Macromolecular cages

Macromolecular cages have three dimensional chambers surrounded by a molecular framework. Macromolecular cage architectures come in various sizes ranging from 1-50 nm and have varying topologies as well as functions.[1] They can be synthesized through covalent bonding or self-assembly through non-covalent interactions. Most macromolecular cages that are formed through self-assembly are sensitive to pH, temperature, and solvent polarity.[1]

Endohedral fullerene

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MOP synthesis

Metal Organic Polyhedra (MOPs) comprise a specific type of self-assembled macromolecular cage that is formed through unique coordination and is typically chemically and thermally stable.[1] MOPs have cage-like frameworks with an enclosed cavity. The discrete self-assembly of metal ions and organic scaffolds to form MOPs into highly symmetrical architectures, is a modular process and has various applications. The self-assembly of various subunits that result in high symmetry is a common occurrence in biological systems. Specific examples of this are ferritin, capsid, and the tobacco mosaic virus, which are formed by the self-assembly of protein subunits into a polyhedral symmetry. Nonbiological polyhedra formed with metal ions and organic linkers are metal based macromolecular cages that have nanocavities with multiple openings or pores that allow small molecules to permeate and pass through.[1] MOPs have been used to encapsulate a number of guests through various host-guest interactions (e.g. electrostatic interactions, hydrogen bonding, and steric interactions).[1] MOPs are biomimetic materials that have potential for biomedical and biochemical applications. In order for the cage to work effectively and have biomedical relevance, it has to be chemically stable, biocompatible, and needs to operate mechanistically in aqueous media. Macromolecular cages in general can be used for a variety of applications (e.g. nanoencapsulation, biosensing, drug delivery, regulation of nanoparticle synthesis, and catalysis).[1][2]

There are also a class of macromolecular cages that are synthetically formed through covalent bonding as opposed to self-assembly. Through the covalent-bond-forming strategy the cage molecules can be synthesized methodically with customizable functionality and regulated cavity size. Cage-shaped polymers are macromolecular analogues of molecular cages such as cryptand.[2] A cage molecule of this type can be tuned by the degree of polymerization. The polymers that are typically used to make the polymer based macromolecular cages are made with star shaped polymers or nonlinear polymer precursors.[3][2][4] The molecular size of the polymeric macromolecular cage is controlled by the molecular weight of the star-shaped polymer or branched polymer. The macromolecular cages made from non-linear polymers are designed to have molecular recognition, respond to external stimuli and self-assemble into higher order structures.[3]

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