Fumi Tatsuzawa

Floral anthocyanins in wild taxa of Petunia (Solanaceae)

The flowers of 20 native taxa of Petunia (Solanaceae) were investigated by HPLC for the occurrence of anthocyanins. The investigation revealed the presence of at least 24 anthocyanins in their flowers, of which 18 known anthocyanins isolated from the flowers of P. exserta, P. guarapuavensis, P. integrifolia, P. occidentalis, and P. reitzii were fully identified by chemical and spectral methods to be 3-glucoside of delphinidin; 3-rutinosides of cyanidin, delphinidin, and petunidin; 3-rutinoside-5-glucosides, 3-trans and -cis-p-coumaroylrutinoside-5-glucosides, and 3-trans-caffeoylrutinoside-5-glucosides of delphinidin, petunidin, and malvidin; and 3-transcaffeoylglucosyl-trans-(caffeoyl or p-coumaroyl) rutinoside-5-glucosides of malvidin. Six novel anthocyanins were isolated from the flowers of P. occidentalis, and their structures were identified to be 3-glucosyl p-coumaroylrutinoside-5-glucosides and 3-glucosylcaffeoylrutinosides of petunidin and malvidin, and also 3-caffeoylglucosylcaffeoylrutinoside-5-glucoside and 3-caffeoylglucosyl p-coumaroylrutinoside-5-glucoside of petunidin. Out of the six pigments, petunidin 3-glucosyl p-coumaroylrutinoside-5-glucoside was unambiguously determined by spectral methods to be petunidin 3-O-[6-O-(4-O-(4-O-(β-d-glucopyranosyl)-trans-p-coumaroyl)-α-l-rhamnopyranosyl)-β-d-glucopyranoside]- 5-O-[β-d-glucopyranoside]. The 20 native taxa of Petunia could be placed into four groups (A, B, C, and D) with one further into five subgroups (D1–D5) regarding their constituents and contents of major anthocyanins and also their pigment biosynthesis with respect to the blocks or inhibitors of the hydroxylation, glucosylation, and acylation reactions in them. The use of anthocyanins as taxonomic markers in the genus Petunia is discussed in relation to the flower colour and possible pollination vectors.

New features of intramolecular copigmentation by acylated anthocyanins

Abstract Three series of structurally related anthocyanins, extracted from the red–purpleflowers of Dendrobium Pramot, xLaeliocattleya cv. Mini Purple, Bletilla striata and Phalaenopsis all belonging to the Orchidaceae family and another series extracted from the pinkflowers of Senecio cruentus (Compositae) allowed the confirmation of the existence of strongintramolecular copigmentation effects. These interactions confer stability to the coloured formsof the molecules, in a wide range of slightly acidic to neutral aqueous media. Moreover, theexistence of structural relationships among the four series stressed the different influencesexerted by the diverse substituent groups. The existence of a malonylglucoside attached toposition 3 of all but three of the molecules put forward a new role for the malonyl residue, in thisparticular position.

Acylated cyanidin glycosides in the violet-blue flowers of Ipomoea purpurea

Six acylated cyanidin glycosides were isolated from violet-blue flowers of Ipomoea purpurea. These anthocyanins were all based on cyanidin 3-sophoroside-5-glucoside, acylated with caffeic acid and/or p-coumaric acid. Three anthocyanin structures were elucidated to be cyanidin 3-O(-)[2-O-(6-O-(trans-3-O-(beta-D-glucopyranosyl)caffeyl)-beta -D-glucopyranosyl)-6-O-(trans-4-O-(6-O-(trans-caffeyl)-beta-D-glucopyran osyl) caffeyl)-beta-D-glucopyranoside]-5-O(-)[beta-D-glucopyranoside], cyanidin 3-O(-)[2-O-(trans-3-O-(beta-D-glucopyranosyl)caffeyl)-beta-D-glucopyrano syl)- 6-O-(trans-caffeyl)-beta-D-glucopyranoside]-5-O(-)[beta-D-glucopyranosid e d and cyanidin 3-O(-)[2-O-(6-O-(trans-caffeyl)-beta-D-glucopyranosyl)-6-O- (trans-caffeyl)-beta-D-glucopyranoside]-5-O(-)[beta-D-glucopyranoside]. These three anthocyanins were present in all 12 violet-blue flower strains as major pigments. The colours of these acylated antocyanins were stabler in neutral solution than their deacyl analogues.

