Impact of Lignosulfonates on the Thermodynamic and Kinetic Parameters of Malvidin-3- O-glucoside in Aqueous Solutions

J Agric Food Chem. 2018 Jun 27;66(25):6382-6387. doi: 10.1021/acs.jafc.8b02273. Epub 2018 Jun 13.

Abstract

The interaction of malvidin-3- O-glucoside (1) and a lignosulfonate was studied by UV-visible spectroscopy, and the results obtained showed the formation of a complex between the negatively charged lignosulfonate and the flavylium cation form (AH+) of this anthocyanin at pH 1. The thermodynamic and kinetic parameters of 1 in the presence of a lignosulfonate were determined by UV-visible spectroscopy and stopped-flow techniques. The main differences were observed in the flavylium cation (AH+)/quinoidal base (A) equilibrium, the AH+ form being more stabilized than A (p Ka1 = 4.4 ± 0.1) compared with 1 in the absence of the lignosulfonate (p Ka1 = 3.9 ± 0.1). Furthermore, comparing the hydration ( kh = 0.028 s-1) and dehydration ( k-h = 40 M-1 s-1) processes of 1 in the presence of the lignosulfonate with the processes of 1 ( kh = 0.12 s-1 and k-h = 35 M-1 s-1) show that the hydration process is slower while the dehydration process is practically unaffected in the presence of the lignosulfonate.

Keywords: UV−visible; calcium lignosulfonate; copigmentation; flavylium cation stabilization; malvidin-3-O-glucoside; stopped-flow.

MeSH terms

  • Anthocyanins / chemistry*
  • Glucosides / chemistry*
  • Hydrogen-Ion Concentration
  • Kinetics
  • Lignin / analogs & derivatives*
  • Lignin / chemistry
  • Models, Chemical
  • Molecular Structure
  • Thermodynamics

Substances

  • Anthocyanins
  • Glucosides
  • malvidin-3-glucoside
  • lignosulfuric acid
  • Lignin