Experimental evidence for intramolecular blue-shifting C-H...O hydrogen bonding by matrix-isolation infrared spectroscopy

Experimental evidence for intramolecular blue-shifting C-H...O hydrogen bonding is presented. Argon matrix-isolation infrared spectra of 1-methoxy-2-(dimethylamino)ethane exhibit a band at 3016.5 cm-1. Spectral behavior with annealing indicates that this band is assigned to the most stable conformer, trans-gauche-(trans|gauche'), with an intramolecular C-H...O hydrogen bond. Density functional calculations show that this band arises from the stretching vibration of the C-H bond participating in the formation of the C-H...O hydrogen bond. The C-H bond is shortened by 0.004 A, and the C-H stretching band is blue-shifted by at least 35 cm-1 on the formation of the hydrogen bond. The (C)H...O distance is calculated as 2.38 A, which is shorter than the corresponding van der Waals separation by 0.3 A.     

Optimum conditions for effective use of the terminating ion in transient isotachophoresis for capillary zone electrophoretic determination of nitrite and nitrate in seawater,with artificial seawater as background electrolyte

We have examined transient isotachophoresis (ITP) conditions, e.g. the nature of the terminating ion, its concentration, and the injection procedure, to improve the limit of detection (LOD) for determination of nitrite and nitrate in seawater by capillary zone electrophoresis (CZE). Artificial seawater containing 3.0 mmol L(-1) cetyltrimethylammonium chloride (CTAC) was used as background electrolyte (BGE). After sample injection 600 mmol L(-1) acetate was separately injected into the capillary as the terminating ion for transient ITP. The LOD for nitrite and nitrate, obtained at a signal-to-noise ratio (S/N) of 3, were 15 and 7.0 microg L(-1) (as nitrogen), respectively. Relative standard deviations (RSD) of peak area for nitrite and nitrate were 7.3 and 0.8%, respectively, and the RSD of peak height were 5.7 and 1.2%, respectively, when the concentrations of nitrite and nitrate were 0.05 and 0.25 mg L(-1). The RSD of migration time for these ions was 0.2%. The proposed method was applied to the determination of nitrite and nitrate in seawater samples. The results for nitrite were nearly in agreement with those obtained by naphthylethylenediamine spectrophotometric analysis (SPA; correlation coefficient 0.9041).     

Thin-layer chromatographic behavior and separation of alkaline earth metals on silica gel in aqueous sodium perchlorate solution

The thin-layer chromatographic behavior of alkaline earth metal ions (Mg2+, Ca2+, Sr2+, and Ba2+) in aqueous sodium perchlorate solutions on silica gel thin-layers impregnated with sodium hydroxide has been surveyed as a function of salt concentration. At salt concentrations above 2 mol 1(-1), the selectivity of the metals increased with a decrease in the crystal ionic radii; with further increases in salt concentration, the selectivity differences among the metals expanded remarkably. In the present systems, it was supposed that the cation exchange, the surface complexation, and the salting-out effect participate simultaneously in the adsorption of the metals on silica gel. Typical chromatograms for the mutual separation of the alkaline earth metals are presented.     

Enantioselective synthesis of axially chiral biaryls through rhodium-catalyzed complete intermolecular cross-cyclotrimerization of internal alkynes

[reaction: see text] We have developed a cationic rhodium(I)/H8-BINAP complex-catalyzed complete intermolecular cross-cyclotrimerization of internal alkynes with dialkyl acetylenedicarboxylates. This reaction was successfully applied to enantioselective synthesis of axially chiral biaryls utilizing internal alkynes bearing ortho-substituted phenyl and acetoxymethyl in each terminal position. The axial chirality is constructed at the formation of benzene rings with high enantioselectivity (up to 96% ee).     

Lithium ion effect on electron injection from a photoexcited coumarin derivative into a TiO2 nanocrystalline film investigated by visible-to-IR ultrafast spectroscopy

The dynamics of ultrafast electron injection from a coumarin derivative (NKX-2311), which is an efficient photosensitizer for dye-sensitized solar cells, into the conduction band of TiO(2) nanocrystalline films have been investigated by means of femtosecond transient absorption spectroscopy in a wide wavelength range from 600 nm to 10 mum. In the absence of Li(+) ions, electron injection into the TiO(2) conduction band occurred in about 300 fs. In the presence of Li(+) ions, however, electron injection occurred within approximately 100 fs, and the oxidized dye generated was found to interact with nearby Li(+) ions. Possible positions of Li(+) ion attachment to the dye molecule were examined by means of semiempirical molecular orbital calculations. The electron injection efficiency was found to increase by a factor of 1.37 in the presence of Li(+) ions. The effects of Li(+) ions on the energy of the TiO(2) conduction band and the electronic interaction between the dye molecule and Li(+) ions are discussed, and the major cause for the acceleration of electron injection was suggested to be a conduction-band shift of TiO(2).     

