Fabrication of Gd/Eu-codoped SmPO4 nanorods for dual-modal magnetic resonance and bio-optical imaging

Ln-based complexes can be used as T1-enhanced contrast agents of magnetic resonance (MR) imaging in clinical field. Herein, we present a facile and feasible biomineralization process to fabricate Gd/Eu-codoped SmPO4 nanorods (NRs) with silk fibroin (SF) peptides (codoped SF-NRs) as T1-enhanced contrast agents, which possess paramagnetic property, photoluminescence (PL), better cyto-/tissue-compatibility and longer half-life in blood due to SF coating on their surface. Their bio-distributions in TB-N mice via tail-vein injection indicated that, although SF-NRs could be safely cleared away through renal and fecal excretion, SF-NRs easily permeated and aggregated in tumors. The results of in vitro MR imaging demonstrate that the longitudinal relaxivity r1 value of codoped SF-NRs (0.31 Sm–Gd mM−1 s−1) is not only significantly higher than those of Gd-doped and Eu-doped SmPO4 SF-NRs, but also higher than those of codoped pure NRs. The tests of in vivo T1 weighted MR imaging via intro-tumor injection and tail-vein injection confirm that, compared to the pure NRs, the codoped SF-NRs exhibited higher positive signal-enhancement ability. Furthermore, the better luminescence imaging of living cells under the fluorescence microscope (94% stronger than that of the NRs without SF). A formation mechanism of codoped SF-NRs is proposed, to explain the synergistic effect of Gd/Eu codoping and SF coating on their enhanced bio-compatibility, half-life in blood, T1-weighted MR imaging and PL imaging.

Graphical abstractCrystal Eu-doped SmPO4 nanorods with silk fibroin peptides (SF-NRs) were fabricated in the template of SF via a facile biomineralization process, and SF coating, higher crystallinity and Eu/Sm ratio in SF-NRs result in their non-toxicity, pink luminescence and good magnetic resonance imaging in vitro and in vivo.Figure optionsDownload full-size imageDownload high-quality image (301 K)Download as PowerPoint slide