title: Crystallization of confined water pools with radii greater than 1 nm in AOT reverse micelles.
abstract: Freezing of water pools inside aerosol sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles has been investigated. Previous freezing experiments suffer from collision and fusion of AOT micelles and resultant loss of water from the water pool by shedding out during the cooling process. These phenomena have restricted the formation of ice to only when the radius of the water pool (Rw) is below 1 nm, and only amorphous ice has been observed. To overcome the size limitation, a combination of rapid cooling and a custom-made cell allowing thin sample loading is applied for instantaneous and homogeneous freezing. The freezing process is monitored with attenuated total reflection infrared spectroscopy (ATR-IR) measurements. A cooling rate of ca. -100 K/min and a sample thickness of ca. 50 μm overcomes the limitations mentioned above and allows the crystallization of water pools with larger radii (Rw > 1 nm). The corresponding ATR-IR spectra of the frozen water pools with Rw < 2.0 nm show similar features to the spectrum of metastable cubic ice (Ic). Further increase of the radius of the water pool (Rw > 2.0 nm), unfortunately, drastically decreased the integrated area of the ν(OH) band observed just after freezing, indicating the breakup of the micellar structure and shedding out of the water pool. In addition, it was revealed that Ic ice can also be formed in flexible organic self-assembled AOT reverse micelles for at least Rw ≤ ca. 2 nm, as well as in inorganic and solid materials with a pore radius of ca. 2 nm. The dependence of the phase transition temperature on the curvature of the reverse micelles is discussed from the viewpoint of the Gibbs-Thomson effect.
authors.affiliation: Department of Chemistry, Faculty of Science, Tokyo University of Science , 1-3 Kagurazaka, Shinjuku-city, Tokyo 162-8601, Japan.
authors.forename: Akira
authors.initials: A
authors.lastname: Suzuki
authors.forename: Hiroharu
authors.initials: H
authors.lastname: Yui
mesh_terms: D008823:Micelles; D014867:Water / Q000737:chemistry*
chemical_list: D008823:Micelles; D014867:Water