Synthesis of β-ketophosphonates with electron rich β-aryl groups as useful organophosphorus reagents in lignans synthesis

Investigation of the oxidation reaction of electron rich alkoxy substituted β-aryl β-hydroxyphosphonates to corresponding β-ketophosphonates, which may be utilized in syntheses of lignans with various oxidizing agents (PCC, PDC, SIBX, CAN, Oxone^®, KMNO₄/SiO₂, KMnO₄/MS 4 Å, KMnO₄/CuSO₄, KMnO₄/CuSO₄/Al₂O₃, MnO₂, CrO₃/SiO₂, H₂O₂/salen) is described. The effect of oxidants and reaction conditions on the reaction efficiency and yield was also investigated.     

H/D isotopic recognition in hydrogen bonded systems: H/D isotopic self-organization effects in the IR spectra of the hydrogen bond in 2-methylimidazole crystals

Polarized IR spectra of H12(3)45 2-methylimidazole and of its H1D2(3)45, D1H2(3)45 and D12(3)45 deuterium derivative crystals are reported and interpreted within the limits of the "strong-coupling" theory. The spectra interpretation facilitated the recognition of the H/D isotopic "self-organization" phenomenon, which depends on a non-random distribution of protons and deuterons in the lattices of isotopically diluted crystal samples. The H/D isotopic "self-organization" mechanism engaged all four hydrogen bonds from each unit cell. These effects basically resulted from the dynamical co-operative interactions involving adjacent hydrogen bonds in each hydrogen bond chain. A weaker exciton coupling involved the closely spaced hydrogen bonds; each belonging to a different chain of associated 2-methylimidazole molecules. The high intensity of the narrow band at ca. 1880cm(-1) was interpreted as the result of coupling between the γ(N-H?N) proton bending "out of plane" vibration overtone and the ν(N-H) proton stretching vibration.     

Nucleoside-metallacarborane conjugates for base-specific metal labeling of DNA

A general approach to the synthesis of nucleoside conjugates between derivatives of thymidine (T), 2'-O-deoxycytidine (dC), 2'-O-deoxyadenosine (dA), and 2'-O-deoxyguanosine (dG), and metallacarborane complexes is described. Metallacarborane-nucleoside derivatives are prepared by reaction of the dioxane-metallacarborane adduct with a base-activated 3',5'-protected nucleoside. In the case of T and dG a mixture of regioisomers, which is easily separable by chromatographic methods, is obtained, thus yielding a series of modifications containing metallacarborane groups at the 2-O, 3-N, 4-O and 1-N, 2-N, 6-O locations, respectively; dC and dA are alkylated at the exo-amino function. The proposed methodology provides a route for the synthesis and study of nucleic acids modified with metallacarboranes at designated locations and a versatile approach to the incorporation of metals into DNA.     

A novel catalytic adsorptive stripping voltammetric method for the determination of germanium ultratraces in the presence of chloranilic acid and the V(IV)·HEDTA complex

A novel, sensitive catalytic adsorptive stripping voltammetric procedure which can be used to determine trace amounts of germanium is described. The method is based on the interfacial accumulation of the complex formed by Ge(IV) and the product of the reduction of chloranilic acid on the hanging mercury drop electrode or the renewable silver amalgam film electrode, and its subsequent reduction from the adsorbed state followed by the catalytic action of the V(IV)·HEDTA complex. The presence of V(IV)·HEDTA greatly enhances the adsorptive stripping response of Ge. The reduction of the Ge(IV) in the presence of chloranilic acid and V(IV)·HEDTA was investigated in detail and the effects of pH, electrolyte composition, and instrumental parameters were studied. Under optimal conditions, the catalytic peak current of germanium exhibited good linearity for Ge(IV) concentrations in the range of 0.75–60 nM (for 60 s of accumulation at −0.1 V, r² = 0.995) and a low limit of detection (LOD = 0.085 nM). The procedure was successfully applied to determine Ge in water samples.

