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

Mora-Soumille, Nathalie; Bittar, Sheiraz Al; Rosa, Maxence; Dangles, Olivier

doi:10.1016/j.dyepig.2012.07.006

Cited by 28 publications

(30 citation statements)

References 15 publications

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“…According to Gottlieb, blue flower color is characteristic of the most highly evolved flowering plants, probably as a result of favoring pollination by hymenoptera, which do not detect red light. Anthocyanins derived from cyanidin, delphinidin, and petunidin, with two or more ortho ‐hydroxyl groups in the B‐ring, form complexes with divalent and trivalent metal cations such as Al 3+ , Fe 2+ /Fe 3+ , and Mg 2+ , transforming the color of the pigment from red or purple to blue . The classical example is Hydrangea , the flowers of which are red when grown on basic soil where aluminum is immobilized as aluminum hydroxide and blue when grown on acidic aluminum‐containing soil where aluminum is available as Al 3+ for uptake by the plant.…”

Section: Photophysics Of Anthocyanin Complexesmentioning

confidence: 99%

Chemistry and photochemistry of natural plant pigments: the anthocyanins

Silva

Freitas

Maçanita

et al. 2016

J of Physical Organic Chem

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Anthocyanins are naturally occurring plant pigments responsible for the red, blue, and purple colors of the majority of fruits, flowers, and leaves. The pH-dependent ground-state chemistry of anthocyanins is extremely rich. Above about pH 2.5, the colored flavylium cation form typically hydrates to form the colorless hemiacetal, followed by ring-opening tautomerization to the (E)-chalcone, which can isomerize to the (Z)-chalcone. The color of anthocyanins can also be modulated and/or stabilized by complexation with metal ions or with colorless organic molecules (copigments) such as hydroxylated benzoic or cinnamic acids. An understanding of the chemistry that contributes to the loss of color is essential for the development of novel and more effective strategies for the stabilization of the color above pH 3, which would permit the use of anthocyanins as natural pigments in a much wider range of foods or consumer products. In the excited state, uncomplexed anthocyanins undergo ultrafast adiabatic deprotonation (5-20 ps) in aqueous solution to give the corresponding short-lived (about 200 ps) excited quinonoidal base. Intermolecular and intramolecular complexes of anthocyanins with organic copigments undergo deactivation that is even faster than deprotonation. The colorless hydration products are photoactive in the ultraviolet; thus, the chalcones undergo E-Z photoisomerization, while the hemiacetal form of anthocyanins exhibits photochemistry typical of a chromene. These photoprocesses all potentially contribute to the photostability of anthocyanins in fruit and flowers and are fully consistent with the biological role of anthocyanins in protecting leaves from excess solar radiation.

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Section: Photophysics Of Anthocyanin Complexesmentioning

confidence: 99%

Chemistry and photochemistry of natural plant pigments: the anthocyanins

Silva

Freitas

Maçanita

et al. 2016

J of Physical Organic Chem

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“…10,[16][17][18][19][20][21][22][23] In the plant vacuoles where anthocyanins concentrate, [24][25][26] the anthocyanin cation AH + can chelate with metal cations 23,27 such as Al 3+ and/or form complexes with colorless organic copigment molecules, such as electron-rich derivatives of hydroxybenzoic or hydroxycinnamic acids, flavones or one of the colorless neutral forms of the anthocyanin itself. 10,[16][17][18][19][20][21][22][23] Metal cation chelation can lead to large changes in the color, primarily from red to blue as, for example, in Hydrangea, 28 but is limited to anthocyanins with two or more free OH groups in the B-ring 23,27,29 (i.e., anthocyanins derived from cyanidin, delphinidin and petunidin). In contrast, copigmentation via complexation with organic molecules results in much smaller red shifts of the absorption, but can increase the pH at which hydration occurs, consistent with steric hindrance to attack of water and charge transfer from the copigment to the anthocyanin as an important contributor to the stability of the anthocyanin-copigment complex.…”

Section: Introductionmentioning

confidence: 99%

Quantum Chemical Investigation of the Intramolecular Copigmentation Complex of an Acylated Anthocyanin

He¹,

Li²,

Silva³

et al. 2018

J. Braz. Chem. Soc.

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Anthocyanins are the natural plant pigments responsible for most of the red, blue and purple colors of flowers and fruit. One method of stabilization of the color of anthocyanins in nature is intramolecular copigmentation, in which a copigment molecule covalently attached to one of the sugar residues complexes with the anthocyanin cation chromophore. In the present work, two quantum chemical methodologies, time-dependent density functional theory (TD-DFT) and secondorder algebraic diagrammatic construction (ADC(2)), were employed to predict the absorption spectra in vacuum and conductor-like screening model (COSMO) water of a natural anthocyanin containing an ester of coumaric acid (copigment) bound to the sugar residue of a cyanidin chromophore. ADC(2) in water adequately reproduces the experimental spectra with and without intramolecular copigmentation, pointing to this theoretical technique as a promising approach for predicting the spectroscopic properties of natural (and nature-inspired) dyes and pigments.

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“…Therefore, the glucuronylation reaction to obtain took place more selectively to the C4−OH. 20 Direct injection in mass spectrometry (ESI−MS) in negative ion mode gave the pseudomolecular ion [M-H] − at m/z 469 which is compatible with the molar mass of the desired compound. Furthermore, this pseudomolecular ion produces the MS 2 ions at m/z 427, 409, 367, 349, and 153, which are in concordance with the fragmentation pattern for this structure.…”

Section: Resultsmentioning

confidence: 99%

Characterization of Kinetic and Thermodynamic Parameters of Cyanidin-3-glucoside Methyl and Glucuronyl Metabolite Conjugates.

et al. 2015

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The determination of rate and equilibrium constants of anthocyanin metabolites with in vivo occurrence, cyanidin-4'-O-methyl-3-glucoside (Cy4'Me3glc) and cyanidin-7-O-glucuronyl-3-glucoside (Cy7Gluc3glc), was carried out for the first time by means of direct and reverse pH jumps. The thermodynamics and kinetics of these compounds are similar to the anthocyanin monoglucosides in particular for the analogous cyanidin-3-glucoside (Cy3glc) and peonidin-3-glucoside (Peo3glc). The rate and equilibrium constants of metabolites were also compared with malvin (malvidin 3,5-diglucoside) and with a bioinspired compound 3',4'-dihydroxy-7-O-glucopyranosyloxyflavylium (DGF). In Cy4'Me3glc and Cy7Gluc3glc the rate of hydration for a fixed pH value is slower than in DGF and the dominant species at moderately acidic solutions is the hemiketal. Oppositely, in DGF trans-chalcone is the dominant species at moderately acidic solutions.

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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

Cited by 28 publications

References 15 publications

Chemistry and photochemistry of natural plant pigments: the anthocyanins

Chemistry and photochemistry of natural plant pigments: the anthocyanins

Quantum Chemical Investigation of the Intramolecular Copigmentation Complex of an Acylated Anthocyanin

Characterization of Kinetic and Thermodynamic Parameters of Cyanidin-3-glucoside Methyl and Glucuronyl Metabolite Conjugates.

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