Selective favorskii rearrangement in macrocyclic rings

A mixture of 2,2-dibromo-12-chlorocyclododecanone (IIa) and 2,12-dibromo-2-chlorocyclododecanone (IIb) by Favorskii rearrangement gave selectively methyl 2-chloro-1-cycloundecene-1-carboxylate (IIIa).     

Synthesis of 2,3,3a,8a-tetrahydroindeno[2,1-b]pyrrole derivatives

A new entry into the 2,3,3a,8a-tetrahydroindeno[2,1-b]pyrrole system, 1 , has been investigated. 2,3,3a,8a-Tetrahydro-3a,8a-dihydroxy-1-methylindeno[2,1–6]pyrrole-2,8-dione, 3 , formed from the reaction of ninhydrin and N-methylacetamide has been subjected to catalytic hydrogenation, hydride reduction, and chlorination reactions to afford a variety of substituted derivatives of 1 .     

Total syntheses of (+)-temisin, (+)-melitensin and related elemanolides from (-)-artemisin

(+)-Temisin, (+)-melitensin, and related sesquiterpene lactones have been synthesized from (-)-artemisin.     

Calculation of exchange coupling constants in solid state transition metal compounds using localized atomic orbital basis sets

The application of theoretical methods based on density functional theory using hybrid functionals and localized, atomic orbital type basis sets is shown to provide good estimates for exchange coupling constants in non-metallic, solid state transition metal compounds with relatively complex crystal structures. The accuracy of the calculated exchange coupling constants is similar to that previously obtained for dinuclear and polynuclear molecular compounds. As an application of this procedure, the magnetic properties of the high-temperature phase of CuGeO₃, the recently synthesized silver copper oxide Ag₂Cu₂O₃, and the family of M[N(CN)₂]₂ (M=Cr(II), Mn(II), Fe(II), Co(II), Ni(II) and Cu(II)) compounds are analyzed via the computation of their most relevant exchange coupling constants.     

Experimental and kinetic modeling study of combustion of gasoline, its surrogates and components in laminar non-premixed flows

Experimental and numerical studies are carried out to construct surrogates that can reproduce selected aspects of combustion of gasoline in non premixed flows. Experiments are carried out employing the counterflow configuration. Critical conditions of extinction and autoignition are measured. The fuels tested are n-heptane, iso-octane, methylcyclohexane, toluene, three surrogates made up of these components, called surrogate A, surrogate B, and surrogate C, two commercial gasoline with octane numbers (ON) of 87 and 91, and two mixtures of the primary reference fuels, n-heptane and iso-octane, called PRF 87 and PRF 91. The combustion characteristics of the commercial gasolines, ON 87 and ON 91, are found to be nearly the same. Surrogate A and surrogate C are found to reproduce critical conditions of extinction and autoignition of gasoline: surrogate C is slightly better than surrogate A. Numerical calculations are carried out using a semi-detailed chemical-kinetic mechanism. The calculated values of the critical conditions of extinction and autoignition of the components of the surrogates agree well with experimental data. The octane numbers of the mixtures PRF 87 and PRF 91 are the same as those for the gasoline tested here. Experimental and numerical studies show that the critical conditions of extinction and autoignition for these fuels are not the same as those for gasoline. This confirms the need to include at least aromatic compounds in the surrogate mixtures. The present study shows that the semi-detailed chemical-kinetic mechanism developed here is able to predict key aspects of combustion of gasoline in non premixed flows, although further kinetic work is needed to improve the combustion chemistry of aromatic species, in particular toluene.     

GBT pre-buckling and buckling analyses of thin-walled members under axial and transverse loads

This paper presents an analytical approach for pre-buckling and buckling analyses of thin-walled members implemented within the framework of the Generalised Beam Theory (GBT). With the proposed GBT cross-sectional analysis, the set of deformation modes used in the analysis is represented by the dynamic modes obtained for an unrestrained frame representing the cross-section. In this manner, it is possible to account for the deformability of the cross-section in both pre-buckling and buckling analyses. Different loading conditions, including both axial and transverse arrangements, are considered in the applications to highlight under which circumstances the use of the GBT deformation modes is required for an adequate representation of the pre-buckling and buckling response. The numerical results have been validated against those determined using a shell element model developed in the finite element software ABAQUS.     

Is It Possible To Get High TC Magnets with Prussian Blue Analogues? A Theoretical Prospect

Theoretical methods based on density functional theory have been employed to search for Prussian blue analogues with Curie temperatures higher than the ones reached today. Our study suggests several possible cyano-bridged compounds as candidates to present stronger exchange coupling and higher ordering temperatures than the well known Cr(III)V(II) derivatives.     

Phase contribution to dynamic gratings recorded in Er-doped fiber with saturable absorption

Experimental observation of phase (i.e. refractive index) component in the dynamic gratings recorded in erbium-doped optical fiber with saturation of optical absorption is reported. We utilized configuration of transient two-wave mixing with rectangular phase modulation of one of counterpropagating recording waves, where unshifted phase grating resulted in a transient energy exchange. The reported experiments were performed with heavily doped (≈5400 ppm erbium) fibers in a wide spectral range of Er³⁺ fundamental absorption at selected laser wavelengths 1492, 1526, 1549, and 1568 nm. Relative contribution of phase grating was especially large (up to ≈100% of the maximal amplitude component) at the opposite sides of the investigated spectral range and was significantly lower in its central part. The amplitude grating was found especially strong at short wavelength side of the spectrum (i.e. at 1492 nm), where the grating amplitude proved to be only two times lower than the theoretically predicted from consideration of two-level model.