{"title":"Identification of novel flower anthocyanins of Delphinium grandiflorum cultivars","authors":"Natsu Tanikawa , Haruka Seto , Seiji Suzuki , Ayaka Omori , Fumi Tatsuzawa","doi":"10.1016/j.dyepig.2024.112250","DOIUrl":null,"url":null,"abstract":"<div><p>Flower color is one of the most important properties of ornamental flowers. Information on the kinds of pigments that flowers can biosynthesize is useful for breeding cultivars focused on flower colors. The flower colors of regular ornamental delphinium cultivars are blue, violet, purple, pink, and white. The pigments of these flowers are delphinidin-based anthocyanins. It has been reported that the typical modification in delphinium anthocyanins involves the transfer of glucose and <em>p</em>-hydroxybenzoic acid molecules to the 7-position of delphinidin one by one, and it was predicted that other unidentified anthocyanins are present in addition to the already reported ones. Recently, light pink flowers that accumulate pelargonidin-based anthocyanins were reported from cultivars derived from <em>Delphinium grandiflorum</em>. Converting delphinidin-based anthocyanins to pelargonidin-based ones is considered key to producing red flowers in delphinium. Hence, we investigated anthocyanins of blue, mauve, light pink, and white flowers of <em>D. grandiflorum</em> cultivars. We isolated anthocyanins and analyzed them using HPLC, TLC, UV–vis spectra, FABMS, and NMR. Using these methods, we identified two novel delphinidin-based anthocyanins and three novel pelargonidin-based anthocyanins: delphinidin 3-<em>O</em>-[6-<em>O</em>-(α-rhamnopyranosyl)-β-glucopyranoside]-7-<em>O</em>-[6-<em>O</em>-(<em>p</em>-hydroxybenzoyl)-β-glucopyranoside] (<strong>2</strong>), pelargonidin 3-<em>O</em>-[6-<em>O</em>-(α-rhamnopyranosyl)-β-glucopyranoside]-7-<em>O</em>-[6-<em>O</em>-(4-<em>O</em>-(6-<em>O</em>-(<em>p</em>-hydroxybenzoyl)-β-glucopyranosyl)-<em>p</em>-hydroxybenzoyl)-β-glucopyranoside] (<strong>5</strong>, rubrodelphin), pelargonidin 3-<em>O</em>-[6-<em>O</em>-(α-rhamnopyranosyl)-β-glucopyranoside]-7-<em>O</em>-[3-<em>O</em>-(β-glucopyranosyl)-6-<em>O</em>-(4-<em>O</em>-(6-<em>O</em>-(<em>p</em>-hydroxybenzoyl)-β-glucopyranosyl)-<em>p</em>-hydroxybenzoyl)-β-glucopyranoside] (<strong>6</strong>), delphinidin 3-<em>O</em>-[6-<em>O</em>-(α-rhamnopyranosyl)-β-glucopyranoside]-7-<em>O</em>-[3-<em>O</em>-(3-<em>O</em>-(6-<em>O</em>-(<em>p</em>-hydroxybenzoyl)-β-glucopyranosyl)-β-glucopyranosyl)-6-<em>O</em>-(4-<em>O</em>-(6-<em>O</em>-(<em>p</em>-hydroxybenzoyl)-β-glucopyranosyl)-<em>p</em>-hydroxybenzoyl)-β-glucopyranoside] (<strong>7</strong>), and pelargonidin 3-<em>O</em>-[6-<em>O</em>-(α-rhamnopyranosyl)-β-glucopyranoside]-7-<em>O</em>-[3-<em>O</em>-(3-<em>O</em>-(6-<em>O</em>-(4-<em>O</em>-(6-<em>O</em>-(<em>p</em>-hydroxybenzoyl)-β-glucopyranosyl)-<em>p</em>-hydroxybenzoyl)-β-glucopyranosyl)-β-glucopyranosyl)-6-<em>O</em>-(4-<em>O</em>-(6-<em>O</em>-(<em>p</em>-hydroxybenzoyl)-β-glucopyranosyl)-<em>p</em>-hydroxybenzoyl)-β-glucopyranoside] (<strong>9</strong>, rosedelphin), along with four known anthocyanins. The flowers of five blue cultivars accumulated cyanodelphin (<strong>8</strong>) as the dominant pigment. The shapes of visible absorption spectra of these five blue flowers were similar, indicating that the color and the absorption spectra were the typical ones for delphinium blue color produced by <strong>8</strong>. The mauve flower color was due to a mixture of delphinidin-based anthocyanins in various polyacylated levels at the 7-position. The light pink flowers accumulated pelargonidin-based anthocyanins <strong>5</strong>, <strong>6</strong>, and <strong>9</strong>. These pigment structures showed that the pelargonidin-based anthocyanins modified in the same way as in the originally biosynthesized delphinidin-based anthocyanins even though aglycone was replaced by pelargonidin in these anthocyanins.</p></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":null,"pages":null},"PeriodicalIF":4.1000,"publicationDate":"2024-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dyes and Pigments","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0143720824003152","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
引用次数: 0
Abstract
