Quantitative Temperature Dependence of the Microscopic Hydration Structures Investigated by Ultraviolet Photodissociation Spectroscopy of Hydrated Phenol Cations.

To discuss the temperature effect on microscopic hydration structures in clusters, relative populations of the isomers having different hydration structures at well-defined temperatures are quite important. In the present study, we measured ultraviolet photodissociation spectra of the temperature-controlled hydrated phenol cation [PhOH(H2O)5]+ trapped in the 22-pole ion trap. Two isomers having a distinct hydration motif with each other are identified in the spectra, and a clear change in the relative populations is observed in the temperature range from 30 to 150 K. This behavior is quantitatively interpreted by statistical mechanical estimation based on density functional theory calculations. A ring with tail-type hydration motif is dominant in cold conditions, whereas a chain-like motif is dominant in hot conditions. The present study provides very quantitative information about the temperature effect on the microscopic hydration structures.

"Colored" inorganic dopants for inducing liquid crystal chiral nematic and blue phases: monitoring of dopant-host interaction by Raman spectroscopy.

A new ruthenium complex that effectively induces chiral nematic and blue phases upon doping with a nematic liquid crystal was developed. The red-colored dopant exhibits strong Raman scattering in solution and nematics even at low concentrations. Further measurements at various concentrations strongly suggested homogeneous dispersion of the dopant in chiral nematics.

Dynamic molecular behavior of semi-fluorinated oleic, elaidic and stearic acids in the liquid state.

Ordinary fatty acids such as oleic, elaidic and stearic acids exist as their hydrogen-bonded dimers in their liquids and in non-polar solvents. Infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy have revealed that semi-fluorinated (SF) acids containing a perfluorooctyl group (C8F17) as a terminal segment exist also as hydrogen-bonded dimers, which are the units of inter- and intramolecular movements in their liquids and CCl4. The dynamic molecular properties, such as self-diffusion coefficients and intramolecular movements of SF-oleic, SF-elaidic, and SF-stearic acids were compared with those of corresponding ordinary fatty acids (H-acids). From the high equilibrium spreading pressures (ESPs) for SF-acids compared with those for their corresponding H-acids, it was expected that the inter-acyl chain interaction is weaker for the SF-acid than for the H-acid: the SF-fatty acids should have higher molecular mobility than the corresponding ordinary H-acids in the liquid state. However, the self-diffusion coefficients obtained for SF-acids were smaller than those for the corresponding H-acids; the apparent activation energies for the self-diffusion process (translational movement) of SF-acids were larger than those for the corresponding H-acids. Namely, the motion of SF-acid molecules in a liquid phase is rather restricted compared with H-acid in spite of lower inter-acyl chain interaction of SF-acid. This unexpected result suggests that the molecular motion of SF-acid in a liquid phase is not directly governed by inter-acyl interaction, but may be interpreted as a reptation movement of an acid molecule, which is related to intramolecular movement. In fact, low intramolecular movements for SF-acid were confirmed by ¹³C-NMR T1 measurements.

CH/pi interaction between benzene and hydrocarbons having six carbon atoms in their binary liquid mixtures.

Molecular interactions between benzene and hydrocarbons having six carbon atoms, such as hexane, cyclohexane and 1-hexene in their binary liquid mixtures were studied through the measurements of density, viscosity, self-diffusion coefficient, (13)C NMR spin-lattice relaxation time and (1)H NMR chemical shift. CH/pi attraction between hexane and benzene in their binary mixture was observed in a relatively benzene rich region, whereas a special attractive interaction was not observed between cyclohexane and benzene. On the other hand, 1-hexene and benzene in their binary mixtures were characteristic in their self-diffusion coefficient behaviors: 1-hexene more strongly attract benzene not only by the CH/pi attraction but also probably by the p/p interaction between the double bond in 1-hexene and the p-electron in benzene ring.

Effects of molecular size and structure on self-diffusion coefficient and viscosity for saturated hydrocarbons having six carbon atoms.

