Cubic versus hexagonal - effect of host crystallinity on the T₁ shortening behaviour of NaGdF₄ nanoparticles

Sodium gadolinium fluoride (NaGdF4) nanoparticles are promising candidates as T1 shortening magnetic resonance imaging (MRI) contrast agents due to the paramagnetic properties of the Gd3+ ion. Effects of size and surface modification of these nanoparticles on proton relaxation times have been widely studied. However, to date, there has been no report on how T1 relaxivity (r1) is affected by the different polymorphs in which NaGdF4 crystallizes: cubic (α) and hexagonal (β). Here, a microwave-assisted thermal decomposition method was developed that grants selective access to NaGdF4 nanoparticles of either phase in the same size range, allowing the influence of host crystallinity on r1 to be investigated. It was found that at 3 T cubic NaGdF4 nanoparticles exhibit larger r1 values than their hexagonal analogues. This result was interpreted based on Solomon-Bloembergen-Morgan theory, suggesting that the inner sphere contribution to r1 is more pronounced for cubic NaGdF4 nanoparticles as compared to their hexagonal counterparts. This holds true irrespective of the chosen surface modification, i.e. small citrate groups or longer chain poly(acrylic acid). Key aspects were found to be a polymorph-induced larger hydrodynamic diameter and the higher magnetization possessed by cubic nanoparticles.