Aronia melanocarpa Fruits as a Rich Dietary Source of Chlorogenic Acids and Anthocyanins: 1H-NMR, HPLC-DAD, and Chemometric Studies.

Aronia melanocarpa (Michx.) Elliott's (chokeberry) besides anthocyanins contains significant amounts of hydroxycinnamic acids: Chlorogenic and its isomer neochlorogenic acid. They exhibit antioxidant, anti-inflammatory, antidiabetic, and antibacterial activities, thus they can have a significant impact on the health-promoting properties of Aronia. The aim of our research was to determine the changes in the content of chlorogenic acids (CGAs) and anthocyanins during fruit development and ripening, with a particular emphasis on acids. Aronia fruit samples were collected from July to October on two organic farms in Poland. The chemical composition of the extracts was determined by NMR spectroscopy and HPLC-DAD. 1H-NMR and HPLC data were analyzed using chemometric analysis and multivariate statistics (PCA). The results showed that the content of chlorogenic acids and anthocyanins changes during ripening and depends on the time of harvest and the region of cultivation. A correlation between the time of CGAs reduction and the appearance of anthocyanins was also noticed. The result of our research was also a database in the form of NMR parameters, which allows analysis of the metabolite profile and tracking of its changes. The 1H-NMR spectrum showing anthocyanin and CGA resonance can be considered the Aronia berry fingerprint.

Effects of Geum urbanum L. root extracts and its constituents on polymorphonuclear leucocytes functions. Significance in periodontal diseases.

ETHNOPHARMACOLOGICAL RELEVANCE: Geum urbanum L. (wood avens) root infusions and decoctions have been used externally for reducing the bleeding and inflammation of gums (gingivitis), and mucous membranes. AIM OF THE STUDY: Taking into account that primed and hyperactivated neutrophils are an important factor in the transition from gingivitis to periodontitis, we investigated the effects of phytochemically characterised (HPLC-DAD-MS(n)) extracts of different polarity from Geum urbanum root on oxidative burst, elastase, metalloproteinase 9 (MMP-9), interleukin 8 (IL-8) and 1ß (IL-1ß), tumour necrosis factor (TNF-α) release, expression of adhesion molecules (CD62L and CD11b) and delayed apoptosis in stimulated neutrophils. As gemin A is a dominating compound in a raw material, so we considered its activity in parallel with the positive control quercetin. MATERIALS AND METHODS: The extracts were characterised by HPLC-DAD- MS(n) method. The inhibition of ROS production by stimulated neutrophils was determined using luminol dependent chemiluminescence method. The effect on MMP-9, IL-1ß, TNF-α and IL-8 production by neutrophils was measured by enzyme-linked immunosorbent assay (ELISA). Neutrophil elastase release was established spectrophotometrically. The expression of adhesion molecules and the apoptosis of neutrophils was analyzed with flow cytometry. RESULTS: The main compounds detected in the extract belong mainly to the group of ellagitannin: pedunculagin, stachyurin, casuarynin and gemin A, and ellagic acid derivatives. Procyanidins and one complex tannin were found as minor compounds. Gemin A significantly affected the functions of stimulated neutrophils by reducing the surface expression of CD11b, and inhibiting the release of reactive oxygen species, and proteases (elastase, MMP-9), chemokines and cytokines (interleukins IL-8, IL-1ß). Interestingly, gemin A stimulated the release of TNF-α, which may be one of the stimulators of apoptosis of neutrophil cells. The primary aqueous extract, the ethyl acetate and the butanolic fractions, all containing the highest level of gemin A, have exerted similar but weaker activity. CONCLUSION: The modulating effect on the neutrophils function of extracts, and its main constituent gemin A, support the traditional use of this plant material in cavity inflammation including mucositis, gingivitis and periodontosis.

¹H and ¹³C NMR-based sugar profiling with chemometric analysis and antioxidant activity of herbhoneys and honeys.

BACKGROUND: Herbhoneys, relatively new bee products, are expected to have interesting medicinal properties. However, there is still a lack of data concerning their composition and antioxidant properties. ¹H and ¹³C NMR spectroscopy coupled with chemometric analysis (PCA and PLS-DA) and antioxidant assays (DPPH-ESR and ORAC-FL) were used to study 25 samples of Polish herbhoneys and honeys. RESULTS: Antioxidant activity varied among the samples. The best properties were exhibited by cocoa and instant coffee herbhoneys. The contents of total polyphenols and total carotenoids in the studied samples were found to be 70-1340 mg GAE kg⁻¹ and 0-28.05 mg kg⁻¹ respectively. No significant differences between herbhoney and honey samples were found in their sugar profiles. The PCA of ¹³C NMR spectra of the samples in DMSO-d6 resulted in sample clustering due to sucrose content. CONCLUSION: Herbhoneys have similar antioxidant properties to traditional honeys, being therefore of equal nutritional value. There was a noticeable influence of the extract concentration on the observed antioxidant effect. For samples with high antioxidant activity, polyphenols were responsible for the observed effect. Sample clustering due to sucrose content in the NMR-PCA study allowed effortless detection of adulteration.