Analogs of anthocyanins with a 3′,4′-dihydroxy substitution: Synthesis and investigation of their acid–base, hydration, metal binding and hydrogen-donating properties in aqueous solution

Glycosides of hydroxylated flavylium ions are proposed as pertinent analogs of anthocyanins, a major class of polyphenolic plant pigments. Anthocyanins with a 3′,4′-dihydroxy substitution on the B-ring (catechol nucleus) are especially important for their metal chelating and electron-donating (antio...

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Published in:Dyes and pigments 2013-01, Vol.96 (1), p.7-15
Main Authors: Mora-Soumille, Nathalie, Al Bittar, Sheiraz, Rosa, Maxence, Dangles, Olivier
Format: Article
Language:English
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Aluminum
Analogs
Anthocyanin
Anthocyanins
Antioxidant
Antioxidants
Conversion
Flavylium
Glycoside
Life Sciences
Pigments
Radicals
Synthesis
Thermodynamics
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creator Mora-Soumille, Nathalie
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Dangles, Olivier
description Glycosides of hydroxylated flavylium ions are proposed as pertinent analogs of anthocyanins, a major class of polyphenolic plant pigments. Anthocyanins with a 3′,4′-dihydroxy substitution on the B-ring (catechol nucleus) are especially important for their metal chelating and electron-donating (antioxidant) capacities. In this work, an efficient chemical synthesis of 3′,4′-dihydroxy-7-O-β-d-glucopyranosyloxyflavylium chloride and its aglycone is reported. Then, the ability of the two pigments to undergo proton transfer (formation of colored quinonoid bases) and add water (formation of a colorless chalcone) is investigated: at equilibrium the colored quinonoid bases (kinetic products) are present in very minor concentrations (
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Anthocyanins with a 3′,4′-dihydroxy substitution on the B-ring (catechol nucleus) are especially important for their metal chelating and electron-donating (antioxidant) capacities. In this work, an efficient chemical synthesis of 3′,4′-dihydroxy-7-O-β-d-glucopyranosyloxyflavylium chloride and its aglycone is reported. Then, the ability of the two pigments to undergo proton transfer (formation of colored quinonoid bases) and add water (formation of a colorless chalcone) is investigated: at equilibrium the colored quinonoid bases (kinetic products) are present in very minor concentrations (&lt;10% of the total pigment concentration) compared to the colorless chalcone (thermodynamic product). The glucopyranosyloxyflavylium ion appears significantly less acidic than the aglycone. The thermodynamics of the overall sequence of flavylium – chalcone conversion is not affected by the β-d-glucosyl moiety while the kinetics appears slower by a factor ca. 8. Although the glucopyranosyloxyflavylium ion and its aglycone display similar affinities for Al3+, the Al3+-glucoside complex is more stable than the Al3+-aglycone complex due to the higher sensitivity of the latter to water addition and conversion into the corresponding chalcone. Finally, the glucopyranosyloxyflavylium ion and its aglycone are compared for their ability to reduce the 1,1-diphenyl-2-picrylhydrazyl radical in a mildly acidic water/MeOH (1:1) mixture as a first evaluation of their antioxidant activity. Glycosidation at C7-OH results in a lower rate constant of first electron transfer to DPPH and a lower stoichiometry (total number of 1,1-diphenyl-2-picrylhydrazyl radicals reduced per pigment molecule). Anthocyanins are difficult to extract from plants in substantial amount. However, the analogs investigated in this work are of easy access by chemical synthesis and express the physico-chemical properties typical of anthocyanins. They can thus be regarded as valuable models for investigating the coloring, metal-binding and antioxidant properties of these important natural pigments. ► Efficient synthesis of 3′,4′-dihydroxy-7-O-β-d-glucopyranosyloxyflavylium chloride (P2). ► P2 and aglycone P1 are mild acids and form colorless chalcones by water addition. ► P2 and P1 form colored chelates with Al3+. 