13C CPMAS NMR as an Alternative Method to Verify the Quality of Dietary Supplements Containing Curcumin.

Turmeric is a traditional Indian spice that has recently become very popular worldwide because it contains a powerful ingredient called curcumin, which has strong anti-inflammatory properties. Hence, dietary supplements containing extracts rich in curcumin have gained great popularity. The main problems related to curcumin-containing dietary supplements are poor water solubility and the fact that they are often faked by using synthetic curcumin instead of the plant extract. In this article, we propose the use of the 13C CPMAS NMR method to control the quality of dietary supplements. The analysis of 13C CPMAS NMR spectra supported by GIPAW computations allowed us to identify a polymorphic form present in dietary supplements (which affected the solubility of curcumin) and to point out a dietary supplement that could be faked by using synthetic curcumin. Further PXRD and HPLC investigations confirmed that the examined supplement contained synthetic curcumin instead of the genuine extract. Our method can be used for routine control, especially because the investigation is performed directly from the capsule/tablet content and does not require any special sample preparation.

Application of 1H NMR in the study of fatty acids composition of vegetable oils.

The fatty acid composition is a parameter that determines the quality and origin of vegetable oils. The standard method used in the analysis of fatty acid composition is gas chromatography (GC). In the last 20 years, however, the 1H NMR method has become more important in the analysis of fatty acids. Thanks to no need of special sample preparation, the high speed of analysis and the possibility to automate the process of analysis, 1H NMR is becoming a popular method of testing vegetable oils. It is possible to test oils both qualitatively and quantitatively, taking into account both the fatty acid profile and the level of minor components. In combination with statistical and chemometric methods, the analysis of 1H NMR spectra allows one to obtain much valuable information about the tested oil, considering its composition, quality, the presence of impurities, or the origin. The paper presents an overview of publications focusing on the application of the 1H NMR method in the profiling of fatty acids in vegetable oils.

1H NMR and chemometric methods in verification of hemp-seed oil quality.

Hemp oil is widely used in the food industry, and also in many other industries. It is characterized by a high content of unsaturated fatty acids with the optimal ratio of ω-6 to ω-3 fatty acids (3:1). Such composition means that this oil is often used in the food, pharmaceutical and cosmetic industries. Due to the popularity of hemp oil and its high content of unsaturated fatty acids, methods for the quick oil quality analysis are sought. Six samples of cold-pressed hemp oil were stored under different conditions (2-8 °C and 30 °C) for one month and then their 1H NMR spectra were recorded. The chemometric methods of PCA and OPLS-DA were used to perform the analysis of the spectra. The combination of those methods made it possible to observe the differences in the oil samples after a month of storage. Based on the 1H NMR spectra, it was possible to differentiate the time and conditions of the oil storage.

Phytochemical Profiling, Antioxidant and Anti-Inflammatory Activity of Plants Belonging to the Lavandula Genus.

Lavender is a valuable medicinal plant belonging to the Lamiaceae family. Currently 39 species are known, but only Lavandula angustifolia is a pharmacopoeial raw material. Lavender has a long history of medicinal use and mainly exhibits antioxidant, anti-inflammatory, sedative, antidepressant, spasmolytic, anticholinesterases, antifungal and antibacterial properties. Used internally, it relieves symptoms of mental stress and insomnia and supports digestion. Topical use of lavender in aromatherapy, neuralgia and antiseptics is also known. The constant interest in lavender, and in particular in Lavandula angustifolia, in the field of medicine and pharmacy is evidenced by the growing number of publications. In view of so many studies, it seems important to review traditional and modern extraction techniques that determine the chemical composition responsible for the antioxidant and anti-inflammatory effects of various extracts from the species of the Lavandula genus.

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.

Geissospermiculatine, a New Alkaloid from Geissospermum reticulatum Bark.

A new alkaloid, geissospermiculatine was characterized in Geissospermum reticulatum A. H. Gentry bark (Apocynaceae). Here, following a simplified isolation protocol, the structure of the alkaloid was elucidated through GC-MS, LC-MS/MS, 1D, and 2D NMR (COSY, ROESY, HSQC, HMBC, 1H-15N HMBC). Cytotoxic properties were evaluated in vitro on malignant THP-1 cells, and the results demonstrated that the cytotoxicity of the alkaloid (30 µg/mL) was comparable with staurosporine (10 µM). Additionally, the toxicity was tested on zebrafish (Danio rerio) embryos in vivo by monitoring their development (0-72 h); toxicity was not evident at 30 µg/mL.

Antigenotoxic, anti-photogenotoxic and antioxidant activities of natural naphthoquinone shikonin and acetylshikonin and Arnebia euchroma callus extracts evaluated by the umu-test and EPR method.

The aim of this study was to evaluate the antigenotoxic and antioxidant potential of shikonin (SH), acetylshikonin (ACS) and Arnebia euchroma callus extract (EXT). The antigenotoxic activity was investigated by the umu-test as the inhibition of the SOS system induction caused by genotoxic chemical agents - 4-nitroquinoline oxide and 2-aminoanthracene. Moreover the ability of SH, ACS and EXT to prevent photogenotoxicity triggered by chlorpromazine under UVA irradiation was measured. The cytotoxicity of EXT toward V79 Chinese hamster cell line was additionally assessed. Shikonin and acetylshikonin had no effect on 4-NQO induced genotoxicity whereas EXT demonstrated an unclear effect. The protection against 2AA induced genotoxicity was observed for all tested substances. The highest protection was demonstrated for EXT with inhibition of 66%. SH and ACS reduced 2AA genotoxicity with inhibition of about 60%. Under UVA the strongest and dose-dependent activity was observed for EXT. Acetylshikonin was a weak anti-photogenotoxin whereas shikonin had no clear effect. EXT was highly cytotoxic toward the V79 cell line - the cells' morphology was affected seriously and apoptosis was impacted. The antioxidant activity of SH, ACS and EXT was studied by means of electron paramagnetic resonance spectroscopy using 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical. All three samples exhibited radical scavenging properties.

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.

Bioactivity-guided fractionation for the butyrylcholinesterase inhibitory activity of furanocoumarins from Angelica archangelica L. roots and fruits.

Isolation and identification of the inhibitors of butyrylcholinesterase (BChE), obtained from the extracts of roots and fruits of Angelica archangelica L., are reported. Our results confirmed the weak inhibitory effect of Angelica roots on acetylcholinesterase activity. BChE inhibition was much more pronounced at a concentration of 100 µg/mL for hexane extracts and attained a higher rate than 50%. The TLC bioautography guided fractionation and spectroscopic analysis led to the isolation and identification of imperatorin from the fruit's hexane extract and of heraclenol-2'-O-angelate from the root's hexane extract. Both compounds showed significant BChE inhibition activity with IC(50) = 14.4 ± 3.2 µM and IC(50) = 7.5 ± 1.8 µM, respectively. Only C8-substituted and C5-unsubstituted furanocoumarins were active, which could supply information about the initial structures of specific BChE inhibitors.