How do chain lengths of acyl-l-carnitines affect their surface adsorption and solution aggregation?

l-carnitines in our body systems can be readily converted into acyl-l-carnitines which have a prominent place in cellular energy generation by supporting the transport of long-chain fatty acids into mitochondria. As biocompatible surfactants, acyl-l-carnitines have potential to be useful in technical, personal care and healthcare applications. However, the lack of understanding of the effects of their molecular structures on their physical properties has constrained their potential use.

This work reports the study of the influence of the acyl chain lengths of acyl-l-carnitines (C_nLC) on solubility, surface adsorption and aggregation. Critical micellar concentrations (CMCs) of C_nLC were determined by surface tension measurements. Neutron reflection (NR) was used to further examine the structure and composition of the adsorbed C_nLC layer. The structural changes of the micellar aggregates under different concentrations of C_nLC, pH and ionic strength were determined by dynamic light scattering (DLS) and small angle neutron scattering (SANS).

C₁₂LC is fully soluble over a wide temperature and concentration range. There is however a strong decline of solubility with increasing acyl chain length. The adsorption and aggregation behavior of C₁₄LC was therefore studied at 30 °C and C₁₆LC at 45 °C. The solubility boundaries displayed distinct hysteresis with respect to heating and cooling. The CMCs of C₁₂LC, C₁₄LC and C₁₆LC at pH 7 were 1.1 ± 0.1, 0.10 ± 0.02 and 0.010 ± 0.005 mM, respectively, with the limiting values of the area per molecule at the CMC being 45.4 ± 2, 47.5 ± 2 and 48.8 ± 2 Å² and the thicknesses of the adsorbed C_nLC layers at the air/water interface increasing from 21.5 ± 2 to 22.6 ± 2 to 24.2 ± 2 Å, respectively. All three surfactants formed core-shell spherical micelles with comparable dimensional parameters apart from an increase in core radius with acyl chain length. This study outlines the effects of acyl chain length on the physicochemical properties of C_nLCs under different environmental conditions, serving as a useful basis for developing their potential applications.