of 2020 in the campus of North-Eastern Hill University, Shillong while it was competing with several other non-native species on poor substratum. An extensive search in the floras of the region revealed that the plant has not been reported previously. It is probable that the plant has arrived here either as a companion with the supplies of packaged seeds of garden flowers procured by the residents from various sources or through some other carrier from nearby villages where it has made presence. Only time will answer if the plant remains oblivious or turns invasive.
The substitution of artificial dyes by natural colouring agents is among the top concerns of food industry to fulfil current consuming trends, justifying the prospection of novel natural sources of these compounds. Herein, the hydrophilic extracts from rose, cornflower and dahlia were tested as potential substitutes to E163 (anthocyanin extract). Besides comparing the colouring capacity, the potential occurrence of changes in the chemical composition of yogurts (nutritional parameters, free sugars and fatty acids) was also assessed throughout storage (up to 7 days) and compared with a “blank” (free of any additive) yogurt formulation. In general, yogurts prepared with flower extracts, presented similar nutritional value and free sugars profile to those prepared with E163 and to the “blank” yogurt. Nevertheless, rose extract turned out to be the most suitable alternative to E163 as these two groups of yogurts had similar nutritional composition, free sugars and fatty acids composition, besides presenting close scores in colour parameters.
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Flower colour results from the preferential absorption of part of the visible light by one, or several, chemical compound(s) synthesized by higher plants. Since plants cannot ‘see’ their own colours, it is conceivable that the colour signals emerging from flowers are messages interpretable by mammals as well as by birds and insects (Harborne, 1976). Thus colour is most likely a link between animals and plants, as are flower shape, scent and taste. In particular, insects and birds attracted by colour pollinate the flowers and aid the survival of plant species. In contrast to man, some insects, especially bees, can perceive in the near ultraviolet (340–380 nm) as well as in the visible.
Anthocyanin pigmentation is almost universal in the flowering plants and provides scarlet to blue colours in flowers, fruits, leaves and storage organs. It continues to provide a challenge to plant biochemists because of the intricate chemical variation and the complexity of biosynthesis, metabolism and regulation. The two most important recent advances in the structural characterization of anthocyanin pigments have been the application of high performance liquid chromatography (HPLC) and of fast atom bombardment mass spectrometry (FAB-MS) to their analyses. Both these procedures have proved of value in studying zwitterionic anthocyanins, a relatively new class of acylated anthocyanin recently recognized to be widespread in the plant kingdom (Harborne and Boardley, 1985). These anthocyanins, which are acylated through sugar by such acids as malonic, are labile in solution and when such pigments are isolated using solvents containing mineral acid, they are rapidly degraded to the corresponding unacylated glycoside.
Anthocyanin is the general name applied to the glycosides of antho-cyanidin chromophores which are the origin of the red, violet, and blue colors found throughout the plant kingdom, such as the colors of petals, leaves and fruits. Only a few anthocyanidin nuclei have been found in spite of the great variety of plant colors. The major anthocyan- idins found in nature are pelargonidin, cyanidin, peonidin, delphinidin,
Open image in new windowFig. 1.3,5-Diglucosides of common anthocyanins (anhydro base form). The name of the anthocyanidin is in parentheses. [From T. GOTOet al: Ann. New York Acad. Sci. 471, 155 (1986), with permission]
petunidin and malvidin (Fig. 1). The most common anthocyanins are 3-glucosides and 3,5-diglueosides of the anthocyanidins, but galactose, rhamnose, xylose and arabinose residues are also found. Many anthocyanins containing acylated sugar moieties are also known. The acyl groups are mostly derivatives of cinnamic acid such as p-coumaric, caffeic, and ferulic acid, but include some aliphatic acids such as malonic, succinic, and acetic acid as well.
Flavonoids are one of the major pigments in higher plants, together with chlorophylls and carotenoids. Though ca. 8,000 kinds of flavonoids have been reported in nature, anthocyanins, chalcones, aurones and some flavonols act as major flower pigments. Flavonoids are present as major components in many flowers. On the other hand, flavones and flavonols, which are colorless or extremely pale yellow, function as copigment substances. Moreover, expression of the flower colors is diversified by inter-molecular and intra-molecular copigmentation, metal chelation, pH change and so on. In this review, I describe the distribution of the flavonoids which act as the pigments, and contribution to flower colors, e.g., yellow, scarlet, red, red-purple, violet, purple, blue and so on, of flavonoids, especially anthocyanins, chalcones, aurones and flavonols.
