Synthesis and chiroptical properties of two new planar-chiral macrocycles

Could simple intraannular-arm macrocyclic systems exist in enantiopure stable forms? The effective synthesis of two representative compounds of such a class, their resolution into enantiomers, and experiments justifying their stability toward racemization are presented.     

Effect of oxygen deficit and nonuniform distribution of technological impurities on the dielectric properties of Y3Fe5O12 crystals

The experimental and calculated values of the optical permittivity ε_∞ have been analyzed and generalized with allowance for the oxygen concentration and possible valences of Fe and O ions in YIG single crystals. It is shown that the deficit of oxygen ions in the samples is accompanied by a decrease in ε_∞. A decrease in the gradient of distribution of Ba ions over the sample thickness decreases the difference between the calculated and experimental values. It is revealed that the ratio of the number of valence electrons to the number of core electrons, with regard to their polarizabilities, is proportional to the ratio of the incoherent and coherent X-ray scattering intensities, nk/k.     

On characterization of Poisson and Jacobi structures

We characterize Poisson and Jacobi structures by means of complete lifts of the corresponding tensors: the lifts have to be related to canonical structures by morphisms of corresponding vector bundles. Similar results hold for generalized Poisson and Jacobi structures (canonical structures) associated with Lie algebroids and Jacobi algebroids.     

Theoretical and experimental investigation of the linear optical response of YBa2Cu4O8 The relevance of LDA calculations

We report results of ellipsometric measurements of the dielectric tensor of YBa₂Cu₄O₈ as well as calculations employing density functional theory in the local density approximation (LDA). For the computation of the one-electron eigenvalues and states the linear-muffin-tin-orbital method (LMTO) was used. Measured and calculated results show good agreement. In particular, the calculation predicts different band structures for YBa₂Cu₃O₇ and YBa₂Cu₄O₈ in the vicinity of the Fermi energy which lead to significant differences in the optical spectra. One such difference is a region of small ε₂ in the near infrared which is a fingerprint of the high (relative to the top of the highest fully occupied band) Fermi energy as compared to the situation in YBa₂Cu₃O₇. Our experimental results confirm the theoretical findings.     

An invariance of geometric mean with respect to Lagrangian means

The invariance of the geometric mean G with respect to the Lagrangian mean-type mapping (Lf,Lg), i.e. the equation G○(Lf,Lg)=G, is considered. We show that the functions f and g must be of high class regularity. This fact allows to reduce the problem to a differential equation and determine the second derivatives of the generators f and g.     

The Transition Products in Substitutional Photochemistry of [Mo(CN)8]4− – Theoretical Approach. X-ray Crystal Structure of (AsPh4)[W(bpy)(CN)6]

The single crystal X-ray structure of (AsPh₄)[W(bpy)(CN)₆] is described. The structure of octa- and hepta-coordinated intermediates of substitutional photolysis of [Mo(CN)₈]⁴⁻ ion in aqueous media were determined by performing semi-empirical calculations. On the basis of obtained results as well as on empirical data the photolysis scheme has been postulated.     

Uniform persistence for nonautonomous and random parabolic Kolmogorov systems

The purpose of this paper is to investigate uniform persistence for nonautonomous and random parabolic Kolmogorov systems via the skew-product semiflows approach. It is first shown that the uniform persistence of the skew-product semiflow associated with a nonautonomous (random) parabolic Kolmogorov system implies that of the system. Various sufficient conditions in terms of the so-called unsaturatedness and/or Lyapunov exponents for uniform persistence of the skew-product semiflows are then provided. Among others, it is shown that if the associated skew-product semiflow has a global attractor and its restriction to the boundary of the state space has a Morse decomposition which is unsaturated or whose external Lyapunov exponents are positive, then it is uniformly persistent. More specific conditions are discussed for uniform persistence in n-species, particularly 3-species, random competitive systems.     

Korrosionsuntersuchung

Ohne Zusammenfassung     

9‐Methyl‐3‐phenyl­diazenyl‐9H‐carbazole: X‐ray and DFT‐calculated structures

The title compound, C₁₉H₁₅N₃, was prepared by condensation of 3‐nitroso­carbazole and aniline with subsequent methyl­ation. The structure is built up of stacks of almost planar mol­ecules. Density functional theory (DFT) calculations predict a completely planar conformation, different from that observed in the crystal lattice. HOMA (harmonic oscillator model of aromaticity) indices, calculated for three aromatic rings, demonstrate the small influence of the azo substituent on π electrons in the carbazole system.     

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. V. Multiblock and random copolymers of L‐lactide with trimethylene carbonate obtained in copolymerizations initiated with zirconium(IV) acetylacetonate

Using zirconium(IV) acetylacetonate as an initiator of lactide/trimethylene carbonate copolymerization allowed us to obtain high‐molecular‐weight copolymers with high efficiency. The reactivity ratios of the comonomers were 13.0 for lactide and 0.53 for trimethylene carbonate. Despite the large differences between the values of the reactivity ratios, copolymers with randomized chain structures were obtained. This phenomenon occurred as a result of an intensive intermolecular transesterification process proceeding along with the reaction of copolymer chain growth and modifying its final structure. Conducting the copolymerization at the relatively low temperature of about 110 °C, which minimized the influence of intermolecular transesterification, made it possible to obtain semicrystalline copolymers with multiblock structures. Increasing the temperature of copolymerization up to 180 °C was associated with strong intensification of the transesterification reactions. At this temperature, amorphous copolymers were obtained with identical compositions but highly randomized chain structures. An analysis of the chain microstructures of the obtained copolymers, determining the average length of the blocks, the intermolecular transesterification ratio, and the degree of chain randomization, was conducted by means of NMR spectroscopy. For this purpose, very specific signal assignment in the carbonyl and methylene carbon regions of the ¹³C NMR spectra to appropriate comonomer sequences of polymeric chains was performed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3184–3201, 2006