Nanostructured Molecular-Network Arsenoselenides from the Border of a Glass-Forming Region: A Disproportionality Analysis Using Complementary Characterization Probes.

Binary AsxSe100-x alloys from the border of a glass-forming region (65 < x < 70) subjected to nanomilling in dry and dry-wet modes are characterized by the XRPD, micro-Raman scattering (micro-RS) and revised positron annihilation lifetime (PAL) methods complemented by a disproportionality analysis using the quantum-chemical cluster modeling approach. These alloys are examined with respect to tetra-arsenic biselenide As4Se2 stoichiometry, realized in glassy g-As65Se35, glassy-crystalline g/c-As67Se33 and glassy-crystalline g/c-As70Se30. From the XRPD results, the number of rhombohedral As and cubic arsenolite As2O3 phases in As-Se alloys increases after nanomilling, especially in the wet mode realized in a PVP water solution. Nanomilling-driven amorphization and reamorphization transformations in these alloys are identified by an analysis of diffuse peak halos in their XRPD patterning, showing the interplay between the levels of a medium-range structure (disruption of the intermediate-range ordering at the cost of an extended-range one). From the micro-RS spectroscopy results, these alloys are stabilized by molecular thioarsenides As4Sen (n = 3, 4), regardless of their phase composition, remnants of thioarsenide molecules destructed under nanomilling being reincorporated into a glass network undergoing a polyamorphic transition. From the PAL spectroscopy results, volumetric changes in the wet-milled alloys with respect to the dry-milled ones are identified as resulting from a direct conversion of the bound positron-electron (Ps, positronium) states in the positron traps. Ps-hosting holes in the PVP medium appear instead of positron traps, with ~0.36-0.38 ns lifetimes ascribed to multivacancies in the As-Se matrix. The superposition of PAL spectrum peaks and tails for pelletized PVP, unmilled, dry-milled, and dry-wet-milled As-Se samples shows a spectacular smoothly decaying trend. The microstructure scenarios of the spontaneous (under quenching) and activated (under nanomilling) decomposition of principal network clusters in As4Se2-bearing arsenoselenides are recognized. Over-constrained As6·(2/3) ring-like network clusters acting as pre-cursors of the rhombohedral As phase are the main products of this decomposition. Two spontaneous processes for creating thioarsenides with crystalline counterparts explain the location of the glass-forming border in an As-Se system near the As4Se2 composition, while an activated decomposition process for creating layered As2Se3 structures is responsible for the nanomilling-driven molecular-to-network transition.

Anticancer Activity of Encapsulated Pearl Millet Polyphenol-Rich Extract against Proliferating and Non-Proliferating Breast Cancer Cells In Vitro.

Plant-derived polyphenols are bioactive compounds with potential health-promoting properties including antioxidant, anti-inflammatory, and anticancer activity. However, their beneficial effects and biomedical applications may be limited due to their low bioavailability. In the present study, we have considered a microencapsulation-based drug delivery system to investigate the anticancer effects of polyphenol-rich (apigenin, caffeic acid, and luteolin) fractions, extracted from a cereal crop pearl millet (Pennisetum glaucum), using three phenotypically different cellular models of breast cancer in vitro, namely triple negative HCC1806, ER-positive HCC1428, and HER2-positive AU565 cells. Encapsulated polyphenolic extract induced apoptotic cell death in breast cancer cells with different receptor status, whereas it was ineffective against non-tumorigenic MCF10F cells. Encapsulated polyphenolic extract was also found to be cytotoxic against drug-resistant doxorubicin-induced senescent breast cancer cells that were accompanied by increased levels of apoptotic and necrotic markers, cell cycle inhibitor p21 and proinflammatory cytokine IL8. Furthermore, diverse responses to the stimulation with encapsulated polyphenolic extract in senescent breast cancer cells were observed, as in the encapsulated polyphenolic extract-treated non-proliferating AU565 cells, the autophagic pathway, here cytotoxic autophagy, was also induced, as judged by elevated levels of beclin-1 and LC3b. We show for the first time the anti-breast cancer activity of encapsulated polyphenolic extract of pearl millet and postulate that microencapsulation may be a useful approach for potentiating the anticancer effects of phytochemicals with limited bioavailability.

