Anthocyanins and anthocyanidins in the flowers of Aconitum (Ranunculaceae)

doi:10.1016/j.bse.2019.103937

Biochemical Systematics and Ecology

Volume 87, December 2019, 103937

https://doi.org/10.1016/j.bse.2019.103937 Get rights and content

Highlights

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Anthocyanidins and anthocyanins in flowers of 30 taxa of Aconitum were surveyed.
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Twenty-nine taxa contain delphinidin as a major anthocyanidin.
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One taxon contains pelargonidin as a major anthocyanidin.
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All flowers contain cyanidin as a minor anthocyanidin.
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Violet and violet-blue flowers contain violdelphin and monodeacylcampanin as major anthocyanins.
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This is the first reported isolation of monodeacylcampanin from Aconitum flowers.

Abstract

The presence of anthocyanidins and anthocyanins were analyzed in flowers of 30 taxa of Aconitum. Delphinidin was detected as a major anthocyanidin from the hydrolysate of 29 taxa with violet and violet-blue flowers. Pelargonidin was identified as a major anthocyanidin in one taxon with white flowers (partially pale reddish purple; White group N155C by R.H.S. Colour Chart). This is the first reported detection of pelargonidin as a major anthocyanidin from Aconitum flowers. Pelargonidin was also found in ten taxa as a minor anthocyanidin, whereas cyanidin was detected from the flowers of all 30 taxa as a minor anthocyanidin.

Two anthocyanins polyacylated by p-hydroxybenzoic acids, violdelphin and monodeacylcampanin were identified from 29 taxa with violet and violet-blue flowers as major anthocyanins. This is the first reported isolation of monodeacylcampanin from Aconitum flowers. The structures of these two anthocyanins were elucidated on the basis of Nuclear Magnetic Resonance (NMR) and Mass Spectrometry (MS).

Graphical abstract

Section snippets

Subject and source

The genus Aconitum L. includes about 340 species (The Plant List: http://www.theplantlist.org/) of annual, biennial, or perennial harbs that are native to temperate regions of the Northern Hemisphere (Huxley et al., 1992). Some Aconitum species are used in traditional Chinese medicine (Liu et al., 2017), whereas other species, such as A. napellus and A. carmichaelii, are used as ornamental flowers (Geneve, 2000).

Little has been published about the floral anthocyanins of Aconitum; however,

Previous work

A search only one revealed published report on acylated anthocyanin from the genus Aconitum. Delphinidin 3-O-(6-O-(α-rhamnopyranosyl)-β-glucopyranoside)-7-O-(6-O-(4-O-(6-O-(p-hydroxybenzoyl)-β-glucopyranosyl)-p-hydroxybenzoyl)-β-glucopyranoside) (Violdelphin) was identified from the purplish blue flowers of A. chinense by means of chromatography, FAB-MS, and ¹H and ¹³C NMR (Takeda et al., 1994). Delphinidin and cyanidin have been identified as anthocyanidins from the flowers of A. napellus by

HPLC analysis and thin layer chromatography (TLC)

HPLC analysis was performed on an LC 10A system (Shimadzu Corporation, Kyoto, Japan) using a Waters C18 (4.6 × 250 mm) column with a flow rate of 1 ml/min at 40 °C, and the eluate was monitored at 260 nm for p-hydroxybenzoic acid and at 530 nm for anthocyanidins and anthocyanins. The eluant was applied to a linear gradient elution for 40 min from 20 to 85% solvent B (1.5% H₃PO₄, 20% HOAc, 25% MeCN in H₂O) in solvent A (1.5% H₃PO₄ in H₂O) (Tatsuzawa, 2013).

TLC was carried out on plastic coated

Chemotaxonomic significance

Comparative identification of anthocyanidins by HPLC analysis showed delphinidin was a major anthocyanidin in 29 of 30 taxa of Aconitum. Only A. napellus f. flore albo did not show existence of delphinidin as a major anthocyanidin in this study (Table 1). Trace cyanidin from all Aconitum taxa was detected by HPLC analysis. In addition, pelargonidin was detected as a major anthocyanidin from A. napellus f. flore albo, and was also detected as a trace anthocyanidin from ten other taxa (Table 1).

Acknowledgement

This work was supported in part by JSPS KAKENHI [grant number JP17K07655 and JP19K06011].

