7α,11β-diacetoxydihydronomilin,a new tetranortriterpenoid from cedrelamexicana

Spectroscopic and chemical evidence is presented in support of the structure of 7α,11β-diacetoxydihydronomilin (I) obtained from a benzene extract of the dehisced fruit capsules of $\text{Cedrela}$$\text{mexicana}$.     

Adsorption d'eau sur la kaolinite: Influence de la nature des sites actifs

Water adsorption on kaolinite is a specific cooperative adsorption which does not satisfy the fundamental hypothesis of the BET theory.The adsorption isotherms on different homoionic samples show the effect of the hydration energy of the active sites (exchangeable cations) on quantitative adsorption data.The corresponding calorimetric curves present a maximum which characterizes interactions in the adsorbed phase. A relationship is apparent between these interactions and the electric field or the polarizability of the fixed cation, these factors determining the nature of the bond between the surface and cation.From the experimental data, we may propose an approximative value for the number of molecules which compose the primary hydration sheath of the active sites.     

Crystal structure of protogenkwanin,C16H14O6

The crystal structure of protogenkwanin, C₁₆H₁₄O₆, has been determined by single-crystal diffraction methods. The compound crystallizes in the monoclinic space groupP2₁/c witha=6.804(4),b=7.457(3),c=26.234(3)Å,=95.66(2)° andZ=4. A total of 3275 unique reflection intensities were recorded on a Rigaku AFC6R diffractometer (MoK radiation) at room temperature. The structure was solved by direct methods and electron density calculations. Full-matrix least-squares refinement gaveR=0.058 for 1257 observed [I>3(I)] reflections. Thecrystal structure confirms results from earlier studies on protogenkwanin and elucidates the steric orientation of the hydroxyl substituents of the cyclohexadiene ring: the hydroxyl groups aretrans orientated.     

Review of the thermodynamic and transport properties of EuBr<Subscript>2</Subscript>–RbBr binary system

Differential Scanning Calorimetry was used to study phase equilibrium in EuBr₂–RbBr binary system. It was established that this system includes two eutectics and three stoichiometric compounds. First of them, Rb₂EuBr₄, decomposes peritectically at 778 K. Second one, RbEuBr₃, undergoes the solid–solid phase transition at 732 K and melts incongruently at 852 K. Third compound, RbEu₂Br₅, melts congruently at 888 K. The composition and temperature values of eutectics were determined as x(EuBr₂) = 0.316; T _eut = 776 K and x(EuBr₂) = 0.797; T _eut = 859 K. Mixing enthalpy was measured by direct calorimetry on the whole composition range. The minimum of the mixing enthalpy occurs around the composition x(EuBr₂) ≈ 0.4. The electrical conductivity of liquid mixtures was also investigated over the whole composition range and measured down to temperatures below solidification. The specific conductance (liquid phase) plotted against the mole fraction of EuBr₂ shows a broad minimum at x(EuBr₂) ~ 0.6. The activation energy for conductivity changes with temperature. Results obtained are discussed in terms of possible complex formation.     

Purification and Characterization of Cell Suspensions Peroxidase from Cotton (<Emphasis Type="Italic">Gossypium hirsutum</Emphasis> L.)

Two peroxidases, cPOD-I and rPOD-II, have been isolated and purified from cotton cell suspension and their biochemical characteristics studied. rPOD-II from R405-2000, a non-embryogenic cultivar, has higher activity than cPOD-I derived from Coker 312, which developed an embryogenic structure. The cPOD-I and rPOD-II had molecular mass of 39.1 and 64 kDa respectively, as determined by SDS-PAGE. Both enzymes showed high efficiency of interaction with the guaiacol at 25 mM. The optimal pH for cPOD-I and rPOD-II activity was 5.0 and 6.0, respectively. The enzyme had an optimum temperature of 25 °C and was relatively stable at 20–30 °C. The isoenzymes were highly inhibited by ascorbic acid, dithiothreitol, sodium metabisulfite, and β-mercaptoethanol. Their activities were highly enhanced by Al³⁺, Fe³⁺, Ca²⁺, and Ni²⁺, but they were moderately inhibited by Mn²⁺ and K⁺. The enzyme lost 50% to 62% of its activity in the presence of Zn²⁺ and Hg²⁺.     

