Nanoparticles shape-specific emergent behaviour on liquid crystal droplets†
Self-assembly attracts enormous research attention because it is at the core of important applications ranging from medical treatments to renewable energy production. Among several classes of self-assembling materials, liquid crystals (LCs) and nanoparticles yield ordered structures under well-defined thermodynamic conditions and could yield supra-molecular aggregates, respectively. In this work, nanoparticle self-assembly on LC nano-droplets is investigated. The LC nano-droplets act as templating agents on which homogeneous and Janus nanoparticles of various geometrical features are adsorbed. LC mesogens and water have low mutual solubility, and under the conditions chosen the LCs yield bipolar nano-droplets. Particle self-assembly on oil nano-droplets is also considered for comparison. Our results reveal that the mesogens can direct the assembly of the nanoparticles. This effect is mainly governed by the nanoparticle size and shape. In some cases, strong evidence of emergent behaviour is observed depending on entropic forces that arise because of the shape and patchiness of the nanoparticles. For example, while one small spherical homogeneous particle does not show preferential adsorption on specific LC nano-droplet locations, 100 spherical nanoparticles preferentially agglomerate at the nano-droplet boojums, providing evidence of emergent behaviour. On the contrary, Janus spherical nanoparticles do not show such a strong emergent behaviour. Cylindrical NPs manifest the opposite trend: while homogeneous nano-cylinders do not exhibit orientational order on the LC nano-droplet, Janus ones either locate at the LC nano-droplet boojums or orient towards the direction vector of bipolar droplets. Quantification of the orientational order within the LC nano-droplets suggests that the self-assembly of the LC mesogens does not significantly change upon nanoparticle adsorption. These simulations clearly suggest an interplay between nanoparticle size, shape and chemical composition upon their self-assembly on LC nano-droplets. The results could be helpful for the design of new sensors and for the directed self-assembly of advanced materials.