Anthocyanins and other flavonoids were isolated from the flowers of eleven Centaurea species, C. macrocephala, C. rupestotilis and C. suaveolens, which produce yellow flowers, and C. achtarovii, C. dealbata, C. montana, C. nigra, C. scabiosa, C. simplicicaulis, C. hypoleuca and C. triumfetti, which have cyanic flowers. Four anthocyanins, cyanidin 3,5-di-O-glucoside, cyanidin 3-O-(6"-malonylglucoside)-5-O-glucoside, cyanidin 3-O-(6"-succinylglucoside)-5- O-glucoside and cyanidin glycoside, were detected in the cyanic flowers of seven Centaurea species. Of these anthocyanins, the first two were found as major anthocyanins. In the cyanic species, four other flavonoids, apigenin 7-O-glucuronide-4'-O-glucoside, malonylated apigenin 7,4'-di-O-glucoside, apigenin 7-0- glucuronide and kaempferol glycoside, were also isolated. On the other hand, nine flavonols and four flavones were isolated from the three yellow-flowered species, and identified as quercetagetin, quercetagetin 7-O-glucoside, quercetagetin 3'-methyl ether 7-O-glucoside, patuletin, patuletin 7-O-glucoside, quercetin 7-O-glucoside, kaempferol 3-methyl ether, kaempferol 3-methyl ether 4'-O-glucuronide and isorhamnetin 3-O-galactoside, and apigenin, apigenin 7- O-glucuronide, luteolin 7-O-glucoside and apigenin 6,8-di-C-glucoside (vicenin-2). Of these flavonoids, the former five flavonols are "yellow flavonols", and it was shown that their flower colors are due to these compounds.
Extraction, purification and analysis of the anthocyanin pigments of ten taxa of the genus Centaurea yielded cyanidin 3-O-(6-O-succinyl-β-D-glucoside)-5-O-β-D-glucoside.
A new anthocyanin acylated with succinic acid has been isolated from pink flowers of Centaurea cyanus. It has been identified as pelargonidin 3-(6″-succinylglucoside)-5-glucoside.
The pigment of bluebells, previously reported as delphinidin 3-p-coumarylglucoside-5-glucoside, has been shown to be malonated and it has been identified as malonylawobanin. A cyanidin derivative present in several members of the Labiatae, has been characterized as the related 3-p-coumarylglucoside-5-malonylglucoside.
The anthocyanin in the purplish-red flowers of carnation (Dianthus caryophyllus) has been considered for many years as cyanidin 3-glucoside (Cy 3-G). However, from chromatographic studies on the flower color in carnation, we previously found that the major anthocyanin was not Cy 3-G but an acylated one attached to an unknown organic acid.In the present studies, we have isolated and crystallized this anthocyanin from purplish-red flowers of carnation and analyzed it by chemical and spectroscopic means. This pigment was identified as cyanidin 3-malylglucoside (Cy 3-MG). Furthermore, by means of direct chromatographic comparison with this pigment, it was also found that Cy 3-MG was widely present in the purplish-red flower cultivars and in the same color hybrids which were obtained from intervarietal crossing of carnations.In addition, we have recently identified another anthocyanin, peralgonidin 3-malylglucoside (Pg3-MG) from a red flower carnation cultivar. Therefore, these results strongly suggest that malylation of anthocyanin is characteristic in the flowers of carnation.
Various flower colors are in great part due to anthocyanins. Recently, we have elucidated two new mechanisms for blue flower color development on blue cornflower and blue morning glory. The composition of protocyanin, a blue pigment from cornflower, Centaurea cyanus, was determined to consist of six molecules of succinylcyanins (Sucy) , six molecules of malonylflavones (Mail) , one ferric ion and one magnesium ion, [Sucy6Mafl6Fe3+Mg2+] . The blue color of protocyanin was due to the LMCT (Ligand to Metal Charge Transfer) interation between Sucy and Fe3+. The structure of protocyanin was examined by using Al, Mg-protocyanin. The gross structure is much similar to that of commelinin. The pigment of blue morning glory, Ipomoea tricolor, is an triacylated anthocyanin, HBA. We measured the vacuoler pH of the petal of morning glory by using a proton selective micro electrode. The pHv of the petal of purplish red bud was 6.6 and that of blue open fiower petal was 7.7. The anhydrobase anion of HBA must be stabilized by intramolecular stacking. We could solve 80 year's problems, one is about cornflower's pigment and the other is the evidence of the pH theory. In both cases hydrophobic interaction followed by formation of supra-molecule is the key of stabilization of anthocyanidin chromophore.
