Anthocyanins with an unusual acylation pattern from stem of Allium victorialis

doi:10.1016/0031-9422(95)90025-Q

Phytochemistry

Volume 40, Issue 6, December 1995, Pages 1809-1812

https://doi.org/10.1016/0031-9422(95)90025-Q Get rights and content

Abstract

Two novel anthocyanins have been isolated from the stem of Allium victorialis. By means of chemical degradation and spectroscopy, especially homo- and hetero-nuclear two-dimensional NMR techniques, the structures were determined to be cyanidin 3-O-(3″,6″-O-dimalonyl-β-glucopyranoside) (76.6%) and cyanidin 3-O-(3″,O-malonyl-β-glucopyranoside) (13.8%). This is the first report of acylation of the 3-position in the sugar moiety of any anthocyanin. The stability of malonyl substitution in the 3″-position on glucose is higher than the corresponding 6″-malonylation.

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To expand the application of acylated blueberry pomace anthocyanins in food and nutraceuticals, their enzymatic acylation reaction and the cytotoxic response were explored. In this study, enzymatic acylation was carried out with cyanidin-3-O-glucoside (C3G) as the main body and Novozyme 435 as the biocatalyst. With a series of improvements, the reaction was carried out under the conditions of lauric acid as the acyl donor, tert-amyl alcohol as the reaction medium, the molar ratio of C3G to lauric acid of 1:10, the reaction time of 24 h and the reaction temperature of 60 °C, and 35.29 % acylation rate was obtained. Moreover, it was found that the lipophilicity, thermostability and photostability of the enzymatic acylated blueberry pomace anthocyanins were improved compared with the untreated blueberry pomace anthocyanins. Cytotoxicity studies showed that acylated blueberry pomace anthocyanins inhibited tumor cells (HeLa, HepG2, and B16 cells) significantly and were less toxic to normal cells (L929 cells) at the maximum concentration (1000 µg/mL) and the longest duration of action (72 h). This study established a method for acylation of blueberry pomace anthocyanins that may be applied to other natural sources of anthocyanins.
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The stability of anthocyanin is not only influenced by temperature, light, metal ions, pH and other external factors, but also greatly influenced by its own molecular structure [20]. For example, anthocyanins containing cornflowers were less stable, while those containing paeoniflorin and mallow pigment were higher [20–23]. Generally speaking, the stability of anthocyanins decreases with the increase of the number of hydroxyl groups in the anthocyanidin B-ring, and increases with the increase of the degree of methylation [24].
Aim at improving the poor stability of natural anthocyanins applied in intelligent color indicator packing materials, anthocyanins from blueberry was acylated with maleic anhydride through means of solid-phase grafting method. Fourier Transform Infrared Spectroscopy (FTIR) analysis demonstrated that maleic acid was successfully grafted onto blueberry anthocyanins. All the four acylated anthocyanins (with different acylated degree) were better in stability, but were slightly less efficient at scavenging the DPPH radical, compared with their native non-acylated form. An-MA2 (acylated degree was 7.68%) got the lowest color loss (27.62% at 19th day), 23.19% lower than that of An-MA0 (native anthocyanins). After reacting with maleic anhydride, anthocyanins kept its pH-color response characteristics and showed distinct color differences at different pH value. In addition, the NH₃ response characteristics of acylated anthocyanins were similar to those of non-acylated anthocyanins, but lagged slightly in response speed.
Improving the color stability and antioxidation activity of blueberry anthocyanins by enzymatic acylation with p-coumaric acid and caffeic acid
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By contrast, the increase in methylation degree is conducive to the improvement of stability. The glycosylation of free hydroxyl groups also enhance the stability of anthocyanins(Andersen & Fossen, 1995). The sugar chains can stack acyl groups on the surface of the 2-phenyl benzopyran skeleton like a ribbon.