Berberis vulgaris L. Root Extract as a Multi-Target Chemopreventive Agent against Colon Cancer Causing Apoptosis in Human Colon Adenocarcinoma Cell Lines.

Berberis vulgaris L. (Berberidaceae) is a shrub that has been widely used in European folk medicine as an anti-inflammatory and antimicrobial agent. The purpose of our study was to elucidate the mechanisms of the chemopreventive action of the plant's methanolic root extract (BVR) against colon cancer cells. Studies were conducted in human colon adenocarcinoma cell lines (LS180 and HT-29) and control colon epithelial CCD841 CoN cells. According to the MTT assay, after 48 h of cell exposure, the IC50 values were as follows: 4.3, 46.1, and 50.2 µg/mL for the LS180, HT-29, and CCD841 CoN cells, respectively, showing the greater sensitivity of the cancer cells to BVR. The Cell Death Detection ELISAPLUS kit demonstrated that BVR induced programmed cell death only against HT-29 cells. Nuclear double staining revealed the great proapoptotic BVR properties in HT-29 cells and subtle effect in LS180 cells. RT-qPCR with the relative quantification method showed significant changes in the expression of genes related to apoptosis in both the LS180 and HT-29 cells. The genes BCL2L1 (126.86-421.43%), BCL2L2 (240-286.02%), CASP3 (177.19-247.83%), and CASP9 (157.99-243.75%) had a significantly elevated expression, while BCL2 (25-52.03%) had a reduced expression compared to the untreated control. Furthermore, in a panel of antioxidant tests, BVR showed positive effects (63.93 ± 0.01, 122.92 ± 0.01, and 220.29 ± 0.02 mg Trolox equivalents (TE)/g in the DPPH•, ABTS•+, and ORAC assays, respectively). In the lipoxygenase (LOX) inhibition test, BVR revealed 62.60 ± 0.87% of enzyme inhibition. The chemical composition of BVR was determined using a UHPLC-UV-CAD-MS/MS analysis and confirmed the presence of several known alkaloids, including berberine, as well as other alkaloids and two derivatives of hydroxycinnamic acid (ferulic and sinapic acid hexosides). The results are very promising and encourage the use of BVR as a comprehensive chemopreventive agent (anti-inflammatory, antioxidant, and pro-apoptotic) in colorectal cancer, and were widely discussed alongside data from the literature.

Common Wheat Pasta Enriched with Ultrafine Ground Oat Husk: Physicochemical and Sensory Properties.

Oat husk (hull) is a byproduct of oat processing that is rich in insoluble fiber. The aim of the study was to evaluate the effect of partially replacing wheat flour with oat husk (at levels of 0, 5, 10, 15, and 20 g/100 g) on the physicochemical properties and sensory acceptance of pasta. Additionally, UPLC-MS/MS analysis was performed to identify phenolic acids and flavonoid compounds, and the cooking properties of the pasta were evaluated. The test results indicate that oat husk significantly (p < 0.05) increased the ash and fiber contents in the pasta, while decreasing the protein and fat contents. Moreover, the redness and yellowness of both raw and cooked pasta increased, while lightness decreased as a result of pasta enrichment with oat husk. Oat husk also led to a decrease in the stretching force of cooked samples, although cooking loss increased significantly but did not exceed 8%. The contents of phenolics and antioxidant activity significantly increased with the incorporation of hull in pasta recipes. UPLC-MS/MS analysis showed that the enriched pasta was especially abundant in ferulic acid. Products with up to 10 g of husk/100 g of wheat flour showed good consumer acceptance. However, higher levels of this additive led to notably lower assessments, particularly in terms of pasta texture.

Layered MoS2: effective and environment-friendly nanomaterial for photocatalytic degradation of methylene blue.

