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. 2021 Apr 8;26(8):2146.
doi: 10.3390/molecules26082146.

Chemical Hemisynthesis of Sulfated Cyanidin-3- O-Glucoside and Cyanidin Metabolites

Sarah Straßmann  1 , Maike Passon  1 , Andreas Schieber  1
Affiliations

Chemical Hemisynthesis of Sulfated Cyanidin-3- O-Glucoside and Cyanidin Metabolites

Sarah Straßmann et al. Molecules. .

Abstract

The metabolism of anthocyanins in humans is still not fully understood, which is partly due to the lack of reference compounds. It is known that sulfation is one way of the complex phase II biotransformation mechanism. Therefore, cyanidin-3-O-glucoside and the cyanidin aglycone were chemically converted to their sulfates by reaction with sulfur trioxide-N-triethylamine complex in dimethylformamide. The reaction products were characterized by UHPLC coupled to linear ion trap and IMS-QTOF mass spectrometry. Based on MS data, retention times, and UV-Vis spectra, the compounds could tentatively be assigned to A-, C-, or B-ring sulfates. Analysis of urine samples from two volunteers after ingestion of commercial blackberry nectar demonstrated the presence of two sulfated derivatives of the cyanidin aglycone and one sulfated derivative of the cyanidin-3-O-glucoside. It was found that both the A ring and the B ring are sulfated by human enzymes. This study marks an important step toward a better understanding of anthocyanin metabolism.

Keywords: HRMS; LC-IMS; anthocyanins; cyanidin; cyanidin-3-O-glucoside; metabolites; sulfation.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Synthesis reactions of cyanidin sulfates and cyanidin-3-O-glucoside sulfates.
Figure 1
Figure 1
Extracted ion chromatograms of the [M]+, m/z 367.0118 (cyanidin monosulfate) after the synthesis reaction (A) and of the 24 h urine sample (B).
Figure 2
Figure 2
UV/Vis spectra of cyanidin (RT 11.7 min) in comparison to three cyanidin monosulfates (RT 7.1, 12.6 and, 12.8 min).
Figure 3
Figure 3
Postulated ESI+ fragmentation scheme for cyanidin (red) and its derivatives (blue) sulfated on the A, B or C ring, based on the proposals of Barnes and Schug [13], González-Manzano et al. [14], and Oliveira et al. [15]. Conjugation positions are arbitrarily selected and may occur at any OH group.
Figure 4
Figure 4
Extracted ion chromatograms of the [M]+, m/z 529.0646 (black line) and 609.0215 (dashed line) (cyanidin-3-O-glucoside mono- and disulfate) after the synthesis reaction.
Scheme 2
Scheme 2
Structure of cyanidin and cyanidin-3-O-glucoside.
See this image and copyright information in PMC

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