Angular dependence of 1H- and 2H-NMR spectra of H2O and D2O absorbed in cellulose acetate film

¹H- and ²H-NMR spectra of H₂O and D₂O absorbed in cellulose acetate films were observed while changing the angle between the plane of the film and the magnetic field. ¹H-NMR spectra show dipolar splittings that vary depending on the angle. The splitting has a maximum when the surface of the film is perpendicular to the magnetic field. From the angular dependence of the dipolar splitting, it is recognized that the proton-proton dipolar axis of water molecules tends to orient perpendicularly to the surface of the film. ²H-NMR spectra that show quadrupolar splittings also indicate that the quadrupolar axis tends to orient perpendicularly to the film. The so-called bound water and free water in the film can exchange rapidly on the NMR time scale, so that the line width and the splitting of the NMR spectra become smaller as the amount of water in the film increases. From the temperature dependence of line widths, the apparent reorientational activation energy of water molecules in the film is estimated to be 25 kJ/mol from ¹H-NMR and 31 kJ/mol from ²H-NMR.     

Quaternary ammonium room-temperature ionic liquid including an oxygen atom in side chain/lithium salt binary electrolytes: ab initio molecular orbital calculations of interactions between ions

Interactions of the lithium bis(trifluoromethylsulfonyl)amide (LiTFSA) complex with N, N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium (DEME), 1-ethyl-3-methylimidazolium (EMIM) cations, neutral diethylether (DEE), and the DEMETFSA complex were studied by ab initio molecular orbital calculations. An interaction energy potential calculated for the DEME cation with the LiTFSA complex has a minimum when the Li atom has contact with the oxygen atom of DEME cation, while potentials for the EMIM cation with the LiTFSA complex are always repulsive. The MP2/6-311G**//HF/6-311G** level interaction energy calculated for the DEME cation with the LiTFSA complex was -18.4 kcal/mol. The interaction energy for the neutral DEE with the LiTFSA complex was larger (-21.1 kcal/mol). The interaction energy for the DEMETFSA complex with LiTFSA complex is greater (-23.2 kcal/mol). The electrostatic and induction interactions are the major source of the attraction in the two systems. The substantial attraction between the DEME cation and the LiTFSA complex suggests that the interaction between the Li cation and the oxygen atom of DEME cation plays important roles in determining the mobility of the Li cation in DEME-based room temperature ionic liquids.     

Magneto-optical trapping of radioactive atoms for test of the fundamental symmetries

We are planning test experiments of fundamental symmetries based on the intrinsic properties of francium. It is expected that the laser cooling and trapping of francium will produce precision measurements. The pilot experiment using rubidium was performed with the goal of francium trapping. The ion beam generated with a francium ion source was investigated using a Wien filter. Each piece of equipment still must be studied in more detail, and the equipment should be upgraded in order to trap radioactive atoms.     

Fabrication and microscopic characterization of a single quantum-wire laser with high uniformity

A T-shaped single quantum-wire laser with high spatial uniformity has been fabricated by a cleaved-edge overgrowth method with molecular beam epitaxy and a growth-interrupt annealing technique. Using micro-photoluminescence imaging and spectroscopy, we confirmed the formation of a spatially uniform quantum wire over 20 μm long without hetero-interface roughness. By optical pumping, we achieved single-mode lasing from the ground state of the single quantum wire at a threshold excitation power as low as 5 mW at 5 K.     

Angular dependence of 1H- and 2H-NMR spectra of water and methanol absorbed in cellulose triacetate film

¹H- and ²H-NMR spectra of water (H₂O and D₂O) and methanol (CH₃OD and CD₃OH) absorbed in cellulose triacetate films have been observed as a function of the angle θ between the film surface and the magnetic field. ¹H-NMR signals of H₂O and CH₃OD are doublets and triplets due to dipole interactions, respectively. ²H-NMR signals of D₂O, CD₃OH, and CH₃OD are doublets due to quadrupole splittings. The magnitudes of these splittings change depending on θ. The analysis of the angle-dependent patterns indicates that the motionally averaged axes of the dipole and the quadrupole moments orient in the direction perpendicular to the film surface. The alignment of water and/or methanol molecules originates from the film morphology, which is anisotropic in the perpendicular direction. From the angle dependence of the chemical shift, the volume diamagnetic susceptibility of the film is estimated to be 0.44 ppm.     

Structure of Ti1−yVyHx alloys studied by X-ray diffraction and by 1H and 51V NMR

The structure of the TiVH system is studied by X-ray diffraction and ¹H and ⁵¹V NMR measurements. It is shown that the solid solution of TiV is separated into a few phases by hydrogenation. They are α-TiVH, β-TiVH, γ-TiVH, and γ-TiH phases, which are assumed to have their origins either in TiH_x or in VH_x. The concentration of each phase can be estimated by NMR, which is dependent on the composition of the system. The phase separation caused by hydrogenation is due to the large stability of the γ-TiH phase.     

