title: Effect of water content on the acid-base equilibrium of cyanidin-3-glucoside.
abstract: Laser Flash Photolysis was employed to measure the deprotonation and reprotonation rate constants of cyanidin 3-monoglucoside (kuromanin) in water/methanol mixtures. It was found that the deprotonation rate constant kd decreases with decreasing water content, reflecting the lack of free water molecules around kuromanin, which may accommodate and stabilize the outgoing protons. On the other hand, the reprotonation rate constant, kp, increases with the decrease in water concentration from a value of kp = 2 × 10(10) l mol(-1) s(-1) in water up to kp = 6 × 10(10) l mol(-1) s(-1) at 5.6M water concentration in the mixture. The higher value of kp at lower water concentrations reflects the fact that the proton is not freely escaping the solvation shell of the molecule. The deprotonation rate constant decreases with decreasing water content, reflecting the lack of free water molecules around kuromanin that can accommodate the outgoing protons. Overall, the acidity constant of the flavylium cation decreases with the decrease in water concentration from pKa values of 3.8 in water to approximately 4.8 in water-depleted media, thus shifting the equilibrium towards the red-coloured form, AH(+), at low water contents. The presence, or lack, of water, will affect the colour shade (red to blue) of kuromanin. This is relevant for its role as an intrinsic food component and as a food pigment additive (E163).
authors.affiliation: Requimte, Dep. Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829 516 Caparica, Portugal.
authors.forename: Isabel B
authors.initials: IB
authors.lastname: Coutinho
authors.affiliation: Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal.
authors.forename: Adilson
authors.initials: A
authors.lastname: Freitas
authors.affiliation: Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal.
authors.forename: António L
authors.initials: AL
authors.lastname: Maçanita
authors.affiliation: Requimte, Dep. Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829 516 Caparica, Portugal.
authors.forename: J C
authors.initials: JC
authors.lastname: Lima
mesh_terms: D000136:Acid-Base Equilibrium; D000872:Anthocyanins / Q000737:chemistry*; D002412:Cations; D005960:Glucosides / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D000432:Methanol / Q000737:chemistry; D010782:Photolysis; D011522:Protons; D014867:Water / Q000032:analysis*
chemical_list: D000872:Anthocyanins; D002412:Cations; D005960:Glucosides; D011522:Protons; C000596494:cyanidin 3-O-glucopyranoside; C462279:cyanidin-3-O-beta-glucopyranoside; D014867:Water; D000432:Methanol
keywords: Acid–base equilibrium; Anthocyanin; Laser Flash Photolysis; Water/methanol