Photocatalytic degradation is a promising method for removing persistent organic pollutants from water because of its low cost (see solar-driven photocatalysis), high mineralisation of pollutants, and low environmental impact. Photocatalysts based on transition metal dichalcogenides (TMDs) have recently attracting high scientific interest due to their unique electrical, mechanical, and optical properties. A MoS2 photocatalyst of the layered structure was managed to photodegrade methylene blue (MB) under visible light irradiation. The catalyst was thoroughly characterised using SEM, AFM, powder XRD, UV-Vis, Raman, and XPS measurements. The photocatalytic degradation of the MB solution was conducted under the following conditions: (i) reductive and (ii) oxidative. The impact of optical and electronic properties, and the MoS2-MB interaction on photocatalytic activity, was discussed. The apparent rate constants (kapp) of degradation were 3.7 × 10-3; 7.7 × 10-3; 81.7 × 10-3 min-1 for photolysis, oxidative photocatalysis, and reductive photocatalysis. Comparison of the degradation efficiency of MB in reductive and oxidative processes indicates the important role of the reaction with the surface electron. In the oxidation process, oxygen reacts with an electron to form a superoxide anion radical involved in further transformations of the dye, whereas, in the reduction process, the addition of an electron destabilises the chromophore ring and leads to its rupture.

Electrospun fiber-based micro- and nano-system for delivery of high concentrated quercetin to cancer cells.

The anticancer potential of quercetin (Q), a plant-derived flavonoid, and underlining molecular mechanisms are widely documented in cellular models in vitro. However, biomedical applications of Q are limited due to its low bioavailability and hydrophilicity. In the present study, the electrospinning approach was used to obtain polylactide (PLA) and PLA and polyethylene oxide (PEO)-based micro- and nanofibers containing Q, namely PLA/Q and PLA/PEO/Q, respectively, in a form of non-woven fabrics. The structure and physico-chemical properties of Q-loaded fibers were characterized by scanning electron and atomic force microscopy (SEM and AFM), X-ray powder diffraction (XRD), differential scanning calorimetry (DSC), goniometry and FTIR and Raman spectroscopy. The anticancer action of PLA/Q and PLA/PEO/Q was revealed using two types of cancer and nine cell lines, namely osteosarcoma (MG-63, U-2 OS, SaOS-2 cells) and breast cancer (SK-BR-3, MCF-7, MDA-MB-231, MDA-MB-468, Hs 578T, and BT-20 cells). The anticancer activity of Q-loaded fibers was more pronounced than the action of free Q. PLA/Q and PLA/PEO/Q promoted cell cycle arrest, oxidative stress and apoptotic cell death that was not overcome by heat shock protein (HSP)-mediated adaptive response. PLA/Q and PLA/PEO/Q were biocompatible and safe, as judged by in vitro testing using normal fibroblasts. We postulate that PLA/Q and PLA/PEO/Q with Q releasing activity can be considered as a novel and more efficient micro- and nano-system to deliver Q and eliminate phenotypically different cancer cells.

Herbicide resistance status impacts the profile of non-anthocyanin polyphenolics and some phytomedical properties of edible cornflower (Centaurea cyanus L.) flowers.

To ensure sufficient food supply worldwide, plants are treated with pesticides to provide protection against pathogens and pests. Herbicides are the most commonly utilised pesticides, used to reduce the growth of weeds. However, their long-term use has resulted in the emergence of herbicide-resistant biotypes in many weed species. Cornflower (Centaurea cyanus L., Asteraceae) is one of these plants, whose biotypes resistant to herbicides from the group of acetolactate synthase (ALS) inhibitors have begun to emerge in recent years. Some plants, although undesirable in crops and considered as weeds, are of great importance in phytomedicine and food production, and characterised by a high content of health-promoting substances, including antioxidants. Our study aimed to investigate how the acquisition of herbicide resistance affects the health-promoting properties of plants on the example of cornflower, as well as how they are affected by herbicide treatment. To this end, we analysed non-anthocyanin polyphenols and antioxidant capacity in flowers of C. cyanus from herbicide-resistant and susceptible biotypes. Our results indicated significant compositional changes associated with an increase in the content of substances and activities that have health-promoting properties. High antioxidant activity and higher total phenolic and flavonoid compounds as well as reducing power were observed in resistant biotypes. The latter one increased additionally after herbicide treatment which might also suggest their role in the resistance acquisition mechanism. Overall, these results show that the herbicide resistance development, although unfavourable to crop production, may paradoxically have very positive effects for medicinal plants such as cornflower.

