Chromatographic fingerprint application possibilities in food authentication

The aim of the study was to compare the effectiveness of the use of low-peak chromatographic fingerprints for the differentiation of various food products. Three groups of unprocessed products (mushrooms, hazelnuts and tomatoes), food preparations (bread, dried herbs and tomato juice) and alcoholic beverages (vodka and two types of blended whiskey) were examined. A commercial electronic nose based on ultrafast gas chromatography (acquisition time 90 s) with a flame ionization detector was used for the research. Static headspace was used as a green procedure to extract volatile compounds without modifying the food matrix. Individual extraction conditions were used for each product group. Similarities and differences between profiles were analyzed by simple Principal Components Analysis. The similarity rating was determined using the Euclidean distances. Global model was built for recognition chromatographic fingerprints of food samples. The best recognition results were 100% and 89% for tomato juices, spices, separate champignon elements and hazelnuts. On the other hand, the worst recognition results were 56% and 77% for breads and strong alcoholic beverages.

Vitis vinifera L. Pruning Waste for Bud-Preparations as Source of Phenolic Compounds–Traditional and Innovative Extraction Techniques to Produce New Natural Products

Herbal products are now considered among the most important sources of phenolic compounds: the FINNOVER project aimed at the creation and development of sustainable supply chains to extract and use natural biologically active agents. Vitis vinifera is one of the most utilised herbal products derived from buds and sprouts as polyphenolic food supplements for its homeostatic and astringent properties. This research was aimed to describe the antioxidant capacity and the phytochemical composition of V. vinifera herbal products by the application of spectroscopic and chromatographic fingerprints considering phenolics as potential markers to significantly differentiate traditional preparations (macerates) from innovative extracts obtained by an ultrasound extraction from V. vinifera buds. Two different commercial products were also considered. Flavonols were the most abundant class in ultrasound extracts (45%), while phenolic acids were the most important class in traditional macerates (49%) and commercial bud-preparations (about 50%). This study may support the potential use of V. vinifera bud-products (starting from pruning byproducts) as food supplements to integrate human diet with good amounts of phenolics. Finally, the use of different extraction methods on the same plant material could be an important development to produce innovative herbal products with a phytochemical composition similar to traditional preparations.

Microextraction of Reseda luteola-Dyed Wool and Qualitative Analysis of Its Flavones by UHPLC-UV, NMR and MS

Detailed knowledge on natural dyes is important for agronomy and quality control as well as the fastness, stability, and analysis of dyed textiles. Weld (Reseda luteola L.), which is a source of flavone-based yellow dye, is the focus of this study. One aim was to reduce the required amount of dyed textile to ≤50 μg for a successful chromatographic analysis. The second aim was to unambiguously confirm the identity of all weld flavones. By carrying out the extraction of 50 μg dyed wool with 25 μL of solvent and analysis by reversed-phase UHPLC at 345 nm, reproducible chromatographic fingerprints could be obtained with good signal to noise ratios. Ten baseline separated peaks with relative areas ≥1% were separated in 6 min. Through repeated polyamide column chromatography and prepHPLC, the compounds corresponding with the fingerprint peaks were purified from dried weld. Each was unequivocally identified, including the position and configuration of attached sugars, by means of 1D and 2D NMR and high-resolution MS. Apigenin-4′-O-glucoside and luteolin-4′-O-glucoside were additionally identified as two trace flavones co-eluting with other flavone glucosides, the former for the first time in weld. The microextraction might be extended to other used dye plants, thus reducing the required amount of precious historical textiles.

