Tailoring Near-Infrared-IIb Fluorescence of Thulium(III) by Nanocrystal Structure Engineering.

Ren, Feng; Huang, Haoying; Yang, Hongchao; Xia, Bin; Ma, Zhiwei; Zhang, Yejun; Wu, Feng; Li, Chunyan et al. · Nano Lett · 2023

basic_science · Level V

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Abstract

Currently, mainstream lanthanide probes with fluorescence located in the second near-infrared subwindow of 1500-1700 nm (NIR-IIb) are predominantly Er(III)-based nanoparticles (NPs). Here we report a newly developed NIR-IIb fluorescent nanoprobe, α-Tm NP (cubic-phase NaYF<sub>4</sub>@NaYF<sub>4</sub>:Tm@NaYF<sub>4</sub>), with an emission at 1630 nm. We activate the 1630 nm emission of Tm(III) in α-Tm NP through the large spread of the Stark split sublevels induced by the crystal-field effect of the α-NaYF<sub>4</sub> host. Further, we systematically investigated the effect of crystalline structure of the host NaYF<sub>4</sub> NP (cubic phase (α) or hexagonal phase (β)), the type and concentrations of dopants (Yb(III), Tm(III), and Ca(II) ions) in the α-phase host, and the thicknesses of the interlayer and inert shell on the NIR-IIb fluorescence of Tm(III). The ultimate nanostructure presents a significant enhancement factor of the NIR-IIb photoluminescence intensity of Tm(III) up to ∼315. With this bright NIR-IIb fluorescent nanoprobe, we demonstrate high-spatial-resolution time-coursing imaging of breast cancer bone metastasis.