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.     

Distribution of melamine in polyester–melamine surface coatings cured under nonisothermal conditions

The influence of experimental cure parameters on the diffusion of reactive species in polyester–melamine thermoset coatings during curing has been investigated with X‐ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared. The diffusion of melamine plays a vital role in the curing process and, therefore, in the ultimate properties of coatings. At a low (<20%) hexamethoxymethylmelamine (HMMM) crosslinker concentration, the matrix composition is uniform, but at high HMMM concentrations, excess HMMM rapidly segregates to the air–coating interface. The rate of migration is governed by the difference in the surface free energies of polyester and HMMM and the concentration gradient of HMMM between the bulk and the surface. An increased rate of energy absorption also increases the rate of migration of HMMM to the surface. A physical model has been proposed to explain this surface segregation phenomenon in terms of cocondensation and self‐condensation reactions. It suggests that an appropriate amount of melamine can be segregated on the surface and allowed to self‐condense to form a desired thickness of a melamine topcoat through the control of the binder composition and cure conditions. This technique can be implemented to apply a melamine topcoat during cure. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 83–91, 2004     

The effect of Fe and Ru substitution on the superconductivity in MgCNi3

We report the effects of partial substitutions of the VIIIa elements: Fe (3d) and Ru (4d) in the intermetallic perovskite superconductor MgCNi₃. In both the MgCNi_3−xRu_x and MgCNi_3−xFe_x systems, the superconducting critical temperature (T_C) decreases monotonically as x is increased. T_C decreases more slowly in the case of Ru, suggesting that the 3d electrons in Fe are magnetically pair breaking. This is supported by the normal state magnetic susceptibility measurements (χ), which shows that χ increases with Fe and decreases with Ru doping. No ferromagnetism is observed in either system.     

Magnetic pole pinning at rectangular defects on MnAs/GaAs(0 0 1)

Strong magnetic poles at characteristic rectangular defects have been observed using a magnetic force microscope on a MnAs(  1 0 0) thin film with the thickness of 30 nm. The MnAs thin film was epitaxially grown on a GaAs(0 0 1) substrate. The magnetic poles were in one-arranging direction, being independent of the magnetization direction of the film. The poles were pinned at the edges of the rectangular defects until just below the Curie temperature, and formed a stable magnetic-field loop on the MnAs surface. The stability of the magnetic pole pinning shows the distinctive feature of the magnetic domain structure on the surface with a strong anisotropy, which was built in the heterostructure of MnAs and GaAs.