Anthocyanins in flowers of genus Rosa, sections Cinnamomeae (=Rosa), Chinenses, Gallicanae and some modern garden roses.

Forty-four taxa of three sections (Cinnamomeae (=Rosa) 26, Chinenses 8 and Gallicanae 10) and eight modern garden roses in the genus Rosa were surveyed for their floral anthocyanins. Eleven anthocyanins: 3-glucosides and 3,5-diglucosides of cyanidin (Cy), pelargonidin (Pg) and peonidin (Pn), 3-rutinosides and 3-rho-coumaroylglucoside-5-glucosides of Cy and Pn, and Cy 3-sophoroside, were isolated from flowers of these taxa and identified by chemical and spectroscopic techniques. Four anthocyanins: Cy 3-rutinoside, Pn 3-rutinoside, Pn 3-rho-coumaroylglucoside-5-glucoside and Cy 3-sophoroside were found for the first time in Rosa flowers.Investigated sections of wild roses showed characteristic distribution of anthocyanins. Cy 3,5-diglucoside was the dominant anthocyanin detected in all three sections, but accumulation of Pn 3,5-diglucoside distinguished sections Cinnamomeae from other sections, and the occurrence of Cy 3-glucoside separates section Chinenses from others.Cy 3-sophoroside was detected in large amount in some taxa of section Cinnamomeae: e.g., R. moyesii and its related cultivars, and R. rugosa cv. Salmon Pink. The acylated Cy glycoside was found in all sections and also in some modern garden roses, while the acylated Pn glycoside was detected in the section Cinnamomeae, but not in sections Chinenses and Gallicanae. According to anthocyanin distribution patterns, eight groups were classified chemotaxonomically in genus Rosa.

Influence of trans-cis isomerisation of coumaric acid substituents on colour variance and stabilisation in anthocyanins

The recently isolated pigments from Petunia integrifolia and Triteleia bridgesii present a distinct feature that sheds new light on the understanding of intramolecular copigmentation of anthocyanins. These are among the infrequent anthocyanins that naturally present a coumaric acid substituent in both cis and trans forms. As a consequence, the two isomers demonstrate substantial variations of their thermodynamic and kinetic constants and also colour properties. A possible explanation for these characteristics is presented, making use of molecular modelling and taking into account the three-dimensional structures of the pigments.

Acylated cyanidin 3-sambubioside-5-glucosides in Matthiola incana

Four acylated cyanidin 3-sambubioside-5-glucosides were isolated from purple-violet flowers of Matthiola incana and their structures were determined by chemical and spectroscopic methods. Three acylated anthocyanins were cyanidin 3-O-(6-O-acyl-2-O-(2-O-sinapyl-beta-D-xylopyranosyl)-beta-D- glucopyranosides)-5-O-(6-O-malonyl-beta-D-glucopyranosides), in which the acyl group is p-coumaryl, caffeyl or ferulyl, respectively. The remaining pigment is free from malonic acid and was identified as cyanidin 3-O-(6-O-trans-ferulyl-2-O-(2- O-trans-sinapyl-beta-D-xylopyranosyl)-beta-D-glucopyranoside)-5-O- (beta-D-glucopyranoside). Analysis of the anthocyanin constituents in 16 purple-violet cultivars revealed that they contained the above triacylated anthocyanins in variable amounts as main pigments. An aromatic pair of pigments containing sinapic and ferulic acids are considered to produce an important intramolecular effect, making bluish colours in these flowers.