Evaluation of the Antioxidant and Anti-Lipoxygenase Activity of Berberis vulgaris L. Leaves, Fruits, and Stem and Their LC MS/MS Polyphenolic Profile.

Berberis vulgaris L. is currently widely studied for its antioxidant and chemopreventive properties, especially with regard to the beneficial properties of its fruits. Although the bark and roots have been well known and used in traditional medicine since ancient times, little is known about the other parts of this plant. The aim of the research was to determine the antioxidant and LOX inhibitory activity effects of extracts obtained from the leaves, fruits, and stems. Another aim of the work was to carry out the quantitative and qualitative analysis of phenolic acids, flavonoid aglycones, and flavonoid glycosides. The extracts were obtained with the use of ASE (accelerated solvent extraction). The total content of polyphenols was determined and was found to vary depending on the organ, with the highest amount of polyphenols found in the leaf extracts. The free radical scavenging activity of the extracts was determined spectrophotometrically in relation to the DPPH (2,2-diphenyl-1-picrylhydrazyl) radical, with results ranging from 63.9 mgTE/g for the leaves to 65.2 mgTE/g for the stem. Antioxidant activity was also assessed using the ABTS test. The lowest value was recorded for the barberry fruit (117.9 mg TE/g), and the highest level was found for the barberry leaves (140.5 mgTE/g). The oxygen radical absorbance capacity test (ORAC) showed the lowest value for the stem (167.7 mgTE/g) and the highest level for the leaves (267.8 mgTE/g). The range of the percentage inhibition of LOX was determined as well. The percentage inhibition of the enzyme was positively correlated with the sum of the flavonoids, TPC, TFC, and the content of selected flavonoids. Phenolic acids, flavonoid aglycones, and flavonoid glycosides were determined qualitatively and quantitatively in individual parts of Berberis vulgaris L. The content of phenolic acids, flavonoid aglycones, and flavonoid glycosides was determined with the LC-MS/MS method. The following phenolic acids were quantitatively and qualitatively identified in individual parts of Berberis vulgaris L.: gallic acid, 3-caffeoylquinic acid, protocatechuic acid, 5-caffeoylquinic acid, 4-caffeoylquinic acid, and caffeic acid. The flavonoid glycosides determined were: eleutheroside E, Eriodictyol-7-glucopyranoside, rutin, hyperoside, isoquercitin, luteoloside, narcissoside, naringenin-7-glucoside, isorhamnetin-3-glucoside, afzeline, and quercitrin. Flavonoid aglycones such as catechin, luteolin, quercetin, and eriodictyol were also determined qualitatively and quantitatively.

Reductive Photodegradation of 4,4'-Isopropylidenebis(2,6-dibromophenol) on Fe3O4 Surface.

BACKGROUND: Advanced Oxidation Processes (AOPs) are the water treatment techniques that are commonly used forthe decomposition of the non-biodegradable organic pollutants. However, some pollutants are electron deficient and thus resistant to attack by reactive oxygen species (e.g., polyhalogenated compounds) but they may be degraded under reductive conditions. Therefore, reductive methods are alternative or supplementary methods to the well-known oxidative degradation ones. METHODS: In this paper, the degradation of 4,4'-isopropylidenebis(2,6-dibromophenol) (TBBPA, tetrabromobisphenol A) using two Fe3O4 magnetic photocatalyst (F1 and F2) is presented. The morphological, structural and surface properties of catalysts were studied. Their catalytic efficiency was evaluated based on reactions under reductive and oxidative conditions. Quantum chemical calculations were used to analyse early steps of degradation mechanism. RESULTS: The studied photocatalytic degradation reactions undergo pseudo-first order kinetics. The photocatalytic reduction process follows the Eley-Rideal mechanism rather than the commonly used Langmuir-Hinshelwood mechanism. CONCLUSIONS: The study confirms that both magnetic photocatalyst are effective and assure reductive degradation of TBBPA.

Identification of sunflower, rapeseed, flaxseed and sesame seed oil metabolomic markers as a potential tool for oil authentication and detecting adulterations.

