Single-Step Synthesis of Highly Sensitive 19 F MRI Tracers by Gradient Copolymerization-Induced Self-Assembly

• Published in: Biomacromolecules 2024-12, Vol.25 (12), p.7685
• Main Authors: Panakkal, Vyshakh M, Havlicek, Dominik, Pavlova, Ewa, Jirakova, Klara, Jirak, Daniel, Sedlacek, Ondrej
• Format: Article
• Language: English
• Subjects: Cell Line, Tumor; Contrast Media - chemical synthesis; Contrast Media - chemistry; Fluorine-19 Magnetic Resonance Imaging - methods; Humans; Hydrophobic and Hydrophilic Interactions; Magnetic Resonance Imaging - methods; Methacrylates - chemistry; Nanoparticles - chemistry; Polyethylene Glycols - chemistry; Polymerization; Polymers - chemical synthesis; Polymers - chemistry
• ISSN: 1525-7797; 1526-4602
• DOI: 10.1021/acs.biomac.4c00915

Amphiphilic gradient copolymers are promising alternatives to block copolymers for self-assembled nanomaterials due to their straightforward synthesis via statistical copolymerization of monomers with different reactivities and hydrophilicity. By carefully selecting monomers, nanoparticles can be synthesized in a single step through gradient copolymerization-induced self-assembly (gPISA). We synthesized highly sensitive F MRI nanotracers via aqueous dispersion gPISA of hydrophilic poly(ethylene glycol) methyl ether methacrylate (PEGMA) with core-forming , -(2,2,2-trifluoroethyl)acrylamide (TFEAM). The PPEGMA-grad-PTFEAM nanoparticles were optimized to achieve spherical morphology and exceptional F MRI performance. Noncytotoxicity was confirmed in Panc-1 cells. In vitro F MR relaxometry and imaging demonstrated their diagnostic imaging potential. Notably, these gradient copolymer nanotracers outperformed block copolymer analogs in F MRI performance due to their gradient architecture, enhancing F relaxivity. The synthetic versatility and superior F MRI performance of gradient copolymers highlight their potential in advanced diagnostic imaging applications.