177 Saponins, Including 11 New Compounds in Wild Ginseng Tentatively Identified via HPLC-IT-TOF-MSn, and Differences among Wild Ginseng, Ginseng under Forest, and Cultivated Ginseng

Wild ginseng (W-GS), ginseng under forest (F-GS, planted in mountain forest and growing in natural environment), and cultivated ginseng (C-GS) were compared via HPLC-DAD and HPLC-IT-TOF-MSn. A total of 199 saponins, including 16 potential new compounds, were tentatively identified from 100 mg W-GS (177 saponins in W-GS with 11 new compounds), F-GS (56 saponins with 1 new compound), and C-GS (60 saponins with 6 new compounds). There were 21 saponins detected from all the W-GS, F-GS, and C-GS. Fifty saponins were only detected from W-GS, including 23 saponins found in ginseng for the first time. Contents of ginsenosides Re (12.36–13.91 mg/g), Rh1 (7.46–7.65 mg/g), Rd (12.94–12.98 mg/g), and the total contents (50.52–55.51 mg/g) of Rg1, Re, Rf, Rb1, Rg2, Rh1, and Rd in W-GS were remarkably higher than those in F-GS (Re 1.22–3.50 mg/g, Rh1 0.15–1.49 mg/g, Rd 0.19–1.49 mg/g, total 5.69–18.74 mg/g), and C-GS (Re 0.30–3.45 mg/g, Rh1 0.05–3.42 mg/g, Rd 0.17–1.68 mg/g, total 2.99–19.55 mg/g). Contents of Re and Rf were significantly higher in F-GS than those in C-GS (p < 0.05). Using the contents of Re, Rf, or Rb1, approximately a half number of cultivated ginseng samples could be identified from ginseng under forest. Contents of Rg1, Re, Rg2, Rh1, as well as the total contents of the seven ginsenosides were highest in ginseng older than 15 years, middle–high in ginseng between 10 to 15 years old, and lowest in ginseng younger than 10 years. Contents of Rg1, Re, Rf, Rb1, Rg2, and the total of seven ginsenosides were significantly related to the growing ages of ginseng (p < 0.10). Similarities of chromatographic fingerprints to W-GS were significantly higher (p < 0.05) for F-GS (median: 0.824) than C-GS (median: 0.745). A characteristic peak pattern in fingerprint was also discovered for distinguishing three types of ginseng. Conclusively, wild ginseng was remarkably superior to ginseng under forest and cultivated ginseng, with ginseng under forest slightly closer to wild ginseng than cultivated ginseng. The differences among wild ginseng, ginseng under forest, and cultivated ginseng in saponin compositions and contents of ginsenosides were mainly attributed to their growing ages.

Liquid Chromatographic Fingerprints for the Characterization of Flavanol-Rich Nutraceuticals Based on 4-Dimethylaminocinnamaldehyde Precolumn Derivatization

Flavanols consist of a great family of bioactive molecules displaying a wide range of health-promoting attributes for humans, including antioxidant, antimicrobial or anti-inflammatory effects. As a result, botanical species rich in this type of compound are often used to develop nutraceutical products or dietary supplements with recognized healthy attributes. This paper aims at characterizing nutraceutical products using liquid chromatographic fingerprints related to flavanol composition. Catechins and their oligomers were exploited to characterize and authenticate various commercial products prepared with extracts of red berries and medicinal plants. These compounds resulted in interesting descriptors of some fruits and vegetables, thus providing an additional perspective for the study of nutraceuticals. For such a purpose, a new method based on liquid chromatography with UV/Vis detection (HPLC–UV/Vis) with precolumn derivatization with 4-dimethylaminocinnamaldehyde was developed. Results indicated that the separation of flavanols was very complex due to the degradation of procyanidin derivatives. The resulting data sets were analyzed using chemometric methods such as principal component analysis and partial least square–discriminant analysis. Despite the complexity of chromatographic fingerprints, nutraceutical samples could be discriminated according to their main ingredients. In general, catechin and epicatechin were the most abundant compounds in the different samples, and procyanidin A2 was highly specific to cranberry.

