Thermal decomposition rate of N2O5 measured by cavity ring‐down spectroscopy

The thermal decomposition rate of N₂O₅ in 760 Torr of air as a function of temperature between 314 and 348 K has been investigated using the technique of pulsed laser cavity ring-down spectroscopy (CRDS) detection of NO₃ radicals at 662 nm. The Arrhenius expression of the thermal decomposition rates determined by the CRDS experiments, which is incorporated with literature values down to 263 K, is given by 1.36 × 10¹⁵ exp{(−11300 ± 200)/T} s⁻¹ over the temperature range 263–348 K. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 679–684, 2008     

Effect of the silanization conditions on chromatographic behavior of an open-tubular capillary column coated with a modified silica-gel thin layer.

The performance of an open-tubular capillary column coated with a modified silica-gel thin layer was investigated, particularly concerning the effect of the silanization process on it. Although the increase in the octadecyltriethoxysilane (ODTES) concentration in the silanization process could enhance the retention factor of naphthalene, its theoretical plate number was significantly reduced (ODTES, 5 to 50%; k, 0.2 to 4.3; N, 79600 to 2600 m(-1)). Namely, the increase in the retention factor was accompanied by a decrease in the theoretical plate number. A similar phenomenon was also observed when octadecyldimethylchlorosilane (ODCS) was used as the silanization regent. However, increases in both the retention factor and the theoretical plate number could be achieved (sample, naphthalene; k, 0.05 to 0.09; N, 149000 to 220000 m(-1)) by a NaOH treatment to the fabricated thin porous silica-gel layer before silanization with ODCS. The electrochromatographic separation of proteins and peptides by using the NaOH-treated column could obtain more peaks than electrophoretic separation.     

Vacuum UV laser-induced fluorescence study of the collisional removal of Br(P1/2) atoms by small molecules

This Letter reports on the application of the vacuum ultraviolet laser-induced fluorescence detection of Br(²P_1/2) atoms at 157.48 nm to the kinetic study of collisional removal of Br(²P_1/2) by small molecules at 295 K. Gas mixtures of a small amount of CH₃Br and an excess amount of collision partners are exposed to pulsed laser irradiation at 193 nm. Temporal decay profile of the Br* LIF intensity has been monitored to determine the collisional removal rate coefficients. The collision partners are H₂, CO₂, CF₄, CF₂H₂, H₂O, CH₃OH, and SF₅CF₃, and the results are compared to literature data.     

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.     

Enantioselective radical cyclizations: a new approach to stereocontrol of cascade reactions

Stereocontrol in a cascade radical addition-cyclization-trapping reaction was achieved by a new approach, which utilizes a hydroxamate ester moiety as a coordinating chiral Lewis acid tether between two radical acceptors. A remarkable feature of this reaction is the construction of three bonds and tertiary and quaternary stereogenic centers through both inter- and intramolecular carbon-carbon bond-forming processes. The chiral Lewis acid mediated reaction of oxime ethers also proceeded smoothly with good enantio- and diastereoselectivities, indicating the usefulness of the cascade approach for the asymmetric synthesis of various gamma-lactams.     

Surface diffusion in reversed-phase liquid chromatography using silica gel stationary phases of different C1 and C18 ligand densities

Surface diffusion phenomena were studied from kinetic and thermodynamic points of view. The existence of a linear free energy relationship between surface diffusion and the retention equilibrium suggests that the mechanism of surface diffusion is the same irrespective of the density of C(1) and C(18) ligands. Surface diffusion coefficient (D(s)) of weakly retained compounds seems to be of the same order of magnitude with corresponding molecular diffusivity. There would be an intimate correlation between surface diffusion and molecular diffusion. The value of D(s) decreases with increasing retention strength. The magnitude of the restriction for surface diffusion is comparable to about one third the enthalpy change due to the sample retention. This means that it is necessary for sample molecules adsorbed to be partially desorbed from the stationary phase surface when they migrate by surface diffusion. The results of this study provide the fundamental information for developing an appropriate model of surface diffusion, which explains some intrinsic characteristics and mechanism of surface diffusion.     

Moment analysis of chromatographic behavior of superficially porous particles

Peak parking experiments were conducted to study the chromatographic behavior in a RPLC system consisting of a column packed with superficially porous C(18)-particles and a mixture of methanol and water (70/30, v/v). The values of the surface diffusion coefficient and the retention equilibrium constant of a column packed with superficially porous C(18)-particles were comparable to those of columns packed with a C(18)-silica monolith and full-porous C(18)-silica gel particles. The flow-rate dependence of HETP was hypothetically calculated by using moment equations to clarify the influence of the structural characteristics on the chromatographic behavior. The column efficiency of a column packed with the superficially porous particles is higher in the high flow-rate range than that with full-porous spherical particles. This is attributed to the smaller contribution of the intraparticulate mass transfer in the superficially porous particles to band broadening. The moment equations are effective for the quantitative analysis of chromatographic behavior of superficially porous particles.     

Absorption spectroscopy of uranium plasma for remote isotope analysis of next-generation nuclear fuel

CdSe/Se multilayer thin films were prepared using sequential thermal evaporation technique by varying the thickness of selenium sublayers. Identifying the prominent peaks observed in the XRD spectra of the top layer CdSe which corresponds to the (100) plane with wurtzite structure, the average size of the crystallites was calculated for the CdSe nanocrystals. Experimentally measured band gaps are larger than bulk band gap of CdSe. This confirms the presence of spin-orbit splitting of energy levels. Size of the crystallites was then calculated with the theoretical prediction of the effective mass approximation model (i.e., Brus model). It resulted in that the diameters of crystallites were much smaller than the Bohr exciton diameter (11.2 nm) of CdSe. Thus the structural and optical properties of CdSe/Se multilayer thin films reveal the effect of quantum confinement of CdSe crystallites in Se matrix for various sublayer thicknesses. Confinement effect is more pronounced while sublayer thickness of selenium increases.     

Rapid identification of microorganisms by mass spectrometry: improved performance by incorporation of in-house spectral data into a commercial database

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is increasingly used as a microbial diagnostic method for species identification of pathogens. However, MALDI-TOF identification of bacteria at the species level remains unsatisfactory, with the major problem being an incomplete database that still needs refinement and expansion. Augmentation of the original MALDI BioTyper 2.0 (Bruker) database by incorporating mass spectra obtained in-house from clinical isolates may increase the identification rate at the species level. We conducted a prospective study to assess whether the augmented database can improve the performance of MALDI-TOF MS for routine identification of species. Cluster analyses revealed distinct differences in MS spectral profiles of clinical isolates obtained in our hospital and those of ATCC strains in the Bruker database. In the first part of the study, which was performed over 3 weeks, 259 bacterial isolates were subjected to analysis by MALDI-TOF MS, and MS spectra of 229 successfully identified isolates (49 species) were incorporated into the original database to give the augmented Bruker-Chiba database. In a second separate analysis, the concordance of identification of 498 clinical isolates of the 49 species with conventional methods was 87.1% (434/498) with the commercial Bruker database and 98.0% (488/498) using the Bruker-Chiba database. These results indicate that refinement of a commercial database can be achieved relatively easy and effectively by incorporating MS spectra of clinical isolates obtained in a clinical laboratory.