Herbal Polyphenols as Selenium Reducers in the Green Synthesis of Selenium Nanoparticles: Antibacterial and Antioxidant Capabilities of the Obtained SeNPs.

Selenium is an essential trace element for the proper functioning of the human body. In recent years, great attention has been paid to selenium nanoparticles (SeNPs) due to their potential for medicinal applications. In this study, herbal extracts were used in the green synthesis of SeNPs. The influence of herbal species, the ratio of the reagents, and post-reaction heating on the antibacterial and antioxidant properties of obtained SeNPs were investigated. The relationship between these properties and the physical parameters of obtained nanoparticles (e.g., size, shape) was also studied. It has been proven that SeNPs showed higher antioxidant and antibacterial properties in comparison to herbal extracts taken for their synthesis. Heating of the post-reaction mixture did not affect the SeNP size, shape, or other studied properties.

Selenium Species in Diabetes Mellitus Type 2.

Selenium is an important trace element for humans and animals as it plays a key role in several major metabolic pathways. Several studies were conducted to better understand the role of selenium against diabetes mellitus (DM), particularly type 2 (T2DM), but the obtained conclusions are contradictory. A simple linear relationship does not exist between the risk of T2DM and selenium levels but is best represented in a dose-dependent manner, getting often the U-graph. This relation also depends on selenium chemical forms that are present in a diet or supplements. Both too low and too high selenium intakes could increase the risk of diabetes. Moreover, the baseline status of Se should be taken into consideration to avoid over-supplementation. The focus of this brief overview is to report the recent updates concerning selenium participation in diabetes mellitus.

Catechins and Selenium Species-How They React with Each Other.

The combination of selenium and tea infusion, both with antioxidant properties, has potentially complementary mechanisms of action. Se-enriched tea has been considered as a possible Se supplement and a functional beverage to reduce the health risk of Se deficiency. This work investigated the interactions between plant catechins present in tea infusions and selenium species based on changes in the concentration of both reagents, their stability in aqueous solutions, and the possibilities of selenonanoparticles (SeNPs) formation. Selenium species exhibited instability both alone in their standard solutions and in the presence of studied catechins; selenocystine appeared as the most unstable. The recorded UV-Vis absorption spectra indicated the formation of SeNPs in the binary mixtures of catechins and selenite. SeNPs have also formed with diameters smaller than 100 nm when selenite and selenomethionine were added to tea infusions. This is an advantage from the point of view of potential medical applications.

The potential of traditionally used medicinal plants for the synthesis of selenium nanoparticles.

Selenium nanoparticles (SeNPs) have the potential to be used in many applications. In recent years green synthesis using plant extracts has gained popularity, due to the use of non-toxic solvents. In this work, the application of plantain (Plantago lanceolata L.), yarrow (Achilea millefolium L.) and nettle (Urtica dioica L.) in the synthesis of SeNPs is presented. The obtained nanoparticles were characterized in terms of size and antioxidant activity. A strong correlation between the dimensions of synthesized nanoparticles and their ability to scavenge hydroxyl radicals was established.

Does the Type Matter? Verification of Different Tea Types' Potential in the Synthesis of SeNPs.

Selenium nanoparticles (SeNPs) are gaining popularity due to their potential biomedical applications. This work describes their green synthesis using various types of tea. Black, green, red and white tea infusions were tested for the content of polyphenolic compounds and antioxidant properties and then used in the synthesis of SeNPs. In each of the syntheses, nanoparticles with dimensions ranging from 3.9 to 12.5 nm, differing in shape and properties, were obtained. All of them were characterized by a very high ability to neutralize hydroxyl radicals, which was about three-times higher than for the tea infusions from which they were obtained. The main inconvenience in obtaining SeNPs was the difficulties with their purification, which should be a further stage in the described research.

The Influence of Synthesis Conditions on the Antioxidant Activity of Selenium Nanoparticles.

Selenium nanoparticles (SeNPs) have attracted great attention in recent years due to their unique properties and potential bioactivities. While the production of SeNPs has been long reported, there is little news about the influence of reaction conditions and clean-up procedure on their physical properties (e.g., shape, size) as well as their antioxidant activity. This study takes up this issue. SeNPs were synthesized by two methods using cysteine and ascorbic acid as selenium reductants. The reactions were performed with and without the use of polyvinyl alcohol as a stabilizer. After the synthesis, SeNPs were cleaned using various procedures. The antioxidant properties of the obtained SeNPs were investigated using DPPH and hydroxyl radical scavenging assays. It was found that their antioxidant activity does not always depend only on the nanoparticles size but also on their homogeneity. Moreover, the size and morphology of selenium nanoparticles are controlled by the clean-up step.

