Slow Relaxation Mode in Mixtures of Water and Organic Molecules:  Supramolecular Structures or Nanobubbles?

Aqueous solutions of tetrahydrofuran, ethanol, urea, and alpha-cyclodextrin were studied by a combination of static and dynamic laser light scattering (LLS). In textbooks, these small organic molecules are soluble in water so that there should be no observable large structures or density fluctuation in either static or dynamic LLS. However, a slow mode has been consistently observed in these aqueous solutions in dynamic LLS. Such a slow mode was previously attributed to some large complexes or supramolecular structures formed between water and these small organic molecules. Our current study reveals that it is actually due to the existence of small bubbles ( approximately 100 nm in diameter) formed inside these solutions. Our direct evidence comes from the fact that it can be removed by repeated filtration and regenerated by air injection. Our results also indicate that the formation of such nanobubbles in small organic molecule aqueous solutions is a universal phenomenon. Such formed nanobubbles are rather stable. The measurement of isothermal compressibility confirms the existence of a low density microphase, presumably nanobubbles, in these aqueous solutions. Using a proposed structural model, that is, each bubble is stabilized by small organic molecules adsorbed at the gas/water interface, we have, for the first time, estimated the pressure inside these nanobubbles.