Near-surface structure of Nafion in deuterated water.

The swelling of a polymer ion-exchange membrane Nafion in water with various heavy isotope contents (D2O) was studied by photoluminescent UV spectroscopy. The photoluminescence arises because of the presence of sulfonic groups attached to the ends of the perfluorovinyl ether groups that form the tetrafluoroethylene (Teflon) backbone of Nafion. The width of the colloidal region, which is formed near the membrane surface as a result of the outgrowth of Nafion microfibers toward the bulk liquid, varies non-monotonically with D2O content, displaying a narrow maximum in the low concentration region. A significant insight into the unexpected isotopic effects revealed in swelling Nafion in deuterated water is provided. Mainly, the polymer swelling is very sensitive to small changes (on the order of several tens of parts per million) in the content of deuterium, which, for instance, can help in understanding the isotopic effects in living tissues.

Droplet-like heterogeneity of aqueous tetrahydrofuran solutions at the submicrometer scale.

A droplet formation in aqueous solutions of tetrahydrofuran (THF) has been experimentally detected at the submicrometer scale using two independent laser diagnostic techniques (dynamic light scattering and laser phase microscopy) and described in terms of THF-water intermolecular hydrogen bonding. It is shown that the nanodroplets have a mean size of 300 nm, their refractive index is higher than that of the ambient liquid, and they are highly enriched with THF molecules. The maximum of light scattering intensity falls within the THF concentration range 2-8 mol. %, which corresponds to the volume number density of the nanodroplets ∼1010-1011 cm-3. A theoretical explanation of forming the nanodroplets with a high content of THF, which is based on a model of dichotomous noise being applied to the so-termed "twinkling" hydrogen bonds and involves spinodal decomposition in the unstable region enclosed within the dichotomous binodal, is proposed. The parameters of hydrogen bonds in the molecular system "water-THF" were found, and the phase diagram of the solution with allowance for cross-linking hydrogen bonds was constructed.

Nanobubble clusters of dissolved gas in aqueous solutions of electrolyte. I. Experimental proof.

Results of experiments with dynamic light scattering, phase microscopy, and polarimetric scatterometry allow us to claim that long-living gas nanobubbles and the clusters composed of such nanobubbles are generated spontaneously in an aqueous solution of salt, saturated with dissolved gas (say, atmospheric air). The characteristic sizes of both nanobubbles and their clusters are found by solving the inverse problem of optical wave scattering in ionic solutions. These experimental results develop our earlier study reported by Bunkin et al. [J. Chem. Phys. 130, 134308 (2009)] and can be treated as evidence for the special role of ions in the generation and stabilization of gas nanobubbles.

Nanobubble clusters of dissolved gas in aqueous solutions of electrolyte. II. Theoretical interpretation.

A quantitative model of ion-stabilized gas bubbles is suggested. Charging the bubbles by the ions, which are capable of adsorption, and the screening by a cloud of counter-ions, which are less absorptable, is modeled. It is shown that, subject to the charge of bubble, two regimes of such screening can be realized. For low-charged bubbles, the screening is described in the framework of the known linearized Debye-Huckel approach, when the sign of the counter-ion cloud is preserved everywhere in the liquid, whereas at large charge this sign is changed at some distance from the bubble surface. This effect provides the mechanism for the emergence of two types of compound particles having the opposite polarity, which leads to the aggregation of such compound particles into fractal clusters. Based on experimental data, arguments in favor of the existence of the clusters composed of the ion-stabilized bubbles in aqueous electrolyte solutions are advanced. This paper provides theoretical grounds for the experimental results presented in the previous paper (part I) published in this journal.

[Coefficient of refraction of water and aqueous solutions in the optical frequency range in the vicinity of naphione].

Within the present experimental working it has been shown that in the vicinity of naphione (ion-exchange membrane) the water refraction coefficient grows approximately by a factor of 1.1 in comparison with its value in a liquid. The refractive coefficient changes at the wavelength of about 50 microns. The effect of the refractive coefficient is measured by the pH value and the temperature of the liquid. In the experimental study of the "glycerin/water" mixture at different concentrations it has been found that the refractive coefficient may increase because naphione surface attracts the dipole of water clusters. This effect occurs due to the swelling of naphione in water and its surface takes a charge.

Role of dissolved gas in optical breakdown of water: differences between effects due to helium and other gases.

It is shown that water contains defects in the form of heterogeneous optical breakdown centers. Long-living complexes composed of gas and liquid molecules may serve as nuclei for such centers. A new technique for removing dissolved gas from water is developed. It is based on a "helium washing" routine. The structure of helium-washed water is very different from that of water containing dissolved atmospheric gas. It is able to withstand higher optical intensities and temperatures of superheating compared with the nonprocessed ones. The characteristics of plasma spark and values of the breakdown thresholds for processed and nonprocessed samples are given.

Nanoscale structure of dissolved air bubbles in water as studied by measuring the elements of the scattering matrix.

Results of experiments with laser modulation interference microscopy and the Mueller-matrix scatterometry show that macroscopic scatterers of light waves are present in doubly distilled water free of external solid impurities. The experimental data can be interpreted using a computational model of micron-scale clusters composed of polydisperse air bubbles having effective radii of 70-90 nm. The fractal dimension of such clusters was evaluated as 2.4-2.8 and their concentration appeared to be approximately 10(6) cm(-3).

Mechanism of low-threshold hypersonic cavitation stimulated by broadband laser pump.

A low threshold acoustic cavitation regime was observed for the excitation of hypersonic waves due to a stimulated Brillouin scattering (SBS) mechanism, when the optical pump lies within the uv frequency range. Cavitation occurs if the optical pump bandwidth Delta(+)>>Omega(0), where Omega(0) is the Stokes frequency shift (the hypersonic frequency). In the opposite case (Delta(+)<