Nicht durch Dekonstruktion sondern durch Rekonstitution konnte die Zusammensetzung des Kornblumen-Pigments Protocyanin geklärt werden. Es ist ein Komplex aus einem Anthocyanin und einem Malonylflavon sowie Eisen(III)- und Magnesium-Ionen, wie aus dem Vergleich der optischen und massenspektrometrischen Befunde von natürlichem und rekonstituiertem Protocyanin hervorgeht.
The yellow pigments, the 4′-malonylsophoroside and 4′-malonylglucoside of butein, have been characterised in the petals of Dahlia variabilis and D. coccinea. They co-occur with malonylated anthocyanins in these flowers. Their presence in the Mexican D. coccinea supports the view that the cultivated D. variabilis could have arisen from hybridisation involving this wild species. This is the first report of chalcone pigments occurring in plants with malonyl attachment.
The major anthocyanins in the red flowers of Zinnia elegans were identified as acetylated pelargonidin and cyanidin 3,5-diglucosides by chromatographic and spectral methods.
Callus cultures which produce anthocyanin under continuous irradiation of UV and white light were derived from the stem of blue-floweredCentaurea cyanus. From the callus a suspension culture, in which anthocyanin synthesis can be induced by UV light, was obtained. The pigment in the cell cultures was identified as cyanidin 3-(6″-malonylglucoside) which occurs in the leaf, but not the flowers, of the parent plant.
The major anthocyanin in pink and red forms of Dianthus caryophyllus has been identified as pelargonidin 3-malylglucoside. The corresponding cyanidin 3-malylglucoside has been found in red flowers of D. deltoides. This is the first complete characterization in plants of anthocyanins substituted with malic acid.
The blue pigment of cornflower, protocyanin, has been investigated for a long time, but its precise structure was not entirely explained until recently. The molecular structure of the pigment was recently shown to be a metal complex of six molecules each of anthocyanin and flavone glycoside, with one ferric iron, one magnesium and two calcium ions by X-ray crystallographic analysis. The studies provided the answer to the question posed in the early part of the last century, "why is the cornflower blue and rose red when both flowers contain the same anthocyanin?" This work was achieved on the basis of the results of long years of the studies made by many researchers. In this review, the author focuses on the investigations of the blue metal complex pigments involved in the bluing of flowers, commelinin from Commelina commusis, protocyanin from Centaurea cyanus, protodelphin from Salvia patens and hydrangea blue pigment.
(Communicated by Shoji SHIBATA, M.J.A.)
1914 machte Willstätter die überraschende Beobachtung, daß ein Pigment verschiedene Farben hervorbringen kann. So findet sich in der blauen Kornblume und in der roten Rose das gleiche Pigment: Cyanin. Die Vielfalt an Blütenfarben führte Willstätter auf unterschiedliche pH-Werte in Lösung zurück. Anthocyan ändert in der Tat die Farbe mit dem pH-Wert: Es erscheint rot in saurer, violett in neutraler und blau in alkalischer wäßriger Lösung. Willstätters pH-Wert-Theorie zur Erklärung der Blütenfarbenvariation ist immer noch in wichtigen Lehrbüchern der Organischen Chemie zu finden. Vor kurzem jedoch zeigten erneute Untersuchungen, daß die Farbvariation und die Stabilisierung von Anthocyanen in wäßriger Lösung andere Ursachen haben könnten, nämlich Selbstassoziation, Copigmentierung und intermolekulare sandwichartige Stapelung. Die Stapelung käme hauptsächlich durch intermolekulare oder intramolekulare hydrophobe Wechselwirkungen zwischen aromatischen Ringen etwa von Anthocyanidinen, Flavonen und aromatischen Säuren zustande. Zusätzlich könnten Wasserstoffbrücken und Charge-Transfer-Wechselwirkungen eine Rolle spielen. Die interessantesten Molekülkomplexe von Anthocyanen sind Metalloanthocyane wie Commelinin und Protocyanin (Pigment der blauen Kornblume). Diese rein blau erscheinenden Komplexe bestehen aus jeweils sechs Anthocyan- und sechs Flavonmolekülen sowie zwei Metall-Ionen. Ihr Molekulargewicht beträgt beinahe 10000. Ein annähernder Strukturvorschlag liegt für Commelinin vor.