Testing the composition, quality and authenticity of edible oils is crucial to safeguard the consumers' rights and health. The aim of our study was to identify oil-specific markers to enable the differentiation and authentication of sunflower, sesame, flaxseed and rapeseed oils, and to evaluate their antioxidant activity, total phenolic and carotenoid content. A metabolomic approach based on liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry was employed for marker discovery. Spectrophotometric method was used for determination of antioxidant activity, total phenolic and carotenoid content. 76 oil samples from the four different manufacturers were examined. We identified 13 oil-specific markers for sunflower seed oil, 8 for rapeseed oil, 5 for sesame seed oil and 3 for flaxseed oil, their retention times, accurate masses, and characteristic fragment ions are reported. The abundances of the markers for each plant species were found to vary depending on the oil producer and the product batch. Significant differences in antioxidant activity, total phenolic and carotenoid content were also observed both between oils and within oil type. The highest total phenolic content (84.03 ± 4.19 to 103.79 ± 3.67 mg of gallic acid/kg) and antioxidant activity (245.67 ± 7.59 to 297.22 ± 2.32 mg Trolox/kg) were found in sesame seed and flaxseed oils, respectively. Identified metabolic markers can be used as qualitative markers to confirm the authenticity or to detect adulterations of oils. Composition, properties and authenticity testing should be more rigorous for food products marketed as health-promoting.

Anticancer Podophyllotoxin Recovery from Juniper Leaves at Atmospheric and High Pressure Using Eco-Friendly Solvents.

Podophyllotoxin (PPT) is a precursor for the synthesis of drugs against cancer and other diseases. The present sources of PPT (Sinopodophyllum hexandrum and Podophyllum peltatum) are endangered species, with PPT production highly dependent on their growing conditions. In connection with the identification of new sources of PPT, the present study aimed to recover PPT from Juniperus virginiana leaves via atmospheric or high pressure extraction methods with a focus on using eco-friendly solvents. PPT quantification was determined by UHPLC/HRMS/MS. A thorough study of conventional extraction was carried out to reveal the optimal conditions (solvent ethyl acetate at room temperature and a duration of 1 h) for maximizing the PPT recovery (about 30 mg/g of dry extract and 3 mg/g of dry initial plant material). Peleg's equation was applied for process kinetics modeling. The best PPT content in the final dry extract (42-45 mg/g of dry extract) was obtained by high pressure methods under supercritical (scCO2 with ethanol or ethyl acetate, 30 MPa, 50 °C and 100 min) or accelerated solvent extraction conditions (solvent ethyl acetate, 10.35 MPa, 20 °C and 3 cycles for 15 min). Seasonal stability and storage stability of the raw material were also determined. The present results have potential applications in the pharmacy for the delivery of PPT from juniper leaves.

Strain-Balanced InAs/AlSb Type-II Superlattice Structures Growth on GaSb Substrate by Molecular Beam Epitaxy.

We demonstrate strain-balanced InAs/AlSb type-II superlattices (T2SL) grown on GaSb substrates employing two kinds of interfaces (IFs): AlAs-like IF and InSb-like IF. The structures are obtained by molecular beam epitaxy (MBE) for effective strain management, simplified growth scheme, improved material crystalline quality, and improved surface quality. The minimal strain T2SL versus GaSb substrate can be achieved by a special shutters sequence during MBE growth that leads to the formation of both interfaces. The obtained minimal mismatches of the lattice constants is smaller than that reported in the literature. The in-plane compressive strain of 60-period InAs/AlSb T2SL 7ML/6ML and 6ML/5ML was completely balanced by the applied IFs, which is confirmed by the HRXRD measurements. The results of the Raman spectroscopy (measured along the direction of growth) and surface analyses (AFM and Nomarski microscopy) of the investigated structures are also presented. Such InAs/AlSb T2SL can be used as material for a detector in the MIR range and, e.g., as a bottom n-contact layer as a relaxation region for a tuned interband cascade infrared photodetector.

Antihyaluronidase and Antioxidant Potential of Atriplex sagittata Borkh. in Relation to Phenolic Compounds and Triterpene Saponins.

