Thin-layer chromatographic behavior of rare earths on silica gel with aqueous alkaline earth metal nitrate solutions as mobile phases

The TLC behavior of all the rare earths except Pm has been surveyed on silica gel (pH 7.0) pretreated with 0.1 mol L(-1) tris(hydroxymethyl)aminomethane and 0.1 mol L(-1) HCl with aqueous nitrate solutions of alkaline earth metals as mobile phases. The RF values of the lanthanides varied in a regular and characteristic way accompanied by the tetrad effect with increasing atomic number, and when the mobile phases were changed the RF values of each metal decreased in the order Mg2+ > Ca2+ > Sr2+ > Ba2+, as the crystal ionic radii of the alkaline earth metals increased. This adsorption sequence was not observed with alkali metal nitrate and alkali metal chloride mobile phases. A brief discussion concerning the effect on RF values of the solvent cations and the adsorption mechanism is included; also presented are typical chromatograms for the separation of multi-component mixtures containing adjacent lanthanides.     

Supramolecular triangular and linear arrays of metal-radical solids using pyrazolato-silver(I) motifs

New chelating radical ligands pzNNH, pzINH, and pzbisINH (3-pyrazolyl nitronyl nitroxide, 3-pyrazolyl imino nitroxide, and pyrazole-3,5-diyl bis(imino nitroxide), respectively) were prepared. Complexation of these ligands with Ag+ gave [Ag(pzNN)]n, [Ag(pzIN)]6, and [Ag(pzbisIN)]n containing the corresponding anionic forms of the ligands. From the X-ray crystal structure analysis, [Ag(pzIN)]6 was characterized as a dimer of almost planar triangular moieties where the pyrazolate worked as a bridge, and metal-metal bonds brought about dimerization of triangles. [Ag(pzbisIN)]n was characterized as a uniform zigzag chain consisting of pyrazolate bridges and Ag ions with a cis-Npz-Ag-Npz coordination structure. Antiferromagnetic interactions observed could be analyzed based on the structures determined for both compounds. Ferromagnetic coupling was observed in [Ag(pzNN)]n, and a polymeric structure was assumed although the crystal structure could not be determined. Novel supramolecular architectures using pyrazolate-substituted imino nitroxides have been developed, using the unique coordinative versatility of the pyrazolate derivatives     

GENERATION AND PARTICIPATION OF O-2 IN 2-NITROPROPANE DIOXYGENASE REACTION

Abstract— 2-Nitropropane dioxygenase (EC 1. 13. 11) of the yeast Hansenula mrakii catalyzes the oxygenative denitrification of 2-nitropropane as follows:

The enzyme is significantly inhibited by superoxide dismutase and various scavengers for superoxide such as cytochrome c , epinephrine, thiols and polyhydric phenols. The scavengers added to the reaction mixture were oxidized or reduced. The addition of superoxide dismutase and the omission of 2-nitropropane or oxygen prevented the oxidation and the reduction of the scavengers. The enzyme catalyzes the formation of nitrite from 2-nitropropane by KO₂ added anaerobically.
One mole of NADH is bound per mole of the enzyme and predominantly the pro-R hydrogen of bound NADH is transferred to superoxide formed enzymatically or provided externally. The enzyme shows incomplete stereospecificity for hydrogen transfer from NADH.     

Effective photoexcitation in gold nanowells based on localized surface plasmon

The localization of the surface plasmon (SP) field in nanospace using wavelength-sized gold wells prepared on a glass substrate and its application to excite fluorophores immobilized on the bottom surfaces have been studied.     

Hydration structure around a non-electrolyte molecule as revealed by monte carlo calculation: have you seen the “iceberg”?

Monte Carlo calculations have been carried out for pure water and an infinitely dilute aqueous solution of methanol at 298.15 K at ordinary density by the Metropolis method in NTV ensemble. The hydration structure around methanol revealed by a graphic display technique indicates a structure-forming effect near the hydrophobic group.     

Reactions of group IV organometallic compounds : XXVII. Some reactions of [(trimethylsilyl)imino]phosphorane

The reaction of [(trimethylsilyl)imino]methyldiphenylphosphorane: Ph₂MePNSiMe₃ (I) with several acid anhydrides or alkyl isocyanates took place by the simple cleavage of silicon-nitrogen bond. In contrast the interaction of (I) with phenyl isocyanate, isothiocyanate or carbon disulphide led to addition-elimination reactions of the Wittig type. Detailed investigation in the case of phenyl isocyanate indicated the usual elimination of Ph₂MePO is suppressed by the strong affinity of the trimethylsilyl group for anionic oxygen atom.     

Synthesis of (−)-terrecyclic acid A. Absolute configuration of terrecyclic acid A and quadrone

(?)-Terrecyclic acid A ($\text{15}$) was synthesized from (+)-fenchone ($\text{1}$). The absolute configuration of terrecyclic acid A and quadrone was established.     

Photoelectron spectra and angular distribution in reson three-photon ionization of atomic iron: J dependence

Kenetic energies and angular distributions of photoelectrons emitted by three-photon ionization fo atomic iron through two-photon resonant state e⁷D_J and e⁵ D_J, were measured, by using visible lasers. J-resolved photoelectron bands attributab to the a⁶D_J and a⁴F_j ionic states are reported.