Magnetic resonance contrast agents that can be activated in response to specific triggers hold potential as molecular biosensors that may be of great utility in non-invasive disease diagnosis. We developed an activatable agent based on superparamagnetic iron oxide nanoparticles (SPIOs) that is sensitive to oxidative stress, a factor in the pathophysiology of numerous diseases. SPIOs were coated with poly(ethylene glycol) (PEG) and complexed with poly(gallol), a synthetic tannin. Hydrogen bonding between PEG and poly(gallol) creates a complexed layer around the SPIO that decreases the interaction of solute water with the SPIO, attenuating its magnetic resonance relaxivity. The complexed interpolymer nanoparticle is in an OFF state (decreased T2 contrast), where the contrast agent has a low T2 relaxivity of 7 ± 2 mM−1 s−1. In the presence of superoxides, the poly(gallol) is oxidized and the polymers decomplex, allowing solute water to again interact with the SPIO, representing an ON state (increased T2 contrast) with a T2 relaxivity of 70 ± 10 mM−1 s−1. These contrast agents show promise as effective sensors for diseases characterized in part by oxidative stress such as atherosclerosis, diabetes, and cancer.

Natural tannins are attractive as building blocks for biomaterials due to their antioxidant properties and ability to form interpolymer complexes (IPCs) with other macromolecules. One of the major challenges to tannin usage in biomedical applications is their instability at physiological conditions and a lack of control over the purity and reactivity. Herein, we report the synthesis and characterization of tannin-like polymers with controlled architecture, reactivity, and size. These pseudotannins were synthesized by substituting linear dextran chains with gallic, resorcylic, and protocatechuic pendant groups to mimic the structure of natural hydrolysable tannins. We demonstrate that these novel materials can self-assemble to form reductive and colloidally stable nanoscale and microscale particles. Specifically, the synthesis, turbidity, particle size, antioxidant power, and cell uptake of IPCs derived from pseudotannins and poly(ethylene glycol) was evaluated.