Collect. Czech. Chem. Commun. 2010, 75, 1097-1114
Published online 2010-11-09 11:53:19

Oxidation pathways of natural dye hematoxylin in aqueous solution

Romana Sokolováa,*, Ilaria Deganob, Magdaléna Hromadováa, Jana Bulíčkováa, Miroslav Gála and Michal Valášekc

a J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Dolejškova 3, 182 23 Prague, Czech Republic
b Department of Chemistry and Industrial Chemistry, University of Pisa, Via Risorgimento 35, 56100 Pisa, Italy
c Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, v.v.i., Flemingovo nám. 2, 166 10 Prague 6, Czech Republic


The oxidation mechanism of hematoxylin was studied in phosphate buffers and 0.1 M KCl by cyclic voltammetry and UV-Vis spectroscopy under deaerated conditions. The redox potential of hematoxylin in buffered solution strongly depends on pH. A two electron oxidation is preceded by deprotonation. The homogeneous rate of deprotonation process of hematoxylin in 0.1 M phosphate buffer is kd = (2.5 ± 0.1) × 104 s–1. The cyclic voltammetry under unbuffered conditions shows the distribution of various dissociation forms of hematoxylin. The dissociation constants pK1 = 4.7 ± 0.2 and pK2 = 9.6 ± 0.1 were determined using UV-Vis spectroscopy. The final oxidation product was identified by gas chromatography with mass spectrometry detection as hemathein. The distribution of oxidation products differs under buffered and unbuffered conditions. The dye degradation in natural unbuffered environment yields hemathein and hydroxyhematoxylin, which is absent in buffered solution.

Keywords: Hematoxylin; Oxidation; Dye degradation; Cyclic voltammetry.

References: 26 live references.