This paper proposes a polaronic stacking fault defect model as the origin of the huge dielectric properties in CaCu 3 Ti 4 O 12 (CCTO) materials. The model reconciles the opposing views of researchers on both sides of the intrinsic versus extrinsic debate about the origin of the unusually high values of the dielectric constant measured for CCTO in its various forms. Therefore, by considering stacking fault as the origin of the high dielectric constant phenomena, it was shown that the internal barrier layer capacitance mechanism is enhanced by another similar, but different in nature, mechanism that operates in the nanoscale range due to polaron defects associated with stacking fault, a mechanism that was referred to as nanoscale barrier layer capacitance (NBLC). The NBLC approach explains the origin of the CCTO's huge dielectric constant coexisting with semiconducting features.

An investigation was made into the non-Ohmic and dielectric properties of a Ca2Cu2Ti4O12 perovskite-type system. Compared to the traditional CaCu3Ti4O12-based composition, the imbalance between the Ca and Cu atoms caused the formation of a polycrystalline system presenting ∼33.3mol% of CaCu3Ti4O12 (traditional composition) and ∼66.7mol% of CaTiO3. As for non-Ohmic properties, the effect of this Ca and Cu atom imbalance was that a nonlinear electric behavior of ∼1500 was obtained. This high nonlinear electrical behavior emerged in detriment to the ultrahigh dielectric property frequently reported. The high non-Ohmic property was explained by the existence of Schottky-type barriers, whose formation mechanism may be similar to that proposed for traditional metal oxide non-Ohmic devices, according to similarities discussed herein.

[reaction: see text] A new iron(III) halide-promoted aza-Prins cyclization between gamma,delta-unsaturated tosylamines and aldehydes provides six-membered azacycles in good to excellent yields. The process is based on the consecutive generation of gamma-unsaturated-iminium ion and further nucleophilic attack by the unsaturated carbon-carbon bond. Homoallyl tosylamine leads to trans-2-alkyl-4-halo-1-tosylpiperidine as the major isomer. In addition, the alkyne aza-Prins cyclization between homopropargyl tosylamine and aldehydes gives 2-alkyl-4-halo-1-tosyl-1,2,5,6-tetrahydropyridines as the only cyclic products.

Enzymes dependent on nicotinamide cofactors are important components of the expanding range of asymmetric synthetic techniques. New challenges in asymmetric catalysis are arising in the field of deuterium labelling, where compounds bearing deuterium ( 2 H) atoms at chiral centres are becoming increasingly desirable targets for pharmaceutical and analytical chemists. However, utilisation of NADH-dependent enzymes for 2 H-labelling is not straightforward, owing to difficulties in supplying a suitably isotopically-labelled cofactor ([4-2 H]-NADH). Here we report on a strategy that combines a clean reductant (H 2 ) with a cheap source of 2 H-atoms ( 2 H 2 O) to generate and recycle [4-2 H]-NADH. By coupling [4-2 H]-NADH-recycling to an array of C=O, C=N, and C=C bond reductases, we demonstrate asymmetric deuteration across a range of organic molecules under ambient conditions with near-perfect chemo-, stereo-and isotopic selectivity. We demonstrate the synthetic utility of the system by applying it in the isolation of the heavy drug (1S,3'R)-[2',2',3'-2 H 3 ]solifenacin fumarate on a preparative scale.

Dielectric spectroscopy was used in this study to examine CaCu3Ti4O12 polycrystalline samples. The analysis involved systems presenting low non-Ohmic properties, and the grain’s internal domain was evaluated separately from the contribution of barrier-layer capacitances associated with Schottky-type barriers in this type of material. The effect of oxygen-rich atmosphere and high cooling rate was evaluated, revealing a strong increase in the dielectric properties of the CaCu3Ti4O12 system under these conditions. This effect was attributed to a chemical change in the grain’s internal domain, which may be considered an internal barrier-layer capacitance of the polycrystalline material.

The structural, microstructural, non-ohmic and dielectric properties of perovskite-type CaCu3Ti4O12 (CCTO) with Ca/Cu stoichiometries of 1/3, 1/1 and 3/1 are discussed. The 1/3 Ca/Cu ratio system presents very high dielectric permittivity (∼9000 at 10 kHz) and a low non-ohmic property (α = 9), whereas the 1/1 Ca/Cu ratio system shows the opposite effect, i.e. the dielectric permittivity decreases (2740 at 10 kHz) and the non-ohmic property increases (α = 42), indicating that these properties are not directly correlated. The results of this work reinforce the idea that the greatest contribution to the very high permittivity is caused by the presence of planar defects inside the CCTO grains, generating internal nanometric domains associated with stacking faults, according to the nanoscale barrier layer capacitance model proposed very recently in the literature [1]. The non-ohmic property is related to the presence and distribution of phases such as CaTiO3 (CTO) and CuO, segregated or precipitated at the grain boundary, which generate large numbers of electrically active interfaces.

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