Lower Rim Substituted tert-Butyl calix[4]arenes (I). The Structure and Complexing Properties in Ion-Selective PVC Membrane Electrodes

Some di- and tetraamide tert-butylcalix[4]areneswere synthesized and described. Their ionophoric properties were studied in liquid membrane ion-selective electrodes. The correlation between thechemical structure (conformation in solution determined by ¹H NMR) and potentiometric ion-selectivity and complex formation constant havebeen studied. The PVC membrane electrodes based on tetraamides 8–11 show high sodium selectivity, are stable and long lasting. Disubstituted amides 1–7 are selective for larger and more lipophilic ions, as for exampleguanidinium ion. The crystal structure of the diamide 4 was determined by single crystal X-ray analysis. Crystals of 4 are triclinic, spacegroup P-1, with: a = 16,669(8), b = 17.795(10), c = 20.984(8) Å, =91.08(4)°, = 91.60(3)°, = 90.73(4)° and Z = 4. Ionophore 4 posseses a distorted cone conformation and is substituted at the proximal phenol rings.     

Observation of the Debye-Waller factor in a colloidal single crystal

Bragg diffraction spot intensities of a colloidal single crystal were found to exhibit a DebyeWaller factor-like decay. The Lindemann parameter and the mean-square displacement after infinite times of the colloidal particles could be obtained.     

Formation of sulfur surface species on a commercial NO<Subscript>x</Subscript>-storage reduction catalyst

The influence of SO₂ exposure under lean (oxidizing) and rich (reducing) reaction conditions on the storage and oxidation/reduction function of a commercial NO_x storage-reduction catalyst was investigated by temperature-programmed uptake experiments and high temperature XRD. Both the storage capacity and the oxidation/reduction function of the catalyst were deactivated by SO₂ exposure under lean and rich reaction conditions. The deactivation of the storage component, i.e. the loss of the NO_x storage capacity, resulted mainly from the formation of Ba-sulfates accumulating in the bulk phase, which have a high thermal stability (>800°C) and, therefore, cannot be removed under the typical operation conditions of a NSR catalyst. For the oxidation function only a temporarily deactivation during lean reaction conditions was observed. Besides the formation of SO^2- ₄ species on the storage component at the beginning of the SO₂ exposure under rich conditions, an adsorption of SO₂ on the noble metal component was observed resulting in the formation of sulfur deposits. The oxidation of these sulfur species with a subsequent spillover of SO^2- ₄ species to the storage component during lean conditions could accelerate the deactivation of the storage capacity.     

Cole-Cole Analysis of the Superspin Glass System Co 80 Fe 20 /Al 2 O 3

Ac susceptibility measurements were performed on discontinuous magnetic multilayers [Co 80 Fe 20 ( t )/Al 2 O 3 (3 nm)] 10 , t = 0.9 and 1.0 nm, by Superconducting Quantum Interference Device (SQUID) magnetometry. The CoFe forms nearly spherical ferromagnetic single-domain nanoparticles in the diamagnetic Al 2 O 3 matrix. Due to dipolar interactions and random distribution of anisotropy axes the system exhibits a spin-glass phase. We measured the ac susceptibility as a function of temperature 20 h T h 100 K at different dc fields and as a function of frequency 0.01 h f h 1000 Hz. The spectral data were successfully analyzed by use of the phenomenological Cole-Cole model, giving a power-law temperature dependence of the characteristic relaxation time c and a high value for the polydispersivity exponent, f , 0.8, typical of spin glass systems.     

Measurement of charge distributions for 229Th(nth,f) and 232U(nth,f)

A gas ΔE ? E_R telescope has been used to measure charge yields and their correlations with kinetic energies for ²²⁹Th and ²³²U. Even-charge yields are enhanced compared with odd-charge yields for both fissioning systems; this enhancement increases for events with higher kinetic energy. The mean odd-even effect $\text{δ}{}_{\mathrm{<mtext>p</mtext>}}\text{is}\text{= (40±4)\%}\text{for}{}^{229}\text{Th}$; it is $\text{(21 ± 3)\%}\text{for}{}^{232}\text{U-the same as for}{}^{233}\text{U}\text{((22.1±2.1)\%)}\text{and}{}^{235}\text{U}\text{((23.7±0.7)\%)}$. The energy-integrated δ_p and δ_p for different energy windows, vary strongly as a function of charge (Z) due to the underlying shells. The δ_p averaged over Z increases fast with kinetic energy, contrary to the existing results for ²³³U and ²³⁵U, where δ_p flattens off at low energies. For both systems, the most probable kinetic energy ē shows a strong odd-even stagger; the mean odd-even effect on energy, $\text{δE}{}_{\mathrm{<mtext>K</mtext>}}{}^{\mathrm{<mtext>o?e</mtext>}}\text{,}\text{is}\text{1.4 ± 0.3}\text{MeV for}{}^{229}\text{Th, and}\text{1.7±0.4}\text{MeV for}{}^{232}\text{U}\text{—}$ the latter is about twice the value for ${}^{233}\text{U}\text{(0.95 ± 0.09}\text{MeV}\text{)}\text{and}{}^{235}\text{U}\text{(0.7}\text{MeV}\text{)}$. These results are discussed in terms of the existing models.     

