Super-efficient surfactant for stabilizing water-in-carbon dioxide microemulsions

The fluorinated double-tailed glutarate anionic surfactant, sodium 1,5-bis[(1H,1H,2H,2H-perfluorodecyl)oxy]-1,5-dioxopentane-2-sulfonate (8FG(EO)(2)), was found to stabilize water-in-supercritical CO(2) microemulsions with high water-to-surfactant molar ratios (W(0)). Studies were carried out here to obtain detailed information on the phase stability and nanostructure of the microemulsions by using a high-pressure UV-vis dye probe and small-angle neutron scattering (SANS) measurements. The UV-vis spectra, with methyl orange as a reporter dye, indicated a maximum attainable W(0) of 60 at 45 and 75 °C, and SANS profiles indicated regular droplet swelling with a linear relationship between the water core nanodroplet radius and W(0). This represents the highest water solubilization reported to date for any water-in-CO(2) microemulsion. Further analysis of the SANS data indicated critical packing parameters for 8FG(EO)(2) at the microemulsion interface >1.34, representing approximately 1.1 times the value for common aerosol-OT in water-in-heptane microemulsions under equivalent conditions.     

Span 80 vesicles have a more fluid, flexible and "wet" surface than phospholipid liposomes

The surface properties of Span 80 vesicles at various cholesterol contents, together with those of various liposomes, were characterized by using fluorescence probes. The membrane fluidity of the Span 80 vesicles was measured by 1,6-diphenyl-1.3.5-hexatriene (DPH) and trimethlyammonium-DPH (TMA-DPH), and the results suggested that the surface of the Span 80 vesicles was fluid due to the lateral diffusion of Span 80 molecules. The depolarization measured by TMA-DPH and the headgroup mobility measured by dielectric dispersion analysis indicated the high mobility of the head group of Span 80 vesicles. This suggested that the surface of Span 80 vesicles was flexible due to the head group structure of Span 80, sorbitol. In addition, spectrophotometric analysis with 6-dodecanoyl-N, N-dimethyl-2-naphthylamine and 8-anilino-1-naphthalenesulfonic acid indicated that the water molecules could easily invade into the interior of the Span 80 vesicle membrane, suggesting that the membrane surface was more wet than the liposome surface. These surface properties indicated that the protein could interact with the interior of vesicle membranes, which was similar to the case of cholesterol. Thus the present results confirmed that the Span 80 vesicle surfaces showed the unique characteristics of fluidity, flexibility, and "wetness", whereas the liposome surfaces did not.     

Synthesis of TiO2 nanocoral structures in ever-changing aqueous reaction systems

A far-from-equilibrium strategy is developed to synthesize coral-like nanostructures of TiO(2) on a variety of surfaces. TiO(2) nanocoral structures consist of anatase base film and rutile nanowire layers, and they are continuously formed on substrates immersed in aqueous TiOSO(4)-H(2)O(2). The sequential deposition of TiO(2) starts with hydrolysis and condensation reactions of titanium peroxocomplexes in the aqueous phase, resulting in deposition of amorphous film. The film serves as adhesive interface on which succeeding growth of rutile nanowires to occur. This initial deposition reaction is accompanied by shift in pH of the reaction media, which is favorable condition for the growth of rutile nanocrystals. During the growth of rutile nanocoral layers, the amorphous base films are transformed to anatase phase. These sequential deposition reactions occur at temperatures as low as 80 °C, and the mild synthetic condition allows the use of a wide range of substrates such as ITO (indium tin oxide), glass, and even organic polymer films. The thickness of nanocoral layer is controllable by repeating the growth reaction of rutile nanocorals. TiO(2) nanocorals show photocatalytic activity as demonstrated by site-specific reduction of Ag(I) ions, which proceeds preferentially on the rutile nanowire layer. The rutile nanowire layer also shows photocatalytic decomposition of acetaldehyde, which is promoted upon increase of the thickness of the nanowire layer. The use of temporally transforming reaction media allows the formation of biphasic TiO(2) nanocoral structures, and the concept of nonequilibrium synthetic approach would be widely applicable to developing structurally graded inorganic nanointerfaces.     

Direct enantioseparation of lipoic acid in dietary supplements by capillary electrophoresis using trimethyl-β-cyclodextrin as a chiral selector

Lipoic acid, an antioxidant, naturally occurs as the (R)-enantiomer, while synthetic lipoic acid is racemic. It is thus of interest to know the (R)-enantiomer content of lipoic acid supplements. Here, we used capillary electrophoresis to directly enantioseparate lipoic acid in dietary supplements by using a sulfonated capillary with an effective voltage of +18 kV and direct detection at 200 nm. Factors affecting migration time and resolution of lipoic acid were investigated. The optimum background electrolyte was found to be 100 mM phosphate buffer (pH 7.0) containing 8 mM trimethyl-β-cyclodextrin as a chiral selector at 20°C. Under the proposed conditions, direct chiral resolution of lipoic acid in dietary supplements was conducted successfully.     

Efficient luminescence from a copper(I) complex doped in organic light-emitting diodes by suppressing C-H vibrational quenching

Efficient luminescence was realized by suppressing not only excited-state distortion but also C-H vibrational quenching in a Cu complex. Organic light-emitting diodes containing the Cu complex as an emitting dopant exhibited a maximum external quantum efficiency of 7.4%.     