Protogenkwanin,a new flavonoid from equisetum arvense L

From the fertile sprouts of Equisetum arvense L. have been isolated protogenkwanin 4'-glucoside and gossypitrin. The structure of protogenkwanin as 5-hydroxy-2-(1,4-dlhydroxy-2,5-cyclohexadienyl)-7-methoxy-4-chromenon is proved on the basis of chemical and physical evidence. It is demonstrated that articulatin a thiamine decomposing substance, from E. arvense, is identical with the known flavonol glycoside gossypitrin (= gossypetin-7-glucoside). The synthesis of 2,5-dihydroxy-2-(4 hydroxyphenyl)-7-methoxy-4-chromanon is reported.     

Monitoring dynamic systems with multiparameter fluorescence imaging

A new general strategy based on the use of multiparameter fluorescence detection (MFD) to register and quantitatively analyse fluorescence images is introduced. Multiparameter fluorescence imaging (MFDi) uses pulsed excitation, time-correlated single-photon counting and a special pixel clock to simultaneously monitor the changes in the eight-dimensional fluorescence information (fundamental anisotropy, fluorescence lifetime, fluorescence intensity, time, excitation spectrum, fluorescence spectrum, fluorescence quantum yield, distance between fluorophores) in real time. The three spatial coordinates are also stored. The most statistically efficient techniques known from single-molecule spectroscopy are used to estimate fluorescence parameters of interest for all pixels, not just for the regions of interest. Their statistical significance is judged from a stack of two-dimensional histograms. In this way, specific pixels can be selected for subsequent pixel-based subensemble analysis in order to improve the statistical accuracy of the parameters estimated. MFDi avoids the need for sequential measurements, because the registered data allow one to perform many analysis techniques, such as fluorescence-intensity distribution analysis (FIDA) and fluorescence correlation spectroscopy (FCS), in an off-line mode. The limitations of FCS for counting molecules and monitoring dynamics are discussed. To demonstrate the ability of our technique, we analysed two systems: (i) interactions of the fluorescent dye Rhodamine 110 inside and outside of a glutathione sepharose bead, and (ii) microtubule dynamics in live yeast cells of Schizosaccharomyces pombe using a fusion protein of Green Fluorescent Protein (GFP) with Minichromosome Altered Loss Protein 3 (Mal3), which is involved in the dynamic cycle of polymerising and depolymerising microtubules.     

3,3]-rearrangements of phosphonium ylides

Allylic phosphonium ylides are readily generated by the combination of an allylic alcohol, a carbene, and a chlorophosphite. Here we demonstrate that these intermediates undergo a thermal [3,3]-rearrangement to provide single isomers of homoallylic phosphonates in good to excellent yields. This new reaction manifold for phosphorus ylides is tolerant of a range of substitution patterns on the reactants and provides access to structurally complex intermediates for the synthesis of enzyme inhibitors, aminophosphonic acids, and natural products.     

Instrumentation and calibration of the Calvet calorimeter

The original Calvet calorimeter, made from aluminum block, were instrumented. The cells for the solution calorimetry measurement have been projected and constructed. The calibration of calorimeter was performed by measurement of the dependence of reference material on temperature and the influence of mechanical events on thermograms. The enthalpies of solution in water and 0.01 M HCl were investigated for chlorides and bromides of alkali metals (Na···Cs), PrBr₃ and Rb₃PrBr₆. The enthalpies of solution of alkali halides have been compared to the reference data obtained for infinite solution. The decomposition of Rb₃PrBr₆ at temperatures lower than 399 K has been stated. The enthalpy of solution PrBr₃ at 298.15 K has been determined.