In 1913 Willstätter made the striking observation that the same pigment can give rise to different colors. Thus, the same pigment, cyanin, is found in the blue cornflower and in the red rose. Willstätter attributed the variety of flower colors to different pH values in solution. Indeed, anthocyanin changes its color with pH; it appears red in acidic, violet in neutral, and blue in basic aqueous solution. Willstätter's pH-theory for explaining flower color variation is still to be found in major text books of organic chemistry. Very recently, however, reinvestigation has disclosed that the color variation and stabilization of anthocyanins in aqueous solution could have other causes, namely self-association, copigmentation and intramolecular sandwich-type stacking. The stacking would be mainly brought about by intermolecular or intramolecular hydrophobic interaction between aromatic nuclei such as anthocyanidins, flavones and aromatic acids. In addition, hydrogen bonds and charge transfer interactions may also be involved. The most interesting molecular complexes of anthocyanins are the metalloanthocyanins such as commelinin and protocyanin (blue cornflower pigment). These seemingly pure blue complexes each consist of six anthocyanin and six flavone molecules and two metal ions; their molecular weight is nearly 10000. A structure is proposed for commelinin.
Reconstruction, not decomposition, was used to determine the composition of the pigment from the blue petals of cornflowers, protocyanin. Comparison of optical and mass spectra of natural and reconstructed protocyanin revealed it to be a complex of an anthocyanin and a malonylflavone with iron(iii) and magnesium ions.
A survey of 31 species from 28 genera in the Compositae showed the presence of zwitterionic anthocyanins in petals or stems of 27 species. Detailed investigations, including the use of FAB-MS, showed that mono- and dimalonated esters of pelargonin and cyanin occurred in Dahlia variabilis cultivars. The corresponding delphin mono- and dimalonates occur in blue flowers Cichorium intybus. A cyanidin 3-dimalonylglucoside was identified in stems of Coleostephus myconis while pelargonidin 3-(6″-malonylg]ucoside) was found in Callistephus petals. A further malonated cyanidin derivative in flowers of Helenium cv. Bruno was found to be the 3-glucuronosylglucoside; this is the first report of an anthocyanin with glucuronic acid. Overall, the results confirm that malonated anthocyanins are widespread in the family and that many pigments previously reported in the Compositae as being unacylated probably contain these labile organic acid attachments.
From a series of wild accessions of Centaurea montana displaying markedly dissimilar flavonoid phenotypes (notably C-glycosides vs. O-glycosides) different experimental breeding operations were performed. Variation was observed in individual glycosidic profiles of progeny, the importance of which depended on the parental phenotypes and the genetic proximity of the partners employed (combinations of wild specimens, inbred, plants or backcrosses operations). Most collections were revealed to be genetically heterogeneous, an expected consequence of the obligate outcrossing reproductive mode of this species. A major feature observed in flavonoid variation was the emergence of C-glycosidic profiles in the progeny of parents displaying O-glycosidic fingerprints, suggesting hypostatic genetic control of the former pathway, probably occurring at a very early stage. Within C-glycoside expression, the multiple discrete steps leading to mono-6-C-glucosides and their O-glycosylated and acylated conjugates have a complex and independent heritability. Because of epistasis, individuals with O-glycosidic phenotypes are either homogeneous or heterogeneous and in the O-glycosidic portion of their flavonoid metabolism important variations were again observed in many progeny. The heritability of the biosynthetic steps in flavonoid metabolism of Centaurea montana is discussed in the light of these observations.
