Ion-Responsive Behavior of Ionic-Liquid Surfactant Aggregates with Applications in Controlled Release and Emulsification

We propose a simple but efficient, rapid, and quantitative ion-responsive micelle system based on counter-anion exchange of a surfactant with an imidazolium unit. The ion-exchange reaction results in the amphiphilic-to-hydrophobic transition of the imidazolium salt, leading to the destruction of the micelles, which has been successfully applied to control led release and emulsification.

Kinetic isotope effects of proton transfer reaction for amines by ultrasonic relaxation methods: Unexpected evidence from the results in ethylamine solutions

Ultrasonic absorption coefficients for ethylamine in heavy water (D2O) and in light water (H2O) have been measured in the frequency range from 0.8 to 220 MHz at 25 degrees C. A single relaxational process has been observed in these two kinds of solutions. From the concentration dependence of the ultrasonic relaxation parameters, and following the reaction mechanism proposed by Eigen et al. for ethylamine in H2O, the causes of the relaxations have been attributed to a perturbation of an equilibrium associated with a deuteron or proton transfer reaction. The rate and equilibrium constants have been estimated from deuterioxide or hydroxide ion concentration dependence of the relaxation frequency, and the kinetic isotope effects have been determined. In addition, the standard volume changes of the reactions have been calculated from the concentration dependence of the maximum absorption per wavelength, and the adiabatic compressibility has also been determined from the density and sound velocity for ethylamine in D2O and in H2O, respectively. These results are compared with those for propylamine and butylamine and are discussed in relation to the different kinetic properties between D2O and H2O, the reaction radii derived by Debye theory, and the structural properties of the reaction intermediate.

Isotope effect in proton-transfer and association-dissociation reactions for butylamine by ultrasonic relaxation methods

Ultrasonic absorption coefficients were measured for butylamine in heavy water (D2O) in the frequency range from 0.8 to 220 MHz and at concentrations from 0.0278 to 2.5170 mol dm(-3) at 25 degrees C; two kinds of relaxation processes were observed. One was found in relatively dilute solutions (up to 0.5 mol dm(-3)), which was attributed to the hydrolysis of butylamine. In order to compare the results, absorption measurements were also carried out in light water (H2O). The rate and thermodynamic parameters were determined from the concentration dependence of the relaxation frequency and the maximum absorption per wavelength. The isotope effects on the diffusion-controlled reaction were estimated and the stability of the intermediate of the hydrolysis was considered while comparing it with the results for propylamine in H2O and D2O. Another relaxation process was observed at concentrations greater than 1 mol dm(-3) in D2O. In order to examine the solution characteristics, proton NMR measurements for butylamine were also carried out in D2O. The chemical shifts for the gamma- and delta-proton in butylamine molecule indicate the existence of an aggregate. From profiles of the concentration dependence of the relaxation frequency and the maximum absorption per wavelength of sound absorption, the source of the relaxation was attributed to an association-dissociation reaction, perhaps, associated with a hydrophobic interaction. The aggregation number, the forward and reverse rate constants and the standard volume change of the reaction were determined. It was concluded from a comparison with the results in H2O that the hydrophobic interaction of butylamine in D2O is stronger than that in H2O. Also, the isotope effect on this reaction was interpreted in terms of the solvent structure.

Ultrasonic relaxation kinetics on fast deuteron transfer reaction

Propylamine has been selected to investigate the isotope effect of a fast deuteron transfer reaction by ultrasonic relaxation method. Ultrasonic absorption coefficients of propylamine in heavy water (D2O) at 25 degrees C in the concentration range from 0.0107 to 0.6300 mol dm(-3) have been measured by pulse and resonance methods over the frequency range from 0.8 to 220 MHz. A Debye-type single relaxation absorption has been observed in the solution. From the dependence of the ultrasonic relaxation parameters on the concentration and solution pH, the source of the observed relaxation has been attributed to a perturbation of the chemical equilibrium associated with the deuteron transfer reaction. The rate and equilibrium constants have been determined by the measurement of the deuteroxyl ion concentration dependence of the relaxation frequency. Also the standard volume change of the reaction has been determined from the concentration dependence of the maximum absorption per wavelength and the adiabatic compressibility has been calculated from the density and the sound velocity in the solution. These results have then been compared with those obtained for propylamine in light water (H2O). The forward rate constant is greater and the reverse rate constant is smaller in DO than in H2O. The standard volume change for deuteron transfer is greater than that for proton transfer reaction, and the adiabatic compressibility shows a similar trend. These data support an argument that there exists a stronger hydrogen bond in D2O than in H2O. The difference of the stability in the intermediate states, R-ND3+... OD- and R-NH3+... OH-, has also been considered from the results of the isotope effects.

