Structural and Photophysical Properties of Lanthanide Nitrate 1:1 Complexes with planar tridentate nitrogen ligands analogous to 2,2′:6′,2′-terpyridine

The ligand 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (mbzimpy, 1 ) reacts with Eu^III to give [Eu(mbzimpy)(NO₃)₃(CH₃OH)] [ 4 ] whose crystal structure (EuC₂₂H₂₁N₈O₁₀, a = 7.658(3) Å, b = 19.136(2) Å, c = 8.882 Å, β = 104.07(1)°, monoclinic, P2₁, Z = 2) shows a mononuclear structure where Eu^III is ten-coordinate by a meridional tridentate mbzimpy ligand, three bidentate nitrates, and one CH₃OH molecule, leading to a low-symmetry coordination sphere around the metalion. Essentially the same coordination is found in the crystal structure of [Eu(obzimpy)(NO₃)₃] ( 8 ) (EuC₃₅H₄₅N₈O₉, a = 9.095(2) Å, b = 16.624(2) Å, c = 26.198(6) Å, β = 95.85(1)°, monoclinic, P2₁/c, Z = 4) obtained by reaction of 2,6-bis(1-octylbenzimidazol-2-yl)pyridine (obzimpy, 2 ) with Eu^III. Detailed photophysical studies of crystalline [Ln(mbzimpy)(NO₃)₃(CH₃OH)] and [Ln(obzimpy)(NO₃)₃] complexes (Ln = Eu, Gd, Tb, Lu) show that 1 and 2 display ¹ππ* and ³ππ* excited states very similar to those observed in 2,2′:6′,2″-terpyridine, leading to efficient ligand to Ln^III intramolecular energy transfer. Spectroscopic results show that an extremely efficient mbzimpy-to-Eu^III transfer occurs in [Ln(mbzimpy)(NO₃)₃(CH₃OH)] and in the case of Tb^III, a Tb^III-to-mbzimpy back transfer is also implied in the deactivation process. The origin of these peculiar effects and the influence of ligand design by going from mbzimpy to obzimpy are discussed. ¹H-NMR and luminescence data indicate that the structure found in the crystal is essentially maintained in solution.     

Winter evolution of DMS and DMSP in Venice lagoon water and sediment

The evolution of dimethylsulphide (DMS) and dimethylsulphoniopropionate (DMSP) concentrations in the water and sediment of the Venice lagoon were studied together with the concentration of chlorophyll a, temperature and the composition and density of phytoplankton to understand the role of the sediment as a source of DMS during the winter period. The temporal trend of water DMS concentration in this period showed a maximum concentration in February (75.7 nmol S l-1) related to low DMSP and chlorophyll a concentrations but to high phytoplanktonic abundance. The DMS and DMSP concentrations were greater in the sediment than in the water. The temporal trend of DMS concentration in sediment showed a maximum in February (1155 nmol S l-1) related to the maximum of DMS concentration in surface water. These observations suggested that in the winter period DMS could be produced by the conversion of the DMSP present in the bulk water but principally by that present in the sediment (microbiological degradation of DMSP or other sulphur-containing compounds) that subsequently diffuse in water.     

The average number of Sylow subgroups of a finite group

We prove that if the average Sylow number (ignoring the Sylow numbers that are one) of a finite group G is ?7, then G is solvable.     

Influence of Oil Content in Paraffins on the Behavior of Wax Emulsions: Wetting and Rheology

In this study, effect and correlation of alkyl chain length (C8, C10, C12, C14, and C16) and concentration of n-alkyl sulfate acid used as representative Br?nsted acid-combined-surfactant catalysts on dehydration esterification of oleic acid with 1-octanol as typical substrates are researched. CMC of the series surfactant are measured by surface tension method. The results indicate that alkyl chain length as well as concentration of catalyst plays an important role in determining conversion of esterifications. Appropriate chain length surfactant and concentration should be chosen for the combined-surfactant catalyzed reaction.     

X-Ray Diffuse Scattering Study of Some (TMTSF)2X and (TMTTF)2X Salts

X-ray diffuse scattering experiments on the superconducting salts (TMTSF)₂X with X = PF₆, AsF₆ and ClO₄ reveal no charge density wave instability, in contrast with the poorly conducting (TMTTF)₂PF₆ salt. New structural phase transitions coinciding with conductivity anomalies are found in (TMTSF)₂NO₃, (TMTSF)₂ReO₄, and (TMTTF)₂ClO₄. It is suggested that they correspond to order-disorder transitions involving the non-centrosymmetric counter ions. Relationships between these structural instabilities and superconductivity are also discussed.     

"Snowflake" H mode in a tokamak plasma

An edge-localized mode (ELM) H-mode regime, supported by electron cyclotron heating, has been successfully established in a "snowflake" (second-order null) divertor configuration for the first time in the TCV tokamak. This regime exhibits 2 to 3 times lower ELM frequency and 20%-30% increased normalized ELM energy (ΔWELM/Wp) compared to an identically shaped, conventional single-null diverted H mode. Enhanced stability of mid- to high-toroidal-mode-number ideal modes is consistent with the different snowflake ELM phenomenology. The capability of the snowflake to redistribute the edge power on the additional strike points has been confirmed experimentally.     

Detailed elucidation of hydrocarbon contamination in food products by using solid-phase extraction and comprehensive gas chromatography with dual detection

The present work is focused on the development/optimization of a comprehensive two-dimensional gas chromatography method, with dual detection [flame ionization (FID) and mass spectrometric], for the simultaneous identification and quantification of mineral-oil contaminants in a variety of food products. The two main classes of contaminants, namely saturated and aromatic hydrocarbons, were previously fractionated on a manually-packed silver silica solid-phase extraction (SPE) cartridge. The quantitative results were compared with those obtained by performing a large volume injection, in a GC-FID system, after the same SPE process and by an on-line liquid–gas chromatography method, with very similar results observed. The presence of a series of unknown compounds, that appeared when using the off-line methods, was investigated using the mass spectrometric data, and were tentatively-identified as esterified fatty acids, most probably derived from vegetable oil based ink.     

SQUID-based measuring systems

A program has been developed and initiated at the Indira Gandhi Centre for Atomic Research (IGCAR) for the utilization of SQUID sensors in various application areas. DC SQUID sensors based on Nb-AlO _x -Nb Josephson junctions have been designed and developed inhouse along with associated flux-locked loop (FLL) electronics. A compact low field SQUID magnetometer insertible in a liquid helium storage dewar has also been developed inhouse and is in use. Efforts to build a high field SQUID magnetometer, SQUID-DAC system, are in progress. A planar gradiometric DC SQUID sensor for non-destructive evaluation (NDE) application to be used in relatively unshielded environment has been designed and developed. An easily portable NDE cryostat with a small lift-off distance, to be used in external locations has been designed and tested. The magnetic field produced by a given two-dimensional current density distribution is inverted using the Fourier transform technique.     

The approximation of generalized turning points\newline by Krylov subspace methods

Summary. Certain types of singular solutions of nonlinear parameter-dependent operator equations were characterized by Griewank and Reddien [5, 6] as regular solutions of suitable augmented systems. For their numerical approximation an approach based on the use of Krylov subspaces is here presented. The application to boundary value problems is illustrated by numerical examples. Received March 8, 1993 / Revised version received December 13, 1993