Hyperfine-structure and isotope-shift measurements in the 6s 5d↔6p 5d transitions of Ba I in the far-red spectral region

Measurements of the hyperfine structures in the 6p5d ¹ D ₂,³ D ₁ and³ F _{2, 3, 4} states of¹³⁵Ba and¹³⁷Ba, and isotope-shifts in several far-red transitions between the 6s 5d and 6p 5d configurations, as well as the transition 6s ^{2 1} S ₀→6s6p ³ P ₁ at 7,911 Å have been performed using high-resolution laser spectroscopy on a collimated atomic beam of natural barium. An analysis of the magnetic-dipole interaction in the 6p 5d configuration using effective one- and two-body hyperfine operators is presented. In particular the contact interaction was studied with respect to the correlation between the two valence electrons. Effects of strong configuration interaction were found. From a King-plot analysis of the isotope shift term- andJ-dependence of the field shift have been evaluated for the transitions between the 6s 5d and 6p 5d configurations. Relativistic Hartree-Fock (RHF) calculations have been performed of electron densities at the nucleus for six different configurations in Ba I and Ba II. The RHF calculations reproduce the experimental King-plot slopes quite well, while the absolute values, of the changes in electron density at the nucleus for the studied transitions, are found to be 9% lower than the results derived from a muonic experiment.     

Properties of Some Character Tables Related to the Symmetric Groups

We determine invariants like the Smith normal form and the determinant for certain integral matrices which arise from the character tables of the symmetric groups S_n and their double covers. In particular, we give a simple computation, based on the theory of Hall-Littlewood symmetric functions, of the determinant of the regular character table _RC of S_n with respect to an integer r 2. This result had earlier been proved by Olsson in a longer and more indirect manner. As a consequence, we obtain a new proof of the Mathas Conjecture on the determinant of the Cartan matrix of the Iwahori-Hecke algebra. When r is prime we determine the Smith normal form of _RC. Taking r large yields the Smith normal form of the full character table of S_n. Analogous results are then given for spin characters.Partially supported by The Danish National Research Council.Partially supported by NSF grant #DMS-9988459.     

Spin Representations,Powers of 2 and the Glaisher Map

Generalizing results on spin character degrees, we determine for a given conjugacy class of odd type in the double cover of S_n spin characters of S_n which have the minimal 2-power on this class in their character value. Surprisingly, the Glaisher map plays an important rôle here. Presented by L. Le BruynMathematics Subject Classifications (2000) 20C30, 05A15.     

Molecular beam surface ionization detection: II. Field reversal and surface ionization study of Na on Re with adsorbed oxygen

The desorption and surface ionization of Na on a polycrystalline Re surface with various amounts of adsorbed oxygen have been studied by field reversal, surface ionization and thermoelectronic emission methods. In this work the unique properties of the field reversal method are taken advantage of, i.e. that both neutral and ionic desorption rate constants can be determined simultaneously. Absolute ionization coefficients have been measured by field reversal and have been compared with values found by the “oxygen coverage” method and by static surface ionization. The application to beam flux density determinations is discussed. The simultaneous variation of the neutral and ionic desorption rate constants during oxygen adsorption and the temperature dependence of them have been studied. The Re surface in 2 × 10^?8 Torr of oxygen and at 1300–1500 K is shown to be very stable and to behave differently than in studies at higher temperatures. The very rapid change in both desorption rate constants at an effective work function Φ^e = 5.35 V is here correlated with the results of LEED experiments (Gorodetskii and Knysh) and is proposed to indicate a change from a stable Re oxide surface at low Φ^e (and oxygen coverage) to a different surface structure at higher Φ^e. Desorption energies have been determined at various values of Φ^e. The neutral desorption energy at low oxygen pressure is 2.70 ± 0.06 eV, which agress well with earlier, here corrected modulated beam results. The energy (Schottky) cycle for surface ionization is shown to be closed at low Φ^e, which has been difficult to show with other methods in any other case.     

The interaction between model biomaterial coatings and nylon microparticles as measured with a quartz crystal microbalance with dissipation monitoring

The interaction between cells and biomaterials has been mimicked using nylon microparticles as pseudo-cells and PLMA and PIBMA as biomaterial model acrylate polymers. The shift of fundamental resonance frequencies was negative for both polymers, indicating mass-coupling to the sensor surface. The shifts of the 3rd, 5th and 7th overtone frequencies were initially positive for both polymers, indicating a particle slip or wobbling on the surface. The QCM technique could discriminate between the two different polymers, showing increased interaction between microparticle and PLMA. The dissipation shift was positive for all overtones on both polymers, but again with faster and more prominent response for PLMA.     

