Reaction of silyl ketene acetals with epoxides: a new method for the synthesis of γ-butanolides

Titanium tetrachloride promoted reaction of silyl ketene acetals with epoxides, followed by acidic work-up, affords butanolides in moderate/good yields. With epihalohydrins the reaction is regioselective and occurs at the less substituted end of the epoxide; the γ-haloalkyl-γ-butanolides thus obtained can be further transformed into various products.     

Time resolved spectroscopic NMR imaging using hyperpolarized Xe

We have visualized the melting and dissolution processes of xenon (Xe) ice into different solvents using the methods of nuclear magnetic resonance (NMR) spectroscopy, imaging, and time resolved spectroscopic imaging by means of hyperpolarized ¹²⁹Xe. Starting from the initial condition of a hyperpolarized solid Xe layer frozen on top of an ethanol (ethanol/water) ice block we measured the Xe phase transitions as a function of time and temperature. In the pure ethanol sample, pieces of Xe ice first fall through the viscous ethanol to the bottom of the sample tube and then form a thin layer of liquid Xe/ethanol. The xenon atoms are trapped in this liquid layer up to room temperature and keep their magnetization over a time period of 11 min. In the ethanol/water mixture (80 vol%/20%), most of the polarized Xe liquid first stays on top of the ethanol/water ice block and then starts to penetrate into the pores and cracks of the ethanol/water ice block. In the final stage, nearly all the Xe polarization is in the gas phase above the liquid and trapped inside the pores. NMR spectra of homogeneous samples of pure ethanol containing thermally polarized Xe and the spectroscopic images of the melting process show that very high concentrations of hyperpolarized Xe (about half of the density of liquid Xe) can be stored or delivered in pure ethanol.     

Dihydropyridine-based MCRs. New reaction pathways in the interaction with ethyl glyoxalate and non-aromatic amines

The Lewis acid-catalyzed interaction of dihydropyridines with ethyl glyoxalate and primary aliphatic amines yields, depending on the reaction conditions, bicyclic aminals or rearranged tetrahydropyridines in one-pot multicomponent reactions.     

Equilibrated thermodesorption studies of adsorption of n-hexane and n-heptane on zeolites Y, ZSM-5 and ZSM-11

Gravimetric measurements of thermodesorption of n-hexane and n-heptane were performed under quasi-equilibrium conditions. Differential thermodesorption profiles for ZSM-5 and ZSM-11 showed two peaks, but for Y zeolites, only one thermodesorption peak was observed. A model function, derived from the Langmiur adsorption model, was fitted to the experimental data, and the model parameters (the adsorption entropy and enthalpy) were estimated. The two-step desorption profiles observed for ZSM-5 and ZSM-11 were attributed to the commensurate freezing effect, i.e. a transition in the adsorbed phase resulting in ordering of the adsorbed molecules in the zeolite channels. The results observed for ZSM-11 indicate that the zigzag channels typical for ZSM-5 micropore system are not necessary for this transition to occur.     

Characterization of Cds clusters in zeolite-A grown in alkaline solution

CdS clusters were synthesized in A type zeolite by reaction in alkaline aqueous solution at temperatures from 30 to 70 °C. The optical properties of the samples were studied by diffuse reflectance and photoluminescence spectroscopy. Their crystalline structure and morphology were studied by X-ray diffraction and by transmission and scanning electron microscopy. We found that at lower temperatures the CdS clusters are encapsulated in the zeolite cages. We compared the properties of these clusters with those encapsulated in the cages of zeolites X and Y, prepared by similar methods. CdS clusters smaller than the CdS exciton diameter are also formed outside the cages in the zeolite matrix. The size of these clusters increases with temperature producing a red-shift of the absorption edge in the optical absorption spectra.     

Limits of tangents and minimality of complex links

We show that the complex link of a large class of space germs (X,x₀) is characterized by its “simplicity”, among the Milnor fibres of functions with isolated singularity on X. This amounts to the minimality of the Milnor number, whenever this number is defined. Such a phenomenon has been first pointed out in case (X,x₀) is an isolated hypersurface singularity, by Teissier (Cycles évanescents, sections planes et conditions de Whitney, in: Singularités à Cargèse 1972, Asterisque, Nos. 7 et 8, Soc. Math. France, Paris, 1973, pp. 285-362).     

A study on the applications of the acoustic design sensitivity analysis of vibrating bodies

The determination of the sensitivity of the acoustical characteristics of vibrating systems with respect to the variation of the design parameters predicting these characteristics is a necessary and important step of the acoustic design and optimization process. Acoustic design sensitivity analysis includes the computation and evaluation of the sensitivity information required for this procedure. In this study, a boundary element code performing the sensitivity analysis of the acoustic pressure by using the matrix sensitivities with respect to different design variables has been developed. The effect of the precision of boundary element discretization on the acoustic pressure sensitivity is examined via this code. The formulation is applied to a multi-source system and the dimension sensitivity analysis of near field pressures of two-dilating-spherical source is performed. The last application is devoted to a real sound source: a washing machine sitting on the floor. Sensitivity of the field pressures to the machine’s dimensions (size), surface velocity and frequency is examined on the bases of the boundary element model of the machine and half-space condition. The impacts of these variables are compared; and a limiting speed for the machine responding both the acoustical and operational requirements is determined.