Forty-nine species or cultivars of the Labiatae were surveyed for their floral anthocyanins. There was a good correlation between flower colour, anthocyanidin type and pollination vector. All six species with long tubular scarlet flowers contained pelargonidin; four also contained some cyanidin. All 17 red-purple and purple flowered species had cyanidin, and five had additionally peonidin. Twenty-one of 26 species with purple-violet, violet or blue flowers had delphinidin, and eight had malvidin; 13 of these species also had some cyanidin. Aromatic acylation with p-coumaryl substitution was more common (in 80%) than such acylation with caffeyl substitution (in 12% of species). Anthocyanins with aromatic acylation commonly occurred as mixtures of cis and trans isomers. Monomalonylated pigments were present in all but one of the plants, while dimalonylated pigments were identified in about half the samples. The four most common pigments in the family are thus cyanidin and delphinidin 3-(6″-p-coumarylglucoside)-5-(6‴-malonylglucoside), present as the cis and trans isomers. Four new pigments were characterized: two monomalonyl esters of peonidin 3,5-diglucoside, and the dimalonyl esters of delphinidin and malvidin 3-(6″-p-coumarylglucoside)-5-glucoside.
An electrophoretic survey of mainly floral tissues of 282 species from 68 families showed the presence of zwitterionic anthocyanins in 38% of the species and in 30% of the families. Families recognised for the first time as having such pigments include the Alliaceae, Gramineae, Orchidaceae and Ranunculaceae. Families where they are rare or absent include the Boraginaceae, Geraniaceae, Iridaceae, Onagraceae and Umbelliferae. Acylating acids so far identified are malic, malonic and succinic and of these three, malonic seems to be the most common. The significance of this acylation appears to be related to the stabilization of anthocyanins in the acidic environment of the cell sap.
The acyltransferase from blue flowers of Centaurea cyanus containing succinylated cyanidin 3,5-diglucosides catalysed the transfer of the succinyl moiety from succinyl-CoA to 3-glucosides of cyanidin and pelargonidin, but not to 3,5-diglucosides. Similar results were obtained using the enzyme from pink flowers containing succinylated pelargonidin 3,5-diglucosides. The enzyme also catalysed these anthocyanidin 3-glucosides to malonylate at nearly the same rate as succinylation.
The genus Centaurea comprises 300-350 species, 22 of which are native to Hungary. Several species have been applied in traditional medicine, however, the rationale of their application has been analyzed only in few studies. The decoction of the aerial parts of Centaurea sadleriana Janka, a species native to Hungary, has been used in Hungarian folk medicine for the healing of wounds of livestock. Its ethnomedicinal use was reported first by our research group. There is no data available for similar application of other members of the genus native to Hungary. This paper summarizes the phytochemical and pharmacological data of all Hungarian Centaurea species (C. apiculata, C. are-naria, C. banatica, C. biebersteinii, C. calcitrapa, C. cyanus, C. diffusa, C. grinensis, C. indurata, C. jacea, C. macroptilon, C. montana, C. nigrescens, C. pannonica, C. phrygia, C. rhenana, C. sadleriana, C. salonitana, C. scabiosa, C. solstitialis, C. stenolepis, C. triumfettii), focusing on compounds and activities relevant to the anticipated wound healing effect. Certain compounds (eg. sesquiterpene lactones, flavonoids, polyacetylenes) are characteristic to the genus, and taking into account that they may play role in the anti-inflammatory and wound healing effect, it is plausible that other Centaurea species beyond C. sadleriana would have wound healing promoting effect. Since C. sadleriana is an endangered species native only to the Carpathian Basin, the investigation of wound healing effect of more prevalent species is scientifically warranted.
The components involved in the formation of protocyanin, a stable blue complex pigment from the blue cornflower, Centaurea cyanus, were investigated. Reconstruction experiments using highly purified anthocyanin [centaurocyanin, cyanidin 3-O-(6-O-succinylglucoside)-5-O-glucoside], flavone glycoside [apigenin 7-O-glucuronide-4'-O-(6-O-malonylglucoside)] and metals, Fe and Mg, showed the presence of another factor essential for the formation of protocyanin. The unknown factor was revealed to be Ca. Reconstructed protocyanin using anthocyanin, flavone, Fe, Mg, and Ca was identical with protocyanin from nature in UV-Vis and CD spectra, and was isolated as crystals for the first time. In addition, substitution of the metal components in protocyanin with other metals was also examined.
