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New books

     

Productive Coreflective Classes in Top

If sequential cardinals do not exist then every topological space is generated from a converging sequence by using finite products, disjoint sums and quotients. The author acknowledges the support of the grants MSM 0021620839 and GAČR 201/06/0933 of Czech Republic.     

Applications of NMR spectroscopy of chiral association complexes. 6. rotation about the C(sp2)—C(aryl) bond in 2,6-disubstituted pivalophenones

For the investigation of the barrier to rotation about the C(sp²)—C(aryl) bond in non-planar pivalophenones five derivatives were prepared and their ¹H and ¹³C NMR spectra assigned. Methyl and bromine groups in the 3-position have opposite substituent effects on the chemical shifts of the ¹H and ¹³C signals of Me² and Me⁴. The ΔG values were determined from the coalescence temperatures of the signal splittings generated by the addition of optically active shift reagents. The accuracy of this method was estimated by using different signals of 3-bromo-2,4,6-trimethylpivalophenone and by computer simulation of the line shape. A buttressing effect of substituents in the aromatic ring was observed. A change of the twist angle by the substitution of methyl by bromine in the tert-butyl group was suggested in order to explain the changes in ΔG and the chemical shifts.     

Theory of the non-radiative recombination of electrons at perturbation centres in polar crystals

Non-radiative recombination of electrons at a perturbation centre in a polar crystal is considered as a single phonon transition of a polaron in a non-adiabatic approximation from the continuous spectrum to the discrete excited state in a perturbation centre. The perturbation causing a transition is taken as the interaction of a polaron with a free phonon field leading to the production and disappearance of phonons in the neighbourhood of the perturbation centre. Calculation is carried out of the recombination coefficient and the effective cross-section for recombination as a function of the temperature for perturbation centres of the Coulomb type in crystals of ZnS.     

S-matrices

A new class of so called S-matrices is introduced which allows investigating links between various known classes of matrices such as Vandermonde matrices, Hankel matrices, companion matrices, etc. For complex S-matrices, the problem of decomposition into a quasidirect sum (a sum for which the sum of the ranks of the summands equals the rank of the given matrix) of indecomposable complex S-matrices is completely solved, and the uniqueness of such a decomposition is proved.     

Application of NMR spectroscopy of chiral association complexes. 8—Rotation about the C(sp2)–C(aryl) Bond in 2,6–disubstituted benzamides

The barrier to rotation about the C(sp²)? C(aryl) single bond in non-planar benzoyl compounds was investigated using N,N-dimethyl, N,N-tetramethylene and N,N-diisopropyl derivatives of 2,4,6-trimethylbenzamide and 2,6-dimethoxybenzamide and N,N-dimethyl derivatives of the corresponding thiobenzamides. Their ¹H and ¹³C NMR spectra were determined and assigned and the splittings in the ¹H spectra due to the addition of the optically active shift reagent (+)-Eu(hfbc)₃, are discussed. The free enthalpy of activation was calculated from the coalescence temperature of the ortho-methyl or -methoxyl signals and from a line-shape analysis. An exact equation for the determination of the rate constant at coalescence and a valid approximation which includes the line-width are presented. A distinct effect of the size of the N-substituent on the barrier to rotation in 2,6-dimethoxybenzamides was observed, while the π values for the 2,4,6-trimethylbenzamides studied are practically identical.     

Long range substituent effects relfected in the 13C NMR spectra of allyl alcohols and their derivatives

Acylation of allyl alcohols induces strong carbon shifts, shielding γ and deshielding δ effects. These shifts are a consequence of through-bond polarization of the olefinic carbons. Allyl ethers show similar, but milder perturbations. The olefinic carbon shifts reveal a strong concentration dependence. This effect, in greatly reduced form, is also observed in non-oxygenated alkenes. Hydrogen bonding by alcohols enhances the chemical shift difference in olefinic carbon pairs by increased polarization.