Flower color is one of the most important properties of ornamental flowers. Information on the kinds of pigments that flowers can biosynthesize is useful for breeding cultivars focused on flower colors. The flower colors of regular ornamental delphinium cultivars are blue, violet, purple, pink, and white. The pigments of these flowers are delphinidin-based anthocyanins. It has been reported that the typical modification in delphinium anthocyanins involves the transfer of glucose and p-hydroxybenzoic acid molecules to the 7-position of delphinidin one by one, and it was predicted that other unidentified anthocyanins are present in addition to the already reported ones. Recently, light pink flowers that accumulate pelargonidin-based anthocyanins were reported from cultivars derived from Delphinium grandiflorum. Converting delphinidin-based anthocyanins to pelargonidin-based ones is considered key to producing red flowers in delphinium. Hence, we investigated anthocyanins of blue, mauve, light pink, and white flowers of D. grandiflorum cultivars. We isolated anthocyanins and analyzed them using HPLC, TLC, UV–vis spectra, FABMS, and NMR. Using these methods, we identified two novel delphinidin-based anthocyanins and three novel pelargonidin-based anthocyanins: delphinidin 3-O-[6-O-(α-rhamnopyranosyl)-β-glucopyranoside]-7-O-[6-O-(p-hydroxybenzoyl)-β-glucopyranoside] (2), pelargonidin 3-O-[6-O-(α-rhamnopyranosyl)-β-glucopyranoside]-7-O-[6-O-(4-O-(6-O-(p-hydroxybenzoyl)-β-glucopyranosyl)-p-hydroxybenzoyl)-β-glucopyranoside] (5, rubrodelphin), pelargonidin 3-O-[6-O-(α-rhamnopyranosyl)-β-glucopyranoside]-7-O-[3-O-(β-glucopyranosyl)-6-O-(4-O-(6-O-(p-hydroxybenzoyl)-β-glucopyranosyl)-p-hydroxybenzoyl)-β-glucopyranoside] (6), delphinidin 3-O-[6-O-(α-rhamnopyranosyl)-β-glucopyranoside]-7-O-[3-O-(3-O-(6-O-(p-hydroxybenzoyl)-β-glucopyranosyl)-β-glucopyranosyl)-6-O-(4-O-(6-O-(p-hydroxybenzoyl)-β-glucopyranosyl)-p-hydroxybenzoyl)-β-glucopyranoside] (7), and pelargonidin 3-O-[6-O-(α-rhamnopyranosyl)-β-glucopyranoside]-7-O-[3-O-(3-O-(6-O-(4-O-(6-O-(p-hydroxybenzoyl)-β-glucopyranosyl)-p-hydroxybenzoyl)-β-glucopyranosyl)-β-glucopyranosyl)-6-O-(4-O-(6-O-(p-hydroxybenzoyl)-β-glucopyranosyl)-p-hydroxybenzoyl)-β-glucopyranoside] (9, rosedelphin), along with four known anthocyanins. The flowers of five blue cultivars accumulated cyanodelphin (8) as the dominant pigment. The shapes of visible absorption spectra of these five blue flowers were similar, indicating that the color and the absorption spectra were the typical ones for delphinium blue color produced by 8. The mauve flower color was due to a mixture of delphinidin-based anthocyanins in various polyacylated levels at the 7-position. The light pink flowers accumulated pelargonidin-based anthocyanins 5, 6, and 9. These pigment structures showed that the pelargonidin-based anthocyanins modified in the same way as in the originally biosynthesized delphinidin-based anthocyanins even though aglycone was replaced by pelargonidin in these anthocyanins.
期刊介绍:
Dyes and Pigments covers the scientific and technical aspects of the chemistry and physics of dyes, pigments and their intermediates. Emphasis is placed on the properties of the colouring matters themselves rather than on their applications or the system in which they may be applied.
Thus the journal accepts research and review papers on the synthesis of dyes, pigments and intermediates, their physical or chemical properties, e.g. spectroscopic, surface, solution or solid state characteristics, the physical aspects of their preparation, e.g. precipitation, nucleation and growth, crystal formation, liquid crystalline characteristics, their photochemical, ecological or biological properties and the relationship between colour and chemical constitution. However, papers are considered which deal with the more fundamental aspects of colourant application and of the interactions of colourants with substrates or media.
The journal will interest a wide variety of workers in a range of disciplines whose work involves dyes, pigments and their intermediates, and provides a platform for investigators with common interests but diverse fields of activity such as cosmetics, reprographics, dye and pigment synthesis, medical research, polymers, etc.