     

Examination of sorption and desorption of hydrogen on several samples of polish hard coals

Performed tests showed that at 298?K hard coals sorb relatively small amounts of hydrogen. Those amounts depend on carbon and oxygen content in tested coals. The most considerable amounts of hydrogen are sorbed by coals characterized by strong surface hydrophobicity and high content of aliphatic hydrocarbons. The hydrophilic nature of coal surface does not lead to higher sorption of hydrogen. It was found that the change in amount of sorbed hydrogen is closely related to the moisture. For high moisture coal a significant decrease in hydrogen sorption is observed. Also tests on hydrogen desorption on hard coals were carried out using method of lowering hydrogen pressure above the sorbent. Obtained results showed that tested coals desorb various amounts of hydrogen. Process of sorption is reversible only for some coals, while for the others the desorption isotherm partially lies beneath the sorption isotherm, which indicates that in addition to hydrogen some other chemical substances are emitted from coal.     

Molecular dynamics of 5-HT1A and 5-HT2A serotonin receptors with methylated buspirone analogues

In the present study experimentally determined ligand selectivity of three methylated buspirone analogues (denoted as MM2, MM5 and P55) towards 5-HT_1A and 5-HT_2A serotonin receptors was theoretically investigated on a molecular level. The relationships between the ligand structure and 5-HT_1A and 5-HT_2A receptor affinities were studied and the results were found to be in agreement with the available site-directed mutagenesis and binding affinity data. Molecular dynamics (MD) simulations of ligand-receptor complexes were performed for each investigated analogue, docked twice into the central cavity of 5-HT_1A/5-HT_2A, each time in a different orientation. Present results were compared with our previous theoretical results, obtained for buspirone and its non-methylated analogues. It was found that due to the presence of the methyl group in the piperazine ring the ligand position alters and the structure of the ligand-receptor complex is modified. Further, the positions of derivatives with pyrimidinyl aromatic moiety and quinolinyl moiety are significantly different at the 5-HT_2A receptor. Thus, methylation of such derivatives alters the 3D structures of ligand-receptor complexes in different ways. The ligand-induced changes of the receptor structures were also analysed. The obtained results suggest, that helical domains of both receptors have different dynamical behaviour. Moreover, both location and topography of putative binding sites for buspirone analogues are different at 5-HT_1A and 5-HT_2A receptors.     

Stereoselective synthesis of isoindolinones and tert-butyl sulfoxides

A reaction of Grignard reagents with an optically pure N-sulfinylimine derived from methyl 2-formylbenzoate yields enantioenriched isoindolinones and tert-butyl sulfoxides. The products are formed by the addition of the nucleophile to N-sulfinylimine followed by cyclization to form N-tert-butylsulfinylisoindolinone, which readily undergoes substitution with a second equivalent of Grignard reagent. The reaction can be carried out in dichloromethane at room temperature or at elevated temperatures without any loss of stereoselectivity. The use of nucleophiles other than Grignard reagents has also been investigated.     

Supplementation with Magnesium Salts—A Strategy to Increase Nutraceutical Value of Pleurotus djamor Fruiting Bodies

The use of substrates supplemented with minerals is a promising strategy for increasing the nutraceutical value of Pleurotus spp. The current research was performed to analyze the effect of substrate supplementation with magnesium (Mg) salts on the Mg content, biomass, and chemical composition of pink oyster mushroom (Pleurotus djamor) fruiting bodies. Before inoculation, substrate was supplemented with MgCl₂ × 6 H₂O and MgSO₄, both salts were applied at three concentrations: 210, 420, and 4200 mg of Mg per 2 kg of substrate. The harvest period included three flushes. Substrate supplementation with 4200 mg of Mg caused the most significant decrease in mushroom productivity, of about 28% for both Mg salts. The dry matter content in fruiting bodies was significantly lower in the treatment in which 210 mg of Mg was applied as MgSO₄ in comparison to the control. Supplementation effectively increased the Mg content in fruiting bodies of P. djamor by 19–85% depending on the treatment, and significantly affected the level of remaining bioelements and anions. One hundred grams of pink oyster fruiting bodies, supplemented with Mg salts, provides more than 20% of the Mg dietary value recommended by the Food and Drug Administration (FDA); thus, supplementation can be an effective technique for producing mushrooms that are rich in dietary Mg. Although P. djamor grown in supplemented substrate showed lower productivity, this was evident only in the fresh weight because the differences in dry weight were negligible. Mg supplementation increased the antioxidant activity of the fruiting bodies, phenolic compounds, and some amino acids, including L-tryptophan, and vitamins (thiamine and l-ascorbic acid).