Separation and spectrophotometric determination of uranium (VI) by extraction with arsenazo III and zephiramine

Summary Microgram quantities of uranium(VI) can be determined at 655 nm after separation by chloroform extraction of its Arsenazo III complex with Zephiramine. The extracted uranium can be back-extracted with an aqueous solution of ammonium carbonate. Uranium can be separated from aluminium, iron(II), and some other elements. Probably the same species, i. e., the ion association compound between the uranium (VI)-Arsenazo III complex and Zephiramine are involved during the extraction and the froth flotation.

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Zusammenfassung Mikrogrammengen Uran(VI) lassen sich nach Chloroformextraktion seines Arsenazo-III-Komplexes mit Zephiramin bei 655 nm messen. Das extrahierte Uran kann man mit wäßriger Ammoniumcarbonatlösung rück-extrahieren. Von Aluminium, Eisen(II) und einigen anderen Elementen kann es so getrennt werden. Wahrscheinlich handelt es sich bei der Extraktion und der Schaumflotation um die gleiche Ionenassoziatverbindung des Uran (VI)-Arsenazo-III-Komplexes mit Zephiramin.

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Presented at the 24th Annual Meeting of the Japan Society for Analytical Chemistry, Sapporo, October, 1975.     

Molecular design of tetraazamacrocyclic derivatives bearing a spirobenzopyran and three carboxymethyl moieties and their metal-ion complexing behavior.

Tetraazacyclododecane and tetraazacyclotetradecane derivatives bearing a spirobenzopyran and three carboxymethyl moieties, 1 and 2, and a diethylenetriamine derivative bearing a spirobenzopyran and four carboxymethyl moieties 3 were synthesized. The isomerization behaviors based on the spirobenzopyran moiety of these ligands were studied by UV-visible spectrophotometry in aqueous solutions containing various metal ions at neutral pH. These ligands formed stable 1:1 complexes with lanthanide ions, while the spirobenzopyran moiety was isomerized to its corresponding merocyanine form even under dark conditions. In aqueous solutions containing a lanthanide ion, the absorption spectra of 1 or 2 showed remarkable blue shifts, while absorbances at the maximum absorption wavelengths in the visible region were enhanced; such changes are attributable to the isomerization to the merocyanine form of the spirobenzopyran moiety. These results suggest that the phenolate anion of the merocyanine moiety interacts very strongly with a lanthanide ion bound by the complexing moiety because of the high charge density of lanthanide ions. In contrast, the absorbance of merocyanine form was decreased by the complexation of the macrocyclic ligand with transition metal ions, such as Cu2+ and Zn2+. This result indicates that macrocyclic ligands, 1 and 2, formed complexes with transition metal ions only by the aminocarboxylate moieties, and the phenolate ion of merocyanine moiety was not able to participate in the complexation. This conclusion was also demonstrated by density functional theory calculations.     

CPP-GMR technology for magnetic read heads of future high-density recording systems

This paper introduces CPP-GMR technology, its features, routes to output enhancement, problems to be solved and possibilities as a recording head. For instance, use of high spin-dependent bulk scattering, high resistivity, or half-metallic magnetic materials for free and reference magnetic layers were shown as ways to improve the output of CPP-GMR. A current state of CPP-GMR head development was also mentioned in view points of sensor downsizing, magnetic head noise and high-density recording demonstration. CPP-GMR still has some points to be improved, however it is believed that the CPP-GMR will actualize a next high-performance magnetic read head in no distant future.     

Very simple,carbuncle-free,boundary-layer-resolving,rotated-hybrid Riemann solvers

In this paper, we propose new Euler flux functions for use in a finite-volume Euler/Navier–Stokes code, which are very simple, carbuncle-free, yet have an excellent boundary-layer-resolving capability, by combining two different Riemann solvers into one based on a rotated Riemann solver approach. We show that very economical Euler flux functions can be devised by combining the Roe solver (a full-wave solver) and the Rusanov/HLL solver (a fewer-wave solver), based on a rotated Riemann solver approach: a fewer-wave solver automatically applied in the direction normal to shocks to suppress carbuncles and a full-wave solver applied, again automatically, across shear layers to avoid an excessive amount of dissipation. The resulting flux functions can be implemented in a very simple and economical manner, in the form of the Roe solver with modified wave speeds, so that converting an existing Roe flux code into the new fluxes is an extremely simple task. They require only 7–14% extra CPU time and no problem-dependent tuning parameters. These new rotated fluxes are not only robust for shock-capturing, but also accurate for resolving shear layers. This is demonstrated by an extensive series of numerical experiments with standard finite-volume Euler and Navier–Stokes codes, including various shock instability problems and also an unstructured grid case.