Stability of selenium compounds in aqueous extracts of dietary supplements during storage.

The stability of two inorganic (selenite Se (IV) and selenate Se(VI)) as well as four organic (selenomethionine (SeMet), selenocystine (SeCys2), selenomethylocysteine (MeSeCys) and selenomethionine selenoxide (SeMetO)) selenium species were investigated in standard solutions and aqueous extracts of dietary supplements. All of the samples were without any stabilizer addition. The effect of the sample solvent pH and the storage temperature was investigated using hydrophilic interaction liquid chromatography coupled to mass spectrometry detection (HILIC-MS). It was proven that sample solvent has a great impact on the selenium stability. The lowest stability of selenium compounds is observed in ammonium acetate samples. Acidification of the solution increase the selenium stability (with the exception of SeMet in yeast sample). The results of the stability of selenium compounds obtained for the standard solutions are different than those for supplement samples, which shows the enormous influence of the sample matrix on the stability of selenium compounds. Light does not affect selenium stability in standard solutions as well as in supplements extracts.

Analytical Problems in Separation of Selenomethionine and Its Oxidative Product in HILIC HPLC.

Selenomethionine (SeMet) is one of the main selenium forms in foods and supplements. Determining its presence in natural food samples creates difficulties due to possible oxidation processes. The objective of this study was to evaluate the possible degradation of SeMet in water extracts of green teas, one of the most consumed beverages worldwide. Such a medium has not been investigated at this time. The HILIC-HPLC MS/MS method with different stationary phases was used to achieve the satisfactory separation of SeMet and selenomethionine oxide (SeMetO). The addition of dithiothreitol and ß-mercaptoethanol, recommended to ensure that SeMet is kept in the reduced form, was also evaluated. The best separation was achieved using the zwitterionic HILIC stationary phase coupled to mass spectrometry and MeOH with water (85/15, v/v) as the eluent. Extraction was done with hot water with the addition of ß-mercaptoethanol. The infusions prepared from Lung-Ching teas (from the Zhejiang Province in China) contained the highest concentration of selenium in a typical cup of tea (12.5-17.3 µg L-1). For other tested teas it decreased in the following order: Yunnan > Dilmah > Lipton. For Lung-Ching teas, the sum of concentrations of SeMet and SeMetO corresponded to about 46-63% of the total selenium in their extracts.

Selenium in plant foods: speciation analysis, bioavailability, and factors affecting composition.

Interest in selenium has been increasing over the past few decades with growing knowledge of its importance to overall health. The ability of several plants to accumulate and transform inorganic selenium forms into its bioactive organic compounds has important implications for human nutrition and health. In this review, we present the studies carried out during the last decade to characterize selenium species produced by different plant foods. Attention is also paid to the effect of selenium treatment on chemical composition and antioxidant properties of plants.

Determination of selenium species in beetroot juices.

Over the past years, there is an increasing demand for healthy, natural foods. Due to the high content of betalains, beetroots are widely used in the food industry as a natural colorant. In this study, beetroot juices are shown as a great source of selenium compounds. The juices were purchased from a local store and the ecological one was purchased form organic street market. The content of organic selenium species, as well as betalains, were evaluated using hydrophilic interaction liquid chromatography (HILIC) chromatography. The concentrations of selenomethionine (SeMet) and methylselenocysteine (MeSeCys) in analyzed juices were comparable except for juice from ecological cultivation. In that case, the concentration of SeMet is the highest of all studied juices, but simultaneously the concentration of MeSeCys was the lowest one. No traces of major inorganic species of Se, such as Se(IV) and Se(VI) was detected. The reducing power of juices evaluated by Folin-Ciocalteu assay was in range 50.78-166.7 mg GA/L. Juices obtained from beetroot from ecological cultivation showed the highest ability to scavenge the 1,1-diphenyl-2- picrylhydrazyl (DPPH) radicals. There was a correlation between the yellow pigment content and the presence of selenocysteine in studied juices.

Investigation of antioxidant activity of selenium compounds and their mixtures with tea polyphenols.

The antioxidant interactions between selenium species and tea polyphenols were investigated using 1,1-diphenyl-2-picryl-hydrazyl (DPPH) radicals, cupric reducing antioxidant capacity (CUPRAC) and Folin-Ciocalteu (FC) assay. Se(IV) exhibited the lowest antioxidant properties in comparison to other selenium compounds in all assays. The highest reducing power was obtained for SeMet, while the highest ability to scavenging DPPH radicals for MeSeCys. The results obtained experimentally for the mixtures containing selenium species and green or black tea infusion were compared with theoretical values calculated by adding up the effects of both individual components analyzed separately. The results obtained from each assay clearly show that observed effect is not additive. In almost every case the theoretical value of antioxidant capacity was significantly higher from that obtained from the activity of the binary mixture of black tea infusion with selenium compound decreased in the order: SeMet > Se(IV) > Se(VI) > MeSeCys, while for similar mixtures with green tea infusion: MeSeCys > Se(VI) > SeMet ~ Se(IV).