Flow injection spectrophotometric determination of calcium in rain and snow with chlorophosphonazo III

Summary A spectrophotometric flow injection technique for the determination of calcium based on its color reaction with chlorophosphonazo III(CPA-III) is described. The complex formation of CPA-III with calcium ions was carried out in the presence of 0.01 mol/l oxalate at pH 2.8. Most of the common foreign ions did not interfere. Only strontium, barium and rare earth metals interfered. Under the optimum conditions, the calibration curve was linear up to 1.2 ppm calcium and the detection limit was 0.01 ppm for a sample volume of 120 l. The relative standard variations for 0.4 and 1.0 ppm calcium were 0.354 and 0.352%, respectively. The method was successfully applied to the determination of calcium in rain and snow.     

Phase transition and conductive acceleration of phosphonium-cation-based room-temperature ionic liquid

An unusual ionic conduction phenomenon related to the phase transition of a novel phosphonium-cation-based room-temperature ionic liquid (RTIL) is reported; we found that in the phase change upon cooling, a clear increase in ionic conductivity was seen as the temperature was lowered, which differs from widely known conventional RTILs; clearly, our finding of abnormality of the correlation between temperature change and ionic conduction is the first observation in the electrolyte field.     

Molecular motions and ion diffusions of the room-temperature ionic liquid 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)amide (DMPImTFSA) studied by 1H, 13C, and 19F NMR

The diffusive properties of an imidazolium room-temperature ionic liquid (RTIL), 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)amide (DMPImTFSA), are studied from the ionic conductivity and the ion diffusion coefficients measured by pulsed field gradient spin echo NMR. The temperature-dependent (1)H, (19)F, and (13)C NMR spin-lattice relaxation time T(1) values were observed, and the (1)H T(1) for DMPIm showed T(1) minima for various protons. According to the Bloemberger-Purcell-Pound (BPP) equation, the correlation time tau(c) values were directly calculated from (1)H NMR. By using the (1)H tau(c) values, an evaluation of the (13)C T(1) was attempted for the carbons having protons. The tau(c) estimated for molecular motions of DMPIm changes from 1.3 ns at 253 K to 72 ps at 353 K. The Stokes-Einstein-Debye (SED) model suggests that the tau(c) is too short for the overall molecular reorientation near room temperature. Consequently, the possibility of small-angle molecular rotation is proposed and tentative flip angles are calculated by using the translational diffusion coefficient, the bulk viscosity measured in this study, and the tau(c) obtained from (1)H T(1) data in the temperature range between 283 and 353 K. The flip amplitude increases with the temperature. DMPIm has isotropic reorientational motions with temperature-dependent amplitude, in addition to fast intramolecular motions such as methylene segmental motions, methyl rotational motion, and conformational exchange of the imidazolium ring. The existence of fast motions of TFSA is also shown. The translational diffusion of the ions is the slowest dynamic process in the present RTIL. Ab initio molecular orbital calculations are performed to understand the geometries of stable complexes of DMPIm(+) and TFSA(-), and the formation energies from the isolated ions are evaluated. The computed results are important for interpreting the (1)H T(1) behaviors observed for the imidazolium ring protons.     

How ionic are room-temperature ionic liquids? An indicator of the physicochemical properties

Room-temperature ionic liquids (RTILs) are liquids consisting entirely of ions, and their important properties, e.g., negligible vapor pressure, are considered to result from the ionic nature. However, we do not know how ionic the RTILs are. The ionic nature of the RTILs is defined in this study as the molar conductivity ratio (Lambda(imp)/Lambda(NMR)), calculated from the molar conductivity measured by the electrochemical impedance method (Lambda(imp)) and that estimated by use of pulse-field-gradient spin-echo NMR ionic self-diffusion coefficients and the Nernst-Einstein relation (Lambda(NMR)). This ratio is compared with solvatochromic polarity scales: anionic donor ability (Lewis basicity), E(T)(30), hydrogen bond donor acidity (alpha), and dipolarity/polarizability (pi), as well as NMR chemical shifts. The Lambda(imp)/Lambda(NMR) well illustrates the degree of cation-anion aggregation in the RTILs at equilibrium, which can be explained by the effects of anionic donor and cationic acceptor abilities for the RTILs having different anionic and cationic backbone structures with fixed counterparts, and by the inductive and dispersive forces for the various alkyl chain lengths in the cations. As a measure of the electrostatic interaction of the RTILs, the effective ionic concentration (C(eff)), which is a dominant parameter for the electrostatic forces of the RTILs, was introduced as the product of Lambda(imp)/Lambda(NMR) and the molar concentration and was compared with some physical properties, such as reported normal boiling points and distillation rates, glass transition temperature, and viscosity. A decrease in C(eff) of the RTILs is well correlated with the normal boiling point and distillation rate, whereas the liquid-state dynamics is controlled by a subtle balance between the electrostatic and other intermolecular forces.