Retention and mass transfer characteristics in reversed-phase liquid chromatography using a tetrahydrofuran-water solution as the mobile phase.

The characteristics of the retention and the mass transfer kinetics in reversed-phase liquid chromatography (RPLC) were measured on a system consisting of a C18-silica gel and a tetrahydrofuran-water (50:50, v/v) solution. These parameters were derived from the first and the second moments of the elution peaks, respectively. Further information on the thermodynamic properties of this system was derived from the temperature dependence of these moments. Some correlations previously established were confirmed for this system, namely, an enthalpy-entropy compensation for both retention and surface diffusion and a linear free-energy relationship. These results are compared with those observed in other similar systems using methanol-water (70:30, v/v) and acetonitnile-water (70:30, v/v) solutions. The contribution of surface diffusion to intraparticle diffusion in C18-silica gel particles was shown to be important. The analysis of the thermodynamic properties of surface diffusion suggests that, in these three RPLC systems, its activation energy is lower than the isosteric heat of adsorption. The nature and the extent of the influence of the mobile phase composition on the parameters describing the retention and the mass transfer kinetics are different but the chromatographic mechanisms involved in RPLC systems appear similar, irrespective of the nature of the organic modifier in the mobile phase.     

Separation of an isotope as a precursor of a gamma-raylaser medium

The nuclear isomer ¹⁷⁸Hf^m2, expected to be the most promising candidate for the gamma-ray medium, is rather difficult to produce in large quantities. There are a few ways to create this isomer, such as the irradiation of ¹⁷⁹Hf with high-energy neutrons through the (n,2n) reaction, the irradiation of ¹⁷⁶Yb with high-energy α particles through the (α,2n) reaction, the irradiation of ¹⁸¹Ta with protons through the (p,2p2n) reaction. In some of these reaction schemes the isotopically pure target works better than the natural one from the viewpoint of spectroscopic purity, handling of radioactive materials and productivity. However, isotope separation of heavy elements for producing a precursor as a target material is difficult in terms of cost/effectiveness. The atomic vapor laser isotope separation (AVLIS) method is expected as the most efficient way compared with the normal electromagnetic separation method. This revised version was published online in August 2006 with corrections to the Cover Date.     

Classifying spaces and homotopy sets of axes of pairings

We consider the maps between classifying spaces of the form . The main theorem shows that if the restriction map on is a weak epimorphism, then the restriction on should factor through the classifying spaces of the center of the compact Lie group . An application implies that is an H-space (Hopf space) if and only if is abelian.

     

New model of surface diffusion in reversed-phase liquid chromatography

A new model of surface diffusion in reversed-phase liquid chromatography (RPLC) was derived by assuming a correlation between surface and molecular diffusion. Analysis of surface diffusion data under different conditions of sample compounds, mobile and stationary phases, and temperature in RPLC systems validates this assumption and shows that surface diffusion should be regarded as a molecular diffusion restricted by the adsorptive interactions between the adsorbate molecule and the stationary phase surface. A surface-restricted molecular diffusion model was proposed as a first approximation for the mechanism of surface diffusion. The model is formulated according to the absolute rate theory. The activation energy of surface diffusion (Es) was quantitatively interpreted assuming that Es consists of the contributions of two processes, a hole-making and a jumping one. The former contribution is nearly equal to the activation energy of molecular diffusion and is correlated with the evaporative energy of the mobile phase solvent. The latter contribution is a fraction of the isosteric heat of adsorption. An appropriate explanation based on this new model of surface diffusion is provided for two contradictory results related to the relationship between retention equilibrium and surface diffusion in RPLC and to the surface diffusion coefficient for weakly retained sample compounds.     

Determination of midazolam and its metabolite as a probe for cytochrome P450 3A4 phenotype by liquid chromatography-mass spectrometry