Asymptotic behaviour and stability to linear non-autonomous neutral delay difference equations

This paper is concerned with the asymptotic behaviour and the stability of a class of linear neutral delay difference equations with variable coefficients and constant delays. Via an appropriate solution of the so-called generalized characteristic equation, an asymptotic criterion and a stability result are established.     

High pressure X-ray diffraction studies on UAI2, UAI2, and UAI4 systems

Abstract

The UAI₂, UAI₂, AND UAI₄ compounds have been studied by high pressure X-ray diffraction up to a maximum pressure of ～ 35 GPa. The compressibility behaviour of UAI₂ has been found to be consistent with the itinerant 5f states, whereas that of UAI₂ and UAI₄, indicate a more localized nature. Further, UAI₂ has been found to undergo a structural transition at ～ 11 GPa and the structure of the high pressure phase has been identified to be of MgNi₂ type with space group P6₃/mmc. The structure of UAI₂ at ambient pressure is of MgCu₂ type with space group Fd3m. From the electronic considerations, for instance, free electrons per atom ratio e/a, it is anticipated that it may transform back to MgCu₂ type structure at still higher pressures. On similar considerations, it is expected that most of the AB₂ type Laves phase compounds of the ‘f’ electron systems may undergo the structural sequence: MgCu₂ – MgZn₂ (or MgNi₂) – MgCu₂ due to increased delocalization of their ‘f’ electron states.     

Study of the ion exchange equilibrium of Cl−, NO_3^{ - } , and SO_4^{{2 - }} ions on the AMX membrane

Equilibrium between the ion exchange membrane and solutions of anions at various valences has been the subject of this investigation. Competitive ion exchange reactions were studied on a strong base anion exchange membrane AMX manufactured by Tokuyama, commercialized by Eurodia, involving Cl^?, $ {\text NO}_3^{ - } $ and $ {\text SO}_4^{{2 - }} $ ions. Solution concentrations studied were 0.05 and 0.1 M for all the systems reported. Experiments were performed with sodium as the counter ion, and the temperature was kept constant (T?=?298 K). Ionic exchange isotherms for the binary systems— $ {{\text Cl}^{ - }}/{\text NO}_3^{ - } $ , $ {{\text Cl}^{ - }}/{\text SO}_4^{{2 - }} $ , and $ {\text NO}_3^{ - }/{\text SO}_4^{{2 - }} $ —were established. The obtained results show that the sulfate was the most strongly sorbed, and the selectivity order is $ {\text SO}_4^{{2 - }} > {\text NO}_3^{ - } > {{\text Cl}^{ - }} $ at 0.05 M and $ {\text NO}_3^{ - } > {\text SO}_4^{{2 - }} > {{\text Cl}^{ - }} $ at 0.1 M under the experimental conditions. Selectivity coefficients $ K_{{{{{\text Cl} }^{ - }}}}^{{{\text NO}_3^{ - }}} $ , $ K_{{2{{{\text Cl} }^{ - }}}}^{{{\text SO}_4^{{2 - }}}} $ , and $ K_{{2{\text NO}_3^{ - }}}^{{{\text SO}_4^{{2 - }}}} $ for the three binary systems were determined. All the results given by this membrane were compared with those obtained, in the same conditions, with the RPA membrane (produced by RHONE POULENC). Ternary equilibrium data were taken for $ {{\text Cl}^{ - }}/{\text NO}_3^{ - }/{\text SO}_4^{{2 - }} $ . The prediction of the ternary system based only on the binary data was consistent with the experimental data obtained for this system. The good agreement between the experimental and the predicted data showed that the proposed framework can be considered as an effective method to predict many ternary systems from binary systems.