Styrene cis—trans photoisomerisation treated through a Heisenberg non-empirical hamiltonian

Using a recently proposed non-empirical Heisenberg hamiltonian, the ground and excited covalent surfaces of the styrene molecule are calculated as functions of the external double-bond twisting angle θ, including full bond-length optimisation. The lowest excited singlet surface exhibits a barrier at 0 ?~ 45° resulting from a weakly avoided crossing of two neutral diabatic surfaces. The isomerisation should proceed from the twisted funnel. This model and the calculated transition energies are in good agreement with experiment.     

Statistical inference and quantum mechanical measurement

We analyze the quantum mechanical measuring process from the standpoint of information theory. Statistical inference is used in order to define the most likely state of the measured system that is compatible with the readings of the measuring instrument and the a priori information about the correlations between the system and the instrument. This approach has the advantage that no reference to the time evolution of the combined system need be made. It must, however, be emphasized that the result is to be interpreted as the statistically inferred state of the original system rather than the state of the system after measurement. The phenomenon of “reduction of states” appears in this light as a consequence of incomplete information rather than the physical interaction between measured system and measuring instrument.     

CI calculations concerning the styrene cis-trans photoisomerization

Using minimal basis sets, the ionic and diradical excited states of the twisted styrene molecule have been calculated through extended CI, after appropriate SCF procedures. The lowest excited state is a diradical, and the photoisomerization should not involve the ionic state.     

Magnetically responsive carboxylated magnetite-polydipyrrole/polydicarbazole nanocomposites of core-shell morphology. Preparation, characterization, and use in DNA hybridization

Novel bis-heterocyclic mono- and dicarboxylated dipyrrole and dicarbazole monomers have been synthesized in a modular manner. Their oxidative polymerization around magnetite nanosized particles has been investigated and optimized toward new magnetic magnetite-polydipyrrole/polydicarbazole nanocomposites (NCs) of a core-shell morphology. These NCs were thoroughly characterized by FT-IR, TGA (Thermal Gravimetric Analysis), low- and high-resolution TEM/HR-TEM microscopies, and M?ssbauer spectroscopy along with magnetization studies. Exploiting the versatile COOH chemistry (activation by water-soluble diimides) introduced by the polymeric shell, DNA hybridization experiments have been conducted onto NC surfaces using an efficient blue-colored HRP-based enzymatic screening biological system. Highly parallel NC-supported DNA hybridization experimentations revealed that these NCs presented an interesting potential for DNA-based diagnostic applications.     

Liquid chromatographic-mass spectrometric assay for simultaneous pyrimethamine and sulfadoxine determination in human plasma samples

We present a liquid chromatographic-mass spectrometric assay for the simultaneous determination of sulfadoxine and pyrimethamine in human plasma samples. Sample clean-up was achieved by adding acetonitrile for protein precipitation. Gradient elution in only 10 min resulted in high throughput capability. Tandem mass spectrometric detection in multiple reaction monitoring was used for quantification. The developed analytical approach was successfully validated and was applied in the pharmacokinetic evaluation of the bioavailability between two sulfadoxine/pyrimethamine formulations available on the Eastern African market, using a cross-over design.     

High-LET radiolysis of liquid water with 1H+, 4He2+, 12C6+, and 20Ne9+ ions: effects of multiple ionization

Monte Carlo simulations are used to investigate the effects of multiple ionization of water molecules on the yields of formation of free radical and molecular species, including molecular oxygen, in the radiolysis of pure, deaerated liquid water by using different types of radiation (1H+, 4He2+, 12C6+, and 20Ne9+ ions) up to approximately 900 keV/microm, at neutral pH and 25 degrees C. Taking into account the double, triple, and quadruple ionizations of water, the primary (or "escape") yields (at 10(-6) s) of the various radiolytic species (G(e(aq)-), G(H*), G(H2), G(*OH), G(HO2*/O2*-), and G(H2O2) are calculated as a function of the linear energy transfer (LET) of the radiation. Our results quantitatively reproduce the large increase observed in G(HO2*/O2*-) at high LET. Under the conditions of this study, the mechanisms of triple and quadruple ionizations contribute only weakly to the production of HO2*/O2*-. With the exception of protons, our calculations also simultaneously predict a maximum in G(H2O2) corresponding to the LET of approximately 4.5-MeV helium ions (approximately 100 keV/microm) and approximately 110-MeV carbon ions (approximately 180 keV/microm). This maximum occurs where G(HO2*/O2*-) begins to rise sharply, suggesting, in agreement with previous experimental data, that the yields of HO2*/O2*- and H2O2 are closely linked. Moreover, our results show a steep increase in the initial and primary yields of molecular oxygen with increasing LET, giving support to the "oxygen in heavy-ion tracks" hypothesis. By contrast, it is found that, in the whole LET range considered, the incorporation of multiple ionization in the simulations has only little effect on the variation of our computed G(e(aq)-), G(H*), G(H2), and G(*OH) values as a function of LET. As expected, G(e(aq)-) and G(*OH) decrease continuously with increasing LET. G(H*) at first increases and then decreases at high LET. Finally, G(H2) monotonically rises with increasing LET. Our calculated yield values compare generally very well with experiment.     

Intertwining unisolvent arrays for multivariate Lagrange interpolation

Generalizing a classical idea of Biermann, we study a way of constructing a unisolvent array for Lagrange interpolation in C^n+m out of two suitably ordered unisolvent arrays respectively in Cⁿ and C^m. For this new array, important objects of Lagrange interpolation theory (fundamental Lagrange polynomials, Newton polynomials, divided difference operator, vandermondian, etc.) are computed. AMS subject classification 41A05, 41A63