Additive-assisted macroscopic self-assembly and control of the shape of assemblies based on host–guest interaction

Abstract

Abstract In these decades, considerable attention has focused on supramolecular polymers due to their unique structures and properties. More recently, macroscopic supramolecular polymers have attracted increasing interest from not only biologists but also materials scientists inspired by the sophisticated structures and functions of living organisms. Since the functions of supramolecular polymers are strongly dependent on their shape, control of the shape is an important issue in controlling the functions of supramolecular polymers. However, the control of shape in macroscopic supramolecular assemblies has not yet been sufficiently investigated. Previously, we studied the macroscopic self-assembly behavior of super absorbent polymer (SAP) microparticles modified with β-cyclodextrin (βCD) and adamantane (Ad) residues (βCD(x)-SAP and Ad(y)-SAP microparticles, where x and y are the mol% contents of βCD and Ad residues, respectively). More elongated assemblies were formed at higher y, indicating that the shape of assemblies can be controlled by varying the interaction strength. The noteworthy is that 1-adamantanamine hydrochloride (AdNH3Cl) assisted the formation of assemblies from βCD(x)-SAP and Ad(y)-SAP microparticles, indicating that AdNH3Cl acts as a chemical stimulus for macroscopic assemblies of βCD(x)-SAP and Ad(y)-SAP microparticles. In this study, we have thus studied the assembling behavior of βCD(x)-SAP microparticles with Ad(y)-SAP microparticles and unmodified SAP microparticles assisted by AdNH3Cl, as well as the shape of the resulting macroscopic assemblies. AdNH3Cl assisted the formation of assemblies from βCD(16.2)-SAP and Ad(15.1)-SAP microparticles, in which AdNH3Cl crosslinked the SAP microparticles through the formation of inclusion complexes of βCD residues with the Ad residue and the electrostatic interaction of ammonium and carboxylate residues. Assemblies of βCD(26.7)-SAP and unmodified SAP microparticles were formed at the concentrations of AdNH3Cl ([AdNH3Cl]0) higher than a certain level (ca. 0.05 mM). The aspect ratio (a/b) of assemblies showed a maximum at [AdNH3Cl]0 ~ 0.10 mM, indicating that the chemical stimulus, i.e., addition of AdNH3Cl, controls the shape of assemblies formed from βCD(26.7)-SAP and unmodified SAP microparticles. This study suggests that other stimuli, e.g., heat, pH, light, redox, and force, can be utilized to control the shape of macroscopic assemblies based on supramolecular interactions.

Keywords

• Macroscopic self-assembly
• Host–guest interaction
• Super absorbent polymer microparticles
• Cyclodextrin
• Amines