ABSTRACT
Magnetic nanoparticles (NPs) are widely employed for remote controlled molecular release applications using alternating magnetic fields (AMF). Yet, they intrinsically generate heat in the process by Néel relaxation limiting their application scope. In contrast, iron oxide NPs larger than ≈15 nm react to AMF by Brownian relaxation resulting in tumbling and shaking. Here, such iron oxide NPs are combined with polymer shells where the shaking motion mechanically agitates and partially detaches the polymer chains, covalently cleaves a fraction of the polymers, and releases the prototypical cargo molecules doxorubicin and curcumin into solution. This heat-free release mechanism broadens the potential application space of polymer-functionalized magnetic NP composites.
ABSTRACT
We report the formation of metal-organic cage-crosslinked polymer hydrogels. To enable crosslinking of the cages and subsequent network formation, we used homodifunctionalized poly(ethylene glycol) (PEG) chains terminally substituted with bipyridines as ligands for the Pd6 L4 corners. The encapsulation of guest molecules into supramolecular self-assembled metal-organic cage-crosslinked hydrogels, as well as ultrasound-induced disassembly of the cages with release of their cargo, is presented in addition to their characterization by nuclear magnetic resonance (NMR) techniques, rheology, and comprehensive small-angle X-ray scattering (SAXS) experiments. The constrained geometries simulating external force (CoGEF) method and barriers using a force-modified potential energy surface (FMPES) suggest that the cage-opening mechanism starts with the dissociation of one pyridine ligand at around 0.5â nN. We show the efficient sonochemical activation of the hydrogels HG3 -6 , increasing the non-covalent guest-loading of completely unmodified drugs available for release by a factor of ten in comparison to non-crosslinked, star-shaped assemblies in solution.
