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.     

Synthesis and Structure of Triphenylscandium-bis(tetrahydrofuran)

Metathesis reaction of ScCl₃(THF)₃ with 3 equiv. of phenyllithium in THF/Et₂O solution affords ScPh₃(THF)₂ ( 1 ) in good yield. The crystallographically determined molecular structure of 1 reveals a trigonal-bipyramidal coordination sphere with the THF molecules in the axial positions and Sc–C bonds of 2.245(4)–2.266(4) Å. The σ-bound phenyl groups are only slightly twisted (0, 8, 18°) with respect to the ScC₃ plane. Ab initio calculations suggest that the THF molecules play some direct role in the moderate coplanarity of the phenyl rings.     

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.     

Synthesis of dipeptidyl peptidase-4 inhibitors: a brief overview

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Looking glass inhibitors: both enantiomeric N-benzyl derivatives of 1,4-dideoxy-1,4-imino-d-lyxitol [a potent competitive inhibitor of α-d-galactosidase] and of 1,4-dideoxy-1,4-imino-l-lyxitol [a weak competitive inhibitor of α-d-galactosidase] inhibit naringinase,an α-l-rhamnosidase competitively

Benzhydryl protection by diphenyldiazomethane of an alcohol in enantiomeric base-sensitive ribonolactones allows short efficient syntheses of 1,4-dideoxy-1,4-imino-d-lyxitol (DIL) and of 1,4-dideoxy-1,4-imino-l-lyxitol (LIL). DIL showed potent [K_i = 0.13 μM]—and LIL showed weak [K_i = 113 μM]—competitive inhibition of α-d-galactosidase. Both enantiomers N-benzyl-DIL [K_i = 64 μM] and N-benzyl-LIL [K_i = 13 μM] were moderate competitive inhibitors of naringinase, an α-l-rhamnosidase.     

A Mössbauer spectroscopic study of salt lake sediments from Qaidam basin

Mössbauer spectroscopy, X-ray diffractometry and chemical fractionation have been used to study the clay smaples in sediments of Charhan playa and Qinghai lake. The spectral components of the Mossbauer spectra of the samples are attributed to Fe²⁺ ions in chlorite and siderite, Fe³⁺ ions in clay minerals and hematite, and partly in amorphous ferric hydroxides. The essential difference in the mineral composition of the sediments of both lakes is the presence of siderite in the samples of Char han playa, whereas it is absent in the samples of Qinghai lake. The fraction of the amorphous ferric hydroxides is higher in the sediments of Qinghai lake. Total Fe²⁺/Fe³⁺ ratios increase with sediment depth of Charhan playa, whereas these ratios are altogether smaller and run through a maximum at a certain depth for Qinghai lake.     

Elastic electron scattering from 40Ar

Cross sections for elastic electron scattering from ⁴⁰Ar have been measured for the momentum transfer range from 0.59 to 1.31 fm^?1. We have analyzed with the Fourier-Bessel ansatz our data as well as the data of former experiments. The rms charge radius we have found is 3.423(14) fm. The results are in excellent agreement with latest muonic data. Furthermore, we have reanalyzed former ⁴⁰Ca data and have discussed the ⁴⁰Ca- ⁴⁰Ar charge distribution.