Identification of ethyl pyruvate and dihydrocinchonidine adducts by electrospray ionization mass spectrometry

Several ethyl pyruvate and dihydrocinchonidine adducts, formed by non-covalent interactions with alkali cations, have been identified for the first time using electrospray ionization mass and tandem mass spectrometry. This type of adduct may have an important role in asymmetric reactions of pyruvates in the presence of cinchonas.     

Ultrasonics in heterogeneous metal catalysis: sonochemical chemo- and enantioselective hydrogenations over supported platinum catalysts

Sonochemical chemo- and enantioselective hydrogenations over supported platinum catalysts are described. We disclose our results with respect to a sonochemical modification of the chemoselective hydrogenation of cinnamaldehyde over supported platinum catalysts, and the asymmetric hydrogenation of ethyl pyruvate promoted by various ultrasonic pretreatments. The ultrasonic pretreatment of the supported platinum catalysts was found to be highly beneficial in almost every case, improving both the catalytic activity and selectivity. The effect of additional experimental variables, such as hydrogen pressure, catalyst support, temperature and the ultrasonic insonation time were also studied. The enantioselectivity of the hydrogenation of ethyl pyruvate increased up to 97.1% ee. In the case of cinnamaldehyde hydrogenation, the selective preparation of cinnamyl alcohol became possible. The theoretical aspects of the working mechanisms in comparison with 'silent' reactions will also be provided.     

Investigation of chiral reactions: the structural detection of new hydrogenated isocinchona alkaloids from mixtures without isolation using electrospray ionization tandem mass spectrometry

The reaction mixture for the hydrogenation of ethyl pyruvate on Pt-alumina catalyst modified with isocinchona alkaloids (alpha-ICN (I) and beta-ICN (II)) was studied by electrospray ionization tandem mass spectrometry (ESI-MS/MS). It was established that part of the chiral modifiers themselves are converted into ions of m/z 299, 305 and 309 in the course of chiral hydrogenation. The experimental data allowed the determination of the probable structure of the ions mentioned. According to ESI-MS/MS spectra the structure of the new cinchona alkaloids was assumed: tetrahydro-isocinchonines (III-VI), decahydro-isocinchonines (VII, VIII) and hydrogenated compounds of VII and VIII by scission of their C--N and C--O bonds (IX/1, IX/2, X). Fragmentation pathways are proposed for these new compounds.     

Dynamic Global Constraints in Backtracking Based Environments

Global constraints provide strong filtering algorithms to reduce the search space when solving large combinatorial problems. In this paper we propose to make the global constraints dynamic, i.e., to allow extending the set of constrained variables during search. We describe a generic dynamisation technique for an arbitrary monotonic global constraint and we compare it with the semantic-based dynamisation for the alldifferent constraint. At the end we sketch a dynamisation technique for non-monotonic global constraints. A comparison with existing methods to model dynamic problems is given as well.     

Regular partitions of dual polar spaces

We describe several classes of regular partitions of dual polar spaces and determine their associated parameters and eigenvalues. We also give some general methods for computing the eigenvalues of regular partitions of dual polar spaces.     

Numerical study of the flow in a three-dimensional thermally driven cavity

Solutions for the fully compressible Navier–Stokes equations are presented for the flow and temperature fields in a cubic cavity with large horizontal temperature differences. The ideal-gas approximation for air is assumed and viscosity is computed using Sutherland's law. The three-dimensional case forms an extension of previous studies performed on a two-dimensional square cavity. The influence of imposed boundary conditions in the third dimension is investigated as a numerical experiment. Comparison is made between convergence rates in case of periodic and free-slip boundary conditions. Results with no-slip boundary conditions are presented as well. The effect of the Rayleigh number is studied.     

Fortschritte in der analytischen Chemie seltener Metalle

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