Simultaneous Organic and Inorganic Host-Guest Chemistry within Pillararene-Protein Cage Frameworks.

Abstract

Supramolecular self‐assembly of biomolecules provides a powerful bottom‐up strategy to build functional nanostructures and materials. Among the different biomacromolecules, protein cages offer various advantages including uniform size, versatility, multi‐modularity, and high stability. Additionally, protein cage crystals present confined microenvironments with well‐defined dimensions. On the other hand, molecular hosts, such as cyclophanes, possess a defined cavity size and selective recognition of guest molecules. However, the successful combination of macrocycles and protein cages to achieve functional co‐crystals has remained limited. In this study, we demonstrate electrostatic binding between cationic pillar[5]arenes and (apo)ferritin cages that results in porous and crystalline frameworks. The electrostatically assembled crystals present a face‐centered cubic (FCC) lattice and have been characterized by means of small‐angle X‐ray scattering and cryo‐TEM. These hierarchical structures result in a multiadsorbent framework capable of hosting both organic and inorganic pollutants, such as dyes and toxic metals, with potential application in water‐remediation technologies.