Rapid analysis of stilbenes and derivatives from downy mildew-infected grapevine leaves by liquid chromatography–atmospheric pressure photoionisation mass spectrometry

Resveratrol, trans-ɛ-viniferin and trans-δ-viniferin are the major stilbenes induced in downy mildew infected grapevine leaves. In addition, nine minor polyphenolic compounds, described as stilbenes derivatives, have been separated and detected among known stilbenes after a methanolic microextraction of small pieces (1–2 mg) from infected grapevine leaves with a rapid, qualitative and optimized HPLC method coupled to mass spectrometry using atmospheric pressure photoionisation (APPI–MSn). The characterization of unknown stilbenic derivatives as six resveratrol dimers, two dimethylated resveratrol dimers and a resveratrol trimer are reported. Therefore, structures have been proposed for the dimethylated resveratrol dimers. Use of an easy sample treatment and the LC–APPI–MSn method results in spectral data of these minor naturally occurring viniferin analogues.