Sedative Effect and Standardization Parameters of Herbal Medicinal Product Obtained from the Ocimum americanum L. Herb

Sedative phytomedications continue to play an important role in the management of a considerable amount of anxiety symptoms because of the various side effects of synthetic sedatives and tranquilizers. However, developing new herbal drugs needs their appropriate quality control according to the relevant requirements. The aim of the study was to determine the sedative properties of the tinctures obtained from the American basil (Ocimum americanum L., Lamiaceae Martinov family) herb and to develop the standardization parameters for the promising herbal medicinal product. The open field test was used to evaluate the sedative effect of the prepared tinctures: (1) with the added of O. americanum essential oil (OATEs) and (2) without adding O. americanum essential oil (OAT). The standardization parameters for the OATEs were developed using validated High-Performance Thin Layer Chromatography (HPTLC) and High-Performance Liquid Chromatography (HPLC) methods. The HPTLC analysis was used for the chromatographic fingerprints of polyphenols and for identifying linalool in the OATEs. The HPLC analysis found the significant content of rosmarinic acid (RA) (0.26%) in the OATEs. In conclusion, the developed OATEs can be considered as the new herbal medicinal product with significant sedative properties.

Extraction and Analyses of Flavonoids and Phenolic Acids from Canadian Goldenrod and Giant Goldenrod

Invasive alien plant species Canadian goldenrod (Solidago canadensis L.) and giant goldenrod (Solidago gigantea Aiton) were investigated as a source of phytochemicals and yellow dyes. Flavonoids and phenolic acids were extracted from the inflorescence of Canadian goldenrod with thirteen extraction solvents ethanol, methanol, acetone, water, and mixtures of organic solvents (70%, 80%, and 90%) with water. High performance thin-layer chromatography (HPTLC) coupled to densitometry and high-performance liquid chromatography with photo-diode array detector (HPLC-PDA) were used for analyses of the obtained sample test solutions (STSs), which showed the best and comparable extraction efficiencies for 70% acetone(aq), 70% methanol(aq), and 70% ethanol(aq). HPTLC combined with image analyses in fluorescent mode resulted in different chromatographic fingerprints for Canadian goldenrod and giant goldenrod STSs (70% acetone(aq)) after development, after post-chromatographic derivatization with NP reagent and after use of PEG reagent. The developed HPLC methods enabled analyses of phenolic acids and flavonoids (aglycones and glycosylated) in STSs and hydrolyzed STSs form inflorescence of Canadian and giant goldenrod. Different contents of chlorogenic acid, rutin, hyperoside, isoquercetin, and quercetin were observed in STSs of both goldenrod species. The analyses of hydrolyzed STSs confirmed that glycosylated flavonoids in Canadian and giant goldenrod inflorescence are mainly glycosides of quercetin, kaempferol, and isorhamnetin. Additional analyses using HPTLC and HPLC coupled to tandem mass spectrometry (MS/MS; HPTLC-MS/MS and LC-MS/MS) enabled tentative identification of phenolic acids and flavonoids (10 with HPTLC-MS/MS and 15 with LC-MS/MS), from which several were identified in Canadian (4 with HPTLC-MS/MS and 8 with LC-MS/MS) and in giant (7 with HPTLC-MS/MS and 9 with LC-MS/MS) goldenrod for the first time.

Spectrum-Effect Relationships of Flavonoids in Glycyrrhiza uralensis Fisch.

Glycyrrhiza uralensis Fisch. is used in large quantities in traditional Chinese medicine. It contains flavonoids, saponins, and polysaccharides, with flavonoids being the main active ingredients. In this study, flavonoids were isolated from the roots of Glycyrrhiza uralensis Fisch. grown in 21 areas in China by water extraction, alcohol precipitation, polyamide resin separation, and other methods. Fingerprints were established by high performance liquid chromatography (HPLC). There were 15 common peaks in the fingerprints by similarity evaluations of the chromatographic fingerprints. The spectrum-effect relationships between the HPLC fingerprints and pharmacological activities of flavonoids in G. uralensis Fisch., including the heat clearing, detoxifying effects, cough relief, and phlegm elimination effects, were assessed by gray relational analysis and partial least squares regression. After HPLC-quadrupole time-of-flight mass spectrometry and standard comparison, these five identified compounds (liquiritin apioside, neoisoliquiritin, licochalcone A, licochalcone B, and licochalcone C) could be used to evaluate licorice quality with regard to its efficacy. This research provides a scientific basis for improving licorice quality and also establishes a model for modernization of traditional Chinese medicines.