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We developed lipid-like ionic liquids, containing 2-mercaptoimidazolium and 2-mercaptothiazolinium headgroups tethered to two long saturated alkyl chains, as carriers for in vitro delivery of plasmid HEK DNA into 293T cells. We employed a combination of modular design, synthesis, X-ray analysis, and computational modeling to rationalize the self-assembly and desired physicochemical and biological properties. The results suggest that thioamide-derived ionic liquids may serve as a modular platform for lipid-mediated gene delivery. This work represents a step toward understanding the structure-function relationships of these amphiphiles with long-range ordering and offering insight into design principles for synthetic vectors based on self-assembly behavior.

This study introduces a novel class of imidazolium- and ammonium-based ionic liquids possessing two C 12 and C 14 tails and thioether linkers designed for lipoplex-mediated DNA delivery. Imidazolium-based ionic liquids displayed efficient gene delivery properties with low toxicity. Thiol-yne click chemistry was employed for the facile and robust synthesis of these thioether-based cationic lipioids with enhanced lipophilicity and low fluidity.

A series of novel lipid-inspired ionic liquids have been synthesized employing the thiol-ene "click" reaction in a single-step process. The thermal properties were determined by differential scanning calorimetry (DSC) and showed observable trends between the C16, C18, and C20 analogues. The minimum melting points for each equivalent chain length series occur at sequential odd sulfur positions, 3, 5, and 7 for the C16, C18, and C20 series, respectively. The magnitude of melting point depression relative to the saturated homologue is observed to have a strong dependence on the position of the sulfur in the side chain. Additionally, the sulfur position corresponding to the lowest melting point for a homologous series shifts further down the chain as the chain length is increased, indicating that the maximum effect takes place near the center of the ion and not the center of the thiaalkyl chain. This synthesis provides tunability and improved thermal stability for 1-methyl-3-thiaalkylimidazolium bistriflimides and insight into structure-property relationships of lipidic ionic liquids.

Ionic liquids of cations bearing two lipid-like aliphatic tails are shown to have values of T(m) that can be very low, and that can be tuned up or down by the addition, deletion, or combination of dipolar modules and side-chain double bonds.

The synthesis of a series of new lipid-inspired ionic liquids through thiol-ene 'click' reaction with a single-step process. This synthesis offers considerable promise as an efficient and orthogonal method to construct structurally diverse imidazolium-type ionic liquids with linear and branched cationic tails, as well as versatility in the placement of the sulfur heteroatom. Profound solvent effect in this ene reaction regioselectivity has been observed. [ABSTRACT FROM AUTHOR]

Abstract: Cyclopropyl moieties embedded in the long aliphatic side chains of imidazolium-type ionic liquids are shown to be highly effective in lowering the T m of such materials relative to counterparts bearing linear, saturated side chains. While not as efficient as olefins in bringing about this effect, ILs incorporating side-chain cyclopropanated modules are likely to be more resistant to aerobic degradation than those employing the former. [Copyright &y& Elsevier]

Correction for ‘Biomimetic design of protic lipidic ionic liquids with enhanced fluidity’ by Richard A. O'Brien et al., New J. Chem., 2016, 40, 7795–7803. [ABSTRACT FROM AUTHOR]

Review: 40 refs. [ABSTRACT FROM AUTHOR]