Developments in the use and fabrication of organic monolithic phases for use with high-performance liquid chromatography and capillary electrochromatography

Capillary electrochromatography suffered in its development because of difficulty in producing stable columns with good permeability. Variability in frit characteristics gave rise to non-reproducible capillaries whose fabrication was extremely difficult and time consuming. Monolithic stationary phases gained popularity in the early 1990s due to the fact that they were easy to fabricate and required no retaining frits. They were also able to be manufactured in a wide variety of chemistries which made them very interesting to the analytical chemist who is constantly looking for materials with different selectivity to the popular silica-based stationary phases.     

Photofragmentation of closo-carboranes part 1: Energetics of decomposition

The ionic fragmentation following B 1s and C 1s excitation of three isomeric carborane cage compounds [closo-dicarbadodecaboranes: orthocarborane (1,2-C2B10H12), metacarborane (1,7-C2B10H12), and paracarborane (1,12-C2B10H12)] is compared with the energetics of decomposition. The fragmentation yields for all three molecules are quite similar. Thermodynamic cycles are constructed for neutral and ionic species in an attempt to systemically characterize single-ion closo-carborane creation and fragmentation processes. Lower energy decomposition processes are favored. Among the ionic species, the photon-induced decomposition is dominated by BH+ and BH2(+) fragment loss. Changes in ion yield associated with core to bound excitations are observed.     

Inhibitive properties and surface morphology of a group of heterocyclic diazoles as inhibitors for acidic iron corrosion

The heterocyclic diazoles 3-amino-1H-isoindole, indazole, imidazole, 4-bromoimidazole, 4-methylimidazole, pyrazole, 4-nitropyrazole, and 4-sulfopyrazole were investigated as corrosion inhibitors of iron in 1 M HCl using ac and dc techniques. The polarization curves showed a decrease in corrosion current for the inhibitor-containing solution. Impedance spectra demonstrate that the charge-transfer resistance in the presence of these inhibitors was greater than in inhibitor-free solution, except for 4-nitropyrazole. The resistance increased with inhibitor concentration and with immersion time. The structural and electronic parameters of these diazoles were calculated using computational methodologies. The elemental composition and the speciation of the treated surfaces were investigated via XPS measurements, and morphological changes were monitored by vertical scanning interferometery.     

Acoustic properties of rarefied gases inside pores of simple geometries

Analytical solutions describing propagation of monochromatic acoustic waves inside long pores of simple geometries and narrow flat slits are obtained with accounting for gas rarefaction effects. It is assumed that molecular nature of gas is important in Knudsen layers near solid boundaries. Outside the Knudsen layers, the continuum approach is used. This model allows for extension of acoustic analysis to regions of low pressures and microscopic cross-sectional sizes of channels. The problem is solved using linearized Navier-Stokes equations with the boundary conditions that resulted from the first-order approximation with respect to small Knudsen number Kn. For slits and pores of circular and square cross sections, the theoretical dependencies of the dynamic density in the low-frequency range are compared with those that resulted from known experimental data on steady-state flows of rarefied gases in uniform channels. Despite the formal restriction Kn < 1 of asymptotic analysis, the theoretical model agrees well with experiments up to Kn approximately 5. It is shown that the molecular phenomena affect acoustic characteristics of micro-channels and pores starting from relatively small Knudsen numbers Kn > 0.01, especially at low frequencies. The obtained results may be used for analyses of acoustic properties of waveguides, perforated panels, micro-channels and pores in wide range of gas pressures as well as for stationary flows of rarefied gases through long uniform pipes etc.     

Static circularly symmetric perfect fluid solutions with an exterior BTZ metric

In this work we study static perfect fluid stars in 2+1 dimensions with an exterior BTZ spacetime. We found the general expression for the metric coefficients as a function of the density and pressure of the fluid. We found the conditions to have regularity at the origin throughout the analysis of a set of linearly independent invariants. We also obtain an exact solution of the Einstein equations, with the corresponding equation of state p = p(), which is regular at the origin.     

New limit on the neutrinoless betabeta decay of 130Te

We report the present results of CUORICINO, a search for neutrinoless double-beta (0nu betabeta) decay of 130Te. The detector is an array of 62 TeO2 bolometers with a total active mass of 40.7 kg. The array is cooled by a dilution refrigerator shielded from environmental radioactivity and energetic neutrons, operated at approximately 8 mK in the Gran Sasso Underground Laboratory. No evidence for (0nu betabeta) decay was found and a new lower limit, T(1/2)(0nu) > or = 1.8 x 10(24) yr (90% C.L.) is set, corresponding to [m(nu)] < or = 0.2 to 1.1 eV, depending on the theoretical nuclear matrix elements used in the analysis.     

Nonlinear response theory with relaxation: the first-order hyperpolarizability

Based on the Ehrenfest theorem, an equation of motion that takes relaxation into account has been presented in wave-function theory, and the resulting response functions are nondivergent in the off-resonant as well as the resonant regions of optical frequencies. The derivation includes single- and multideterminant reference states. When applied to electric dipole properties, the response functions correspond to the phenomenological sum-over-states expressions of Orr and Ward [Mol. Phys. 20, 513 (1971)] for polarizabilities and hyperpolarizabilities of an isolated system. A universal dispersion formula is derived for the complex second-order response function. Response theory calculations are performed on lithium hydride and para-nitroaniline for off-resonant and resonant frequencies in the electro-optical Kerr effect and second-harmonic generation.     

Optical crystallographic properties of some antihistaminic compounds

Summary The optical crystallographic properties of eleven antihistamines have been determined. The optical properties vary sufficiently so that identification of the individual members is possible.

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Zusammenfassung Die physikalischen und optischen Konstanten der Kristalle von elf Anti-histaminen wurden bestimmt. Die optischen Eigenschaften unterscheiden sich genügend, um die Identifizierung einzelner Glieder der untersuchten Gruppe möglich zu machen.

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Résumé Les propriétés cristallographiques optiques de onze antihistaminiques ont été déterminées. Les propriétés optiques varient de façon suffisante pour permettre l'identification de chacun des individus.

     

INHIBITION AND ENHANCEMENT OF SINGLET OXYGEN ('Ag) DIMOL CHEMILUMINESCENCE

Abstract— Various nitrogen containing compounds have previously been shown to quench singlet oxygen (10z). When measuring the dimol ¹O₂ light emission arising from the H ₂O₂ /OCI- reaction, we found that certain cyclic diamines increase the emission of light, while other amines were inhibitory. This increase of light emission was seen with both 1, 4diazabicyclo[2.2.2]octane and N, N'-dimethylpi-perazine but not with acyclic analogues. Sodium azide inhibited both the normal and enhanced light emission. The enhanced light emission shows spectral properties characteristic of ^lO₂ dimol emission.     

Stirring of a viscous fluid

Zusammenfassung Untersucht wird die stationäre strömende Geschwindigkeit, die durch eine kreisförmige rührende Bewegung eines starren Zylinders induziert wird. Die Amplitude dieser kreisförmigen Bewegung wird im Vergleich zum Durchmesser des Zylinders als klein angenommen. Es wird gezeigt, dass bei genügend hohen Frequenzen der nicht-stationäre Wirbeleffekt auf eine dünne Stokes-Scherwellenschicht beschränkt ist, dass aber die induzierte Strömung ausserhalb dieser Region bestehen bleibt. Für den besonderen Fall eines runden Zylinders ergibt sich, dass diese stationäre Strömung von der Reynolds-Zahl unabhängig ist.