Conformational relaxation dynamics of a poly(N-isopropylacrylamide) aqueous solution measured using the laser temperature jump transient grating method

We observed phase transition and phase relaxation processes of a poly(N-isopropylacrylamide) (PNIPAM) aqueous solution using the heterodyne transient grating (HD-TG) method combined with the laser temperature jump technique. The sample temperature was instantaneously raised by about 1.0 K after irradiation of a pump pulse to crystal violet (CV) molecules for heating, and the phase transition was induced for the sample with an initial temperature just below the lower critical solution temperature (LCST); the following phase relaxation dynamics was observed. Turbidity relaxation was observed in both the turbidity and HD-TG responses, while another relaxation process was observed only in the HD-TG response, namely via the refractive index change. It is suggested that this response is due to formation of globule molecules or their assemblies since they would have nothing to do with turbidity change but would affect the refractive index, which is dependent on the molar volume of a chemical species. Furthermore, the grating spacing dependence of the HD-TG responses suggests that the response was caused by the counter propagating diffusion of the coil molecules as a reactant species and the globule molecules as a product species and the lifetime of the globule molecules ranged from 1.5 to 5 seconds. Thus, we conclude that the turbidity reflects the dynamics of aggregate conditions, not molecular conditions. The coil and globule sizes were estimated from the obtained diffusion coefficient. The sizes of the coil molecules did not change at the initial temperatures below the LCST but increased sharply as it approaches LCST. We propose that the coil-state molecules associate due to hydrophobic interaction when the initial temperature was higher than LCST minus 0.5 K and that the globule-state molecules generated from the coil-state molecules showed a similar trend in temperature. The phase transition was also induced by heating under a microscope, and the relaxation process was followed using the fluorescence peak shift of a fluorescent molecule-labeled PNIPAM. The result also supports the existence of a globule molecule or its assembly remains for several seconds in the phase relaxation.     

Simple and exact approach to the electronic polarization effect on the solvation free energy: formulation for quantum-mechanical/molecular-mechanical system and its applications to aqueous solutions

We present a simple and exact numerical approach to compute the free energy contribution δμ in solvation due to the electron density polarization and fluctuation of a quantum-mechanical solute in the quantum-mechanical/molecular-mechanical (QM/MM) simulation combined with the theory of the energy representation (QM/MM-ER). Since the electron density fluctuation is responsible for the many-body QM-MM interactions, the standard version of the energy representation method cannot be applied directly. Instead of decomposing the QM-MM polarization energy into the pairwise additive and non-additive contributions, we take sum of the polarization energies in the QM-MM interaction and adopt it as a new energy coordinate for the method of energy representation. Then, it is demonstrated that the free energy δμ can be exactly formulated in terms of the energy distribution functions for the solution and reference systems with respect to this energy coordinate. The benchmark tests were performed to examine the numerical efficiency of the method with respect to the changes in the individual properties of the solvent and the solute. Explicitly, we computed the solvation free energy of a QM water molecule in ambient and supercritical water, and also the free-energy change associated with the isomerization reaction of glycine from neutral to zwitterionic structure in aqueous solution. In all the systems examined, it was demonstrated that the computed free energy δμ agrees with the experimental value, irrespective of the choice of the reference electron density of the QM solute. The present method was also applied to a prototype reaction of adenosine 5'-triphosphate hydrolysis where the effect of the electron density fluctuation is substantial due to the excess charge. It was demonstrated that the experimental free energy of the reaction has been accurately reproduced with the present approach.     

Dinuclear complexes of tetravalent cerium in an aqueous perchloric acid solution

Primary aquo species of tetravalent cerium (Ce(IV)) in perchloric acid has been identified as a single oxo-bridging dinuclear complex, not a mononuclear one, by extended X-ray absorption fine structure (EXAFS) spectroscopy combined with density functional theory (DFT) calculations.     

π-Electron-system-layered polymer: through-space conjugation and properties as a single molecular wire

[2.2]Paracyclophane-based through-space conjugated oligomers and polymers were prepared, in which poly(p-arylene-ethynylene) (PAE) units were partially π-stacked and layered, and their properties in the ground state and excited state were investigated in detail. Electronic interactions among PAE units were effective through at least ten units in the ground state. Photoexcited energy transfer occurred from the stacked PAE units to the end-capping PAE moieties. The electrical conductivity of the polymers was estimated using the flash-photolysis time-resolved microwave conductivity (FP-TRMC) method and investigated together with time-dependent density functional theory (TD-DFT) calculations, showing that intramolecular charge carrier mobility through the stacked PAE units was a few tens of percentage larger than through the twisted PAE units.     

Second harmonic generation of thermally poled ZnCl2 or ZnBr2-B2O3-TeO2 glasses and its mechanism

Second harmonic generation (SHG) was observed from halide, in specific, chlorine or bromine-containing tellurite glasses. The magnitude of SHG increased with increasing halides concentration and poling time. Although the mechanism of SHG is still controversial, it is generally accepted that the idea of the deficiency of cations near the anode side cause SHG. However, in the preset oxyhalide glass system without any singly positive charge cation, the polishing of the anode side showed no effect on SHG. On the other hand, the polishing of the cathode side significantly decreased the magnitude of SHG in the present alkali-free oxyhalide glasses. Therefore, the SHG mechanism in the present oxyhalide glass systems is made evident in which the movement of anions results in an anion-deficient layer near the cathode side.