Fluorescence, electrophoretic and chromatographic fingerprints of herbal medicines and their comparative chemometric analysis

• Neat herbal medicines extracts front face spectral fluorescence signature analysis.
• Comparative chemometric study of medicinal herb polyphenolic fingerprints.
• SFS-PARAFAC-PCA/CA method was quick, efficient and non-destructive.

The aim of the present study was to compare the polyphenolic compositions of 47 medicinal herbs (HM) and four herbal tea mixtures from Central Estonia by rapid, reliable and sensitive Spectral Fluorescence Signature (SFS) method in a front face mode. The SFS method was validated for the main identified HM representatives including detection limits (0.037 mg L−1 for catechin, 0.052 mg L−1 for protocatechuic acid, 0.136 mg L−1 for chlorogenic acid, 0.058 mg L−1 for syringic acid and 0.256 mg L−1 for ferulic acid), linearity (up to 5.0–15 mg L−1), intra-day precision (RSDs=6.6–10.6%), inter-day precision (RSDs=6.4–13.8%), matrix effect (−15.8 to +5.5) and recovery (85–107%). The phytochemical fingerprints were differentiated by parallel factor analysis (PARAFAC) combined with hierarchical cluster analysis (CA) and principal component analysis (PCA). HM were clustered into four main clusters (catechin-like, hydroxycinnamic acid-like, dihydrobenzoic acid-like derivatives containing HM and HM with low/very low content of fluorescent constituents) and 14 subclusters (rich, medium, low/very low contents). The average accuracy and precision of CA for validation HM set were 97.4% (within 85.2–100%) and 89.6%, (within 66.7–100%), respectively. PARAFAC-PCA/CA has improved the analysis of HM by the SFS method. The results were verified by two separation methods CE-DAD and HPLC-DAD-MS also combined with PARAFAC-PCA/CA. The SFS-PARAFAC-PCA/CA method has potential as a rapid and reliable tool for investigating the fingerprints and predicting the composition of HM or evaluating the quality and authenticity of different standardised formulas. Moreover, SFS-PARAFAC-PCA/CA can be implemented as a laboratory and/or an onsite method.

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