Temperature-Induced, Selective Assembly of Supramolecular Colloids in Water

[Image: see text] In this article, we report the synthesis and physical characterization of colloidal polystyrene particles that carry water-soluble supramolecular N,N′,N″,-trialkyl-benzene-1,3,5-tricarboxamides (BTAs) on their surface. These molecules are known to assemble into one-dimensional supramolecular polymers via noncovalent interactions. By tethering the BTAs to charge-stabilized particles, the clustering behavior of the resulting colloids was dictated by a balance between interparticle electrostatic repulsion and the BTA-mediated attractions. Through careful tuning of the dispersing medium’s ionic strength, a regime was found in which particle aggregation could be reversibly induced upon heating the dispersion. These findings clearly indicate that hydrophobic interactions, which become stronger upon heating, play an important role during the clustering process. Besides the thermoreversible nature of the generated hydrophobic interparticle attractions, we found the clustering to be selective, that is, the BTA-functionalized colloids do not interact with nonfunctionalized hydrophobic polystyrene particles. This selectivity in the association process can be rationalized by the preferred stacking of the surface-tethered BTAs. These selective intermolecular/particle bonds are likely stabilized by the formation of hydrogen bonds, as previously observed for analogous molecular BTA assemblies. The resulting driving force responsible for particle clustering is therefore dual in nature and depends on both hydrophobic attractions and hydrogen bonding.