4-t-Butylphenoxo complexes of oxovanadium(V)

Summary Complexes of composition [VOCl₂(OC₆H₄Bu-t-4)] (1) and [VOCl(OC₆H₄Bu-t-4)₂] (2) have been synthesized by the reaction of VOCl₃ with equimolar and bimolar amounts, respectively, of 4-t-BuC₆H₄OSiMe₃ in CCl₄ and characterized by physio-chemical techniques. The complexes react with -hydroxyaldehydes and ketones such as 2-hydroxybenzaldehyde (salicylaldehyde, salH), and 2-hydroxy-2-phenylacetophenone (benzoin, benzH), 2-hydroxyacetophenone (hapH) and also with the potassium salt of p-chlorobenzohydroxamic acid (KBHACl) in 11 and 12 molar ratios, to yield five- and six-coordinate complexes.     

Influence of preferential solvation on the interpolymer complex formation between methacrylic acid–methacrylamide copolymer and poly(vinyl pyrrolidone)

Interpolymer complex formation has been studied between methacrylic acid–methacrylamide copolymer and poly(vinyl pyrrolidone) in acetone–water mixtures of different compositions. At a specific composition of the solvent (e.g., 70% water + 30% acetone by volume), the intrinsic viscosity of the copolymer and the reduced viscosity of 1:1 interpolymer complex had minimum values. Preferential solvation coefficients (λ/C) have been calculated for the various compositions of the solvent mixtures. An excellent coincidence could be obtained between the maximum (λ/C) and the minimum in the viscosity of the polymer solutions. Interpretations have been sought in terms of conformational change of the copolymer at the specific composition of the solvent mixture.     

Solution properties of poly p-isopropyl α-methylstyrene

Two series (S and F) of poly p-isopropyl α-methylstyrene were characterized by viscometry, light scattering (LS), osmometry and gel permeation chromatography (GPC). S-samples were prepared by bulk anionic polymerization whereas F-samples were obtained on fractionation by preparative GPC of a polymer also prepared in bulk but with a different initiator. The K parameter in the Mark-Houwink relation was 5.55 × 10^?4 for series-S and 4.50 × 10^?4 for series-F, whereas the exponent a was 0.55 for both series. The Mark-Houwink equations for series-S and -F hold good at 25 and 30° for both toluene and tetrahydrofuran as solvents and have been corrected for polydispersity. The chain dimensions obtained with LS were much higher than those computed from the viscosity data indicating that the hydrodynamic theories in their present state should not be used for the calculation of chain dimensions. The deviations from the GPC universal calibration curve of polystyrene observed with some samples were attributed to structural differences among the polymers and to their high polydispersity.     

Thermal conductivity of C60 and C70 crystals

We have performed thermal conductivity measurements on C₆₀ and C₇₀ crystals grown by sublimation. For single crystal C₆₀, the thermal conductivity k is 0.4 W/m K at room temperature and is nearly temperature independent down to 260K. We observed a sharp orientational phase transition at 260K, indicated by a 25% jump in k. Below 90K, k is time dependent, which manifests itself as a shoulder-like structure at 85K. The temperature and time dependence of k below 260K can be described by a simple model which accounts for the thermally activated hopping of C₆₀ molecules between two nearly degenerate orientations, separated by an energy barrier of 240 meV. It is found that solvents have a strong influence on the physical properties of C₇₀ crystals. For solvent-free C₇₀ crystal, k is about constant above 300K. There is a broad first-order phase transition in k at 300K with a 25% jump. We associate this transition with the aligning of the fivefold axes of the C₇₀ molecules along the c-axis of the hexagonal lattice. Upon further cooling, k increases and is time independent.     

Intradiffusion coefficients in perchloric acid solutions: Water at 5°C; water and perchlorate ion at 25°C

Intradiffusion coefficients for tritiated water (³HHO) and perchlorate ion (³⁶ClO ₄ ^- ) were measured in perchloric acid solutions. At 5°C the diffusion coefficient measured for the tritiated species increases to a maximum near 1.3 mol-dm^–3. The data at 25°C have been used to calculate distinct diffusion coefficients, D _ij ^d . As a precursor for those calculations, new estimates were made of the Onsager phenomenological coefficients, l _ij . The l _ij and D _ij ^d are similar to the respective coefficients in hydrochloric acid solutions.     

Increased paraoxon detection by acetylcholinesterase inactivation with ionic liquid additives

This is the first study using ionic liquids (ILs) as additive in the aqueous solvent medium for detection of paraoxon by acetylcholinesterase inhibition method. A systematic comparison of various ILs with organic solvents has been made. The aqueous buffer solution containing ionic liquid ethylpyridinium hexafluorophosphate [EtPy]⁺[PF₆]⁻ has been found to give the best results. The inhibition kinetic follows the first order model. Ionic liquids modified aqueous solutions show the potential to provide a promising and effective medium in detection of paraoxon with acetylcholinesterase.     

Equilibrium anionic polymerization of α-methylstyrene in p-dioxane

The equilibrium anionic polymerization of α-methylstyrene in p-dioxane, with potassium as initiator, has been investigated at 5, 15, 25, and 40°C by using high-vacuum techniques. The comparison of these results with those obtained previously for the equilibrium polymerization of α-methylstyrene in tetrahydrofuran revealed that, although the values of ΔG_1c, the free-energy change upon the polymerization of 1 mole of liquid monomer to 1 bases-mole of liquid amorphous polymer of infinite chain length, are the same for both systems, there is a distinct effect of the solvent. This effect is reflected in the value of monomer equilibrium concentration and its variation with polymer concentration and is explained in terms of a solvent–monomer and solvent–polymer interaction parameter.     

Acceptor properties of titanium(IV) phenoxides

Summary Compounds of composition TiCl_4–n(OPh)_n · 2L (L = monodentate ligand, n = 1–4) have been prepared by the reaction of the parent titanium phenoxides (1 mol) with the ligand (2 mols) and characterized by elemental analysis, molar conductance, molecular weight and i.r. spectral studies.     

Determination of strange quark suppression in hadronic vacuum

We study the forward-backward rapidity correlation slope in \(\bar p\) p interactions at high energies. We show that the measurement of this slope in different rapidity intervals, yields direct information on multiple-scattering. It turns out that the particles produced in inelastic rescattering are concentrated neary=0. This is a key feature of the multi-chain dual parton model, and leads to a simple explanation of the main features of multi-hadron production at very high energies, such as the energy dependence of the height and shape of the rapidity distribution, approximate K.N.O. scaling etc. We also show that the large values of the forward-backward correlation slope measured at ISR and SPS, are obtained in the model using the standard idea of short-range order in a single inelastic collision.     

1,1,1,1-Tetrakis(o-fluorophenylamino)silane tris[titanium(IV) chloride]. Evidence for a new titanium cation [Ti2Cl7]+

Si(NHC₆H₄F-o)₄ · 3TiCl₄ (1) has been obtained from the disproportionation of (CF₃CH₂O)₃SiNHC₆H₄F-o and TiCl₄ in petroleum ether (40–60 °C) at –10 °C. The analytical (elemental analysis, molar conductance) and spectral (i.r., ¹H- and ¹⁹F-n.m.r.) data suggested that (1) behaves as [Si(NHC₆H₄F-o)₄ · Ti₂Cl₇]⁺ [TiCl₅]^–. The presence of these ions has been confirmed by characterising the products of metathetical reactions of (1) with R₄NX (R = Bu and Et; X = I and Br) and with AgNO₃. The data suggest the presence of a new titanium cation [Ti₂Cl₇]⁺.