Potentilla erecta (L.) rhizomes as a source of phenolic acids.

The aim of this study was to evaluate the content of major phenolic acids from Potentilla erecta rhiozomes. Water and ethanol-water mixture was used for extraction of these compounds. The extracts were also evaluated for the quantification of total phenolic content and the antioxidant capacity. The contents of phenolic acids and resulting antioxidant activities are dependent on the nature of extracting solvent due to the presence of different antioxidant compounds. Results showed that P. erecta rhiozomes contained high amount of gallic and p-HBA acids. The contents of chlorogenic and protocatechuic acids in the extracts of Potentilla species have not been reported yet. The results suggested that the extracts could be used as the active cosmetics ingredients and nutraceuticals.

Comparison of the contents of selected elements and pesticides in honey bees with regard to their habitat.

The inspiration for this study was the anxiety of Warsaw beekeepers, who raised the question whether location of hives in large urban agglomerations results in changes in concentrations of xenobiotics, toxic elements, and micronutrients in honey bees. Preliminary studies required elaboration of the research methodology, as the studied object is characterized by a low degree of homogeneity and the method of sample preparation affects obtained results. From many tested approaches, the use of washed and milled abdomens of the bees is recommended. Results obtained for such prepared samples are slightly lower than for whole bees, but their repeatability is higher, which enables easier interpretation of the trends and comparison of different locations. The contents of selected elements (As, Al, Cd, Co, Cr, Cu, Mn, Pb, and Zn) were compared in bees from urban and rural areas. The studies were supported by pesticides analysis. Also, it was checked whether these substances are accumulated on the surface or inside the bee's body. The research indicates the markers of contamination: Al, As, and Cr on the surface and Cd inside the bodies of honey bees. The location of the hives does not influence significantly the content of "toxic," nutrient metals and metalloids in bees (slightly higher levels of As, Al, Pb, and Cd were found in bees from urban areas). In terms of exposure to these elements and pesticides, the large city environment is not harmful for honey bees.

Alpha-Tocopherol Serum Levels Are Increased in Caucasian Women with Uterine Fibroids: A Pilot Study.

Uterine fibroids (UFs) are benign tumors of the reproductive tract, arising from smooth muscle cells of the uterus. Steroid hormones, estrogen, and progesterone are considered to be the most important links in the pathophysiology of UFs. Alpha-tocopherol (AT) is the most active form of vitamin E. What is important as far as UFs are concerned is that ATs contain structural determinants, which makes them possible ligands for estrogen receptors (ERs). We present a retrospective cohort study performed in a university teaching hospital. We included a total of 162 patients divided into 2 groups: with UFs and controls. The effects of age, body mass index (BMI), positive medical history, parity, and AT serum concentrations on the risk for the development of UFs were investigated. Mean AT serum concentrations were 11.66 ± 4.97 µg/ml and 7.83 ± 3.13 µg/ml (medians 10.56 µg/ml and 7.42 µg/ml) in patients with UFs confirmed on ultrasound and controls, respectively. The presented difference was statistically significant. Higher BMI, positive family history, and low parity were found to be major risk factors for UFs. In our study, we confirmed that elevated serum AT concentration might be an important risk factor for UFs in Caucasian women. Further research in this area is necessary.

Investigation of antioxidant interaction between Green tea polyphenols and acetaminophen using isobolographic analysis.

The antioxidant interactions between acetaminophen (APAP) and green tea polyphenols were investigated using 1,1-diphenyl- 2-picryl-hydrazyl (DPPH) radicals and cupric reducing antioxidant capacity (CUPRAC). The results obtained experimentally for the mixtures were compared with theoretical values calculated by adding up the effects of both individual components analyzed separately. The potential antagonistic, additive or synergistic effects were also evaluated using the isobolographic analysis and interaction indexes. The results obtained for DPPH assays suggest the antagonistic type of interaction, while the results from CUPRAC method showed synergism. The observed differences in the type of interactions were probably a result of different reaction mechanisms between two used assays.

Hydrophilic interaction liquid chromatography in the speciation analysis of selenium.

