A rapid access to chiral alkylidene cyclopentenone prostaglandins involving ring-closing metathesis reaction

A synthesis of the alkylidene cyclopentenone prostaglandin TEI 9826 has been realized. The synthesis involved the preparation of the chiral 1,5-diene 8 using a stereoselective Claisen rearrangement from the allylic alcohol 6 giving the ester 7 after vinylation. Then a key RCM reaction allowed the preparation of the cyclopentenol 9 which, after oxidation, gave the cyclopentenone 10, precursor of the prostaglandin.     

Experimental study of the frequency response of electrochemical split probes to transversal velocity fluctuations

An experimental investigation of the frequency response of electrochemical probes to transversal velocity fluctuation is reported. The study has been focused on wall shear stress for a modulated flow due to an oscillating cylinder along its own axes since the wall shear stress has been first numerically determined for this flow. Results indicate that a frequency response correction to probe outputs is required and that this correction depends on the amplitude of fluctuations.List of symbols A total area of the electrode - A _i area of the part i of the electrode - a amplitude of oscillation - C concentration - c fluctuation of concentration - D cylinder diameter - D diffusion coefficient - h dimensionless velocity normal to the wall - H transfer function modulus - K _i transfer coefficient - l electrode length - n frequency - S wall shear - S fluctuation of the wall shear - U mean value of the fluid velocity far from the wall - u streamwise component of the fluid velocity - spanwise component of the fluid velocity (along the cylinder axis) - w component of the fluid velocity perpendicular to the wall - x direction of the mean flow - y direction parallel to the cylinder axis - z direction perpendicular to the wall - v kinematic viscosity - dimensionless distance perpendicular to the wall (z) - dimensionless distance (x) - phase shift - azimuthal angle - modulation frequency     

Finite size effects on structure and magnetism in mass-selected CoPt nanoparticles

In this paper, the one-way absorption property in one-dimensional dielectric/metal photonic crystal structure with a dielectric defect layer is studied. The effects of incident angle and state of polarization on one-way absorption behaviour of the anti-resonant (AR) mode are investigated. The normally incident wave from left to right propagation is totally allowed to penetrate to the structure but right to left propagation totally reflected at the same wavelength. It is found that, with increasing of the incident angle, the AR mode shifts to the lower wavelengths and its intensity decreases. Simultaneously, another AR mode with reversed one-way property appears at higher wavelength. The one-way behaviour on absorption is observed at the both states of polarizations but is localized on different wavelengths. Those effects, are suggesting that the proposed structure can be used as a direction sense polarization splitter or reflector/antireflector device.     

Main sequence stars with asymmetric dark matter

We study the effects of feebly or nonannihilating weakly interacting dark matter (DM) particles on stars that live in DM environments denser than that of our Sun. We find that the energy transport mechanism induced by DM particles can produce unusual conditions in the cores of main sequence stars, with effects which can potentially be used to probe DM properties. We find that solar mass stars placed in DM densities of ρ(χ)≥10(2) GeV/cm(3) are sensitive to spin-dependent scattering cross section σ(SD)≥10(-37) cm(2) and a DM particle mass as low as m(χ)=5 GeV, accessing a parameter range weakly constrained by current direct detection experiments.     

Nuclear quantum effects on the thermal expansion coefficient of hexagonal boron nitride monolayer

This work examines the importance of vibrational delocalization on a basicthermomechanical property of a hexagonal boron nitride monolayer, namely its thermalexpansion coefficient (TEC). Using a recently parametrized bond-order potential of theTersoff type, the TEC was theoretically obtained from the thermal variations of thelattice parameter a(T) calculated using threedifferent methods: (i) the quasiharmonic approximation; (ii) its anharmonic improvementbased on self-consistent phonons; (iii) fully anharmonic Monte Carlo simulations possiblyenhanced within the path-integral framework to account for nuclear quantum effects. Theresults obtained with the three methods are generally consistent with one another and withother recently published data, and indicate that the TEC is negative at least up to ca.700 K, quantum mechanical effects leading to a significant expansion by about 50% relativeto the classical result. Comparison with experimental data on bulk hexagonal BN suggestssignificant differences, which originate from possible inaccuracies in the model that tendto underestimate the lattice parameter itself, and most likely from the 2D nature of themonolayer and the key contribution of out-of-plane modes. The effects of isotopic purityin the natural abundances of boron are found to be insignificant.     

Ab initio investigation of the electronic and vibrational properties for the (CaLi)+ ionic molecule

A wide adiabatic study has been performed for numerous electronic states of CaLi⁺ molecular ion. The adiabatic potential energy curves and their spectroscopic constants (R_e, D_e, ω_e and T_e) have been calculated using an ab initio approach including a nonempirical pseudo-potential for the Ca and Li cores with the core polarisation potentials operator through full configuration interaction (FCI). Thereafter, the energies of vibrational levels and their spacing for all these states have been reported. In addition, the electric dipole moment curves have been investigated for the (1-19) Σ, (1-12) Π and (1-8) Δ electric states. Moreover it lets us check the extreme transition dipole moments (TDM). These behaviours of TDM are more accustomed to estimate the radiative lifetimes for all vibrational levels in 2¹Σ⁺ and 3¹Σ⁺ states. Also, the bound-bound and the bound-free contribution have been calculated precisely and by employing a Franck–Condon (FC) approximation.     

Improvement of the recursive projection method for linear iterative scheme stabilization based on an approximate eigenvalue problem

An algorithm for stabilizing linear iterative schemes is developed in this study. The recursive projection method is applied in order to stabilize divergent numerical algorithms. A criterion for selecting the divergent subspace of the iteration matrix with an approximate eigenvalue problem is introduced. The performance of the present algorithm is investigated in terms of storage requirements and CPU costs and is compared to the original Krylov criterion. Theoretical results on the divergent subspace selection accuracy are established. The method is then applied to the resolution of the linear advection–diffusion equation and to a sensitivity analysis for a turbulent transonic flow in the context of aerodynamic shape optimization. Numerical experiments demonstrate better robustness and faster convergence properties of the stabilization algorithm with the new criterion based on the approximate eigenvalue problem. This criterion requires only slight additional operations and memory which vanish in the limit of large linear systems.     

An ab initio molecular dynamics study of ionic conductivity in hexagonal lithium lanthanum titanate oxide La0.5Li0.5TiO3

To date, the fastest lithium ion-conducting solid electrolytes known are the perovskite-type ABO₃ oxide, with A = Li, La and B = Ti, lithium lanthanum titanate (LLTO) Li_3x La_{( 2 \mathord}

Convenient and easy access to 2-hydroxycyclopent-2-enones from acylcyanohydrins

A convenient access to 2-hydroxycyclopentenones was designed from acylcyanohydrins, by using titanacyclopropane complexes as nucleophilic partners and an intramolecular aldol condensation in basic conditions. The development of a one-pot procedure allows a step- and atom-economic process, and the use of Grignard reagents other than ethylmagnesium bromide provided valuable 3,4-disubstituted 2-hydroxycyclopentenones. The utility of the hydroxy group was illustrated by further functionalization of the α-position using palladium-mediated cross-coupling reactions.