Selenium-catalyzed oxidative halogenation

Organoselenides catalyze the oxidation of halides by H₂O₂. Furthermore, these selenides catalyze the transfer of oxidized halogens from N-halosuccinimides to olefins and ketones. Thus, organoselenides catalyze oxidative halogenation reactions including halolactonization, α-halogenation of ketones, and allylic halogenation. The ability of selenium to undergo reversible 2e⁻ oxidation-reduction chemistry facilitates halogenation through selenium-bound halogen intermediates.     

A SAXS study of the nanostructural characteristics of TEOS-derived sonogels upon heat treatment up to 1100 °C

Xerogels obtained from the acid-catalyzed and ultrasound stimulated hydrolysis of TEOS were submitted to heat treatment at temperatures ranging from 60 to 1100 °C and studied by small-angle X-ray scattering (SAXS). The SAXS intensity as a function of the modulus of the scattering vector q was obtained in the range from q₀=0.19 to q_m=4.4 nm⁻¹. At 60 °C the xerogels exhibit an apparent surface fractal structure with a fractal dimension D_S∼2.5 in a length scale ranging from 1/q₁∼1 to 1/q_m∼0.22 nm. This structure becomes extremely rough at 120 °C (D_S∼3) and at 150 °C, it apparently converts to a mass fractal with a fractal dimension D∼2.4. This may mean an emptying of the pores with preservation of a share of the original mass fractal structure of the wet aged gel, for it had presented a mass fractal dimension D∼2.2. A well characterized porous structure formed by 2.0 nm mean size pores with smooth surface of about 380 m²/g is formed at 300 °C and remains stable until approximately 800 °C. At 900 °C the SAXS intensity vanishes indicating the disappearance of the pores in the probed length scale. The elimination of the nanopores occurs by a mechanism in which the number of pores diminishes keeping constant their mean size. The xerogels exhibit a foaming phenomenon above 900 °C and scatter following Porod's law as does a surface formed by a coarse structure.     

Linguistic knowledge and new technologies

Modern language studies are characterized by a variety of forms, ways, and methods of their development. In this connection, it is necessary to specify the problem of the development of their internal differentiation and classification, which lead to the formation of specific areas knowledge. An example of such an area is speechology—a field of science belonging to fundamental, theoretical, and applied linguistics.     

Unconventional antiferromagnetic correlations of the doped Haldane gapsystem Y 2 BaNi 1 - x Zn x O 5

We make a new proposal to describe the very low temperature susceptibility of the doped Haldane gap compound Y₂BaNi_1-xZn_xO₅. We propose a new mean field model relevant for this compound. The ground state of this mean field model is unconventional because antiferromagnetism coexists with random dimers. We present new susceptibility experiments at very low temperature. We obtain a Curie-Weiss susceptibility χ( T ) ∼ C /(Θ + T ) as expected for antiferromagnetic correlations but we do not obtain a direct signature of antiferromagnetic long range order. We explain how to obtain the “impurity” susceptibility ( T ) by subtracting the Haldane gap contribution to the total susceptibility. In the temperature range [1 K, 300 K] the experimental data are well fitted by T ( T ) = C _imp 1 + T _imp / T . In the temperature range [100 mK, 1 K] the experimental data are well fitted by T ( T ) = A ln( T / T _c ), where T _c increases with x. This fit suggests the existence of a finite Néel temperature which is however too small to be probed directly in our experiments. We also obtain a maximum in the temperature dependence of the ac-susceptibility ( T ) which suggests the existence of antiferromagnetic correlations at very low temperature. Received 17 July 2001     

Vertical variability of sound fields in a coastal wedge

The results of measuring the vertical variability of sound fields are presented for a coastal wedge off the Pacific shelf of the Kamchatka peninsula. It is shown that the vertical radius of sound field correlation can reach ～30 m for frequencies within 600–800 Hz. The scatter of the specific parameters of the variability is in rather wide limits depending on the location of a vertical chain of receiving hydrophones, the hydrological conditions, the azimuth angle of the sound source, and the relief and bottom structure of the coastal wedge.     

Linear Volterra Integral Equations

The Kurzweil-Henstock integral formalism is applied to establish the existence of solutions to the linear integral equations of Volterra-typewhere the functions are Banach-space valued. Special theorems on existence of solutions concerning the Lebesgu3 integral setting are obtained. These sharpen earlier results.     

Mass transport in anharmonic potentials

We investigate the effect of nuclear shell structure on the mass transport in low-energy heavy-ion collisions. The shell-correction energy leads to anharmonic driving potentials and thus, to nonlinear drift coefficients in the Fokker-Planck equation. Results for²³⁸U (7.42 MeV/nucleon)+²³⁸U are presented. The drift towards the closed Pb-shell enhances the fluctuations in the mass transport and provides an explanation for the large variances found experimentally. Local maxima in the mass distribution at the shell minima disappear due to the temperature dependence of the driving potential.     

Liquid chromatographic analysis of prednisolone, prednisone and their 20-reduced metabolites in perfusion media

A reversed-phase liquid chromatographic assay was developed to quantitate prednisolone, prednisone and the 20 alpha-dihydro and 20 beta-dihydro reduced metabolites of both parent compounds in tissue culture media from in vitro perfusions of the human placental lobule. Steroids were extracted from perfusate, using reversed-phase cartridges, with average recoveries of 95.2% or greater. The internal standard for the analyses was 6 alpha-methylprednisolone. In this assay cortisol coelutes with prednisolone, however, no other significant interferences were found. Assay of each steroid was linear in the range 0-1 microgram/ml. Intra-assay coefficients of variation were measured at 10 and 750 ng/ml with ranges of 3.4% (20 alpha-dihydroprednisone) to 8.8% (20 beta-dihydroprednisolone) and 4.1% (20 beta-dihydroprednisone) to 8.8% (prednisone). The corresponding inter-assay coefficients of variation were 3.3% (20 alpha-dihydroprednisone) to 9.1% (20 beta-dihydroprednisolone) and 1.9% (prednisolone) to 3.5% (prednisone). The analyses utilized two C18 columns which were linked together and maintained at 40 degrees C.     

Modeling synchronization and suppression of spontaneous otoacoustic emissions using Van der Pol oscillators: effects of aspirin administration

Many of the aspects of the interaction of spontaneous otoacoustic emissions with external tones (suppression and synchronization) can be qualitatively simulated by the behavior of a single driven Van der Pol oscillator. Analytical and numerical investigations of a model of spontaneous otoacoustic emissions based on such an oscillator (with appropriate parametric changes in the nonlinear and negative damping components) lead to predictions of the nature of the changes in suppression and synchronization (frequency-locking) tuning curves when the levels of spontaneous otoacoustic emissions are modified. Observations of the suppression and synchronization of spontaneous otoacoustic emissions by external tones of different frequencies and levels were obtained while the levels of spontaneous emissions were altered by aspirin administration. Modeling an emission as a single Van der Pol oscillator qualitatively accounts for: (1) the reduction of the level of an external tone required to suppress the emission by a decibel amount equivalent to the level reduction induced by aspirin administration; (2) the broadening of the frequency-locking tuning curve of an emission whose level is reduced; and (3) the pulling of the emission frequency by an external tone. It does not account for: (1) the observed asymmetry in the slopes of the external-tone suppression curves (more gradual for frequencies of the suppressor tone higher, rather than lower, than that of the emission); and (2) the frequency pushing of the emission by an external tone.