Liquid-liquid extraction of copper (I) and copper (II) as ion-paired complexes with acyclic 2-thienyl-containing polythioether and triphenylmethane dye anion

Three acyclic polythioethers containing 2-thienyl units at both ends were synthesized and the effect of substituent on the extraction of copper(II) was studied. The methyl groups in the terminal thiophene ring have imparted an appreciable degree of increase in the percent extraction of copper(II), while the introduction of chlorine atoms into the 2-thienyl unit resulted in the reverse effect. Among the counter dye anions examined, tetrabromophenolphthalein ethylester was the best one for copper(II) extraction. The composition of extracted species was evaluated to be 122 (Cu(II)/polythioether/dye anion). Quantitative extraction of copper(I) was attained as complexes with various triphenylmethane dyes, i.e., bromocresol green, bromothymol blue, bromo-phenol blue and pyrogallol red. Copper(I) in organic phase was completely back-extracted with 2 mole/l sulfuric acid containing 10% hydrogen peroxide.     

Spin dynamics and spin correlations in the spinS=1 two-dimensional square-lattice Heisenberg antiferromagnet La2NiO4

The static and dynamic spin fluctuations in the spinS=1, two-dimensional (2D) square-lattice antiferromagnet La₂NiO₄ have been studied over a wide temperature range using neutron scattering techniques. The spin correlations in La₂NiO₄ exhibit a crossover from two- to three-dimensional (3D) behavior as the Néel temperature is approached from above. Critical slowing down of the low-energy spin fluctuations is also observed just aboveT _N . The correlation length, (T), and the static structure factor,S(0), have been measured and are compared with recent theoretical calculations for the quantum 2D Heisenberg antiferromagnet using microscopic parameters determined from previous spin-wave measurements. Good agreement for (T) is found with the exact low-temperature result of Hasenfratz and Niedermeyer provided that 2 p _s is renormalized by 20% from the spin-wave value.     

Origin of Hole-Trapping States in Solution-Processed Copper(I) Thiocyanate and Defect-Healing by I2 Doping

Solution-processed copper(I) thiocyanate (CuSCN) typically exhibits low crystallinity with short-range order; the defects result in a high density of trap states that limit the device's performance. Despite the extensive electronic applications of CuSCN, its defect properties are not understood in detail. Through X-ray absorption spectroscopy, pristine CuSCN prepared from the standard diethyl sulfide-based recipe is found to contain under-coordinated Cu atoms, pointing to the presence of SCN⁻ vacancies. A defect passivation strategy is introduced by adding solid I₂ to the processing solution. At small concentrations, the iodine is found to exist as I⁻ which can substitute for the missing SCN⁻ ligand, effectively healing the defective sites and restoring the coordination around Cu. Computational study results also verify this point. Applying I₂-doped CuSCN as a p-channel in thin-film transistors shows that the hole mobility increases by more than five times at the optimal doping concentration of 0.5 mol.%. Importantly, the on/off current ratio and the subthreshold characteristics also improve as the I₂ doping method leads to the defect-healing effect while avoiding the creation of detrimental impurity states. An analysis of the capacitance-voltage characteristics corroborates that the trap state density is reduced upon I₂ addition.     

Instantons and representations of an associative algebra

We give the correspondence between instantons onS ⁴ and some representations of an associative algebra. For the given structure group, we get simultaneous imbeddings to (the inductive limit) of the moduli spaces for instantons onS ⁴ of all instanton numbers.     

Water-swellable polyelectrolyte microgels polymerized in an inverse microemulsion using a nonionic surfactant

A series of poly(dimethylacrylamide-co-2-acrylamido-2-methyl-1-propanesulfonic acid) microgels slightly crosslinked by methylene-bis-acrylamide (MBA) were polymerized in a novel inverse microemulsion polymerization (IMEP) system. To determine a suitable composition of the IMEP system, the phase diagram of a pseudoternary system was made. The pseudoternary polymerization system consisted of n-hexane, a nonionic surfactant (polyoxyethylene oleyl ether, C18En), and an aqueous monomer solution. Polymerization was performed in a single-phase reversed micelle solution. The reversed micelles were about 50 nm in diameter, as determined by FF-TEM. The viscometric characteristics of the polymers extracted from the IMEP system were studied in 3 mM sodium chloride aqueous solution. The intrinsic viscosity values for the noncrosslinked and crosslinked (0.1 mol% MBA was incorporated) samples were 25 and 7.4 dl/g, respectively. The overlap concentration (c*) of crosslinked polymer microgel occurred at c[eta] = 1 in the solvent. When the volume fraction (phi) of the microgel was 0.7, the value of the apparent yield stress of the microgel solution was observed. These results show that the microgel has a significant thickening effect above c* due to friction between the microgel particles. It is assumed that the microgels polymerized in a confined space retain the shape or size of the nanosized reactor with a diameter on the order of 50 nm.     

RECENT PROGRESS OF NANO-MECHANICAL MAPPING

 Nano-mechanical mapping by atomic force microscopy has been developed as an useful application to measure mechanical properties of soft materials at nanometer scale. To date, the Hertzian theory was used for analyzing force-distance curves as the simplest model among several contact mechanics between elastic bodies. However, the preexisting methods based on this theory do not consider the adhesive interaction in principle, which cannot be neglected in the ambient condition. A new analytical method was introduced to estimate the elasticity and the adhesive energy simultaneously by means of the JKR theory, describing adhesive contact between elastic materials. Poly(dimethylsiloxane) (PDMS) and isobutylene-co-isoprene rubber (IIR) were analyzed to verify the applicable limit of the JKR analysis. For elastic samples such as PDMS, the force-deformation plots obtained experimentally were consistent with JKR theoretical curves. Meanwhile, for viscoelastic samples, especially for IIR, the experimental plots revealed large deviations from JKR curves depending on scanning velocity and maximum loading force. Some nano-rheological arguments were employed based on the difference between these specimens.     

Base-labile tert-butoxycarbonyl (Boc) group on phenols

Phenols are deprotected with weak bases from their tert-butoxycarbonyl (Boc) derivatives. Boc deprotection with bases can avoid side reactions during the deprotection with acids. We note the lability of the Boc to bases and are able to utilize it as a new cleavage condition for synthetic studies.