High-performance thin-layer chromatography–direct bioautography combined with chemometrics for the distinction of goldenrod species

Thirteen root extract samples of four goldenrod (Solidago) species present in Europe were investigated by hyphenated high-performance thin-layer chromatography (HPTLC). Only S. virgaurea is native, whereas S. gigantea, S. canadensis, and S. graminifolia have been introduced from North America. The bioactive zones in the Aliivibrio fischeri bioautogram were identified as polyacetylenes, labdane diterpenes, or clerodane diterpenes by HPTLC coupled to high-resolution mass spectrometry, exploiting the two interfaces, heated electrospray ionization, and direct analysis in real time. Principal component analysis of the obtained bioprofiles enabled the discrimination of the Solidago species. Furthermore, chemometrics pointed to the discriminative components, the main bioactive markers of the species: Z,Z-matricaria ester from S. virgaurea, solidagenone from S. canadensis, solidagoic acid A, and a dialdehyde clerodane diterpene from S. gigantea, and Z-dehydromatricaria ester from S. graminifolia.