Examination of Oil Structural Motifs and Temperature in Promoting Reversible Self-Assembly of Gold Nanoparticle Langmuir Films.

The interaction between gold nanoparticles (AuNPs) with other components and phases has important consequences on their use in materials and devices as well as their fate in the environment or at biological interfaces. Previously we determined that long oil chain lengths and lower temperatures optimized the mixing of -alkanes with alkanethiol-capped AuNPs which improved nanoparticle self-assembly into superlattices at aqueous interfaces. In this study, a variety of liquid phase hydrocarbon oils with structural and functional variations were surveyed for their mixing efficacy and propensity to enable reversible self-assembly of nanoparticle domains. Transmission electron microscopy (TEM) images and pressure vs area isotherms across this series reveal isotherm features that distinguish between the mixing and inclusion of the oil at the interface and that which enables reversible self-assembly. Structural and functional characteristics of the oil for promoting reversible self-assembly are identified which surpass the importance of chain length previously described. Temperatures below the ligand order-disorder transition were found to improve the reversibility of AuNP domains and are understood by application of a reparametrized x-DLVO model.