This study demonstrated the analysis of midazolam and its metabolites by liquid chromatography-mass spectrometry (LC-MS) with a sonic spray ionization (SSI) interface. The analytical column was a YMC-Pak Pro C18 (50 mm x 2.0 mm i.d.) using 10 mM ammonium acetate (pH 4.8)-methanol (1:1) at a flow rate of 0.2 ml min(-1). The drift voltage was 100 V. The sampling aperture was heated at 110 degrees C and the shield temperature was 230 degrees C. The lower limits for the detection of midazolam and 1'-hydroxymidazolam were 26.3 and 112.76 pg injected, respectively. The calibration curves for midazolam and 1'-hydroxymidazolam were linear in the range of 0.1-5 microg ml(-1). Within-day relative standard deviations was less than 7%. The method was applied to the determination of midazolam in monkey plasma, and the analysis of midazolam and its metabolites in an in vitro study with recombinant cytochrome P450 (CYP) 3A4. This method is sufficiently sensitive and useful to elucidate the kinetics of midazolam metabolite formation. We also investigated the effect of propofol on the metabolism of midazolam using recombinant CYP3A4. Propofol competitively inhibited the metabolism of midazolam to 1'-hydroxymidazolam by CYP3A4.     

Investigation of nuclear-spin couplings in the lithium fluorides as possible candidates for crystal nuclear magnetic resonance quantum computing devices

We have performed ⁷Li and ¹⁹F nuclear magnetic resonance (NMR) in two lithium fluorides BaLiF₃ and YLiF₄ to explore the possibility of a crystal NMR quantum computing device. We find that (1) both the absolute values and the angular dependences of the line widths can primarily be accounted for by the nuclear dipolar fields, and (2) the spin–lattice relaxation times are long enough for quantum computations. These characteristics indicate that these crystals can be possible candidates for quantum computing devices. We also find that, in the perovskite structures like BaLiF₃, magic angles are quite effective to diminish the nuclear dipole fields, which enables us to treat some nuclei as ‘isolated’. We propose using this feature to create low-dimensional nuclear-spin networks in the crystals. Received: 29 January 2001 / Accepted: 6 February 2001 / Published online: 3 April 2001     

Bis(2,2′‐bi­pyridine‐κ2N,N′)(1,10‐phen­anthroline‐κ2N,N′)­ruthenium(II) tetra­cyano­platinate(II)

In the title compound, [Ru(C₁₀H₈N₂)₂(C₁₂H₈N₂)][Pt(CN)₄], cations and anions alternate along the a axis to afford a one‐dimensional network. The one‐dimensional character arises from the π–π stacking as well as from the electrostatic interactions formed between the phen (1,10‐phenanthroline) and [Pt(CN)₄]²⁻ units. Two adjacent one‐dimensional chains form further stacks based on the π–π stacking interactions between the phen moieties, where the interplanar spacing is 3.50 (1) Å.     

External mass transfer in high performance liquid chromatography systems

External mass transfer in a HPLC system operated in the reversed-phase mode was studied by pulse response experiments, using a column packed with non-porous C(18)-silica gel spherical particles, 18 microm in diameter. The first and second moments of the elution peaks, measured under different flow velocities and temperatures, were analyzed by the moment method to determine the external mass transfer coefficient (k(f)). The dependence of the Sherwood number on the Reynolds and the Schmidt numbers is almost the same as that observed in previous investigations of conventional literature correlations. The exponent of the last two nondimensional parameters was derived as being in the range from 0.28 to 0.41. When the Kataoka equation is used, the mean square deviation was calculated to be 0.21 for the values of k(f) estimated in this study. It is concluded that conventional correlations can be used to estimate k(f) values, even when the particle diameter is of the order of a micrometer.     

Evaluation of chromatographic performance of various packing materials having different structural characteristics as stationary phase for fast high performance liquid chromatography by new moment equations

Chromatographic performance of various separation media having different structural characteristics as the stationary phase for fast HPLC was quantitatively evaluated by using the new moment equations recently developed with considering the shape and porous structure of the packing materials. Four types of separation media, i.e., full-porous, partially porous (pellicular or shell) type, and non-porous spherical particles and full-porous cylindrical fiber, were chosen as examples. The moment equations were used for predicting the chromatographic behaviors of benzene under hypothetical RPLC conditions. The overall performance of the four types of packing materials as the separation media for fast HPLC was compared with each other from the viewpoint of the peak capacity, which depends on both the retention equilibrium and the mass transfer kinetics. It seems that the full-porous cylindrical fiber and the pellicular type spherical particle are more preferable than the others, i.e., the full-porous and non-porous spherical particles. Now we can use the new moment equations for the quantitative prediction of the chromatographic behaviors of the various packing materials on the basis of a related experimental information and for the evaluation of their performance from various chromatographic points of view. The new moment equations are effective not only for the detailed analyses of chromatographic behaviors but also for the preliminarily evaluation of new types of separation media for fast HPLC.