Aqueous solubilization of hydrophobic compounds by inorganic nano-ions: An unconventional mechanism

J Colloid Interface Sci. 2023 May 15:638:561-568. doi: 10.1016/j.jcis.2023.01.115. Epub 2023 Jan 26.

Abstract

Hypothesis: Solubilization of hydrophobic compounds in water is commonly performed by using organic solubilizers such as hydrotropes, surfactants, co-solvents, and macrocycles to form host-guest complexes. 3,3'-commo-bis[closo-1,2-dicarba-3-cobaltadodecaborane] derivatives (COSANs) are fully inorganic and non-amphiphilic ionic boron clusters with nanometric size (nano-ions) showing superchaotropic properties as they strongly bind to neutral organic molecules. Therefore, we expect COSANs to act as solubilizers of sparingly water-soluble molecules, but with a mechanism different from all other organic solubilizers known so far.

Experiments: The aqueous solubilization efficiency of COSANs towards butanol was evaluated by determining phase diagrams and comparing them to classical solubilizers. Nanostructuration of the mixture was studied using UV spectroscopy, small-angle X-ray, and neutron scattering with contrast variation.

Findings: COSANs act as efficient aqueous solubilizers of medium-chain alcohols (0.6 < log P < 1.5). Unlike surfactants, COSAN is an efficient solubilizer in its monomeric state, at concentrations well below its critical aggregation concentration. Solubilization by COSAN takes place with a bi-dimensional anisotropic growth of COSAN/butanol co-assemblies, whereas solubilization by surfactant occurs via an isotropic swelling of micelles. Appealingly, COSANs/2-butanol co-assemblies efficiently solubilize more hydrophobic compounds with log P values up to around 6, offering new opportunities in many applied fields.

Keywords: Aqueous solubilization; Butanol; COSAN; Co-assembly; Drug; Dye; Hydrophobic compound; Nano-ion; Perfume.