Fragmentation paths of O- and S-phenyl N-phenylbenzohydrazonates,and the isomeric N,N-diphenylbenzohydrazides upon electron impact

The mass spectra of O- and S-phenylbenzohydrazonates and the isomeric N, N-diphenylbenzohydrazides have been examined. The benzohydrazonates decompose by expulsion of a phenoxy (thiophenoxy) radical, or by elimination of phenol (thiophenol); the latter is a new example of the mass spectral retro 1, 3-dipolar cycloaddition reaction. There are no indications of a mass spectral Chapman rearrangement in these compounds, while evidence is adduced for a mass spectral retro Chapman rearrangement in the spectrum of N, N-diphenylthiobenzohydrazide.     

Development of 7TM receptor-ligand complex models using ligand-biased, semi-empirical helix-bundle repacking in torsion space: application to the agonist interaction of the human dopamine D2 receptor

Prediction of 3D structures of membrane proteins, and of G-protein coupled receptors (GPCRs) in particular, is motivated by their importance in biological systems and the difficulties associated with experimental structure determination. In the present study, a novel method for the prediction of 3D structures of the membrane-embedded region of helical membrane proteins is presented. A large pool of candidate models are produced by repacking of the helices of a homology model using Monte Carlo sampling in torsion space, followed by ranking based on their geometric and ligand-binding properties. The trajectory is directed by weak initial restraints to orient helices towards the original model to improve computation efficiency, and by a ligand to guide the receptor towards a chosen conformational state. The method was validated by construction of the β₁ adrenergic receptor model in complex with (S)-cyanopindolol using bovine rhodopsin as template. In addition, models of the dopamine D₂ receptor were produced with the selective and rigid agonist (R)-N-propylapomorphine ((R)-NPA) present. A second quality assessment was implemented by evaluating the results from docking of a library of 29 ligands with known activity, which further discriminated between receptor models. Agonist binding and recognition by the dopamine D₂ receptor is interpreted using the 3D structure model resulting from the approach. This method has a potential for modeling of all types of helical transmembrane proteins for which a structural template with sequence homology sufficient for homology modeling is not available or is in an incorrect conformational state, but for which sufficient empirical information is accessible.     

A Non-normal-mode Marginal State of Convection in a Porous Box with Insulating End-Walls

Transport in Porous Media - The 4th order Darcy–Bénard eigenvalue problem for the onset of thermal convection in a 3D rectangular porous box is investigated. We start from a recent 2D...     

Three-Body Recombination with Two-Channel Contact Interactions

We use a two-channel contact interaction model to describe a system of three identical bosons. The two-channel model quantitatively describes the phenomena of Feshbach resonance in agreement with the phenomenological expression relating scattering length to magnetic detuning. The model also has a finite effective range. We investigate finite range effects in three-body recombination. The simpler one-channel contact interaction model predicts a characteristic geometric scaling of minima in the recombination coefficient as a function of scattering length with scaling parameter 22.7. We show that this factor is reduced when the effective range is included. We compare calculations to experiment.     

A new interpretation of Hund's first rule

The diagonal elements of the first and second order spinless density matrices have been calculated for the lowest excited¹ P and³ P terms of Be, B⁺ and C⁺⁺ using wavefunctions at different levels of approximations published in the literature. The analysis of these functions has resulted in a new interpretation of Hund's first rule in terms of an anisotropic screening effect.     

Electron correlation forms in the LiH molecule—fermi correlation

Correlation forms for electrons of the same spin small molecules are analyzed by taking the LiH molecule as an example. The analyses are carried out on the basis of the reduced density matrix theory and for both the ground state and the first excited state. It turns out that although there is a certain similarity, the correlated motions of parallel-spin electrons in this four-electron molecule are more complicated than those found for the two-electron molecule. The correlation forms are not always constant. They vary essentially from one state to another, but are insensitive to fairly large changes of the internuclear distance for a given state.     

Onset of Convection in a Porous Layer with Continuous Periodic Horizontal Stratification. Part I. Two-Dimensional Convection

The onset of convection in a horizontal porous layer is investigated theoretically. The permeability of the porous medium is a continuous periodic function of the horizontal x coordinate. Floquet theory has been employed to determine the favoured two-dimensional mode of convection. For a wide range of periods of the permeability variation, a matrix eigenvalue technique with eighth order accuracy has been employed to find the critical Darcy– Rayleigh number. This is supplemented by a multiple-scales analysis of the large-period limit, and a brief consideration of the anisotropic limit for very short periods.     

Determination of mercury in natural samples at the sub-nanogram level using inductively coupled plasma/mass spectrometry after reduction to elemental mercury

Inductively coupled plasma/mass spectrometry was used to determine mercury. Sodium borohydride was used to reduce the mercury to its elemental form, which was purged directly to the plasma using the nebulizer gas. Applications to natural waters and reference sediment are demonstrated. The detection limit, defined as three times the standard deviation of the blank, is 8 pg. The precision at the 100-pg level is 3%. The ability to make isotope dilution measurements is demonstrated.