Etude par diffraction X et microscopie electronique du système CaTiO3---Ca2Fe2O5

In order to check the extended defect model previously proposed for the nonstoichiometric perovskite A_nM_nO_3n−1 (n 2), the Ca₂Ti_2−2xFe_2xO_6−x solid solution has been studied by means of X-ray diffraction and electron microscope investigations. The results show the existence of a continuous evolution (0 x 1) with two different regions. Close to the CaTiO₃ composition (0 x 0.40) the oxygen vacancies seem to be randomly distributed and the symmetry remains pseudocubic. In the composition range 0.55 x 1, the electron microscope patterns show an ordering of the defects: the oxygen vacancies are ordered in the (0k0) planes in strings parallel to the [101] direction. It is concluded from these observations that perpendicular to the Oy direction isolated planes of tetrahedra arranged in rows separate planes of corner-linked octahedra. The n = 2; 2.5; 3, et 4 terms of the A_nM_nO_3n−1 series have been identified. C.S. planes characteristic of classical nonstoichiometric oxides with small cations do not appear: instead, tetrahedra planes succeed to the previous octahedra planes as the degree of nonstoichiometry increases.

Résumé

Afin de vérifier le modèle de non-stoechiométrie proposé dans un travail précédent pour les perovskites lacunaires A_nM_nO_3n−1 (n 2), la solution solide Ca₂Ti_2−2xFe_2xO_6−x a été, étudiée par diffraction X et microscopie électronique. Les résultats montrent l'existence d'une évolution continue (0 x 1) avec deux domaines différents. Pour les compositions proches de CaTiO₃ (0 x 0.40), les lacunes oxygénées semblent être distribuées statistiquement et la symétrie demeure pseudocubique. Dans le domaine de compositions 0.55 x 1, les images de microscopie électronique montrent un ordre des défauts: les lacunes d'oxygène sont ordonnées dans les plans (0k0) en rangées parallèles à la direction [101]. Ces observations ont permis de conclure que perpendiculairement à la direction Oy des plans isolés de files de tétraèdres séparent des plans d'octaèdres liés par leurs sommets. Les termes n = 2; 2.5; 3 et 4 des séries A_nM_nO_3n−1 ont été identifiés. Des plans de cisaillement rencontrés dans les oxydes non-stoechiométriques classiques de petits cations n'ont pas été mis en évidence: par contre, des plans de tétraèdres se substituent aux plans d'octaèdres initiaux lorsque le degré de non-stoechiométrie augmente.     

Synthese de N-(tetrazol-5-yl) azetidin-2-ones

The title compounds were obtained by addition of a glycine enolate to a N-(tetrazol-5-yl) imine followed by cyclisation. This route provided both the $\text{cis}$ and the $\text{trans}$ substituted azetidinones. The $\text{cis}$ compounds possessed improved antibiotic activity as compared to the $\text{trans}$ counterparts.     

Randregularität des\bar \partial -Problems für die Halbkugel in ℂn

Let f be a -closed (0, q+1)-form defined on the half ball B₊ in ⁿ, which is of class C^k on ¯B. We prove the existence with C^k-estimates of a solution u of the equation .

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Die Anregung zu dieser Arbeit verdanke ich auch Herrn Piotr Jakóbczak aus Krakau, der sich eine gewisse Zeit am Max-Planck-Institut für Mathematik in Bonn aufhielt. Während dieser Zeit untersuchten wir die C⁰-Abschätzungen für die Halbkugel in ⁿ     

Laser spectroscopic investigation of salicylic acids hydrogen bonded with water in supersonic jets: Microsolvation effects for excited state proton dislocation

Geometric structures and excited-state proton dislocation of size-selected salicylic acid clusters (salicylic acid and 5-methoxysalicylic acid) with water were studied by using laser spectroscopic techniques. Fluorescence excitation, dispersed fluorescence, and infrared (IR) spectra of those clusters in supersonic jets were examined for both the electronic ground (S0) and first excited (S1) states. The geometric structures of the clusters were determined on the basis of the IR spectra of the OH stretch region with the help of quantum chemical calculations. The hydroxyl group of the water moiety in the clusters forms a ring involving the carboxylic group of the salicylic acid moiety. The IR spectra in S0 show that the intramolecular hydrogen bond in the salicylic acid moiety is still held upon cluster formation, but the phenolic OH stretch band intensity is remarkably weaken in the clusters. The IR spectra in the S1 state and dispersed fluorescence spectra indicated that the intramolecular excited state proton dislocation is hardly affected by the microsolvation with water, in contrast with the strong suppression of the dislocation in the self-solvation.     

Rapid synthesis of 2,5‐disubtituted 1,3,4‐thiadiazoles under microwave irradiation

The one pot, three‐components condensation of aromatic aldehydes, hydrazine and sulfur in ethanol under microwave irradiation provided symmetrically 3,5‐disubstituted 1,3,4‐thiadiazoles in high yields and good purity. This reaction must be conducted under pressure of hydrogen sulfide produced in‐situ. The structure of the compounds was confirmed by ¹H, ¹³C NMR, MS and elemental analysis.     

Rapid analysis of triterpenic acids by liquid chromatography using porous graphitic carbon and evaporative light scattering detection

An original system which uses Porous Graphitic Carbon as support and a mixture of organic solvents as mobile phase is proposed for the analysis of triterpenic acids by liquid chromatography. The separation of betulinic acid, ursolic acid, oleanolic acid, and 18alpha- and 18beta-glycyrrhetinic acids was carried out within a short time and monitored by evaporative light scattering detection as universal detection method. Molecular modelling studies show that the main contribution to the selectivity comes from the electrostatic interaction characterised by the dipole moment of the products.     

On xenon molecule excited state lifetimes

Time-resolved excitation spectra of xenon vapor in the 150 nm region are analysed in terms of four main fluorescence lifetimes corresponding to decays of four stable excited electronic states of the Xe dimer. The two shortest decay times, ≈ 2 ns and ≈ 60 ns, are assigned to the direct radiative relaxation of the two lowest excited ungerade states, (¹Σ⁺_u)0⁺_u and (³Σ⁺_u))1 u respectively. The two longest decay times, ≈ 150 ns and ≈ 500 ns, must correspond to the overall depopulation rates of the two lowest excited gerade states, (³Σ⁺_g)1g and (¹Σ⁺_g)0⁺_g, decaying into the gerade ground state by cascading down through the intermediate ungerade states.     

Isolement de l'acide 3-amino 12-methyl tetradecanoique et de l'acide 3-amino 12-methyl tridecanoique a partir de l'iturine,antibiotique de Bacillus subtilis

lturin, a peptide antibiotic from Bacillus subtilis, was separated into three iturins: A, B, C by thin-layer chromatography. Iturin A, which has an antifungal activity, contains Asp, Glu, Tyr, Ser, Pro in a molar ratio 3:1:1:1:1 and a lipid moiety AL. The latter was shown to be a mixture of C₁₄ (40%) and C₁₅, (60%) amino-acids. The structure of these was determined by combined gas chromatography-mass spectrometry of the N-acetylmethyl esters. Strong peaks at m/e = 144 and m/e = 102 indicate a β-amino group. Identification of acetone and methylethylketone after chromic acid oxidation indicates an iso and anteiso structure. After comparison of the natural amino-acids with synthetic 3-amino pentadecanoic acid it is concluded that the lipid AL is a mixture of 3-amino 12- methyltetradecanoic acid and 3-amino 12-methyltridecanoic acid.