Where Are Sodium Ions in AOT Reverse Micelles? Fluoride Anion Probes Nanoconfined Ions by ¹⁹F Nuclear Magnetic...

Confining water to nanosized spaces creates a unique environment that can change water's structural and dynamic properties. When ions are present in these nanoscopic spaces, the limited number of water molecules and short screening length can dramatically affect how ions are distributed compared to the homogeneous distribution assumed in bulk aqueous solution. Here, we demonstrate that the chemical shift observed in ¹⁹F NMR spectroscopy of fluoride anion, F^-, probes the location of sodium ions, Na⁺, confined in reverse micelles prepared from AOT (sodium dioctyl sulfosuccinate) surfactants. Our measurements show that the nanoconfined environment of reverse micelles can lead to extremely high apparent ion concentrations and ionic strength, beyond the limit in bulk aqueous solutions. Most notably, the ¹⁹F NMR chemical shift trends we observe for F^- in the reverse micelles indicate that the AOT sodium counterions remain at or near the interior interface between surfactant and water, thus providing the first experimental support for this hypothesis.