Extraction Equilibria between Benzene and Water of Uni- and Bivalent Metal Picrates with Lariat 16-Crown-5: Effect of the Side Arms on the Extraction Ability and Selectivity

The overall extraction constants (K_ex) of uni- andbivalent metal picrates with 15-(2,5-dioxahexyl)-15-methyl-16-crown-5(L16C5) were determined between benzene and water at 25°C. TheK_ex values were analyzed into the constituent equilibriumconstants, i.e., the extraction constant of picric acid, the distributionconstant of the crown ether, the stability constant of the metalion–crown ether complex in water, and the ion-pair extraction constantof the complex cation with the picrate anion. The K_ex valuedecreases in the orders Ag⁺ > Na⁺ >Tl⁺ > K⁺ > Li⁺ andPb²⁺ > Ba²⁺ > Sr²⁺ for theuni- and bivalent metals, respectively, which are the same as those observedfor 16C5. The extraction selectivity was found to be governed by theselectivity of the ion-pair extraction of the L16C5–metal picratecomplex rather than by that of the complex formation in water. Theextraction ability of L16C5 is smaller for all the metals than that of 16C5,which is mostly attributed to the higher lipophilicity of L16C5. Differencesin the extraction selectivity between L16C5 and 16C5 were observed for thebivalent metals but little for the univalent metals. The side-arm effect onthe extraction selectivity was interpreted on the basis of the negativecorrelation between the effect on the complex stability constant in waterand that on the ion-pair extraction constant.     

Evaluation of interfacial toughness curve of bimaterial in submicron scale

A novel method combining the experimental data at only two different mixed mode fractures and an empirical interface toughness function has been proposed to establish the interfacial toughness function of a bimaterial in submicron scale. The modified four-point bend specimen was used in experiment to evaluate the first type of mixed mode fracture, while the sandwiched cantilever specimen was employed to get the second one. An empirical interface toughness function reflecting quite accurately the delamination behavior was adopted as a typical one. The obtained results investigated that the proposed method could be used to calibrate not only the interfacial fracture criteria at pure modes but also at any mixed mode fracture of bimaterials in submicron scale.     

Cubic phases of 4′-n-alkoxy-3′-nitrobiphenyl-4-carboxylic acids (ANBC-n)

The structure of the thermotropic cubic phases of 4′- ⁿ -alkoxy-3′-nitrobiphenyl-4-carboxylic acids (ANBC- ⁿ , where ⁿ indicates the number of carbon atoms in the alkoxy group) was studied by X-ray diffraction. For the homologues with ⁿ = 15, 16, 17, and 18, the cubic phase was of an ^Ia 3 ^d type, whereas the homologues with ⁿ = 19, 20, and 21 exhibited an ^Im 3 ^m cubic structure; for these seven homologues the same type of cubic structure was observed both on heating and cooling. Further lengthening of the alkoxy chain to ⁿ = 22 and 26, however, gave two types of cubic structure in the cubic phase region on heating, one with ^Im 3 ^m symmetry in the low temperature region and the other with ^Ia 3 ^d symmetry in the high temperature region. On cooling, the two homologues exhibited the ^Ia 3 ^d cubic structure only. This is the first example in the cubic phase region of a series of homologues containing two types of structure, dependent on temperature and ⁿ . Such a complicated phase diagram in the cubic region is clearly understood qualitatively in terms of Gibbs free energy-temperature diagrams. The dependence of structural parameters such as the cubic lattice constant on the alkoxy chain length ⁿ are also presented and discussed.     

Homojunction-structured ZnO light-emitting diodes fabricated by dressed-photon assisted annealing

We formed a p?Cn homojunction by implanting nitrogen ions, serving as a p-type dopant, into an n-type ZnO crystal. A forward bias current was injected into the crystal while irradiating it with light, bringing about Joule heating which annealed the crystal and changed the spatial distribution of the N-dopant concentration. This activated the N-dopant, causing its concentration distribution to be modified in a self-organized manner so as to be suitable for generating dressed photons. A light-emitting diode fabricated by this dressed-photon assisted annealing method showed electroluminescence at room temperature. In a device fabricated by annealing under irradiation with 407 nm-wavelength light, at a forward bias current of 20 mA, the peak wavelength of the electroluminescence was 436 nm, the optical output power was 6.2 ??W, and the external quantum efficiency was 1.1×10^?4. The emission spectral profile depended on transitions from intermediate phonon states.     

Synthesis and Reactions of 1-Phenylbenzo[b]thiophenium Salts

1-Phenylbenzo[b]thiophenium salts are prepared and reacted under thermal and photochemical conditions. The chemical behaviors are discussed.     

Surface effects on the polarization reversal of the ferroelectric liquid crystal 8SI*

Abstract

The activation field for the switching time (τ_1/2) in the truly ferroelectric liquid crystal 8SI* (CE8; ΔS-(+)-4-(2′-methylbutyl) phenyl-4′-n-octylbiphenyl-4 carboxylate) has been studied for various surface conditions of the transparent electrode (SnO₂), in order to understand the memory effect, the polarization reversal mechanism and its surface effect. We prepared five different surfaces, namely one coated with polyvinyl alcohol (PVA) and the other four by scratching N-times(N = 0, 10, 20 and 30) with a paste made of Cr₂O₃ powder (about 0·1 μm). The number and the area of scratches on the electrode surface obviously increase with N. The polarization reversal processes are influenced by this treatment. τ_1/2 decreases with increasing N, but no change is observed in the contrast of the light transmittance. Two different activation fields, E _a1, for the applied field E > E ₀ and E _a2 for E < E ₀ are observed, where E ₀ is a certain field depending on the sample. Here E _a1 is much larger than E _a2; typically E _a1, = 260 kV cm^?1 and E _a2 = 144 kV cm^?1 for N = 0. This means that nucleation for the higher field needs a large activation energy which therefore has strong barriers. In contrast with this, nucleation for the low field occurs easily. Changing a surface condition, E _a2 clearly decreases with increasing N although E _a1 is almost independent of the surface scratching. This may suggest that E _a1 corresponds to the activation field for the bulk pinning and nucleation, and E _a2 for the surface pinning. The PVA treatment gives an intermediate influence between N = 0 and 10.     

First-principles calculations of stable local structures and electronic structures of magnesium secondary battery cathode materials,MgCo2−xMnxO4 (x = 0, 0.5), in second charged state after first discharge

Journal of Solid State Electrochemistry - The stable structures associated with the second charge of MgCo2−xMnxO4 (x = 0, 0.5), where Mg is removed from the stable first-discharge...     

Tuning the Solid‐State Optical Properties of Tetracene Derivatives by Modification of the Alkyl Side‐Chains: Crystallochromy and the Highest Fluorescence Quantum Yield in Acenes Larger than Anthracene

In the solution state, there were no notable differences between the optical properties of a range of alkyl‐substituted tetracenes. However, in the solid state, their photophysical properties changed with respect to the length, shape, number, and substitution pattern of the alkyl side chains, as well as the distribution of two regioisomers. Remarkably, in the solid state, 1,4,7,10‐tetraisopropyltetracene exhibited the highest reported fluorescence quantum yield of any tetracene derivative (0.90). The changes in the optical characteristics of these tetracenes according to the arrangement of the tetracene rings and the color‐change mechanism in the solid state are discussed. Moreover, the world record in solid‐state fluorescence efficiency in acenes larger than anthracene is described. DOI 10.1002/tcr.201200003