Synthesis, aggregation behavior and drug-binding interactions of fatty acid-imidazolium-based surface-active ionic liquids

Abstract

The renewable fatty acid-based surface-active ionic liquids (SAILs) containing ethyl-substituted imidazolium head groups were prepared and structurally analyzed by Fourier transform infrared spectroscopy (FTIR), ¹HNMR and ¹³CNMR spectroscopy. The products were named as; 3-ethyl-1-(2-dodecanoyl oxy) ethylimidazolium bromide [C₁₂Eeim]Br, 3-ethyl-1-(2-tetradecanoyl oxy) ethylimidazolium bromide [C₁₄Eeim]Br and 3-ethyl-1-(2-hexadecanoyl oxy) ethylimidazolium bromide [C₁₆Eeim]Br. The critical micelle concentration (cmc) values of the three SAILs have been evaluated using conductivity measurements, probe-less UV-visible spectroscopy and fluorescence spectroscopy. The obtained cmc values were compared with the earlier reported non-functionalized SAILs such as [C_nmim]Br and [C_neim]Br where n = 12, 14, 16. The values were found to be 3-9 times lower mainly due to the presence of ester chain and also ethyl substituted imidazole ring. Thermodynamic parameters were evaluated by conductivity data at three different temperatures. Further, the aggregation behavior of SAILs with anesthetic drug, lidocaine hydrochloride (LC) has been studied using fluorescence. The fluorescence and UV-visible studies showed strong synergistic interactions operating between SAILs and drug molecules involving H bonding and cation-π interactions. The interactions grew stronger with the elongation of SAIL-chain length (12-16C). Dynamic light scattering (DLS) and transmission electron microscopy (TEM) measurements suggested the formation of vesicles in SAIL-LC mixtures. These studies may thus offer an effective candidate which would serve as vectors for drug molecules in terms of their enhanced solubilization, permeability and target-specific delivery.

Keywords: Aggregation behavior; Binding; Drug delivery; Lidocaine hydrochloride; Surface-active ionic liquid; Vesicle.