Acylated cyanidin glycosides in the purple-red flowers of Bletilla striata

Abstract Eight acylated anthocyanins were isolated from the purple-red flowers of Bletilla striata as major anthocyanins. These pigments were based on cyanidin 3,7,3′-triglucoside as their deacylanthocyanins, and were acylated with malonic, p-coumaric and caffeic acids and/or glucosylated hydroxycinnamic acids. Four structures were determined by spectral and chemical methods: cyanidin 3-O-[6-O- (malonyl)-β- d -glucopyranoside]-3′ -O-[6-O-(trans-4-O-(6-O-(trans-4-O- (β- d -glucopyranosyl) -p- coumaryl )-β- d -glucopyranosyl) -p- coumaryl )-β- d -glucopyranoside ]-7-O-[6-O-(trans-p- coumaryl )-β- d -glucopyranoside ] ; the demalonyl derivative; cyanidin 3-O-[6-O- (malonyl)-β- d -glucopyranoside ]-3′-O-[6-O-(trans-4-O-(6-O-(trans-4-O- (β- d - glucopyranosyl)-caffeyl)-β- d -glucopyranosyl)-caffeyl)-β- d -glucopyranoside ]-7-O-[6-O-(trans- caffeyl)-β- d -glucopyranoside ]; and the demalonyl derivative.

Acylated pelargonidin glycosides in red-purple flowers of Ipomoea purpurea

Four acylated pelargonidin glycosides were isolated from the red-purple flowers of Ipomoea purpurea. The acylated anthocyanins were all based on pelargonidin 3-sophoroside-5-glucoside, acylated with caffeic acid and/or glucosylcaffeic acids. Three novel anthocyanins were elucidated to be pelargonidin 3-O-[2-O-(6-O-(trans-3-O-(beta-D-glucopyranosyl)-caffeyl)- beta-D-glucopyranosyl)-6-O-(trans-4-O-(6-O-(trans-caffeyl)-beta-D- glucopyranosyl)-caffeyl)-beta-D-glucopyranoside]-5-O- [beta-D-glucopyranoside], pelargonidin 3-O-[2-O-(6-O-(trans-caffeyl)-beta-D-glucopyranosyl)-6-O- (trans-4-O-(6-O-(trans-caffeyl)-beta-D-glucospyranosyl)-ceffeyl )-beta-D- glucopyranoside]-5-O-[beta-D-glucopyranoside] and pelargonidin 3-O[2-O-(2-O-(6-O-(trans-caffeyl)-beta-D-glucopyranosyl)-6-O- (trans-caffeyl)-beta-D-glucopyranoside]-5-O-[beta-D-glucopyoside]. Another anthocyanin was pelargonidin 3-O-[2-O-(glucosylcaffeylglucosyl)-6-O-(caffeyl)-glucoside]-5-gluc oside, which was reported to be present in the red-purple flowers of Pharbitis nil. Apart from the second pigment cited, these are analogous pigments of the violet-blue Ipomoea anthocyanins which are composed of acylated cyanidin glycosides, instead of pelargonidin.

Differences in the floral anthocyanin content of red petunias and Petunia exserta.

In order to resolve a conflict between previous papers regarding the floral anthocyanins of red flowers of Petunia exserta, a naturally occurring species, the HPLC profile of this species was compared with that of commercial red garden petunias. Both HPLC profiles extremely superficially resemble each other in terms of relative amounts and retention times of the major anthocyanins. However, co-elution on HPLC of the mixed sample resulted in clear separation of the components. Three major anthocyanins in red petunias were determined to be cyanidin 3-sophoroside, cyanidin 3-glucoside and peonidin 3-glucoside, which exhibited similar behaviors on HPLC to delphinidin 3-glucoside. delphinidin-3-rutinoside and petunidin 3-rutinoside, respectively, the major floral anthocyanins of P. exserta.

Acylated cyanidin glycosides in the red-purple flowers of Phalaenopsis

Abstract Four acylated anthocyanins were isolated from the red-purple flowers of Phalaenopsis hybrid cultivars as major anthocyanins and their distribution was investigated in the flowers of five species; P. equestris, P. intermedia, P. leucorrhoda, P. sanderiana and P. schilleriana cultivar ‘Pink Butterfly’. These four pigments were based on cyanidin 3,7,3′-triglucoside as their deacylanthocyanin, which was acylated with two molecules of hydroxycinnamic acid and/or one molecule of malonic acid. Two anthocyanins were characterized as cyanidin 3-O-[6-O-( malonyl )-β- d -glucopyranoside ]-7,3′-O-di-[6-O-(trans- sinapyl )-β- d -glucopyranoside ] and its demalonyl derivative by spectral and chemical methods.