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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Biophysics

Background:

  • Fluid fatty alcohols, such as hydrated n-octanol, are widely considered amorphous solvents.
  • Their nanostructured nature has been hypothesized but not definitively characterized.

Purpose of the Study:

  • To investigate the structural properties of dry octanol and hydrated octanol using small-angle X-ray scattering (SAXS).
  • To determine if short fluid n-alkanols form mesophases and how additives affect their structure.

Main Methods:

  • Small-angle X-ray scattering (SAXS) was employed to study octanol, hydrated octanol, and mixtures with octane and ketoprofen.
  • Analysis of SAXS diffractograms, including the inner peak and Guinier's signal, to elucidate structural motifs.

Main Results:

  • Octanol and other short fatty alcohols form a mesophase characterized by regularly packed polar nanoclusters.
  • Additives like octane and ketoprofen cause only moderate changes to nanoclusters due to packing frustration.
  • Certain additives transform nanoclusters into aqueous lacunae, forming a proto-microemulsion, indicated by a novel Guinier's SAXS signal.

Conclusions:

  • The established concept of the octanol-water partition coefficient is challenged by the observed coexistence of nanoclusters and variable lacunae.
  • Findings suggest reinterpreting partition coefficient data as association/binding constants for improved lipophilicity description.
  • The identified mesophase structure and proto-microemulsion formation open new avenues for interfacial catalysis research.