Superparamagnetic nanoparticles have been proposed for many applications in biotechnology and medicine. In this paper, it is demonstrated how the excellent colloidal stability and magnetic properties of monodisperse and individually densely grafted iron oxide nanoparticles can be used to manipulate reversibly the solubility of nanoparticles with a poly(N-isopropylacrylamide)nitrodopamine shell. “Grafting-to” and “grafting-from” methods for synthesis of an irreversibly anchored brush shell to monodisperse, oleic acid coated iron oxide cores are compared. Thereafter, it is shown that local heating by magnetic fields as well as global thermal heating can be used to efficiently and reversibly aggregate, magnetically extract nanoparticles from solution and spontaneously redisperse them. The coupling of magnetic and thermally responsive properties points to novel uses as smart materials, for example, in integrated devices for molecular separation and extraction.

Superparamagnetic iron oxide nanoparticles (NPs) are used in a rapidly expanding number of applications in e.g. the biomedical field, for which brushes of biocompatible polymers such as poly(ethylene glycol) (PEG) have to be densely grafted to the core. Grafting of such shells to monodisperse iron oxide NPs has remained a challenge mainly due to the conflicting requirements to replace the ligand shell of as-synthesized NPs with irreversibly bound PEG dispersants. We introduce a general two-step method to graft PEG dispersants from a melt to iron oxide NPs first functionalized with nitrodopamine (NDA). This method yields uniquely dense spherical PEG-brushes (∼3 chains per nm² of PEG(5 kDa)) compared to existing methods, and remarkably colloidally stable NPs also under challenging conditions.

Hydrophilic polymer-coated iron oxide nanoparticles are potential materials for a plethora of applications in the biotechnological field. Typical such polymers, e.g. dextran or poly(ethylene glycol), lack the ability to tailor the biological response to an environmental trigger, while common responsive polymers such as poly(N-isopropylacrylamide) or poly(acrylic acid) are not suitable for biomedical applications. We present the synthesis and characterization of superparamagnetic iron oxide nanoparticles with thermoresponsive polyoxazoline brushes grafted at unprecedented density using nitrodopamine anchor chemistry. Reversible aggregation/deaggregation is observed in water and biological medium, confirming control over the colloidal stability. Thermal switching of the solubility could only be achieved by global heating of the sample, while local magnetothermal heating did not produce a sufficiently strong temperature gradient through the brush. Varying the polymer composition allows for tuning of the lower critical solution temperature (LCST) as well as the average nanoparticle cluster size obtained upon heating. The LCST of polyoxazolines and the thermal colloidal stability are shown to be greatly affected by ion concentration, by polymer grafting density and also by the presence of serum protein; this shows that transition temperatures of free polymers in water can be very misleading for the design of polymer-coated nanomaterials for biomedical applications. Finally, the thermoresponsive SPION are shown to be non-cytotoxic and with a low cell uptake scaling with the hydration of the polymer brush, which is tuned by the polymer composition. Thus, we demonstrate that pozylated nanoparticles provide the advantages of PEG- and PNIPAM-grafted nanoparticles, but provide a tunable and more easily functionalizable platform for further development.

Magnetic polymersomes were prepared by self-assembly of the amphiphilic block copolymer poly(isoprene-b-N-isopropylacrylamide) with monodisperse hydrophobic superparamagnetic iron oxide nanoparticles (SPION). The specifically designed thermoresponsive block copolymer allowed for efficient incorporation of the hydrophobic nanoparticles in the membrane core and encapsulation of the water soluble dye calcein in the lumen of the vesicles. Magnetic heating of the embedded SPIONs led to increased bilayer permeability through dehydration of the thermoresponsive PNIPAM block. The entrapped calcein could therefore be released in controlled doses solely through exposure to pulses of an alternating magnetic field. This hybrid SPION-polymersome system demonstrates a possible direction for release applications that merges rational polymersome design with addressed external magnetic field-triggered release through embedded nanomaterials.