Colorimetric selective quantification of anthocyanins with catechol/pyrogallol moiety in edible plants upon zinc complexation

Here is examined the colour development from common anthocyanins (i.e., cyanidin, delphinidin, malvidin, and pelargonidin glycosides) and from anthocyanins-rich extracts (i.e., bilberries, strawberries, and raspberries), using zinc-anthocyanin complexes as molecular probe. We have observed the absorbance increase in the blue region in presence of large excess of zinc ion at acidic pH for cyanidin and delphinidin derivatives, likely due to quinoidal base stabilization from catechol and pyrogallol moiety. The assay condition were studied and applied to natural extracts containing these compounds. The same behaviour was observed for bilberry and, to a minor extent, for raspberry extracts, due to the larger cyanidin/delphinidin contents in the former than in the latter. Anthocyanin standard UV–Vis analysis in buffer has shown a very good linear correlation for cyanidin and delphinidin (R2 = 0.995 and 0.997, respectively), good precision (CV% = 7.4% and 5.3% respectively), high sensitivity (Cyε600nm = 8300 M−1 cm−1, LOD = 0.264 ± 0.005 mg L−1, LOQ = 0.478 ± 0.007 mg L−1, and Dpε600nm = 15,900 M−1 cm−1, LOD = 0.143 ± 0.002 mg L−1, LOQ = 0.478 ± 0.007 mg L−1). The effectiveness of this colorimetric method for the selective quantification of catechol/pyrogallol-based anthocyanins has been demonstrated in the aforementioned complex real matrices and compared to LC-MS/MS analysis and pH-differential method, offering a valuable tool to characterize plant and food extracts particularly rich in zinc-coordinating anthocyanins.