Determination of the effect of acylation of anthocyanins with malic acid on retention under conditions of reversed phase chromatograph
Abstract
In this study, the species composition of anthocyanins of carnation flowers of traditional red and unusual dark red and violet colours was determined, and the contribution of malic acid substituents to the total retention of anthocyanins during separation under conditions of reversed-phase HPLC using diode-matrix and mass spectrometric detection was determined. The main components of the extracts of flowers of two varieties of clove carnation, with a scarlet and dark red colour, 3-glycosides of pelargonidin and cyanidin (Pg3Glu and Cy3Glu), respectively, mainly acylated with malic acid in position 6”-Pg3 (6"MalylGlu) and Cy3 (6"MalylGlu) were established. In this case, the anthocyanins of the clove carnation of the third variety (with a purple colour) had different basis and consisted mainly of cyanidin-3,5-diglucoside derivatives (Cy3,5diGlu), also mainly acylated with malic acid, but already in a different form, connecting both glucoside radicals in a cycle. In all cases, the electronic absorption spectra of the compounds were only slightly (by 0.5-1 nm) bathochromically shifted upon acylation. Anthocyanins of dry flowers of the variety “Mirage” of sweet William consisted of derivatives of Cy3Glu and Cy3,5diGlu, also acylated with malic acid. The elution sequence of all compounds did not depend on the compositions of the mobile phases of the “acetonitrile – formic acid – water” system, which are acceptable for HPLC analysis. It is noted that the retention factor, k(i), of anthocyanins increased by 2.5-3.5 times depending on the composition of the mobile phase upon acylation with malic acid at the 6 position of Cy3Glu and Pg3Glu, and only by 25-40% for Cy3.5diGlu, allowing to analyse the composition of anthocyanins in the isocratic elution mode. For the first time, two variants of separation maps were compared as logk(i) vs ϕ (volume fraction of CH3CN) using a quadratic dependence and as logk(i) vs logk(Cy3Glu). It was shown that the extrapolation of retention to mobile phases with zero water content leads to similar results in both cases.
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