1,3,6,9,12,14,17,20-octaethynyltetrabenz[a,b,f,j,k,o]-4,5,10,11,15,16,21,22- octadehydro[18]annulene: a carbon-rich hydrocarbon

Dodecaynes 1a-d have been prepared via a convergent strategy that employs Sonogashira couplings as the carbon-carbon bond-forming tool. Due to the steric bulk of the DMTS groups, 1c adopts a nonplanar conformation, the dynamics of which have been probed by VT-NMR. The cobalt-catalyzed isomerization of 1a,b produced the new conjugated phenylenes 2a,b and 3a,b, respectively. [structure: see text]     

Transition metal complexes with Girard reagent-based ligands

The ligand, salicylaldehyde Girard-T hydrazonium chloride, [H₂SalGT]Cl (1), and two complexes [Cu(HSalGT)X₂]·H₂O (X = Br(2); Cl(3)) were synthesized and their crystal structures were determined by single-crystal X-ray analysis. In the two isostructural complexes, the Cu(II) is located in a square-pyramidal environment, with the chelating ligand and one halogen atom in the basal plane and the second halogen in the apical position. The most apparent structural difference between the 1 and its complexes 2 and 3 is the orientation of the N(CH₃)₃ group: in 1, it is practically coplanar to the rest of the molecule, while in 2 and 3 it is oriented to the side of the axially bonded halogen, which can be explained by the C–H…X intramolecular interactions. The compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and electronic absorption spectra.     

Sorption of chromium(VI) and chromium(III) on aluminium hydroxide

Factors that influence the sorption of Cr(VI) and Cr(III) on aluminium hydroxide were investigated. The sorption of chromates decreases as the pH of the suspension increases. The mechanism of CrO ₄ ^2– sorption was interpreted in terms of reactions between chromates and –OH and/or H₂O groups at the hydroxide/liquid interface. It has been shown that chromates are more tightly sorbed on aluminium hydroxide compared to other anions, e.g. chlorides. On the other hand, specifically absorbed anions, such as molybdates, compete strongly with chromates for the sorption sites. The sorption of chromium(III) increases with the pH of the suspension. Also, the sorption of chromium(III) is suppressed in the presence of citrate ions. The best conditions for the fixation of Cr(VI) and Cr(III) by aluminium hydroxide are presented.     

Some trace elements in the waters,marine organisms and sediments of the Adriatic by neutron activation analysis

A number of investigations of trace elements in the waters, organisms and sediments of the Adriatic, using neutron activation analysis with radiochemical, separations are reported. These include studies of Hg in mussels from the Northern Adriatic, of Hg and Se in edible animals from the Rijeka region, and of seven elements (As, Cd, Cu, Hg, Mn, Se and Zn) in marine invertebrates from the Slovene coast. Additionally, plankton, sediment cores and water samples were taken from a grid of stations covering the whole Adriatic and analyzed for 6 to 11 of the trace elements As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Sb and Zn (Hg only in water). Generally, levels found were not indicative of pollution as compared with oceanic samples, but some evidence of locally increased levels was found, especially for Hg. The levels of eleven trace elements in three marine Intercomparison samples prepared by the IAEA Monaco Laboratory are also presented.     

Phase Analysis of the Binary System of Cryolite (Na3AlF6) and Sodium Metasilicate (Na2SiO3)

The phase analysis of cryolite (Na₃AlF₆) and sodium metasilicate (Na₂SiO₃) was performed by thermal analysis. The eutectic system with a region of two immiscible substances at a concentration of Na₂SiO₃ between 42.8 and 46.3 mol‐% was identified and the eutectic temperature determined to (886±2) °C. Based on the results of mass‐loss measurements, it was assumed that the introduced Na₂SiO₃ reacts with Na₃AlF₆ due to the formation of some nonvolatile stable compounds. The stable reaction products were identified by X‐ray diffraction analysis and IR spectroscopy of the spontaneously cooled samples, which established the formation of NaF and stable amorphous aluminosilicate compounds.     

Non-isothermal kinetics of dehydration of equilibrium swollen poly(acrylic acid) hydrogel</o:p>

Summary Kinetics of dehydration of equilibrium swollen poly(acrylic acid) hydrogel was investigated using methods of non-isothermal thermal analysis. Methods of Kissinger, Coats-Redfern, Van Krevelen and Horowitz-Metzger were applied for determination the kinetics parameters: activation energy (E), pre-exponent (lnA) as well as the kinetics model ƒ(69) for the process of hydrogel dehydration under different heating rates. An existence of good agreement between determined values of kinetic parameters (Eand A), which were obtained applying different methods under the same heating rate. Functional relationship between changes of kinetic parameters of dehydration and changes of heating rate was established. An existence of compensation effect is accepted and explanation of compensation effect appearance during the hydrogel dehydration is suggested.     

Ab-initio molecular dynamics based on non-local density functional procedure with Gaussian basis; study of structural and temperature behaviour of metallic clusters

An ab-initio molecular dynamics procedure without precalculation of the Born-Oppenheimer energy surface based on an iterative non-local density functional method employing Gaussian atomic basis has been developed. Analytical gradients are calculated and used for the propagation of nuclei. Sufficiently long trajectories can be calculated at an acceptable computational cost, allowing for analysis of dynamical behaviour of small metallic clusters. This is illustrated on an example of the Li₈ cluster. Temperature behaviour of different type of isomers has been investigated. Calculated power spectra allow to identify the presence of more than one isomeric forms along the given trajectories.     

Zur Kenntnis von Natrium-hexafluoromanganat(III)

Sodium hexafluoromanganate(III) has been synthesized by heating equimolecular quantities of Na₂MnF₅ and NaF in argon atmosphere. The compound is monoclinic witha=5.56 (1) Å,b=5.84 (1) Å,c=8.10 (2) Å, =90.7 (2) andZ=2. It is a high spin complex with _eff and the deformation of the octahedra is evident from its IR-spectra. Two enantiotropic transitions (at 562 and 653°C) and the melting point at 800°C have been observed.

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8. Mitt.: Mh. Chem.106, 483 (1975).