Showing papers by "Akihiro Wakisaka published in 2004"

Molecular Association in Binary Mixtures of tert-Butyl Alcohol−Water and Tetrahydrofuran−Heavy Water Studied by Mass Spectrometry of Clusters from Liquid Droplets

Abstract: The cluster structures observed by means of mass spectrometry for binary mixtures-tert-bulyl alcohol (TBA)-H 2 O and tetrahydrofuran (THF)-D 2 O-with varying mixing ratios exhibit striking contrast, even though both TBA andTHF are miscible with water at any mixing ratio. In the TBA-H 2 O mixtures at TBA mole fractions of (X T B A ) ≤ 0.01-0.025, some of the H 2 O molecules in the H 2 O clusters are replaced by TBA molecules. For 0.01-0.025 ≤ X T B A ≤ 0.2-0.3, the self-aggregation of TBA forms dominant cluster structures, and the hydrogen-bonded water clusters are disintegrated with increasing X T B A . This TBA self-aggregation is reduced with further increasing TBA at X T B A ≥ 0.3. However, in the THF-D 2 O mixtures, THF molecules have a weak additional interaction with D 2 O clusters, and the self-aggregation of THF is not promoted in the THF-D 2 O mixtures. The D 2 O clusters still exist, even at a THF mole fraction of X T H F = 0.3. On the basis of the observed cluster structure, the mechanism for the mixing between water and the organic solvent and the controlling factors in the self-aggregation are proposed.

Nature of the chemical bond formed with the structural metal ion at the A9/G10.1 motif derived from hammerhead ribozymes.

Abstract: We have studied the interaction between metal ions and the metal ion-binding motif in hammerhead ribozymes, as well as the functions of the metal ion at the motif, with heteronuclear NMR spectroscopy. In this study, we employed model RNA systems which mimic the metal ion-binding motif and the altered motif. In Co(NH3)6(III) titrations, we observed large 1H and 31P chemical shift perturbations for the motif and found that outer-sphere complexation of Co(NH3)6(III) is possible for this motif. From the reinvestigation of our previous 15N chemical shift data for Cd(II) binding, in comparison with those of organometallic compounds, we conclude that Cd(II) can form an inner-sphere complex with the nucleobase in the motif. Therefore, the A9/G10.1 site was found to accept both inner-sphere and outer-sphere complexations. The Mg(II) titration for a slightly different motif from the A9/G10.1 site (G10.1−C11.1 to A10.1−U11.1) revealed that its affinity to Mg(II) was drastically reduced, although the ribozyme with th...

Preferential Solvation and Self-Association in Alcohol−Acetonitrile Mixtures Observed through Mass Spectrometric Analysis of Clusters: Influence of Alkyl Chain Length

Abstract: Molecular clusters formed by fragmentation of liquid droplets of alcohol (methanol or n-butanol)-acetonitrile mixtures have been detected and analyzed by means of a specially designed mass spectrometer. In the methanol-acetonitrile mixture, methanol clusters retain a sizable magnitude through most of the composition range, whereas acetonitrile clusters decrease in intensity upon increasing the concentration of methanol. Hydrogen bonding among methanol molecules controls the clustering. On the other hand, in n-butanol-acetonitrile mixtures, self-association of n-butanol through hydrogen bonding is remarkably promoted by the mixing with acetonitrile. With decreasing the acetonitrile contents, however, n-butanol self-associated clusters disintegrate completely. The interaction among n-butanol molecules changes from hydrogen bonding to dispersive, depending on the mixing ratio. When phenol is added as a solute to these binary mixtures, the solvation of phenol is found to be controlled by the solvent molecular clustering.

Cluster Formation of 1-Butanol–Water Mixture Leading to Phase Separation

Abstract: Microscopic structures of 1-butanol (1-BuOH)–water mixtures in the presence and absence of salts are studied through the mass spectrometric analysis of clusters generated from the fragmentation of liquid droplets. The analysis of cluster structures provides information on the phase separation of 1-BuOH–water mixtures from the microscopic viewpoint. In a saturated solution of 1-BuOH in water, 1-BuOH exists as hydrated 1-BuOH clusters and self-associated 1-BuOH clusters. With further addition of 1-BuOH, a 1-BuOH rich phase is generated. When the salt (LiCl, NaCl, MgCl2, etc.) coexists in the 1-BuOH–water mixtures, the cation is preferentially solvated by the 1-BuOH to form M +(1-BuOH) m or M 2+(1-BuOH) m clusters: M + = Li+, Na+, Mg2+ = Mg2+, etc., m = 1, 2, 3, ... Since the formation of M +(1-BuOH) m corresponds to an increase of the self-associated 1-BuOH clusters in water, the presence of the salt induces the phase separation at lower 1-BuOH concentrations.

Direct Observation of the Li+–18-Crown-6 Complex Working as H2O Capture in Acetone–Water Mixture

Abstract: The complex formation of alkali metal ion (Li+ or Na+) with 18-crown-6 in an acetone–water mixed solvent was studied by means of the specially designed mass spectrometer. The Li+–18-crown-6 complex...