The hydrophilic interaction liquid chromatography (HILIC) coupled to mass spectrometry was employed to study retention behavior of selected selenium compounds using two different HILIC stationary phases: silica and zwitterionic. Two organic solvents - acetonitrile and methanol - were compared as a component of mobile phase. Separation parameters such as a content of organic modifier, the eluent pH and inorganic buffer concentration were investigated. Based on all observations, methanol seems to be beneficial for the separation of studied compounds. The optimal HILIC separation method involved silica column and eluent composed of 85% MeOH and CH3COONH4 (8 mM, pH 7) was compared to RP method in terms of time of the single run, the separation efficiency and limit of detection.

Biophenols and antioxidant activity in wild and cultivated heather.

Over the last decade, there has been an increasing interest to study the antioxidants from natural sources which can be applied to replace the synthetic compounds commonly used in food or as cosmetic ingredients. Calluna vulgaris (L.) Hull (heather), a plant grown in most parts of Europe and Northern America, has been used in ethnopharmacology. The content of selected biophenols and the antioxidant capacity of the extracts of wild heather collected from natural environmental localities of central Poland were assessed in this study and compared with cultivated plant. Chlorogenic acid was the major biophenolic compound present in the extracts, followed by a high amount of catechins. The reducing power of the extracts evaluated by Folin-Ciocalteau assay was in the range of 75.7-89.1 mg GA/g dry flowers. The cultivated plant extract showed the largest radical scavenging on 1,1-diphenyl-2-pirylhydrazyl (DPPH) radicals.

Application of Hydrophilic Interaction Liquid Chromatography for the Quantification of Flavonoids in Genista tinctoria Extract.

Hydrophilic interaction chromatography (HILIC) was employed to investigate chromatographic behavior of selected flavonoids from their different subgroups differing in polarity. Chromatographic measurements were performed on two different HILIC columns: unmodified silica (Atlantis-HILIC) and zwitterionic sulfoalkylbetaine (SeQuant ZIC-HILIC). Separation parameters such as content and type of organic modifier were studied. On ZIC column retention factors were observed to be inversely proportional to the buffer content in the mobile phase, which is the typical partitioning mechanism. In the case of bare silica column more or less apparent dual retention mechanism was observed, depending on the water component content in the mobile phase. ZIC-HILIC showed better selectivity (in comparison to silica column) with the detection limit of 0.01 mg/L (only for rutin was 0.05 mg/L). Finally, this chromatographic procedure was validated and applied for the determination of some flavonoids in Genista tinctoria L. extract.

Retention Study of Flavonoids Under Different Chromatographic Modes.

The goal of this study was to investigate the chromatographic behavior of selected flavonoids from their different subgroups (flavonols, flavanones, flavones and isoflavones) in hydrophilic interaction liquid chromatography (HILIC). Chromatographic measurements were made on two different HILIC columns: cross-linked DIOL (Luna HILIC) and zwitterionic sulfoalkylbetaine (SeQuant ZIC-HILIC). Separation parameters such as the content of acetonitrile and pH of an eluent were studied. On the ZIC column, the retention factors of flavonoids increased with decreasing water content in the mobile phase. The increase in pH of the aqueous component mainly affects the polarity of the analytes. DIOL stationary phase shows more or less apparent dual retention mechanism, HILIC at the acetonitrile (ACN) content ≥75% and reversed phase (RP) with lower content of organic modifier. In the presence of ammonium acetate in the mobile phase, the retention of flavonoids onto the DIOL column increases without change in the selectivity of the separations. The similar effect, but considerably smaller was observed for aglycones on the ZIC column. The retention of studied glycosides (hesperidin, rutin) decreases in the presence of salt in the mobile phase. The significantly higher mass spectrometry sensitivity was observed under HILIC conditions in comparison with the most often used RP LC due to much higher content of ACN in the mobile phase. Finally, under optimal chromatographic conditions, the method was validated and applied for the determination of flavonoids in chamomile (Matricaria chamomilla L.) infusion.

Effects of brewing process on phenolic compounds and antioxidant activity of herbs.

Traditionally used medicinal plants contain a wide range of polyphenolic compounds that act as powerful antioxidants. The content of phenolic compounds in the infusions and decoctions of chamomile (Matricaria chamomilla L.) and St. John's wort (Hypericum perforatum), which are traditionally used medicinal herbs, was evaluated via liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. To obtain relevant antioxidant/reducing capacity of the prepared extracts, cupric reducing antioxidant capacity and Folin-Ciocalteu assay were applied. Rutin and apigenin were the major flavonoids in the aqueous extract of chamomile, whereas the predominant phenolic compounds of St. John's wort water extracts were rutin and catechin followed by chlorogenic acid. A longer time of infusion and decoction of St. John's wort herb significantly affected the rutin content. The increase of extraction time had very little impact on the antioxidant activities for chamomile but considerably higher impact on those for St. John's wort.