Ion-stabilized gas nanobubbles (the so-termed "bubstons") and their clusters are investigated in bulk aqueous solutions of NaCl at different ion concentrations by four independent laser diagnostic methods. It turned out that in the range of NaCl concentration 10(-6) < C < 1 M the radius of bubston remains virtually unchanged at a value of 100 nm. Bubstons and their clusters are a thermodynamically nonequilibrium phase, which has been demonstrated in experiments with magnetic stirrer at different stirring rates. Different regimes of the bubston generation, resulting from various techniques of processing the liquid samples, were explored.
Ion-stabilized nanobubbles in bulk aqueous solutions of various electrolytes were investigated. To understand the ion-specific mechanism of nanobubble stabilization, an approach based on the Poisson--Boltzmann equation at the nanobubble interface and in the near-surface layer was developed. It has been shown that the stabilization of nanobubbles is realized by the adsorption of chaotropic anions at the interface, whereas the influence of cosmotropic cations is weak. With increasing temperature, it should be accounted for by blurring the interface due to thermal fluctuations. As a result, the adsorbed state of ions becomes unstable: the nanobubble loses its stability and vanishes. This prediction was proven in our experiments. It turned out that in the case of liquid samples being kept in hermetically sealed ampules, where the phase equilibrium at the liquid-gas interface is fulfilled for any temperature, the volume number density of nanobubbles decreases with increasing temperature and this decrease is irreversible.
Long-lived luminescence in the blue region was found to occur in deionized water saturated with atmospheric gases following mechanical shaking. Luminescence intensity decreased exponentially after the cessation of stress. During vigorous mechanical shaking, we observed gas bubbles in solution, and the liquid–gas interface area increased noticeably. At the same time, the concentration of molecular oxygen decreased, which could not be attributed to the water warming up with exposure to mechanical stress. However, deaerated water rapidly became saturated with gases following mechanical stress. The recommendation that cell culture media should be mixed after they are removed from the fridge in order to allow saturation with oxygen is probably misleading. It was shown that gases existed in water both in the form of individual molecules and nanobubbles. Mechanical stress did not influence the number or size of nanobubbles. While gas nanobubbles were absent in freshly prepared deaerated water, they appeared following exposure to mechanical stress. In addition, in mechanically treated gas-saturated water, there was seemingly an equilibrium shift towards the decomposition of carbonic acid to water and carbon dioxide. At the same time, the pH of water tended to increase immediately after mechanical stress. It was demonstrated that reactive oxygen species (ROS) form in gas-saturated water under mechanical stress (30 Hz, amplitude of 5 mm). The relative generation rate of hydrogen peroxide and of the hydroxyl radical was 1 nM/min and 0.5 nM/min, respectively. It was found that with an increase in the frequency of mechanical action (f), the rate of ROS generation increased in proportion to f 2. The major pathways for hydrogen peroxide generation are probably associated with the formation of singlet oxygen and its further reduction, and the alternative pathway is the formation of hydrogen peroxide as a result of hydroxyl radical recombination.
Structural
characterization by three complementary methods of laser
diagnostics (dynamic light scattering, laser phase microscopy, and
laser polarimetric scatterometry) has established that shaking of
immunoglobulin G (IgG) dispersions in water and ethanol–water
mixtures (36.7 vol %) results in two effects. First, it intensifies
the aggregation of IgG macromolecules. Second, it generates bubbles
with a size range that is different in each solvent. The aggregation
is enhanced in ethanol–water mixtures because of IgG denaturation.
IgG aggregates have a size of ∼300 nm in water and ∼900
nm in ethanol–water mixtures. The flotation of IgG is much
more efficient in water. This can be explained by a better adsorption
of IgG particles (molecules and aggregates) on bubbles in water as
compared to ethanol–water mixtures. Bulk nanobubbles and their
association with IgG aggregates were visualized by laser phase microscopy
in water but were not detected in ethanol–water mixtures. Therefore,
the nanobubble flotation mechanism for IgG aggregates acting in water
is not feasible for ethanol–water mixtures.
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