Shaping Magnetite by Hydroxyl Group Numbers of Small Molecules

Despite numerous reports on magnetite formation with the assistance of various additives, the role of hydroxyl group (-OH) numbers in small polyol molecules has not yet been understood well. We selected small molecules containing different -OH numbers, such as ethanol, ethylene glycol, propanetriol, butanetetrol, pentitol, hexanehexol, and cyclohexanehexol, as additives in coprecipitation. By increasing the -OH number in these small polyol molecules, the formation of crystallization was slowed, and the size and shape of magnetite were regulated as well possibly due to the changed complexation strength and the stability of the precursor. The increase in temperature and the Fe²⁺/Fe³⁺ ratio can reduce the complexation strength. The nucleation and growth of magnetite proceed possibly through the aggregation of polyol-stabilized amorphous complexes and two-line ferrihydrite with low crystallinity based on the -OH numbers, suggesting a nonclassical pathway. The as-prepared magnetite showed a r₂/r₁ ratio after in vitro MRI measurement as follows: Fe₃O₄@He-6OH rod < Fe₃O₄@Pr-3OH sheet < Fe₃O₄@Pe-5OH cube. The Fe₃O₄@He-6OH rod and Fe₃O₄@Pr-3OH sheet displayed T₁-T₂ dual modal contrast ability, while the Fe₃O₄@Pe-5OH cube can be T₂-dominated. This research provides a simple but an essential approach for designing MRI contrast agents.