Growth of Potamageton maackianus under low-light stress in eutrophic water

Decline of submersed macrophytes in Lake Donghu of China with the progress of eutrophication is assumedly due to low light stress by algae blooming. I conducted a laboratory experiment to study the impact of low-light stress on the growth of Potamogeton maackianus A. Been, a dominant submersed macrophyte of the lake before the 1970s. Plants were grown for six weeks in aquaria with Lake Donghu sediment and enriched water. Light delivered to aquaria was adjusted to simulate the typical Lake Donghu light intensities that exist at several water depths from 0.6m to 1.7m. Biomass growth of the plant was inversely related to light intensity at the simulated depths of greater than or equal to 1.0m (r = 0.96, p < 0.05, n=6) and was negative at the depths of greater than or equal to 1.4m. These results indicate that photosynthetic light saturation and compensation points of the plant in Lake Donghu should be ca. 0,9m and ca. 1.5m depths, respectively. Chlorophyll content, growth of main shoot, total shoot lengths and density of the plant all peaked at 1.2-1.3m simulated depths. These results indicate that P. maackianus responds to low light stress primarily by elongation of shoots, and increase of density. Its biomass growth and nutrient uptake rate did not correlate with the accelerated shoot growth. Below the light intensities of water deeper than 1.2-1.3m, shoot growth rate decreased. The flexible tolerant strategy of P. maackianus to low-light stress suggests that the disappearance of this plant from the lake was not mainly due to eutrophication-induced low-light stress.

Photocatalytic water reduction under visible light on a novel ZnIn2S4 catalyst synthesized by hydrothermal method

A novel ZnIn2S4 catalyst synthesized by hydrothermal method shows high and stable photocatalytic activity for water reduction under visible light illumination.

Water reduction and oxidation on Pt-Ru/Y2Ta2O5N2 catalyst under visible light irradiation

Y2Ta2O5N2 is presented as a novel photocatalyst with high activity for water splitting under visible-light irradiation in the presence of appropriate sacrificial reagents; the activity for reduction to H-2 is increased by the incorporation of Pt or Ru as a co-catalyst, with a significant increase in production efficiency when both Pt and Ru are present.

The interaction between poly(vinylpyrrolidone) and reversed micelles of water/AOT/n-heptane

The interactions between poly(vinylpyrrolidone) (PVP) and the reversed micelles composed of water, AOT, and n-heptane are investigated with the aid of phase diagram, measurements of conductivity and viscosity, Fourier transform infrared (FTIR) spectrum, and dynamic light scattering (DLS). The phase diagrams of water/AOT/heptane in the presence of and absence of PVP are given. The conductivity of the water/AOT/heptane reversed micelle without PVP initially increases and then decreases with the increase of water content, ω0 (the molar ratio of water to AOT), while the plots of conductivity (K) versus ω0 of the reversed micelle in the presence of PVP depend on the PVP concentrations. The plot of K versus ω0 with 2.0%wt PVP is similar to that without PVP. Only the ω0,max (the water content that the maximum conductivity corresponds to) is larger than that without PVP. Nevertheless, the conductivity of the reversed micelle containing more than 4%wt PVP always rises with the increase of the water content in the measured range. The DLS results indicate that the hydrodynamic radius (Rh) in the presence and absence of PVP rises with the increase of ω0. The plots with PVP and without PVP have almost the same value when ω0<17; and after that, it quickly increases with the increase of ω0. It is interesting to find that there is almost no effect of the PVP concentration on the viscosity and Rh of the reversed micelle at ω0 = 15. The FTIR results suggest that the contents of SO3--bound water and Na+-bound water both decrease with PVP added, while the content of the bulky-like water increases. However, the trapped water in the hydrophobic chain of the surfactant is nearly unaffected by PVP. It is also found from the FTIR that the carbonyl group stretching vibration of AOT is fitted into two sub-peaks, which center at 1740 and 1729 cm-1, corresponding to the trans and cis conformations of AOT, respectively.