The genus Atriplex provides species that are used as food and natural remedies. In this work, the levels of soluble phenolic acids (free and conjugated) and flavonoids in extracts from roots, stems, leaves and flowers of the unexplored Atriplex sagittata Borkh were investigated by LC-ESI-MS/MS, together with their antioxidant and antihyaluronidase activity. Phenolic acids were present in all parts of A. sagittata; and were most abundant in the leaves (225.24 µg/g dw.), whereas the highest content of flavonoids were found in the flowers (242.71 µg/g dw.). The most common phenolics were 4-hydroxybenzoic and salicylic acids, kaempferol-3-glucoside-7-rhamnoside, kaempferol-3-rutinoside and the rare narcissoside, which was present in almost all morphotic parts. The stem extract had the highest antioxidant activity and total phenolic content (611.86 mg/100 g dw.), whereas flower extract exerted the most potent antihyaluronidase effect (IC50 = 84.67 µg/mL; control-quercetin: IC50 = 514.28 µg/mL). Phytochemical analysis of the flower extract led to the isolation of two triterpene saponins that were shown to be strong hyaluronidase inhibitors (IC50 = 33.77 and 168.15 µg/mL; control-escin: IC50 = 307.38 µg/mL). This is the first report on the presence of phenolics and saponins in A. sagittata. The results suggest that both groups of metabolites may contribute to the overall activity of this plant species.

Polyphenolic Characterization, Antioxidant, Antihyaluronidase and Antimicrobial Activity of Young Leaves and Stem Extracts from Rubus caesius L.

Fruits are the main food part of the European dewberry (Rubus caesius L.), known as a source of polyphenols and antioxidants, while very little attention is paid to leaves and stems, especially young first-year stems. The purpose of this work was to analyze for the first time water and ethanol extracts obtained from young, freshly developed, leaves and stems of the European dewberry to determine their antioxidant and biological activity, whereas most of the papers describe biological properties of leaves collected during summer or autumn. As the phytochemical profile changes during the growing season, the quantitative and qualitative content of flavonoid glycosides and flavonoid aglycones was analyzed using reversed phase liquid chromatography/electrospray ionization triple quadrupole mass spectrometry (LC-ESI-MS/MS) with multiple reaction monitoring (MRM). The ability to inhibit hyaluronidase as well as antioxidant activity (2,2 diphenyl-1-picrylhydrazyl: DPPH and ferric antioxidant power: FRAP) were estimated. Extracts were also analyzed against Gram-positive and Gram-negative bacteria. The results of the qualitative phytochemical analysis indicated the presence of flavonoid aglycones and flavonoid glycosides, with the highest amount of tiliroside, hyperoside, isoquercetin, astragalin, rutin and catechin in ethanol extracts. DPPH and FRAP tests proved the high antioxidant activity of the extracts from leaves or stems and the antihyaluronidase assay revealed for the first time that water and ethanol extracts obtained from the stems exhibited the ability to inhibit hyaluronidase activity resulting in an IC50 of 55.24 ± 3.21 and 68.7 ± 1.61 µg/mL, respectively. The antimicrobial activity has never been analyzed for European dewberry and was the highest for Clostridium bifermentans and Clostridium sporogenes-anaerobic sporulation rods as well as Enterococcus faecalis for both water and ethanol extracts.

Alternating magnetic field and NIR energy conversion on magneto-plasmonic Fe3O4@APTES-Ag heterostructures with SERS detection capability and antimicrobial activity.

Multipurpose Fe3O4@APTES-Ag heterostructures for mutual heat generation, SERS probing, and antimicrobial activity were fabricated using a three-step process. Silver metallic particles were precipitated on a thin silica shell that served as an interlayer with Fe3O4 nanocubes. The structural properties were studied by means of the powder X-ray diffraction technique, and selected area electron diffraction. Particle size, distribution, and morphology were evaluated using transmission electron microscopy, while element mapping was performed using the STEM-EDS technique. The presence of the silica shell and the effectiveness of the Ag reduction were checked by FTIR-ATR spectroscopy. The heat generation ability was studied by using AMF and NIR contactless external stimulations working separately and simultaneously. We demonstrated that the dual mode stimulation leads to a SAR (specific absorption rate) of 1000 W g-1 with the predominant role of the mechanism associated with the light interaction. The SERS effect was recorded with the use of the R6G standard molecule showing high capability of the heterostructures for Raman signal augmentation. Fe3O4 nanocubes decorated with Ag particles have shown antibacterial activity against P. aeruginosa. The Fe3O4@APTES-Ag presents promising potential as a multipurpose platform for biological applications ranging from photomagnetic therapies, to analytical probes exploiting the SERS effect and antibacterial activity.

