Enantioselective separations by capillary GC on derivatized cyclodextrins. Part 2: Determination of enantiomeric excess of some racemic 2,3-isopropylidene-1,2,3-cyclohexanetriol derivatives on permethyl α-, β-, and γ-cyclodextrins

Capillary GC on permethyl α-, β-, and γ-cyclodextrins has been applied to separate and quantify the enantiomers of some 2,3-iso-propylidene-1,2,3-cyclohexanetriol derivatives. Quantitative CGC data are compared to those obtained with chiral shift ¹H NMR.     

Determination of iphosphamide and seven metabolites in blood plasma,as stable trifluoroacetyl derivatives,by electron capture chemical ionization GC-MS

A method is described for the determination of the antitumor agent iphosphamide and seven of its metabolites in the plasma of cancer patients by multiple ion monitoring (MIM) GC-MS, mainly using the electron capture chemical ionization mode, of stable methyl and/or trifluoroacetyl derivatives. The metabolites determined were 2- and 3-dechloroethyliphosphamide, 4-ketoiphosphamide, carboxyiphosphamide, iphosphamide mustard, and two previously undetected metabolites, chloroethylamine and 1,3-oxazolidine-2-one. The isolation of the acidic and neutral metabolites was performed by solid phase extraction on to C₁₈ adsorbent at pH 4. The weakly acidic iphosphamide mustard, isolated under these conditions with a yield of ca 50%, was measured as a stable methyltrifluoroacetyl derivative, in contrast to the corresponding phosphoramide mustard of the isomer cyclophosphamide which decomposes during derivatization. Chloroethylamine and 1,3-oxazolidine-2-one were isolated with high yield by liquid extraction with ethyl acetate at pH 10. Selective measurement of several metabolite derivatives with similar retention times was performed by multiple ion monitoring MS of specific ion masses, using a methyl phenyl siloxane capillary column previously employed in the study of cyclophosphamide metabolites. Quantitation of metabolites in patient plasma samples could be performed in the concentration range 3 ng to 20 μg per ml of original plasma.     

Special geometry,cubic polynomials and homogeneous quaternionic spaces

The existing classification of homogeneous quaternionic spaces is not complete. We study these spaces in the context of certainN=2 supergravity theories, where dimensional reduction induces a mapping betweenspecial real, Kähler and quaternionic spaces. The geometry of the real spaces is encoded in cubic polynomials, those of the Kähler and quaternionic manifolds in homogeneous holomorphic functions of second degree. We classify all cubic polynomials that have an invariance group that acts transitively on the real manifold. The corresponding Kähler and quaternionic manifolds are then homogeneous. We find that they lead to a well-defined subset of the normal quaternionic spaces classified by Alekseevskiî (and the corresponding special Kähler spaces given by Cecotti), but there is a new class of rank-3 spaces of quaternionic dimension larger than 3. We also point out that some of the rank-4 Alekseevskiî spaces were not fully specified and correspond to a finite variety of inequivalent spaces. A simpler version of the equation that underlies the classification of this paper also emerges in the context ofW ₃ algebras.Communicated by K. Gawedzki     

Investigation of the Separation of Higher Fatty Acid Methyl Esters by Reversed-Phase HPTLC

JPC – Journal of Planar Chromatography – Modern TLC - Separations of eight methyl esters of higher fatty acids on RP-18 stationary phase with methanol—water and...     

Consequences of an algorithm for bridged graphs

Chepoi showed that every breadth first search of a bridged graph produces a cop-win ordering of the graph. We note here that Chepoi's proof gives a simple proof of the theorem that G is bridged if and only if G is cop-win and has no induced cycle of length four or five, and that this characterization together with Chepoi's proof reduces the time complexity of bridged graph recognition. Specifically, we show that bridged graph recognition is equivalent to (C₄,C₅)-free graph recognition, and reduce the best known time complexity from O(n⁴) to O(n^3.376).     

Synthesis of enantiomeric-pure cyclohexenyl nucleoside building blocks for oligonucleotide synthesis

Lipases were used for the resolution of (±) (4aR, 7R, 8aS)-2-phenyl-4a,7,8,8a-tetrahydro-4H-1,3-benzodioxine. This separation was carried out on preparative scale and used for the synthesis of eight phosphoramidites of cyclohexenyl nucleosides (d- and l-series).     

Local effect of electric and magnetic fields on the position of an attached shock in a supersonic diffuser

Effective ways for controlling shock wave configurations by means of external actions are sought. One such way is a local effect of electric and magnetic fields. In this paper, the local effect of external fields is implemented by current localization in a limited region of a diffuser. The experiment is carried out in a diffuser providing the complete internal compression of the gas with a Mach number at the inlet M=4.3. As a working medium, a xenon plasma is used. The plasma flow is formed in a shock tube equipped with an accelerating nozzle. Two ways of current localization are tested. In the first one, the diffuser inlet is a short channel of Faraday generator type. In this case, the ponderomotive force basically decelerates or accelerates the flow depending on the direction of the electric field. In the second way, the current flows through a narrow near-wall region between adjacent electrodes. In this case, the ponderomotive force compresses or expands the gas. In both cases, it is shown that the angle of an attached shock due to MHD interaction can be both decreased and increased. The central problem with the MHD control of shock waves is near-electrode and near-wall phenomena.     

A simple proof of an inequality of Bourgain,Brezis and Mironescu

A simpler proof of a recent inequality of Bourgain, Brezis and Mironescu is given. To cite this article: J. Van Schaftingen, C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

Metallo‐supramolecular micelles: Studies by analytical ultracentrifugation and electron microscopy

In aqueous solutions, amphiphilic block copolymers in which a polystyrene (PS) segment is connected to a poly(ethylene oxide) (PEO) block via a bis(2,2′:6′,2″‐ terpyridine ruthenium) complex can form micelles. Such micelles of the protomer type PS₂₀‐[Ru]‐PEO₇₀, according to the preparation procedure representing frozen micelles, were studied by sedimentation velocity and sedimentation equilibrium analysis in an analytical ultracentrifuge and by transmission electron microscopy, with different techniques applied for the sample preparation. The particles obtained were surprisingly multifarious in size. In ultracentrifugation experiments performed at relatively low salt concentrations, the distributions of the sedimentation coefficient s_20,w showed a pronounced peak at 9.6 S and a broad, only partly separated second peak around 14 S. The molar mass of the particles at the peak was around 430,000 g/mol, corresponding to an aggregation number of approximately 85. The average hydrodynamic diameter of the particles in the peak fraction was approximately 13 nm. In electron micrographs of negatively stained samples, spheres of diameters between 10 and 25 nm were the most abundant particles, but larger ones with a wide size range were also visible. The latter particles apparently were composed of smaller ones. The data from both sedimentation analysis and electron microscopy showed that (1) the studied compound formed primary micelles of diameters around 20 nm and (2) the primary micelles had a tendency toward aggregation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3159–3168, 2003