EPR and XPS measurements of polymeric catalysts doped with hereopolyacids in oxygen adsorption studies

The goal of our studies was to determine the nature of interactions between catalytic active samples, such as polypyrrole (PPy) doped with: chloride anions, heteropolyacids such as H₅PMo₁₀V₂O₄₀, or H₄SiW₁₂O₄₀, and oxygen particles. In order to reveal the mechanism of the linkage between the catalysts and oxygen we provided the electron paramagnetic resonance (EPR) measurements of synthesized samples in O₂ and N₂ flow. Moreover, the X-ray photoelectron spectroscopy (XPS) measurements were performed to show the properties of doped heteropolyacids and the state of nitrogen in polypyrrole matrix. The results of EPR studies of PPy(Cl), PPy(H₄SiW₁₂O₄₀), PPy(H₅PMo₁₀V₂O₄₀) samples, show that the polypyrrole doped with chloride anions interacts much easier with oxygen than polypyrrole doped with heteropolyacids (in the above given order, of preference with the most active polypyrrole system first). It correlates with XPS results, which show that a molybdenium-vanadium anion is more reduced than a silicon-tungsten one. The redox reactions of heteropolyacids involve the oxidation-reduction of the conjugated polymer chain, leaving no or little place for interactions with oxygen. Polypyrrole doped with H₄SiW₁₂O₄₀ shows some oxygen sensitivity as observed in the EPR studies, as opposed to polypyrrole doped with H₅PMo₁₀V₂O₄₀, which is in line with the XPS results.     

Biferrocenes and terferrocenes

Russian Chemical Bulletin -     

The structure of the hydrazones formed fromβ-dicarbonyl compounds under the conditions of the azo-coupling reaction

Summary The arylhydrazones formed from -dicarbonyl compounds under the conditions of the azo-coupling reaction have a chelate structure with an intramolecular hydrogen bond attached to one of the carbonyl groups.     

Anion-sealed single-molecule capsules

A new approach to anion recognition utilizing electrostatic and hydrogen bonding interactions has been demonstrated by placement of the whole ion-pair in a molecular capsule.     

Comparison of the absolute calibration method with the method of standard addition for the determination of halothane in blood by gas chromatographic headspace analysis

As long-term exposure to exhaled halothane can be a cause of hepatitis and/or damage to the liver, the determination of halothane in blood is important in clinical practice. Gas chromatographic headspace analysis appears to be the most successful method. In the present study, two methods of quantitative evaluation of the analysis were compared by statistical treatment and direct comparison. The absolute calibration method was found to be unsuitable since it yields entirely unreliable results. This is due to different contents of lipoid and other components in the blood of the normal population, and this influences the vapour phase concentration of halothane and results in different values for the slopes of calibration curves for different blood samples. The standard addition method gives reliable results.     

Innovative Freeze-Dried Snacks with Sodium Alginate and Fruit Pomace (Only Apple or Only Chokeberry) Obtained within the Framework of Sustainable Production

The aim of the work has been to develop freeze-dried fruit snacks in the form of bars with the use of by-products derived from fruit processing. In effect 14 product designs of fruit gels based on: apple pulp, apple juice, water, sodium alginate and only apple or only chokeberry pomace were prepared. The snacks were freeze-dried. The dry matter content, water activity, structure, colour, mechanical properties, as well as organoleptic evaluation were determined. Freeze-dried bares were obtained according to sustainability production which in this case was relied on application of fruit pomace. The freeze-drying process ensures the microbiological safety of the product without the need to use chemical preservatives. Freeze-dried samples obtained low water activity in the range of 0.099–0.159. The increase in pomace concentration (3–9%) boosted the dry matter content to above 98%, and decreased the brightness of the freeze-dried bars about 6 to 10 units. Mechanical properties varied depending on the product design. With the increase in the amount of pomace, the shear force increased at 23% to 41%. Based on the results, the best variant, that has the most delicate structure and the best organoleptic properties, has proven to contain 1% sodium alginate and 2% pomace.     

