Détermination de traces de mercure dans les systèmes biologiques par activation de neutrons

Résumé Une méthode simple et rapide de détermination de traces de mercure est présentée utilisant l'activation de neutrons. Le mercure 197 sous forme de complexe (HgCl₄ ^2–) est retenu sur une résine échangeuse d'anion qui est comptée directement. La méthode est appliquée à des milieux biologiques très divers. Les échantillons contiennent des quantités de mercure allant de 10 p. p. b. à 200 p. p. m. La déviation standard dans ces cas est de ± 10%.

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Determination of traces of mercury in biological material by neutron activation

Summary A simple and rapid technique for the trace analysis of mercury by neutron activation is presented. The activated mercury, as an HgCl₄ ^2– complex, is retained on an anion exchange resin which is counted directly. Results obtained for biological samples containing 10 p. p. b. to 200 p. p. m. are given. In this range, results had a ± 10% standard deviation.

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Zusammenfassung Ein einfaches und rasches Verfahren zur Bestimmung von Spuren Quecksilber durch Neutronenaktivierung wurde beschrieben. Das aktivierte Quecksilber wird als HgCl₄ ^2– an einem Anionenaustauscherharz adsorbiert und seine Aktivität direkt gemessen. Biologische Proben mit 10 ppb bis 200 ppm Hg wurden analysiert. In diesem Bereich betrug die Standardabweichung ± 10%.

     

Enantioenriched dihydropyrones from beta-lactone templates

[reaction: see text] Optically active 4-substituted 2-oxetanones provide conduits for preparing 2,3-dihydro-4H-pyrone heterocycles. Enantioenriched beta-lactones are prepared by asymmetric catalytic acyl halide-aldehyde cyclocondensation reactions. Hydrazone anion-mediated beta-lactone ring opening and ensuing cyclization-dehydroamination of the derived beta-ketohydrazone afford the desired dihydropyrones (68-81%). Optimized lactone ring-opening-cyclization reaction conditions render a variety of optically active 4-substituted-2-oxetanones as effective precursors to enantioenriched 2,3-dihydro-4H-pyrones.     

Examination of the electrophoretic behavior of liposomes

The electromigration of liposomes is a complex process resulting in many unexpected behaviors that are difficult to address with existing theories. In this study, the electrophoretic behaviors of liposome populations under various conditions were examined through the use of capillary electrophoresis and the results compared to classical electrokinetic, colloid, and spheroid theories. To elucidate the possible effects of applied field strength, bilayer rigidity, and surface charge on these behaviors, the electrophoretic mobilities of liposome populations were monitored while varying the applied potential, ionic strength of the medium, and the surface charge and cholesterol content of the liposomes. On the basis of comparisons made to the theoretical predictions, our results suggest that liposomal deformation and field-induced polarization may occur during electrophoresis and these mechanisms help to describe many of the observed behaviors.     

Internal rotation in peroxynitrous acid (ONOOH)

Using higher levels of wave-function-based electronic structure theory than previously applied, as well as density functional theory (B-LYP and B3-LYP functionals), all theoretical models conclude that three ONOOH conformers are stationary point minima, in disagreement with some of the previous studies that we survey. In order of increasing energy, these are the cis-cis, cis-perp, and trans-perp conformers. Basis sets including diffuse functions seem to be needed to obtain a qualitatively correct representation of the internal rotation potential energy surface at higher levels of theory. Internal rotation about the peroxide bond involving the cis-cis, cis-gauche transition structure (TS), cis-perp, and cis-trans TS conformers is studied in detail. To help ascertain the relative stability of the cis-perp conformer, multireference configuration interaction energy calculations are carried out, and rule of thumb estimates of multireference character in the ground-state wave functions of the ONOOH conformers are considered. CCSD(T)/aug-cc-pVTZ physical properties (geometries, rotational constants, electric dipole moments, harmonic vibrational frequencies, and infrared intensities) are compared with the analogous experimental data wherever possible, and also with density functional theory. Where such experimental data are nonexistent, the CCSD(T) and B3-LYP results are useful representations. For example, the electric dipole moment |mu(e)| of the cis-cis conformer is predicted to be 0.97+/-0.03 D. CCSD(T) energies, extrapolated to the aug-cc-pVNZ limit, are employed in isodesmic reaction schemes to derive zero Kelvin heats of formation and bond dissociation energies of the ONOOH stationary point minima. In agreement with recent gas-phase experiments, the peroxide bond dissociation energies of the cis-cis and trans-perp conformers are calculated as 19.3+/-0.4 and 16.0+/-0.4 kcalmol, respectively. The lowest energy cis-cis conformer is less stable than nitric acid by 28.1+/-0.4 kcalmol at 0 K.     

