Preparation and Characterization of Protocatechuic Acid Sulfates.

Protocatechuic acid (3,4-dihydroxybenzoic acid; PCA) is a phenolic acid present in plants as a secondary metabolite and is also produced in the human organism as a metabolite from the degradation of polyphenols by the intestinal microbiota, particularly of flavonoids. However, PCA, like most polyphenols, is biotransformed in the human body to different conjugates as sulfates, which are found circulating in blood and could be involved in the bioactivity of the original compound. This paper describes a simple process for the preparation of PCA monosulfates with satisfactory yields. Two compounds were obtained that were identified as PCA-3-sulfate and PCA-4-sulfate by mass spectrometry and ¹H and 13C nuclear magnetic resonance using one- and two-dimensional techniques (heteronuclear single-quantum coherence and heteronuclear multiple-bond correlation). Differential MS fragmentation behavior and UV spectra were observed for each compound, which could be used for their identification in samples of unknown composition. The described procedure can be used for the preparation of these polyphenol metabolites in view of their use in in vivo and in vitro studies, as well as standards for their analysis in biological fluids, to contribute to the elucidation of biological effects of dietary polyphenols.

New flavanol-anthocyanin condensed pigments and anthocyanin composition in guatemalan beans (Phaseolus spp.).

It has long been considered that the pigments resulting from direct condensation between anthocyanins and flavanols were formed exclusively during storage and processing, both in plant-derived foods and in drinks. Recently, however, the minor presence of this type of pigment has been shown in different plant extracts, among them beans. In this work we have studied this family of pigments in beans from Guatemala belonging to two distinct species of the genus Phaseolus, confirming the presence of (epi)gallocatechin carbon-carbon linked to the aglycone of delphinidin and (epi)catechin-cyanidin-3-glucoside. Furthermore, for the first time in this foodstuff another three flavanol-anthocyanin condensed pigments formed by the linkage of (epi)catechin with the corresponding aglycones of cyanidin, petunidin, and peonidin have been described. Also, the natural occurrence of anthocyanidins in this matrix has been confirmed in some of the samples analyzed in this work, the majority being components of their anthocyanin composition. The corresponding aglycones of delphinidin, cyanidin, petunidin, pelargonidin, and malvidin have been identified as well as two aglycones with identical mass to those of peonidin and petunidin, but with different retention times, which leads to the supposition that they are probably methylated derivatives of cyanidin and delphinidin, respectively.