Phenolic acids as chemotaxonomic markers able to differentiate the Euphrasia species.

The objective of this study was to get the answer on the question, which phenolic compounds may serve as chemical markers in taxonomy of Euphrasia spp. (E. nemorosa, E. rostkoviana, E. stricta) collected from the wild. Moreover, it is still unknown how and which environmental parameters can impact on the quantity of polyphenols, flavonoids and phenolic acids. To the authors' knowledge, this is the first study that analyses such a broad spectrum of phenolic compounds in the genus Euphrasia and takes into account the habitat conditions of their synthesis. The species of Euphrasia differ significantly in the content of phenolic compounds. Euphrasia rostkoviana has the highest total content of polyphenols and flavonoids. Euphrasia stricta contains the largest amounts of phenolic acids, such as 5-O-caffeoylquinic, p-coumaric, protocatechuic and salicylic acid. It has been evidenced that the content of metabolites in the Euphrasia herb depends on a number of habitat parameters. The increased content of phenolic acids in E. stricta can be attributed to the fact that this species occupies drier habitats, with lower content of nitrogen and organic carbon compared to E. nemorosa and E. rostkoviana. The compounds that can be considered as chemotaxonomic markers are salicylic and protocatechuic acid for E. stricta, 5-O-caffeoylquinic acid for E. rostkoviana and ferulic acid for E. nemorosa. These findings provide theoretical and empirical basis for a chemotaxonomic classification of those species, which taken together with morphological characteristics should prevent misidentification.

LC-ESI-MS/MS Polyphenolic Profile and In Vitro Study of Cosmetic Potential of Aerva lanata (L.) Juss. Herb Extracts.

The aim of the present study was to investigate the phenolic composition and the biological properties of different Aerva lanata (L). Juss. herb extracts obtained with the use of accelerated solvent extraction (ASE), i.e., a green, ecological method, for cosmetic purposes. All samples exhibited high DPPH• (9.17-119.85 mg TE/g) and ABTS•+ (9.90-107.58 mg TE/g) scavenging activity. The extracts exhibited considerable anti-lipoxygenase (EC50 between 1.14 mg/mL and 3.73 mg/mL) and anti-xanthine oxidase (EC50 between 1.28 mg/mL and 3.72 mg/mL) activities, moderate chelating activity (EC50 between 1.58 mg/mL and 5.30 mg/mL), and high antioxidant potential in the ORAC assay (0.36-3.84 mM TE/g). Changes in the polyphenol profile of the analysed samples depending on the solvent and temperature used for the extraction were determined with the liquid chromatography/electrospray mass spectrometry (LC-ESI-MS/MS) method. Twenty-one phenolic compounds, including flavonoids and phenolic acids, were detected and quantified. It was shown that tiliroside was one of the main phenolic metabolites in the A. lanata (L.) Juss. herb., which may suggest that this compound may be largely responsible for the observed anti-inflammatory activity of the extracts. In addition, the studied extracts exhibited promising skin-related (anti-tyrosinase, anti-elastase, anti-collagenase, and anti-hyaluronidase) activity. This study showed that Aerva lanata (L.) Juss. contains high amounts of phenolic compounds, including tiliroside, and has good skin-related activities. Therefore, the plant may be interesting as a novel source of bioactive agents for cosmetic industries.

Berberine, a Herbal Metabolite in the Metabolic Syndrome: The Risk Factors, Course, and Consequences of the Disease.