Unusual vesicle-micelle transitions in a salt-free catanionic surfactant: temperature and concentration effects

The spontaneous formation of vesicles by the salt-free surfactant hexadecyltrimethylammonium octylsulfonate (TASo) and the features of an unusual vesicle-micelle transition are investigated in this work. In a previous work, we have shown that this highly asymmetric catanionic surfactant displays a rare lamellar miscibility gap in the concentrated regime. Here, we analyze in detail the aggregation behavior in the dilute regime (less than 3 wt % surfactant) as a function of both concentration and temperature. The phase diagram is dominated by a two-phase region consisting of a dispersion of a swollen lamellar phase (Lalpha') in the excess solvent phase (L1). Stable vesicles form in this two-phase region, and upon temperature increase, a transition to a single solution phase containing only elongated micelles occurs. The structural characterization of the aggregates and the investigation of their equilibrium properties have been carried out by light microscopy, cryo-TEM, water self-diffusion NMR, and SANS. Similarly to the lamellar-lamellar coexistence, the changes in microstructure at high dilution and high temperature can be understood from solubility differences, electrostatic interactions, and preferred aggregate curvature. Surface charge in the aggregates stems from the higher solubility of the octylsulfonate (So-) ion as compared to that of the hexadecyltrimethylammonium ion (TA+). Upon temperature increase, the ratio of free So(-) relative to the neutral TASo increases. Consequently, the surface charge density of the aggregates increases, and this ultimately induces a transition to a higher-curvature morphology (elongated micelles). Vesicles can also be spontaneously formed by cooling solutions from the micellar region, and the mean size obtained is practically independent of cooling rate, suggesting that dissociation/charge effects also control this process.     

Redox Properties and in Vivo Magnetic Resonance Imaging of Cyclodextrin-Polynitroxides Contrast Agents

This paper reports the synthesis, characterization and in vivo application of water-soluble supramolecular contrast agents (Mw: 5–5.6 kDa) for MRI obtained from β-cyclodextrin functionalized with different kinds of nitroxide radicals, both with piperidine structure ( CD2 and CD3 ) and with pyrrolidine structure ( CD4 and CD5 ). As to the stability of the radicals in presence of ascorbic acid, CD4 and CD5 have low second order kinetic constants (≤0.05 M⁻¹ s⁻¹) compared to CD2 (3.5 M⁻¹ s⁻¹) and CD3 (0.73 M⁻¹ s⁻¹). Relaxivity (r₁) measurements on compounds CD3 - CD5 were carried out at different magnetic field strength (0.7, 3, 7 and 9.4 T). At 0.7 T, r₁ values comprised between 1.5 mM⁻¹ s⁻¹ and 1.9 mM⁻¹ s⁻¹ were found while a significant reduction was observed at higher fields (r₁≈0.6-0.9 mM⁻¹ s⁻¹ at 9.4 T). Tests in vitro on HEK293 human embryonic kidney cells, L929 mouse fibroblasts and U87 glioblastoma cells indicated that all compounds were non-cytotoxic at concentrations below 1 μmol mL⁻¹. MRI in vivo was carried out at 9.4 T on glioma-bearing rats using the compounds CD3 - CD5 . The experiments showed a good lowering of T₁ relaxation in tumor with a retention of the contrast for at least 60 mins confirming improved stability also in vivo conditions.     

Yoctomole analysis of ganglioside metabolism in PC12 cellular homogenates

We report an ultrasensitive method for the analysis of glycosphingolipid catabolism. The substrate G(M1) and the set of seven metabolites into which it can be degraded (G(A1), G(M2), G(A2), G(M3), LacCer, GlcCer, and Cer) were labeled with the highly fluorescent dye tetramethylrhodamine. CE with LIF detection was used to assay these compounds with 150 +/- 80 yoctomole mass (1 ymol = 10(-24) mol = 0.6 copies) detection limits and 5 +/- 3 pM concentration detection limits. An alignment algorithm based on migration of two components was employed to correct for drift in the separation. The within-day and between-day precision in peak height was 20%, in peak width 15%, and in adjusted migration time 0.03%. After normalization to total sample injected, the RSD in peak height reduced to 2-6%, which approaches the limit set by molecular shot noise in the number of molecules taken for analysis. PC12 cells were incubated with the labeled G(M1). Fluorescent microscopy demonstrated uptake by the cells. CE was used to separate a cellular homogenate prepared from these cells. A set of peaks was observed, which were tentatively identified based on comigration with the standards. Roughly 120 pL of homogenate was injected, which contained a total of 150 zmol of labeled substrate and products. Metabolite that preserves the fluorescent label can be detected at the yoctomole level, which should allow characterization of this metabolic pathway in single cells.