A straightforward access to pyrrolidine-based ligands for asymmetric synthesis

A straightforward and flexible method for the preparation of ligands based on the pyrrolidine scaffold is presented. The synthetic strategy involves a diastereoselective allylation of phenylglycinol-derived imines, followed by a cyclization promoted by a hydrozirconation/halogenation sequence. Enantioselectivities of up to 84% ee in the asymmetric allylic allylation were obtained using these ligands.     

Impact of some parameters on investments in oligopolistic electricity markets

It is seldom the case that one has the opportunity to compare investments as projected by a long-term multi-period model to what is eventually realized in practice. Further, although sensitivity analysis is of common use in any optimization setting, the impact of some parameters on strategic investments is not yet fully assessed in the context of the deregulated electricity industry. Starting with a benchmark model of the Finnish industry, we precisely explore the impact on equilibrium investments of varying such parameters as direct- and cross-price elasticities, length of the planning horizon and the depreciation rate of capacity. We run the model with different parameter values and compare the predicted equilibrium with what companies have actually done. The model is a stochastic dynamic game involving three players and played over a ten-year period.Our results show the depreciation rate and the planning horizon have a notable effect on investment levels, whereas price elasticities seem to play a lesser role. Although the model’s results are rather well aligned to total industry investments, it diverges from individual levels. This may be due to the cost parameter used and/or to the open-loop information structure adopted in the computations. In any event, these results should be of methodological and practical interest to scholars and practitioners involved in strategic investment in the electricity industry.     

Binding of a truncated form of lecithin:retinol acyltransferase and its N- and C-terminal peptides to lipid monolayers

Lecithin:retinol acyltransferase (LRAT) is a 230 amino acid membrane-associated protein which catalyzes the esterification of all-trans-retinol into all-trans-retinyl ester. A truncated form of LRAT (tLRAT), which contains the residues required for catalysis but which is lacking the N- and C-terminal hydrophobic segments, was produced to study its membrane binding properties. Measurements of the maximum insertion pressure of tLRAT, which is higher than the estimated lateral pressure of membranes, and the positive synergy factor a argue in favor of a strong binding of tLRAT to phospholipid monolayers. Moreover, the binding, secondary structure and orientation of the peptides corresponding to its N- and C-terminal hydrophobic segments of LRAT have been studied by circular dichroism and polarization-modulation infrared reflection absorption spectroscopy in monolayers. The results show that these peptides spontaneously bind to lipid monolayers and adopt an α-helical secondary structure. On the basis of these data, a new membrane topology model of LRAT is proposed where its N- and C-terminal segments allow to anchor this protein to the lipid bilayer.     

The A′(3Π2) state of ICl

Although $\text{A′(}{}^3\text{Π}{}_2\text{) ← X(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)}$ is forbidden in near case c molecules the A′ ← X transition can be efficiently accomplished by the three-step sequence $\text{A′(}{}^3\text{Π}{}_2\text{) ← D′(2) ← A(}{}^3\text{Π}{}_1\text{) ← X(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)}$. Transitions to a range of levels of A′, v_A′ = 2–38, have been recorded by this means, using J-selective polarization-labeling spectroscopy. Principal constants of the A′ state of I³⁵Cl are T_e = 12682.05, ω_e = 224.57, ω_eχ_e = 1.882, ω_ey_e = ?0.0107, B_e = 0.08653, and α_e = 0.000675 cm^?1. The A′ state is therefore similar in its physical characteristics to two other (relatively) deep states, $\text{A(}{}^3\text{Π}{}_1\text{)}$ and $\text{B(}{}^3\text{Π}{}_0\text{+)}$, of the 2431 configuration.     

Citation for the 2003 ICMI Felix Klein medal to Guy Brousseau

Information

Citation for the 2003 ICMI Felix Klein medal to Guy Brousseau     

Excitons in carbon nanotubes: an ab initio symmetry-based approach

The optical absorption spectrum of the carbon (4,2) nanotube is computed using an ab initio many-body approach which takes into account excitonic effects. We develop a new method involving a local basis set which is symmetric with respect to the screw-symmetry of the tube. Such a method has the advantages of scaling faster than plane-wave methods and allowing for a precise determination of the symmetry character of the single-particle states, two-particle excitations, and selection rules. The binding energy of the lowest, optically active states is approximately 0.8 eV. The corresponding exciton wave functions are delocalized along the circumference of the tube and localized in the direction of the tube axis.     

On-line measurement of texture,thickness and plastic strain ratio using laser-ultrasound resonance spectroscopy

Laser-ultrasound resonance spectroscopy, a non-contact ultrasonic technique, was used to determine reliably and rapidly the crystallographic texture, the average plastic strain ratio, and the thickness of sheet metal on the production line. As with laser-ultrasonics, a short laser pulse is used to generate a wide-band pulse of ultrasound and a laser interferometer is used for its detection. In this paper, a large number of echoes are collected and analyzed together using Fourier techniques to measure the natural resonance frequencies in the thickness of the sheet. One longitudinal and two shear resonance frequencies were measured together with their harmonics. From these frequencies, two crystallographic orientation distribution coefficients, W(400) and W(420), are obtained, as well as a highly accurate measurement of the sheet thickness that is corrected for changes in ultrasonic velocity caused by texture variations. Using these coefficients, the average and in-plane twofold and fourfold variations of the plastic strain ratio, respectively r delta(2)r, and delta(4)r, can be evaluated. These parameters are indications of the formability of metals sheets, which is of industrial interest. Measurements on 1 mm thick, low carbon steel sheets have shown the following measurement accuracies: r to within +/-0.08, delta(2)r, and delta(4)r to within +/-0.1, and thickness to better than +/-1 microm. On-line tests at LTV Steel Company showed that the sensitivity of the apparatus is sufficient to detect systematic variations in texture along the length of similar production coils and that the on-line repeatability for r was of order +/-0.02.     

Tin Mössbauer spectroscopy of tin-rich iridium-tin alloys

Ir₅Sn₇, Ir₃Sn₇ and newly obtained IrSn₄ /4/ exhibit complex Mössbauer spectra. The positions of the individual lines range from 0.82 to 3.0 mm/s and the average isomer shift \(\overline {IS} \) derived for each compound of Sn atomic percentage x follows the relationship: \(\overline {IS} = 0.60 + 0.0194 x\) . Rather large quadrupole splittings are obtained. The f factors are about 0.20 at 295 K and 0.37 at 78 K, from which Debye temperatures of 200 to 300 K have been calculated.