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Pigment 12 was identified by direct HPLC comparison with authentic standards (FUJIFILM Wako Pure Chemical Corporation, Osaka, Japan) and by HR-FABMS and NMR measurement (Section 3.7.12). Pigments 1 - 5, and 8 - 11 have been previously identified as delphinidin 3-O-[6-O-(rhamnosyl)-glucoside]-7-O-glucoside (1), cyanidin 3-O-[6-O-(rhamnosyl)-glucoside]-7-O-glucoside (2), pelargonidin 3-O-[6-O-(rhamnosyl)-glucoside]-7-O-glucoside (3), delphinidin 3-O-[6-O-(rhamnosyl)-glucoside]-7-O-[6-O-(4-O-(glucosyl)-p-hydroxybenzoyl)-glucoside] (4), delphinidin 3-O-[6-O-(rhamnosyl)-glucoside]-7-O-[6-O-(4-O-(6-O-(4-O-(glucoside)-p-hydroxybenzoyl)-glucosyl)-p-hydroxybenzoyl)-glucoisde] (5; monodeacylcampanin), delphinidin 3-O-[6-O-(rhamnosyl)-glucoside]-7-O-[6-O-(4-O-(6-O-(4-O-(6-O-(p-hydroxybenzoyl)-glucoside)-p-hydroxybenzoyl)-glucosyl)-p-hydroxybenzoyl)-glucoisde] (8; campanin), cyanidin 3-O-[6-O-(rhamnosyl)-glucoside]-7-O-[6-O-(4-O-(6-O-(4-O-(6-O-(p-hydroxybenzoyl)-glucoside)-p-hydroxybenzoyl)-glucosyl)-p-hydroxybenzoyl)-glucoisde] (9; purprocampanin), delphinidin 3-O-[6-O-(rhamnosyl)-glucoside]-7-O-[6-O-(4-O-(6-O-(p-hydroxybenzoyl)-glucosyl)-p-hydroxybenzoyl)-glucoside] (10; violdelphin), and pelargonidin 3-O-[6-O-(rhamnosyl)-glucoside]-7-O-[6-O-(4-O-(6-O-(4-O-(6-O-(p-hydroxybenzoyl)-glucoside)-p-hydroxybenzoyl)-glucosyl)-p-hydroxybenzoyl)-glucoisde] (11; ruburocampanin) (Kondo et al., 1990; Brandt et al., 1993; Tatsuzawa et al., 2019; Toki et al., 2006, 2009), respectively (Supplemental data 1). However, this study reaffirmed them using HPLC, HR-FABMS, and NMR measurement (Supplemental data 2).
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Aconitum georgei Comber is a China-specific Aconitum (Ranunculaceae) plant. In the present study, eighteen compounds, including fourteen diterpenoid alkaloids (1–14) and four nonalkaloidal constituents (15–18) were isolated from the roots of A. georgei. Among them, fifteen compounds (1–11 and 14–18) have not previously been found in this species, and 3-methoxymethylbenzoate (17) has not previously been isolated from the Aconitum genus. The chemotaxonomic value of these compounds was explored through network analysis. The results showed that some of these compounds such as falconeridine (6) and 14-anisoyl-N-deethylaconine (10) showed limited distribution in the genus, which could help to narrow species identification to A. georgei where other phenotypic characters are limited.
Aconitum carmichaelii Debeaux: A systematic review on traditional use, and the chemical structures and pharmacological properties of polysaccharides and phenolic compounds in the roots
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Flavonoids are commonly found in the aerial parts of Aconitum plants and are considered as the chemotaxonomical biomarkers beside alkaloids (Yin et al., 2019). Anthocyanins are responsible for the purple-blue color of the flowers (Tatsuzawa et al., 2019). Flavonoids are known for their antioxidant, anti-inflammatory, cardiovascular, immunomodulatory, antibacterial, antiviral, and antifungal activities and are regarded as health beneficial (Jucá et al., 2020).
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Anthocyanins and anthocyanidins in the flowers of Aconitum (Ranunculaceae)

Highlights

Abstract

Graphical abstract

Section snippets

Subject and source

Previous work

HPLC analysis and thin layer chromatography (TLC)

Chemotaxonomic significance

Acknowledgement

Phytochemistry

Mol. Phylogenetics Evol.

Tetrahedron Lett.

J. Ethnopharmacol.

Phytochemistry

Phytochemistry

Phytochemistry

J. Plant Physiol.

Phytochemistry

Phytochemistry

Phytochemistry

Phytochemistry

Phytochemistry