Geminal bis-ureas as gelators for organic solvents: gelation properties and structural studies in solution and in the gel state

Several geminal bis-urea compounds were synthesised by means of an acid-catalysed condensation of various benzaldehydes with different monoalkylureas. Many of these compounds form thermoreversible gels with a number of organic solvents at very low concentrations (<3mM) and which are stable to temperatures higher than 100 degrees C. Electron microscopy revealed a three-dimensional (3D) network of intertwined fibres, which are several tens of micrometers long and have a width ranging from approximately 30 to 300 nm. The possible aggregate forms and aggregate symmetries were evaluated by means of molecular mechanics calculations. 1H NMR, 2D NMR, 13C NMR and 13C-CP/MAS NMR techniques were used to obtain information about the aggregation and possible aggregate symmetry of geminal bis-ureas in solution, in the gel state, and in the solid state.     

Long-range sigma-pi interactions in tetrahydro-4H-thiopyran end-capped oligo(cyclohexylidenes). Photo-electron spectroscopy, ab initio SCF MO calculations, and natural bond orbital analyses

Long-range sigma-pi interactions in tetrahydro4H-thiopyran end-capped oligo(cyclohexylidenes) were identified by He(I) photoelectron spectroscopy (PES) and ab initio RHF/6-31G* calculations. The vertical ionization energies Ivj of the highest occupied molecular orbitals (MO's) were assigned using Koopmans' theorem (Iv,j = -epsilonj) and by correlation with the ionizations of related reference compounds. The experimental (PES) and theoretical (RHF/6-31G*) results are in good agreement. For tercyclohexylidene derivatives which contain two nonconjugated pi-bonds splittings deltaIv,j of the pi-bands in the range from approximately 0.5 to 0.7 eV (delta-epsilonj approximately 0.6 to 0.9 eV). For the bi- and tercyclohexylidene compounds containing two sulfur atoms at their alpha- and omega-end positions the pi-type sulfur lone pair bands [Lppi(S)] split significantly by deltaIvj approximately 0.3 to 0.4 eV (delta-epsilonj approximately 0.3 to 0.4 eV), i.e. sigma-pi interactions over distances of ca. 8 and 12 A, respectively, occur. The magnitude of the interactions and the observed splittings are independent of the anti and syn conformations of the oligo(cyclohexylidene) hydrocarbon skeletons. RHF/6-31G* Natural Bond Orbital analyses reveal that the Hax-C-C-Hax precanonical MO's (PCMO's) centered on the cyclohexyl-type rings are paramount for the relay of the through-bond sigma-pi interactions; no through-space sigma-pi interactions were identified.     

Polymorphic Phase Transformation in In2La and CeIn2

Nuclear quadrupole interactions of ¹¹¹Cd probes in In₂La and CeIn₂ were measured using perturbed angular correlation of gamma rays (PAC). Near room temperature, a single non-axially symmetric quadrupole interaction was observed in each compound, with ω ₀ = eQV _zz /ℏ = 78.8(2) Mrad/s and η = 0.312(1) for In₂La at 11°C and ω ₀ = 80(1) Mrad/s and η = 0.29(2) for CeIn₂ at 34°C. The observed non-axial symmetry is consistent with the reported CeCu₂ structure of the phases. The non-axially symmetric interactions were replaced completely by axially symmetric interactions (η = 0) at 524°C, with ω ₀ = 101.0(1) Mrad/s in In₂La and ω ₀ = 96.9(4) Mrad/s in CeIn₂. The change in symmetry is attributed to a polymorphic phase transformation. Based on symmetry information from the quadrupole interaction and on chemical arguments, it is proposed that high-temperature phases of In₂La and CeIn₂ both have the AlB₂ (C32) structure.     

Efficient Pricing of Derivatives on Assets with Discrete Dividends

It is argued that due to inconsistencies in existing methods to approximate the prices of equity options on assets which pay out fixed cash dividends at future dates, a new approach to this problem may be useful. Logically consistent methods which are guaranteed to exclude arbitrage exist, but they are not very popular in practice due to their computational complexity. An algorithm is defined which is easy to understand, computationally efficient, and which guarantees to generate prices which exclude arbitrage possibilitites. It is shown that for the method to work a mild uniform convergence condition must be satisfied and this condition is indeed satisfied for standard European and American options. Numerical results testify to the accuracy and flexibility of the method.     

Determination of the crystal structures of In70-Ni30 and In70-Pd30 using perturbed angular correlation

According to phase diagrams based on x-ray measurements, In70-Pt30 has the cubic Sn₇Ir₃ crystal structure (D8_f, cI40) but the alloys In70-Ni30 and In70-Pd30 have been variously reported to have either a cubic gamma-brass (D8_1???3, cI52) or the Sn₇Ir₃ structures. In this study, hyperfine interaction measurements are applied as an alternate method to identify phases. Perturbed angular correlation (PAC) measurements were made of characteristic nuclear quadrupole interactions of ¹¹¹In/Cd probe atoms, and demonstrated a common, characteristic “signature” of the Sn₇Ir₃ structure in all three alloys. The Sn₇Ir₃ structure has two inequivalent Sn-sites with a 3:4 ratio of atoms and point symmetries indicate that the electric-field gradients at both sites should be axially symmetric. Measured perturbation functions for all three alloys exhibited two axially symmetric quadrupole interaction signals having the expected 3:4 ratio of amplitudes, as expected for the structure. Furthermore, ratios of the two quadrupole interaction frequencies in each alloy were characteristically large, with frequencies for probe atoms on In(3) sites roughly five times greater than on In(4) sites. Taken together, these observations confirm that all three phases have the Sn₇Ir₃ structure. Quadrupole interaction frequencies are also reported for isostructural alloys of gallium with Pt, Pd and Ni. Negligible inhomogeneous broadening was observed in measurements near room temperature in all six phases, indicating excellent atomic ordering at the stoichiometric 70:30 compositions.     

A new measurement of the ratio of the cross sections of muon-neutrino and muon-antineutrino scattering on electrons

A new experimental determination of the electro-weak mixing angle θ_W is reported based on a second exposure of the CHARM calorimeter to the CERN-SPS wide-band beam. The ratio R of muon-neutrino- and muon-antineutrino-electron scattering cross section has been determined from a sample of 37 ± 10 and 35 ± 10 events. The experimental result is R = 1.26_?0.45^+0.72, corresponding to a value of sin²θ_W = 0.216 ± 0.055. The total sample of events collected in the CHARM calorimeter during the two exposures is $\text{(83 ± 16)ν}{}_{\mathrm{\mu }}\text{e}\text{events and}\text{(112 ± 21)}\text{ν}{}_{\mathrm{\mu }}\text{e}$ events, leadint to the final result sin²θ_W = 0.215 ± 0.032. The systematic error is estimated to be ± 0.012.     

About separation by cones

The notion of separation by hyperplanes is extended, so as to include separation by acute polyhedral cones.