Distribution of Pu(VI) from nitric acid to tri-n-butyl phosphate saturated with uranium(VI)

Solvent extraction of plutonium(VI) from nitric acid (1 to 5M) into 20% and 30% TBP in dodecane saturated with uranium(VI) (0% to 80%) has been studied. For a particular nitric acid concentration, the distribution coefficient (K _d ) is found to decrease with the increase in saturation of organic phase with uranium(VI). At a fixed organic phase the saturationK _d increased with increase in nitric acid concentration, however, the magnitude of this increase inK _d decreased with the increase in saturation.     

A mild and efficient method for large scale synthesis of 3-aminocoumarins and its further application for the preparation of 4-bromo-3-aminocoumarins

A wide variety of 3-aminocoumarins have been synthesized in large scale from the corresponding 3-acetamidocoumarins by regioselective cleavage of carbon–nitrogen bond using 70% sulfuric acid under reflux conditions. The synthesized 3-aminocoumarins were further brominated regioselectively at the 4-position of 3-aminocoumarin using BDMS as brominating agent.     

Ammonia Borane,NH3BH3: A Threshold Photoelectron–Photoion Coincidence Study of a Potential Hydrogen-Storage Material

We have investigated the photoionization of ammonia borane (AB) and determined adiabatic ionization energy to be 9.26±0.03 eV for the X^{+ 2}E←X ¹A₁ transition. Although the threshold photoelectron spectrum appears at first glance to be similar to the one of the isosteric ethane, the electronic situation differs markedly, due to different orbital energies. In addition, an appearance energy AE_0K(NH₃BH₃, NH₃BH₂⁺)= 10.00±0.03 eV has been determined, corresponding to the loss of a hydrogen atom at the BH₃-site. From the data, a 0 K bond dissociation energy for the B−H bond in the cation of 71.5±3 kJ mol⁻¹ was derived, whereas the one in the neutral compound has been estimated to be 419±10 kJ mol⁻¹.     

Entropic noise-induced nonequilibrium transition

We consider a system of Brownian particles confined in a two-dimensional bilobal enclosure. Varying cross-section of the confinement results in an effective entropic potential in reduced dimension. We show that the system may undergo an entropic noise-induced transition when the shape of the stationary probability density changes qualitatively from bimodal to trimodal type under the influence of a multiplicative noise.     

Auto-redox reaction: tin(II) chloride-mediated one-step reductive cyclization leading to the synthesis of novel biheterocyclic 5,6-dihydro-quinazolino[4,3-b]quinazolin-8-ones with three-point diversity

[reaction: see text] A tin(II) chloride-mediated short, efficient, and practical regioselective synthesis of biheterocyclic 5,6-dihydro-quinazolino[4,3-b]quinazolin-8-ones with three-point diversity is reported. A one-step reductive transformation of 2-(2-nitrophenyl)-3H-quinazolin-4-one in various alcohols furnished the desired tetracyclic product in good yields with high purity.     

A parametric variant of resonant activation: two-state model approach

Mean first passage time of a periodically driven particle for its escape over a fluctuating barrier with wells remaining unbiased exhibits a resonance when the frequency of the driving field is varied. This parametric variant of resonant activation and associated features of noise induced transition are realized in terms of a two-state model to estimate analytically several quantifiers of the escape event. Numerical simulation on a continuous double-well model collaborates our theoretical analysis.     

Electrophoretic mapping of highly homologous keratins: A novel marker peptide approach

Identification of the intermediate filament proteins (IFPs) in the wool proteome has formerly been hampered by limited sequence information, the high degree of IFP homology and their close proximity on 2‐DE maps. This has been partially rectified by the recent acquisition of four new Type I and two Type II wool IFP sequences. Among closely migrating proteins, such as IFP clusters in a 2‐DE map, proteins with higher sequence coverage will be assigned higher scores, but the identification of unique peptides in such tight clusters may distinguish these closely migrating proteins. Two approaches were adopted for the study of wool IFPs. In the first, searches were conducted for peptides known to be unique to each member of the family in each spot. In the second, MALDI imaging was employed to examine peptides bound to a PVDF membrane from a poorly resolved part of the Type I IFP region of the 2‐DE map. As a result, a distinct picture has emerged of the distribution of the six Type I and four Type II IFPs across the 2‐DE wool protein map.     

Graph-theoretical parameters for π-MO calculation of a series of aromatic amines in the light of DFT theory: comparison with experimental CT transition energies

Expressions for the energies of the highest occupied π-molecular orbitals of a series of aromatic amines have been derived in terms of the vertex weight h _N (for amine nitrogen) and edge weight k _C–N (for the C–N bond) by representing the amine molecule in terms of vertex- and edge-weighted graphs. Graph-theoretical methods have been used to evaluate the quantities involved in such expressions. The HOMO energies of the amines calculated by density functional theory using the 6-31++G** basis set have been correlated with these expressions to estimate the perturbational parameter h _N and the Coulomb integral α. The acceptability of the estimated values of α and h _N has been tested by their ability to explain the experimentally observed trends in the CT transition energies of a series of charge-transfer complexes of amines with tetracyanoethylene. An important structural feature, namely rotation of the –NH₂ group about the C–N bond due to steric repulsion with the nearest H-atom in the case of 1-amino compounds, has been observed by such a correlation. The result agrees well with the DFT-optimized geometries of the structures.     

Conformational relaxation in the excited electronic states of benzil and naphthyl

A time-resolved study of the emission from benzil and naphthyl in semi-solid glasses (e.g. alcoholic glass near the melting point) using a pulsed N₂-laser as an excitation source is reported. The emission from the relaxed excited triplet shows a growth followed by a decay. This growth provides a convincing proof of geometrical relaxation occurring in the excited states of benzil and naphthyl.     

Thermal decomposition of manganese(II)bis(oxalato)nickelate(II)tetrahydrate

Summary A mixed metal oxalate, manganese(II)bis(oxalato)nickelate(II)tetrahydrate, has been synthesized and characterized by elemental analysis, IR spectral and X-ray powder diffraction (XRD) studies. Thermal decomposition studies (TG, DTG and DTA) in air showed that the compound decomposed mainly to Mn₂O₃, MnO₂ and NiO at ca.1000°C, via. the formation of several intermediates. DSC study in nitrogen upto 500°C showed the endothermic decomposition. The tentative mechanism for the thermal decomposition in air is proposed.