Charge transport in a mixed ionically/electronically conducting, cationic, polyacetylene ionomer between ion-blocking electrodes

The electrical behavior of the cationic, polyacetylene-based, conjugated ionomer, poly[(2-cyclooctatetraenylethyl)trimethylammonium trifluoromethanesulfonate], sandwiched between gold electrodes is reported. The steady-state current of this mixed ionically/electronically conducting system is assigned to be unipolar diffusive hole transport for voltages below approximately 1.4 V, giving way to bipolar migratory transport above approximately 1.4 V. In the low-voltage regime, a non-Faradaically controlled doping model is proposed where p-doping at the anode is balanced by the charging of an ionic double layer at the cathode. In the high-voltage regime, n- and p-type regions extend from the electrodes as the voltage becomes sufficient to drive disproportionation and the electric field required by the redistribution of ions begins to substantially influence carrier transport. The assignment of a transport mechanism is primarily based on analyzing the decay of the steady-state system under short-circuit and open-circuit conditions. First, it is shown that the power describing the power-law decay of the short-circuit current is characteristic of the steady-state carrier profile. Second, it is argued that a component of the time-dependent, open-circuit voltage decaying more rapidly than the time scale for ion motion is indicative of a substantial migratory component to steady-state transport, as observed in the high-voltage regime. The hole and electron mobilities are estimated to be on the order of 10(-7)-10(-6) cm(2) V(-1) s(-1).     

Genäherte Lösung der Hartree-Fock-Gleichungen wechselwirkender Moleküle im Bereich der geringen Überlappung

A perturbational approach has been developed in order to determine the interaction energy of two molecules in the region of small overlap in an attempt to obtain some information upon reactivity. The total wavefunction of the interacting molecules is set up as a single determinantal wavefunction, whose basisfunctions are constructed as linear combinations of all occupied and unoccupied molecular orbitals. The coefficients are determined by an approximate solution of the Hartree-Fock-Roothaan equations of the total system. The SCF-iteration is performed analytically until all first and second order terms are included in the expression for the interaction energy. Due to the analytical procedure of the SCF-cycle the interaction energy contains no numerically iterated quantities. The interaction between a molecule with an open shell and a molecule with a closed shell is treated in the framework of the unrestricted Hartree-Fock-approximation. The interaction energy in the molecular orbital basis is transformed into an atomic orbital basis by using the LCAO-MO-approximation and introducing approximations for several integrals. Useful expressions for calculations are also derived, which contain only quantities of the isolated molecules, together with interatomic distances and overlap integrals. These formulae for the interaction energy are suitable for detailed interpretation of the different interaction terms and reveal the role of the interacting centres.     

The role of angular momentum in collision-induced vibration-rotation relaxation in polyatomics

Vibrational relaxation of the 6(1) level of S(1)((1)B(2u)) benzene is analyzed using the angular momentum model of inelastic processes. Momentum-(rotational) angular momentum diagrams illustrate energetic and angular momentum constraints on the disposal of released energy and the effect of collision partner on resultant benzene rotational excitation. A kinematic "equivalent rotor" model is introduced that allows quantitative prediction of rotational distributions from inelastic collisions in polyatomic molecules. The method was tested by predicting K-state distributions in glyoxal-Ne as well as J-state distributions in rotationally inelastic acetylene-He collisions before being used to predict J and K distributions from vibrational relaxation of 6(1) benzene by H(2), D(2), and CH(4). Diagrammatic methods and calculations illustrate changes resulting from simultaneous collision partner excitation, a particularly effective mechanism in p-H(2) where some 70% of the available 6(1)-->0(0) energy may be disposed into 0-->2 rotation. These results support the explanation for branching ratios in 6(1)-->0(0) relaxation given by Waclawik and Lawrance and the absence of this pathway for monatomic partners. Collision-induced vibrational relaxation in molecules represents competition between the magnitude of the energy gap of a potential transition and the ability of the colliding species to generate the angular momentum (rotational and orbital) needed for the transition to proceed. Transition probability falls rapidly as DeltaJ increases and for a given molecule-collision partner pair will provide a limit to the gap that may be bridged. Energy constraints increase as collision partner mass increases, an effect that is amplified when J(i)>0. Large energy gaps are most effectively bridged using light collision partners. For efficient vibrational relaxation in polyatomics an additional requirement is that the molecular motion of the mode must be capable of generating molecular rotation on contact with the collision partner in order to meet the angular momentum requirements. We postulate that this may account for some of the striking propensities that characterize polyatomic energy transfer.     

Application of ionic liquids as low-volatility plasticizers for PMMA

Room temperature ionic liquids (ILs) based on imidazolium salts, were found to be excellent plasticizers for poly(methyl methacrylate), with improved thermal stability, and the ability to reduce glass transition temperatures to near 0 °C. Because ILs have environmentally benign properties, they can be used in place of traditional chemicals in numerous products and processes. In this work, PMMA was formulated using dioctyl phthalate, DOP, as a traditional plasticizer, and properties were compared to PMMA plasticized with two ILs: butyl methylimidazolium/hexafluorophosphate, [bmim⁺][PF₆⁻], and hexyl methylimidazolium/hexafluorophosphate, [hmim⁺][PF₆⁻]. Formulations incorporated up to 30 vol.% DOP and 50 vol.% ILs. Bulk and plasticized polymers were characterized for glass transition temperature, elastic modulus, and the thermal stability of the plasticizers.     

Solid-phase synthesis of 4-biaryl-piperidine-4-carboxamides

A novel solid-phase synthesis of 4-biaryl-piperidine-4-carboxamides has been developed using FDMP resin with a carboxamide as the anchor point. With this approach, three points of diversity were incorporated into a GPCR-directed scaffold. Final products were obtained in good purity and yield.