title: Fluorescence, electrophoretic and chromatographic fingerprints of herbal medicines and their comparative chemometric analysis.
abstract: 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 (0.037mgL(-1) for catechin, 0.052mgL(-1) for protocatechuic acid, 0.136mgL(-1) for chlorogenic acid, 0.058mgL(-1) for syringic acid and 0.256mgL(-1) for ferulic acid), linearity (up to 5.0-15mgL(-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.
authors.affiliation: Department of Chemistry, Tallinn University of Technology, Akadeemia tee 15, 12816 Tallinn, Estonia; NarTest AS, Kopliranna 49, 11713 Tallinn, Estonia. Electronic address: jekaterina.mazina@gmail.com.
authors.forename: Jekaterina
authors.initials: J
authors.lastname: Mazina
authors.affiliation: Department of Chemistry, Tallinn University of Technology, Akadeemia tee 15, 12816 Tallinn, Estonia.
authors.forename: Merike
authors.initials: M
authors.lastname: Vaher
authors.affiliation: Department of Chemistry, Tallinn University of Technology, Akadeemia tee 15, 12816 Tallinn, Estonia.
authors.forename: Maria
authors.initials: M
authors.lastname: Kuhtinskaja
authors.affiliation: NarTest AS, Kopliranna 49, 11713 Tallinn, Estonia.
authors.forename: Larisa
authors.initials: L
authors.lastname: Poryvkina
authors.affiliation: Department of Chemistry, Tallinn University of Technology, Akadeemia tee 15, 12816 Tallinn, Estonia.
authors.forename: Mihkel
authors.initials: M
authors.lastname: Kaljurand
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D016000:Cluster Analysis; D004586:Electrophoresis / Q000379:methods*; D029001:Herbal Medicine; D013058:Mass Spectrometry / Q000379:methods*; D010936:Plant Extracts / Q000032:analysis*; D059808:Polyphenols / Q000032:analysis*; D025341:Principal Component Analysis; D013050:Spectrometry, Fluorescence / Q000379:methods*
chemical_list: D010936:Plant Extracts; D059808:Polyphenols
keywords: Capillary electrophoresis-diode array detector; Chemometric methods; Herbal fingerprinting; Herbal medicine; High-performance liquid chromatography-diode array detector-mass spectrometer; Spectral fluorescence signature