In recent years, the health of patients exposed to the consequences of the metabolic syndrome still requires the search for new solutions, and plant nutraceuticals are currently being intensively investigated. Berberine is a plant alkaloid possessing scientifically determined mechanisms of the prevention of the development of atherosclerosis, type 2 diabetes, and obesity, as well as cardiovascular complications and cancer. It positively contributes to elevated levels of fasting, postprandial blood glucose, and glycosylated hemoglobin, while decreasing insulin resistance. It stimulates glycolysis, improving insulin secretion, and inhibits gluconeogenesis and adipogenesis in the liver; by reducing insulin resistance, berberine also improves ovulation. The anti-obesity action of berberine has been also well-documented. Berberine acts as an anti-sclerotic, lowering the LDL and testosterone levels. The alkaloid exhibits an anti-inflammatory property by stalling the expression of cyclooxygenase 2 (COX-2) and prostaglandin E2. Berberine is neuroprotective and acts as an antidepressive. However, the outcomes in psychiatric patients are nonspecific, as it has been shown that berberine improves metabolic parameters in schizophrenic patients, acting as an adjuvant during antipsychotic treatment. Berberine acts as an anticancer option by inducing apoptosis, the cell cycle arrest, influencing MAPK (mitogen-activated protein kinase), and influencing transcription regulation. The inhibition of carcinogenesis is also combined with lipid metabolism.

LC-ESI-MS/MS Characterization of Concentrated Polyphenolic Fractions from Rhododendron luteum and Their Anti-Inflammatory and Antioxidant Activities.

The high biological potential of polyphenols encourages the search for new natural sources of and biomedical applications for these compounds. Rhododendron luteum Sweet was previously reported to contain pharmaceutically active polyphenols. The present research investigates the polyphenolic fractions in R. luteum leaves, including a determination of the free and bound phenolic acid and flavonoid contents and their anti-inflammatory and antioxidant activities. LC-ESI-MS/MS (liquid chromatography/electrospray ionization triple quadrupole mass spectrometry) analysis revealed a great abundance of free (e.g., 5-O-caffeoylquinic acid, ferulic acid, protocatechuic acid, catechin, and dihydromyricetin) and bound (e.g., caffeic acid, p-coumaric, protocatechuic acid, myricetin, quercetin) phenolics. The R. luteum samples exhibited high anti-inflammatory potential in lipoxygenase (IC50: 0.33 ± 0.01-2.96 ± 0.06 mg dry extract (DE)/mL) and hyaluronidase (IC50: 78.76 ± 2.09 - 429.07 ± 31.08 µg DE/mL) inhibition capacity assays. Some samples also had the ability to inhibit cyclooxygenase 1 (IC50: 311.8 ± 10.95 µg DE/mL) and cyclooxygenase 2 (IC50: 53.40 ± 5.07; 608.09 ± 14.78 µg DE/mL). All fractions showed excellent antioxidant activity in the Oxygen Radical Absorbance Capacity (ORAC) assay (5.76-221.81 g Trolox/g DE), ABTS•+ radical scavenging ability (0.62 ± 0.03 - 5.09 ± 0.23 g Trolox/g DE), and moderate ion (Fe2+) chelating power. This paper expands our knowledge of the phytochemistry and pharmacological activity of R. luteum polyphenols. It reveals, for the first time, the presence of dihydromyricetin, afzelin, and laricitrin in the plant material. It indicates biologically active polyphenolic fractions that should be further investigated or which could be efficiently used in pharmaceutical, cosmetic, or nutraceutical applications.

A new look at edible and medicinal mushrooms as a source of ergosterol and ergosterol peroxide - UHPLC-MS/MS analysis.

Ergosterol (ES) and ergosterol peroxide (EP) are secondary metabolites common for different mushrooms and responsible for health promoting effects, including anti-inflammatory, anticancer, antiviral activity, and reduction of the incidence of cardiovascular disease. In this study, a new method for determination of both ES and EP in mushroom extracts was developed. Two methods for UHPLC-MS/MS with the use of APCI and APPI sources were developed and compared. The UHPLC-APPI-MS/MS method was found to be more effective and convenient for the analysis of both compounds in 21 edible and 9 medicinal mushrooms. Among the investigated mushrooms, M. procera was found to contain the highest level of ES, while G. dryophilus constituted the richest source of EP. Therefore, it can be suggested that mushrooms are a valuable source of ES and EP in everyday human diet and can be used for development of nutraceuticals and functional food ingredients.