In Vitro Inhibitory Effects of Viburnum opulus Bark and Flower Extracts on Digestion of Potato Starch and Carbohydrate Hydrolases Activity

One of the effective treatments for diabetes is to reduce and delay the absorption of glucose by inhibition of α-amylase and α-glucosidase in the digestive tract. Currently, there is a great interest in natural inhibitors from various part of plants. In the present study, the phenolic compounds composition of V. opulus bark and flower, and their inhibitory effects on in vitro potato starch digestion as well as on α-amylase and α-glucosidase, have been studied. Bark and flower phenolic extracts reduced the amount of glucose released from potato starch during tree-stage simulated digestion, with IC₅₀ value equal to 87.77 µg/mL and 148.87 µg/mL, respectively. Phenolic bark extract showed 34.9% and 38.4% more potent inhibitory activity against α-amylase and α-glucosidase, respectively, but the activity of plant extracts was lower than that of acarbose. Chlorogenic acid (27.26% of total phenolics) and (+)-catechin (30.48% of total phenolics) were the most prominent phenolics in the flower and bark extracts, respectively. Procyanidins may be responsible for the strongest V. opulus bark inhibitory activity against α-amylase, while (+)-catechin relative to α-glucosidase. This preliminary study provides the basis of further examination of the suitability of V. opulus bark compounds as components of nutraceuticals and functional foods with antidiabetic activity.     

Cornelian Cherry (Cornus mas L.) Extracts Exert Cytotoxicity in Two Selected Melanoma Cell Lines—A Factorial Analysis of Time-Dependent Alterations in Values Obtained with SRB and MTT Assays

Despite the fact that phytochemicals of Cornaceae species have long been discussed as possible auxiliary agents in contemporary treatment, the insights on their properties remain relatively scarce. This study focuses on Cornus mas L. (Cornelian cherry), the extracts of which are reported to exert a pleiotropic effect shown in both in vivo and in vitro studies. This study aimed to explore the cytotoxic effect of extracts from fruits of red (Cornus mas L. ‘Podolski’) and yellow (Cornus mas L. ‘Yantarnyi’ and ‘Flava’) Cornelian cherries on two melanoma cell lines (A375 and MeWo). The extracts were characterized in the context of the concentration of bioactive compounds of antioxidative properties. Cytotoxicity was investigated with the use of the following two assays: SRB and MTT. An additional, alternative protocol for the SRB assay was used in this study so as to account for possible bias. Cytotoxicity was assessed as a difference in the whole time series of cell viability, instead of analyzing differences in raw values (often found in the literature). Both extracts from Cornus mas L. induced cytotoxicity in both A375 and MeWo cell lines, although the response of these cells was different. Moreover, based on this study, there is no evidence for claiming a different magnitude of cytotoxicity between these two extracts.     

Acid–Base Equilibrium and Self-Association in Relation to High Antitumor Activity of Selected Unsymmetrical Bisacridines Established by Extensive Chemometric Analysis

Unsymmetrical bisacridines (UAs) represent a novel class of anticancer agents previously synthesized by our group. Our recent studies have demonstrated their high antitumor potential against multiple cancer cell lines and human tumor xenografts in nude mice. At the cellular level, these compounds affected 3D cancer spheroid growth and their cellular uptake was selectively modulated by quantum dots. UAs were shown to undergo metabolic transformations in vitro and in tumor cells. However, the physicochemical properties of UAs, which could possibly affect their interactions with molecular targets, remain unknown. Therefore, we selected four highly active UAs for the assessment of physicochemical parameters under various pH conditions. We determined the compounds’ pK_a dissociation constants as well as their potential to self-associate. Both parameters were determined by detailed and complex chemometric analysis of UV-Vis spectra supported by nuclear magnetic resonance (NMR) spectroscopy. The obtained results indicate that general molecular properties of UAs in aqueous media, including their protonation state, self-association ratio, and solubility, are strongly pH-dependent, particularly in the physiological pH range of 6 to 8. In conclusion, we describe the detailed physicochemical characteristics of UAs, which might contribute to their selectivity towards tumour cells as opposed to their effect on normal cells.