1.In order to qualify the properties of useful solvent mixtures, paper chromatographic exami ations were carried out using authentic samples of various anthocyanins. As illustrated in Fig. 1, interesting relationship was found between Rf values and pigment structures.2. Interesting also is the fact that diglycosides are degraded stepwise into monoglucosides, when treated with warm hydrochloric acid and the resuts can be clearly demonstrated chromatographically. Thus, the glycoside type of anthocyanins is indicated by paper chromatographic examination of the products of partial hydrolysis.
A new, crystalline, deep blue pigment has been isolated from cornflowers (Centaurea cyanus L.). The pigment is an iron complex of 4 molecules of cyanidin 3,5-diglucoside and 3 molecules of a “bisflavone” glucoside. The “bisflavone” glucoside is liberated on acid decomposition of the blue pigment, and chromatographic examination indicates that it is a single substance. On acid hydrolysis, however, it yields 7-O-methylapigenin and a second flavone which appears to be new and has not yet been positively identified. It is spectrally identical with 7-O-methylapigenin, and on the basis of its Rf values it may be the 7-O-methyl derivative of vitexin. The reported properties of commelinin, the blue pigment of Commelina communis L., are strikingly similar to those of the cornflower pigment and suggest that these two pigments have an essentially identical type of structure.
Organic acids are of great significance in plant and animal metabolism. They ordinarily occur as complex mixtures, from which isolation and identification are difficult or impossible by methods currently available. Several recent papers have pointed toward the possibility of chromatographic separations. However, these have been of limited usefulness either because accurate identification was difficult or because they failed to include many important naturally occurring acids. The method reported uses an initial separation on a silica gel column followed, when necessary, by additional separations using both chromatographic and chemical techniques. It provides for separation and tentative identification of 16 biologically important organic acids. This method has been applied to the separation and identification of acids in tomato fruits and Bryophyllum leaves. It should have applications in metabolic studies as well as in identification of acids present in a wide variety of biological materials.
Bei der Kondensation von Dicarbonylverbindungen und o-Amino-phenol entstehen zunächst Bis-benzoxazolyle, welche sich unter dem Einfluß von Metallsalzen oder Alkalien in die Hydroxyanile umlagern und Metallkomplexe bilden. Während mit Schwermetallsalzen des Kupfers, Kobalts, Urans, Nickels die Umlagerung und Komplexbildung schon in saurem Medium verläuft, werden Erdalkalikomplexe nur gebildet, wenn vorher die Umlagerung zu den isomeren Hydroxyanilen in alkalischem Medium ausgeführt wird. Mittels IR-Spektren, UV-Spektren und Hydrierungen wird die Oxazolin-Hydroxyanil-Umlagerung einiger Komplexbildner studiert.
Die im blauen Kornblumenfarbstoff enthaltenen Eisen(III)- und Aluminiumchelate werden synthetisiert und deren Struktur angegeben. Die synthetischen Cyanin-Chelate unterscheiden sich vom natürlichen Komplex nur dadurch, daß an Stelle des Polysaccharides Anionen gebunden sind. – Komplexe des Cyanidins mit anderen Metellionen, wie Uran, Titan und Kupfer werden beschrieben.
Der cyaninhaltige blaue Farbstoff der Kornblume wurde isoliert und als Aluminium-Eisen-Komplex des Cyanins erkannt. De nicht dialysierbare Komplex ist in saurem pH-Bereich stabil. Die Variation der Blütenfarben wird allgemein auf Aluminium- und Eisenkomplexe zurückgeführt, da nur diese Verbindungen zwischen pH 3.8 – 5.5, dem pH der Blütenblätter, stabil sind. Die synthetisch zugänglichen Aluminium- und Eisenkomplexe des Cyanins stimmen in ihrer Farbintensität und pH-Stabilität mit dem natürlichen Farbstoff überein und sind somit die künstlichen Modelle für den Farbstoff der Blüte.
Synthese der blauen, im Kornblumenfarbstoff enthaltencn Chelate
- K Nether
- H Egeter
--, K. NETHER AND H. EGETER. 1960. Synthese der blauen, im Kornblumenfarbstoff enthaltencn Chelate. Chem. Ber. 93: 2871-2879.
Natürliche und synthetische Anthocyan-Metallkomplexe
- E Bayer
Über den Farbstoff der Kornblume
- R Anda E Willstätter
- Everest
- R. Willstätter