Generalization of the anthocyanins kinetics and thermodynamics multistate to 2,6-bis(2-hydroxybenzylidene)cyclohexanones

A. Alejo-Armijo, Artur J. Moro, A. Jorge Parola, João Carlos Lima, Fernando Pina, Livia Corici, Sergiu Shova, Liliana Cseh

Research output: Contribution to journalArticle

Abstract

The thermodynamic and kinetic behavior of 4-(2,4-dihydroxybenzylidene)-6-hydroxy-1,2,3,4-tetrahydroxanthylium chloride was studied in detail. Similarly to anthocyanins, this compound generates a multistate of species that are reversibly interconverted by pH stimuli. The multistate system was studied by NMR and UV–visible (conventional spectroscopy and stopped-flow techniques). A theoretical approach adapted from the one reported for anthocyanins and related compounds was used to rationalize the complex multistate. In particular, the thermodynamic diagram where all the species are positioned was extended to the ionized species. Cis and trans isomers of flavylium cation, quinoidal bases, and ionized chalcone at extremely high pH values were identified. The multistate is dominated in the range 5 < pH < 8 by the spiro form in equilibrium with a small fraction of quinoidal bases. The spiro opening rates follow a different route and pH dependence in very acidic or moderately acidic pHs.

LanguageEnglish
Pages573-588
Number of pages16
JournalDyes and Pigments
Volume163
DOIs
Publication statusPublished - 1 Apr 2019

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Cyclohexanones
Anthocyanins
Thermodynamics
Chalcone
Kinetics
Isomers
Cations
Chlorides
Positive ions
Nuclear magnetic resonance
Spectroscopy

Keywords

  • Anthocyanins
  • Curcumin analogue
  • Flavylium cation
  • Spiro compounds
  • Stopped-flow

Cite this

@article{3ac885ad71784c79a9f59548b07acb68,
title = "Generalization of the anthocyanins kinetics and thermodynamics multistate to 2,6-bis(2-hydroxybenzylidene)cyclohexanones",
abstract = "The thermodynamic and kinetic behavior of 4-(2,4-dihydroxybenzylidene)-6-hydroxy-1,2,3,4-tetrahydroxanthylium chloride was studied in detail. Similarly to anthocyanins, this compound generates a multistate of species that are reversibly interconverted by pH stimuli. The multistate system was studied by NMR and UV–visible (conventional spectroscopy and stopped-flow techniques). A theoretical approach adapted from the one reported for anthocyanins and related compounds was used to rationalize the complex multistate. In particular, the thermodynamic diagram where all the species are positioned was extended to the ionized species. Cis and trans isomers of flavylium cation, quinoidal bases, and ionized chalcone at extremely high pH values were identified. The multistate is dominated in the range 5 < pH < 8 by the spiro form in equilibrium with a small fraction of quinoidal bases. The spiro opening rates follow a different route and pH dependence in very acidic or moderately acidic pHs.",
keywords = "Anthocyanins, Curcumin analogue, Flavylium cation, Spiro compounds, Stopped-flow",
author = "A. Alejo-Armijo and Moro, {Artur J.} and Parola, {A. Jorge} and Lima, {Jo{\~a}o Carlos} and Fernando Pina and Livia Corici and Sergiu Shova and Liliana Cseh",
note = "This work was supported by the Associate Laboratory Research Unit for Green Chemistry - Technologies and Processes Clean – LAQV , financed by national funds from FCT/MEC ( UID/QUI/50006/2013 ) and co-financed by the ERDF under the PT2020 Partnership Agreement ( POCI-01-0145-FEDER -007265 ). A.A.-A. is grateful for the Post-doctoral fellowship from Fundaci{\'o}n Alfonso Mart{\'i}n Escudero. A.J.M. thanks LAQV-REQUIMTE for the post-doctoral fellowship grant ( LAQV/BPD/002/2017 ). S.S. thanks for the POSCCE-O 2.2.1, SMIS-CSNR 13984-901, No. 257/28.09.2010 Project, CERNESIM. The Romanian authors from Institute of Chemistry Timisoara of Romanian Academy acknowledge the support of the Romanian Academy , Program 4, Project 4.1. Appendices",
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AU - Alejo-Armijo, A.

AU - Moro, Artur J.

AU - Parola, A. Jorge

AU - Lima, João Carlos

AU - Pina, Fernando

AU - Corici, Livia

AU - Shova, Sergiu

AU - Cseh, Liliana

N1 - This work was supported by the Associate Laboratory Research Unit for Green Chemistry - Technologies and Processes Clean – LAQV , financed by national funds from FCT/MEC ( UID/QUI/50006/2013 ) and co-financed by the ERDF under the PT2020 Partnership Agreement ( POCI-01-0145-FEDER -007265 ). A.A.-A. is grateful for the Post-doctoral fellowship from Fundación Alfonso Martín Escudero. A.J.M. thanks LAQV-REQUIMTE for the post-doctoral fellowship grant ( LAQV/BPD/002/2017 ). S.S. thanks for the POSCCE-O 2.2.1, SMIS-CSNR 13984-901, No. 257/28.09.2010 Project, CERNESIM. The Romanian authors from Institute of Chemistry Timisoara of Romanian Academy acknowledge the support of the Romanian Academy , Program 4, Project 4.1. Appendices

PY - 2019/4/1

Y1 - 2019/4/1

N2 - The thermodynamic and kinetic behavior of 4-(2,4-dihydroxybenzylidene)-6-hydroxy-1,2,3,4-tetrahydroxanthylium chloride was studied in detail. Similarly to anthocyanins, this compound generates a multistate of species that are reversibly interconverted by pH stimuli. The multistate system was studied by NMR and UV–visible (conventional spectroscopy and stopped-flow techniques). A theoretical approach adapted from the one reported for anthocyanins and related compounds was used to rationalize the complex multistate. In particular, the thermodynamic diagram where all the species are positioned was extended to the ionized species. Cis and trans isomers of flavylium cation, quinoidal bases, and ionized chalcone at extremely high pH values were identified. The multistate is dominated in the range 5 < pH < 8 by the spiro form in equilibrium with a small fraction of quinoidal bases. The spiro opening rates follow a different route and pH dependence in very acidic or moderately acidic pHs.

AB - The thermodynamic and kinetic behavior of 4-(2,4-dihydroxybenzylidene)-6-hydroxy-1,2,3,4-tetrahydroxanthylium chloride was studied in detail. Similarly to anthocyanins, this compound generates a multistate of species that are reversibly interconverted by pH stimuli. The multistate system was studied by NMR and UV–visible (conventional spectroscopy and stopped-flow techniques). A theoretical approach adapted from the one reported for anthocyanins and related compounds was used to rationalize the complex multistate. In particular, the thermodynamic diagram where all the species are positioned was extended to the ionized species. Cis and trans isomers of flavylium cation, quinoidal bases, and ionized chalcone at extremely high pH values were identified. The multistate is dominated in the range 5 < pH < 8 by the spiro form in equilibrium with a small fraction of quinoidal bases. The spiro opening rates follow a different route and pH dependence in very acidic or moderately acidic pHs.

KW - Anthocyanins

KW - Curcumin analogue

KW - Flavylium cation

KW - Spiro compounds

KW - Stopped-flow

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DO - 10.1016/j.dyepig.2018.12.020

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VL - 163

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T2 - Dyes And Pigments

JF - Dyes And Pigments

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