Synthesis of D-Glucose-based Azacrown Ethers with Phosphinoxidoalkyl Side Chains and Their Application to an Enantioselective Reaction

Five chiral -D-glucose-based monoaza-15-crown-5 ethers with phosphinoxidoalkyl side chains of one to five carbon atoms (5a–e)have been synthesised. The cation binding ability of the new lariat ethers was evaluated bythe picrate extraction method. The substituents at the nitrogen atom were not a major influenceon the cation extraction ability of the azacrown ether; the compounds showed, however, a significant asymmetric induction as phase transfer catalysts in the Michael addition of2-nitropropane to chalcone (95% ee).     

Solitons in the one-dimensional forest fire model

Fires in the one-dimensional Bak-Chen-Tang forest fire model propagate as solitons, resembling shocks in Burgers turbulence. The branching of solitons, creating new fires, is balanced by the pairwise annihilation of oppositely moving solitons. Two distinct, diverging length scales appear in the limit where the growth rate of trees, p, vanishes. The width of the solitons, w, diverges as a power law, 1/p, while the average distance between solitons diverges much faster as d approximately exp(pi2/12p).     

Electrical properties of TiO<Subscript>2</Subscript>: equilibrium vs dynamic electrical conductivity

The present work reports semiconducting properties of high purity TiO₂ determined in the gas/solid equilibrium, as well as during controlled heating and cooling in the range 300–1,273 K. The activation energy of the electrical conductivity is considered in terms of the activation enthalpy of the formation of ionic defects and the activation enthalpy of the mobility of electronic defects. These data, determined from the dynamic electrical conductivity experiments, are compared to the electrical conductivity data determined in equilibrium. It is shown that only the equilibrium electrical conductivity data for high-purity TiO₂ are well defined. It is shown that the activation energy of the electrical conductivity determined in equilibrium differs substantially from that for the dynamic electrical conductivity data during cooling and heating. It is concluded that the formation enthalpy term determined from the dynamic conductivity data is determined by the heating/cooling rate rather than materials’ properties.     

Interactions of oxygen with yttria-stabilized zirconia at room temperature

This paper reports the results of work function and EPR studies of yttria-stabilized zirconia (10Y-ZrO₂). The experimental data are considered in terms of the formation of oxygen chemisorbed species and subsequent oxygen incorporation as well as related charge transfer. It is concluded that oxygen chemisorption on 10Y-ZrO₂ at room temperature in its initial stage results in the formation of O ₂ ⁻ species. These species are then transformed into O ₂ ²⁻ , O⁻ species and, finally, are slowly incorporated into the oxide lattice. These processes take place without presence of Pt or any other electrode material.     

Pyridine carbon charges

By means of microwave spectra of six isotopic pyridines and dipole moment and proton magnetic resonance data the magnitude of the charges on the carbon atoms of pyridine is estimated. Each of the ortho carbon atoms has a charge of ca. +0·08 e, the meta atoms are uncharged, while the para carbon atom has a charge of ca. 0·04 e. The result is in rough agreement with quantum-mechanical estimates.     

Asymmetric epoxidation of substituted chalcones and chalcone analogues catalyzed by α-d-glucose- and α-d-mannose-based crown ethers

The chiral monoaza-15-crown-5 lariat ethers annellated to methyl-4,6-O-benzylidene-α-d-glucopyranoside-1 or mannopyranoside 2 have been applied as phase-transfer catalysts in the epoxidation of substituted chalcones and chalcone analogues with tert-butylhydroperoxide resulting in significant asymmetric induction. It was found that the position of the substituents in the aromatic ring of the chalcone had an influence both on the chemical yields and enantiomeric excesses. The lowest enantioselectivities (62–83% ee) were found in the case of ortho-substituted model compounds. The highest ee values (ee of 83–97%) were obtained in the case of para-substituted models. From among the chalcone analogues, the maximum ee (90–92%) was detected for the model compound having α-tert-butyl- and β-aryl groups. Using glucose-based crown ether 1, formation of the (?)-enantiomer was preferred, while applying mannose-based 2 as the catalyst, the (+)-enantiomer was in excess.     

Defect chemistry and electrical properties of La1−xSrxCoO3−δ III. Oxygen nonstoichiometry

This paper concerns verification of the defect chemistry models of La_1−xSr_xCoO_3−δ (LSC), involving the random defect model and the cluster defect model, against empirical data of oxygen nonstoichiometry. It appears that the experimental data may well be explained within the random defect model.