Synthesis and biological evaluation of 6-oxa-nor-tropane glycomimetics as glycosidase inhibitors

The preparation of polyhydroxylated 6-oxa-nor-tropane glycomimetics structurally related to the glycosidase inhibitor family of the calystegines is reported. The synthetic strategy involves the furanose→piperidine rearrangement of 5-deoxy-5-ureido-l-idose precursors, followed by intramolecular glycosylation involving the primary hydroxyl group. Inversion of the configuration at C-3 in the resulting 6-oxa-(+)-calystegine B₂ analogue allows accessing the elusive 3-epi-6-oxa-(+)-calystegine B₂ skeleton. Acid-catalyzed opening of the nor-tropane bicycle was observed, however, which could be avoided by careful neutralization of the reaction mixture. The inhibition results suggest that (+)-calystegine B₂ derivatives and the corresponding C-3 epimers can be seen as glucomimetics and galactomimetics, respectively, pointing to a 1-azasugar mode of action for this family of alkaloids.     

Application of extraction disks in dissolution tests of clenbuterol and levothyroxine tablets by capillary electrophoresis

Sample preparation procedures using octadecyl (C₁₈) extraction disks were developed to obtain accurate and reproducible results for determinations of clenbuterol (20 μg per dose) and levothyroxine (100 μg per dose) in dissolution media of solid oral dosage forms. Preconcentration of samples allowed final concentrations of 1.1 μg/ml of clenbuterol and 4.0 μg/ml of levothyroxine to be reached prior to CE analysis. The results obtained by CE were in good agreement with those of HPLC. The precision of the migration time, peak area, peak height and accuracy were determined in both intea-day (n = 6) and inter-day (n =18) assays. Linearity was demonstrated over the ranges 0.5–80.0 μg/ml of clenbuterol and 1.0–30.0 μg/ml of levothyroxine. The mean recoveries were higher than 94.0%, ranging from 50 to 125% levels with respect to dose potencies. The proposed methodology may be generally applied to determine drugs at ng/ml concentrations.     

Laser-induced charge transfer in the LiH3+ quasi-molecule

The laser-induced charge-transfer cross section for Li³⁺ + H collisions is calculated using the perturbation approach of Copelang and Tang, and is compared to the collision-induced cross section. The validity of perturbation theory and the use of simple criteria based on the Landau-Zener formula to extend the usefulness of the theory are examined.     

Influence of Temperature and Time on the Stability of Silver in Silica Sol-Gel Glasses

The darkening of silica sol-gel glasses doped with 0.05 mol% silver was studied. Six sols were prepared from TEOS and silver nitrate. Different additives were used, to influence the chemical and physical states of silver: oxidizing or reducing agents (H₂O₂, As₂O₅), colloid stabilizer (sodium citrate) and network modifiers (Li₂O, CaO). Sols were gelified at 60°C and densified at 600°C. The samples without additives and those prepared with H₂O₂ at room temperature even if they were protected from light. With increased temperature, the darkening became samples were heated above, 400°C, reversible bleaching took place. This darkening-bleaching is of thermal nature (“thermochromic effect”) and seems to be determined by a reversible aggregation-disaggregation of tiny silver particles. The presence of sodium citrate, as an additive delayed the darkening effect and the presence of CaO delayed it even further. Lithium oxide inhibited it totally.     

Semicarbazones and thiosemicarbazones,XII: Crystal structure of salicylaldehyde semicarbazone

Summary The crystal and molecular structure of salicylaldehyde semicarbazone was obtained by single crystal X-ray diffraction. The O atom of the semicarbazone fragment isanti to the N atom of the hydrazinic group. The distribution of bond lengths in the semicarbazone fragment indicates delocalization of the -electrons. The crystal structure is stabilized by intra- and intermolecular hydrogen bonds.

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Semicarbazone und Thiosemicarbazone, 12. Mitt.: Die Kristallstruktur des Salicylaldehyd-Semicarbazons

Zusammenfassung Die Kristallstruktur und die molekulare Struktur des Salicylaldehyd-Semicarbazons wurde über Einkristall-Röntgenstreuung ermittelt. Das O-Atom des Semicarbazonteils stehtanti zum N-Atom der Hydrazin-Gruppierung. Die Bindungslängen in der Semicarbazoneinheit zeigen eine Delokalisierung der -Elektronen an. Die Geometrie der Verbindung wird durch stabilisierende intra- und intermolekulare Wasserstoffbrückenbindungen bestimmt.

     

Defect concentration in Ti-substituted YIG from TG curves

The article discusses theory and experiment about the measurement of defect concentration in Ti-substituted yttrium iron garnet by means of thermogravimetry techniques. The two possible cases arising from oxygen interchange with atmosphere, oxygen vacancies and interstitial cations, may be analyzed quantitatively from the derived expressions. The possibility of another type of defects being present in the samples, not associated to oxygen evolution, is not excluded. Measurements were carried out in air and CO₂ for different Ti contents. The substitution tends to increase slightly the defect parameter θ in YIG, while a CO₂ reducing atmosphere is much more effective than the Ti substitution for increasing θ. Calculations for a given single-phased sample sintered in air show two possibilities: a deficit of one oxygen atom for every 2.5 unit cells of 96 atoms, or one excess cation for every 3.5 cells. Other samples show very similar results. The accuracy involved in the measurements is about 2–3%.     

Study on the stability of noradrenaline and on the determination of its acidity constants

Noradrenaline is a catecholamine which has been largely recognised to play a very important role in biological systems. In view of the neurotransmitter's alleged importance, this work aimed at showing the influence of time on its spectral behaviour using different analytical methods and determining its acidity constants through spectrophotometric titration and by the so-called point-by-point analysis, where the samples are freshly prepared for each pH value investigated at the instant required. Because the catecholamines are light-sensitive and likely to react with the oxygen in the surrounding air, both methods used preclude its incidence onto the samples being analysed under the presence of a nitrogen atmosphere maintained over the solutions. The constants obtained through point-by-point analysis were log beta1 = 30.71+/-0.16, log beta2 = 22.00+/-0.15 and log beta3 = 11.69+/-0.16.