In this work, p-coumaric acid and caffeic acid were grafted on blueberry anthocyanins through enzyme catalysis method to improve their colour stability and antioxidant activity. The acylation degrees of p-coumaric acylated anthocyanins (Co-An) and caffeic acid anthocyanins (Ca-An) reached 5.38% and 5.68%, respectively. The results from Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ultraviolet visible spectroscopy and hydrogen nuclear magnetic resonance implied that p-coumaric acid and caffeic acid grafted on the 6-OH of glucoside and galactoside and the 5-OH of arabinose through esterification reaction. As revealed in the in vitro experiment on antioxidation activity and the experiment on colour stability, Co-An and Ca-An showed stronger antioxidant activity in DPPH assay and β-carotene bleaching assay and higher colour stability during storage at 25 °C, 40 °C and 60 °C than native blueberry anthocyanins.
A natural colorant system from corn: Flavone-anthocyanin copigmentation for altered hues and improved shelf life
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This is evidenced by the glycoside peak (3 and 4) increases seen in the chromatograms in Fig. 4. The first step in the degradation of cyanidin 3-(6″-malonylglucoside) is the loss of an acyl moiety (Andersen & Fossen, 1995), suggesting degradation of C3MG and Pg3MG would produce analogous C3G and Pg3G as degradation products, indistinguishable from naturally occurring C3G and Pg3G. This inability to account for the conversion of acylated to unacylated anthocyanins may also account for the lower R2 values associated with the half-lives calculated for these peaks.
Anthocyanins are a major source of natural red colorants but currently face difficulties matching the hue range, stability, and affordability of synthetic options. Purple corn offers an FDA and EFSA-approved economical source of anthocyanin-based colorants. A C-glycosyl flavone and anthocyanin copigmentation system consisting of a flavone-rich anthocyanin-poor line and two anthocyanin-rich flavone-poor lines containing either pelargonidin or cyanidin-derived anthocyanins is described. This system offers a broad hue range and can improve stability. Cyanidin-rich model beverages had better stability than pelargonidin-rich beverages over time, but the addition of flavone-rich extract to both resulted in significantly longer half-lives (up to 50% longer). Flavone copigments produced hyperchromic and bathochromic shifts in both. A protective effect from flavone copigmentation was observed for glycosides. In contrast acylated forms displayed significantly shorter half-lives. Results suggest that corn C-glycosyl flavone-rich extracts could serve as a color enhancing and stabilizing agent for anthocyanin colorants.
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ii) The attachment sites of the acyl groups on the glycosyl groups are related to the stability of the anthocyanins. For example, for the acylated anthocyanins from Allium victorialis stem, the malonylation at the 3″-position in the sugar moiety resulted in better stability than that at the 6″ position (Andersen & Fossen, 1995). Therefore, the acylation sites including the attachment sites of the acylated glycosyl groups on the anthocyanidins and the attachment sites of the acyl groups on the glycosyl groups jointly influence the stability of the acylated anthocyanins due to their effects on the efficiency of the intramolecular copigmentation and the stability of the intramolecular copigmented complexes of the anthocyanins.
This review comprehensively summarizes the existing knowledge regarding the chemical implications of anthocyanin glycosyl acylation, the effects of acylation on the stability of acylated anthocyanins and the corresponding mechanisms. Anthocyanin glycosyl acylation commonly refers to the phenomenon in which the hydroxyl groups of anthocyanin glycosyls are esterified by aliphatic or aromatic acids, which is synthetically represented by the acylation sites as well as the types and numbers of acyl groups. Generally, glycosyl acylation increases the in vitro and in vivo chemical stability of acylated anthocyanins, and the mechanisms primarily involve physicochemical, stereochemical, photochemical, biochemical or environmental aspects under specific conditions. Additionally, the acylation sites as well as the types and numbers of acyl groups influence the stability of acylated anthocyanins to different degrees. This review could provide insight into the optimization of the stability of anthocyanins as well as the application of suitable anthocyanins in food, pharmaceutical and cosmetic industries.

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Plant chemistryAnthocyanins with an unusual acylation pattern from stem of Allium victorialis

Abstract

J. Food Prot.

J. Food Sci.

Plant chemistry
Anthocyanins with an unusual acylation pattern from stem of Allium victorialis