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Guido Momerency Karel Van Cauwenberghe Ernst A. De Bruijn Allan T. Van Oosterom Martin S. Highley Peter G. Harper 《Journal of separation science》1994,17(9):655-661
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. 相似文献
3.
Improved reaction conditions for the preparation of poly(p‐phenylene sulfide) (PPS) directly from bis(4‐bromophenyl) disulfide (BBD) have been established. Heating BBD with magnesium metal afforded only a low molecular weight polymer. PPS with a melting temperature around 280 °C was obtained from BBD in the presence of sodium carbonate or zinc metal. The best results were obtained with the addition of a catalytic amount of KI to the zinc–BBD mixture. Polymers prepared by the above methods are semicrystalline and dissolve in 1‐chloronaphthalene and have properties comparable to commercial PPS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 900–904, 2006 相似文献
4.
Allan Pinkus 《Constructive Approximation》1988,4(1):85-96
C 1(K) is the space of real continuous functions onK endowed with the usualL 1,-norm where \(K = \overline {\operatorname{int} K}\) is compact inR m · U is a finite-dimensional subspace ofC 1,(K). The metric projection ofC 1,(K) ontoU contains a continuous selection with respect toL 1, -convergence if and only ifU is a unicity (Chebyshev) space forC 1,(K). Furthermore, ifK is connected andU is not a unicity space forC 1,(K), then there is no continuous selection with respect toL ∞-convergence. An example is given of aU and a disconnectedK with no continuous selection with respect toL 1-convergence, but many continuous selections with respect toL ∞-convergence. 相似文献
5.
Analysis of caffeine and its metabolites is of interest with respect to caffeine exposure, for kinetic and metabolism studies and for opportunistic in vivo estimation of drug metabolizing enzyme activity in humans and animals. For the latter, analysis is usually done by high-performance liquid chromatography (HPLC) with UV detection. However, this method is close to the detection limit for certain of the metabolites and requires very long chromatography, 30-60 min. We have developed a fast method for the quantification of caffeine and its metabolites 1-methylxanthine, 1-methyluric acid, 1,7-dimethyluric acid, 5-acetylamino-6-amino-3-methyluracil (AAMU) and 5-acetylamino-6-formylamino-3-methyluracil (AFMU) by HPLC tandem mass spectrometry (MS/MS) in urine that requires only its dilution with buffer and centrifugation before injection into the HPLC/MS/MS system. The chromatography lasts 7 min and is followed by 4.5 min for re-equilibration of the HPLC column, giving a total analysis time of 11.5 min. The method provides a great sensitivity improvement with detection limits for all analytes 相似文献
6.
Three new Ni(BDC)/2,2'-bipy compounds, Ni2(BDC)(HBDC)2(2,2'-bipy)2 (2), Ni3(BDC)3(2,2'-bipy)2 (3), and Ni(BDC)(2,2-bipy)2.2H2O (5), in addition to the previously reported Ni(BDC)(2,2'-bipy).0.75H2BDC (1) and Ni(BDC)(2,2'-bipy)(H2O) (4) [BDC = 1,4-benzenedicarboxylate; 2,2'-bipy = 2,2'-bipyridine], have been synthesized by hydrothermal reactions. A systematic investigation of the effect of the reaction temperature and pH resulted in a series of compounds with different compositions and dimensionality. The diverse product slate illustrates the marked sensitivity of the structural chemistry of polycarboxylate aromatic ligands to synthesis conditions. Compound 1, which has a channel structure containing guest H2BDC molecules, is formed at the lowest pH. The guest H2BDC molecules are connected by hydrogen bonds and form extended chains. At a slightly higher pH, a dimeric molecular compound 2 is formed with a lower number of protonated carboxylate groups per nickel atom and per BDC ligand. Reactions at higher temperature and the same pH lead to the transformation of 1 and 2 into the two-dimensional, layered trinuclear compound 3. As the pH is increased, a one-dimensional polymer 4 is formed with a water molecule coordinated to Ni2+. Bis-monodentate and bischelating BDC ligands alternate along the chain to give a crankshaft rather than a regular zigzag arrangement. A further increase of the pH leads to the one-dimensional chain compound 5, which has two chelating 2,2'-bipy ligands. Crystal data: 2, triclinic, space group P, a = 7.4896(9) angstroms, b = 9.912(1) angstroms, c = 13.508(2) angstroms, alpha = 86.390(2) degrees , beta = 75.825(2) degrees, gamma = 79.612(2) degrees, Z = 2; 3, orthorhombic, space group Pbca, a = 9.626(2) angstroms, b = 17.980(3) angstroms, c = 25.131(5) angstroms, Z = 4; 5, orthorhombic, space group Pbcn, a = 14.266(2) angstroms, b = 10.692(2) angstroms, c = 17.171(2) angstroms, Z = 8. 相似文献
7.
Paul V. Bernhardt Dr. Geoffrey A. Lawrance Brian W. Skelton Allan H. White 《无机化学与普通化学杂志》2007,633(7):1036-1039
Cations derived by protonation of the ligand title compound (L1) have been structurally characterized in their di‐ and tetra‐ protonated forms in the salts [H2L1][ClO4]2·2H2O and [H4L1][ZnCl4]2·4H2O. In both structures, one half of the formula unit comprises the asymmetric unit of the structure, the macrocycle being centrosymmetric, with the two macrocycles adopting similar conformations. In both salts, a pair of diagonally opposed macrocyclic secondary amine groups are protonated; in the [H4L1]4+ salt, the additional pair of protons are accommodated on the exocyclic pendant amine groups. The dispositions of the pendent amines differ between the two structures, being ‘equatorial’ with respect to the macrocyclic ring in the [H2L1]2+ salt, and ‘axial’ in the [H4L1]4+ salt. In other structurally characterized compounds containing [H4L1]4+ the equatorial disposition was found in the ferricyanide adduct, while in the tetraperchlorate salt the axial disposition was identified. The differences in disposition of the exocyclic groups are ascribed to the extensive H‐bonding in the lattices. 相似文献
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10.
M. Terao C. Harel A. Salin R. J. Allan 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1988,7(4):319-332
We present a detailed theoretical treatment of single-electron transfer between He2+ and H?. The total cross section is calculated using stationary molecular states which are appropriate in the energy range covered by the experiments (between 0.5 and 2250 eV in the centre of mass frame). We use an expansion on a two-electron basis built with one-electron diatomic molecule (OEDM) orbitals and including the common translation factor of Errea et al. All coupling terms are calculated explicitly. Because of the small binding energy of H? compared to that of the ground state of He+, capture occurs into highly excited states of He+. Results obtained with a straight-line quasiclassical calculation are in good agreement with the experimental data. At low energy, He+ (n=5) +H(1s) is the dominant capture channel; at higher energy, the He+ (n=4) + H(1s) channel becomes important. The rise in the cross section below 6 eV can be attributed to the Coulomb attraction in the incoming channel. To account for this effect, a fully quantal calculation has been performed. The agreement with the low-energy measurements is then excellent. 相似文献