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Although the glucopyranosyloxyflavylium ion and its aglycone display similar affinities for Al3+, the Al3+-glucoside complex is more stable than the Al3+-aglycone complex due to the higher sensitivity of the latter to water addition and conversion into the corresponding chalcone. Finally, the glucopyranosyloxyflavylium ion and its aglycone are compared for their ability to reduce the 1,1-diphenyl-2-picrylhydrazyl radical in a mildly acidic water/MeOH (1:1) mixture as a first evaluation of their antioxidant activity. Glycosidation at C7-OH results in a lower rate constant of first electron transfer to DPPH and a lower stoichiometry (total number of 1,1-diphenyl-2-picrylhydrazyl radicals reduced per pigment molecule). Anthocyanins are difficult to extract from plants in substantial amount. However, the analogs investigated in this work are of easy access by chemical synthesis and express the physico-chemical properties typical of anthocyanins. They can thus be regarded as valuable models for investigating the coloring, metal-binding and antioxidant properties of these important natural pigments. ► Efficient synthesis of 3′,4′-dihydroxy-7-O-β-d-glucopyranosyloxyflavylium chloride (P2). ► P2 and aglycone P1 are mild acids and form colorless chalcones by water addition. ► P2 and P1 form colored chelates with Al3+. 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Anthocyanins with a 3′,4′-dihydroxy substitution on the B-ring (catechol nucleus) are especially important for their metal chelating and electron-donating (antioxidant) capacities. In this work, an efficient chemical synthesis of 3′,4′-dihydroxy-7-O-β-d-glucopyranosyloxyflavylium chloride and its aglycone is reported. Then, the ability of the two pigments to undergo proton transfer (formation of colored quinonoid bases) and add water (formation of a colorless chalcone) is investigated: at equilibrium the colored quinonoid bases (kinetic products) are present in very minor concentrations (&lt;10% of the total pigment concentration) compared to the colorless chalcone (thermodynamic product). The glucopyranosyloxyflavylium ion appears significantly less acidic than the aglycone. The thermodynamics of the overall sequence of flavylium – chalcone conversion is not affected by the β-d-glucosyl moiety while the kinetics appears slower by a factor ca. 8. Although the glucopyranosyloxyflavylium ion and its aglycone display similar affinities for Al3+, the Al3+-glucoside complex is more stable than the Al3+-aglycone complex due to the higher sensitivity of the latter to water addition and conversion into the corresponding chalcone. Finally, the glucopyranosyloxyflavylium ion and its aglycone are compared for their ability to reduce the 1,1-diphenyl-2-picrylhydrazyl radical in a mildly acidic water/MeOH (1:1) mixture as a first evaluation of their antioxidant activity. Glycosidation at C7-OH results in a lower rate constant of first electron transfer to DPPH and a lower stoichiometry (total number of 1,1-diphenyl-2-picrylhydrazyl radicals reduced per pigment molecule). Anthocyanins are difficult to extract from plants in substantial amount. However, the analogs investigated in this work are of easy access by chemical synthesis and express the physico-chemical properties typical of anthocyanins. They can thus be regarded as valuable models for investigating the coloring, metal-binding and antioxidant properties of these important natural pigments. ► Efficient synthesis of 3′,4′-dihydroxy-7-O-β-d-glucopyranosyloxyflavylium chloride (P2). ► P2 and aglycone P1 are mild acids and form colorless chalcones by water addition. ► P2 and P1 form colored chelates with Al3+. The (Al3+-P2) color is more stable. ► P1 reduces the 1,1-diphenyl-2-picrylhydrazyl radical more efficiently than P2.</abstract><pub>Elsevier Ltd</pub><doi>10.1016/j.dyepig.2012.07.006</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0002-1987-8433</orcidid></addata></record>
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subjects Aluminum
Analogs
Anthocyanin
Anthocyanins
Antioxidant
Antioxidants
Conversion
Flavylium
Glycoside
Life Sciences
Pigments
Radicals
Synthesis
Thermodynamics
title Analogs of anthocyanins with a 3′,4′-dihydroxy substitution: Synthesis and investigation of their acid–base, hydration, metal binding and hydrogen-donating properties in aqueous solution
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