Magnetic resonance imaging (MRI) is a widely used non-invasive
medical imaging tool. Nanoparticle-based MRI contrast agents have
received considerable attention due to their high loading capability
for magnetic species, enhanced accumulation in lesions, and versatile
surface functionalization. Anisotropic nanoparticles such as nanofibers
can exhibit significant advantages over their well-explored spherical
counterparts in terms of their pharmacokinetic and biodistribution
profiles. Herein, we report the retrosynthetic design, synthesis,
and characterization of uniform and length-tunable paramagnetic core-shell
nanofibers for MRI through the use of the seeded-growth “living”
crystallization-driven self-assembly (CDSA) approach. Triblock copolymer
(TriBCP) precursors with a crystallizable polycarbonate core-forming
segment, a nitroxide-bearing central region, and a hydrophilic poly(ethylene
glycol) (PEG) terminal corona-forming segment were prepared via sequential
living organocatalytic ring-opening polymerization (ROP). Low dispersity
nanofibers of length ca. 80 nm relevant for biomedical applications
were prepared for detailed studies by living CDSA and these possessed
an average number of nitroxides per nanofiber of >8000. Subsequent
evaluation of the water-proton relaxivities demonstrated that tuning
the hydrophilicity of the central segment in the TriBCP allowed access
to nanofibers with impressive performance compared to most existing
polymer-based nitroxide-based contrast agents. As a result of their
1D morphology, the synthetic nanofibers therefore represent promising
organic radical contrast agents (ORCAs) for MRI applications.