Self-diffusion coefficients and viscosities for the saturated hydrocarbons having six carbon atoms such as hexane, 2-methylpentane (2MP), 3-methylpentane (3MP), 2,2-dimethylbutane (22DMB), 2,3-dimethylbutane (23DMB), methylcyclopentane (McP) and cyclohexane (cH) were measured at various constant temperatures; obtained results were discussed in connection with their molar volumes, molecular structures and thermodynamic properties. The values of self-diffusion coefficients as the microscopic property were inversely proportional to those of viscosities as the macroscopic property. The order of their viscosities was almost same to those of their melting temperatures and enthalpies of fusion, which reflect the attractive interactions among their molecules. On the other hand, the order of the self-diffusion coefficients inversely related to the order of the melting temperatures and the enthalpies of the fusion. Namely, the compound having the larger attractive interaction mostly shows the less mobility in its liquid state, e.g., cyclohexane (cH), having the largest attractive interaction and the smallest molar volume exhibits an extremely large viscosity and small self-diffusion coefficient comparing with other hydrocarbons. However, a significant exception was 22DMB, being most close to a sphere: In spite of the smallest attractive interaction and the largest molar volume of 22DMB in the all samples, it has the thirdly larger viscosity and the thirdly smaller self-diffusion coefficient. Consequently, the dynamical properties such as self-diffusion and viscosity for the saturated hydrocarbons are determined not only by their attractive interactions but also by their molecular structures.

Effect of cholesterol and other additives on viscosity, self-diffusion coefficient, and intramolecular movements of oleic acid.

It has been empirically known that cholesterol largely increases the viscosity of oleic acid. To clarify the mechanism of the effect of cholesterol on the intermolecular and the intramolecular (segmental) movements of oleic acid in the liquid state, we measured density, viscosity, IR, 1H NMR chemical shift, self-diffusion coefficient, and 13C NMR spin-lattice relaxation time for the liquid samples of oleic acid containing a small amount of cholesterol. Furthermore, the above measurements were also carried out for the samples of oleic acid containing a small amount of cholestanol, cholestane, cholesteryl oleate, ethanol, or benzene. Cholesterol, possessing one OH group and one double bond in its molecular structure, largely increased the viscosity and reduced the self-diffusion and the intramolecular movement of oleic acid. Cholestanol, possessing one OH group but not a double bond, and cholesteryl oleate, not possessing an OH group, also reduced the self-diffusion and the intramolecular movement; cholestane, not possessing an OH group, slightly reduced the self-diffusion and the intramolecular movements. In contrast with these sterols, ethanol and benzene reduced the viscosity and increased the self-diffusion and the intramolecular movements. In addition, cholesterol and ethanol, both having one OH group, promoted the upfield shift of the 1H NMR signal of the carboxyl group of oleic acid; IR difference spectra for the cholesterol/oleic acid system quite resemble those for the ethanol/oleic acid system. These results suggest that oleic acid makes a complex with cholesterol as well as with ethanol. On the basis of the formation of the complex, we have revealed the role and the functional mechanism of cholesterol to the intermolecular and the intramolecular movements of oleic acid in the liquid state.

Dynamical dimer structure and liquid structure of fatty acids in their binary liquid mixture: decanoic/octadecanoic acid and decanoic/dodecanoic acid systems.

Dimer structure and liquid structure of fatty acids in their binary mixtures such as decanoic acid (DA)/octadecanoic acid (SA) and DA/dodecanoic acid (LA) were studied through the measurements of self-diffusion coefficient (D), differential scanning calorimetry (DSC), density and viscosity. The obtained phase diagrams showed that DA and SA form a eutectic in the solid state but partly a solid solution in the SA-rich region; DA and LA form an incongruent-melting compound which forms a eutectic with DA. In the liquid mixture of DA and SA, the D of DA is larger than that of SA over the entire range of compositions and tends to approach the D of SA with increasing SA-mole fraction; the D of DA in the DA/LA system is also larger than that of LA especially in the LA-poor region and steeply approaches that of LA with increasing LA-mole fraction. These D values and phase diagrams were compared with those for the binary mixtures of n-alkanes (C14/C20, C19/C20 and C20/C24); it is concluded that the two kinds of fatty acids always form their individual homodimers in their liquid mixtures regardless of their compositions and temperatures.

Dynamical dimer structure and liquid structure of fatty acids in their binary liquid mixture: dodecanoic and 3-phenylpropionic acids system.

Dimer structure and liquid structure of fatty acids in the binary liquid mixture of dodecanoic (LA) and 3-phenylpropionic acids (PPA) were studied through the measurements of DSC, self-diffusion coefficient (D), density, viscosity, 13C NMR spin-lattice relaxation time, small-angle X-ray scattering (SAXS), and small-angle neutron scattering (SANS). The phase diagram of LA/PPA mixture exhibited a typical eutectic pattern, which means that LA and PPA are completely immiscible in solid phase. In the liquid phase of the LA/PPA mixture, D of LA always differed from that of PPA irrespective of their compositions. This exhibited that, in the liquid phase of the binary mixture of fatty acids giving a complete eutectic in the solid phase, the fatty acid dimers are composed of the same fatty acid species irrespective of their compositions. The liquid structure of the LA/PPA mixture was clarified through the SAXS and also the SANS measurements.