Upconversion (UC) process in lanthanide-doped nanomaterials has attracted great research interest for its extensive biological applications in vitro and in vivo, benefiting from the high tissue penetration depth of near-infrared excitation light and low autofluorescence background. However, the 980 nm laser, typically used to trigger the Yb(3+)-sensitized UC process, is strongly absorbed by water in biological structures and could cause severe overheating effect. In this article, we report the extension of the UC excitation spectrum to shorter wavelengths, where water has lower absorption. This is realized by further introducing Nd(3+) as the sensitizer and by building a core/shell structure to ensure successive Nd(3+) → Yb(3+) → activator energy transfer. The efficacy of this Nd(3+)-sensitized UC process is demonstrated in in vivo imaging, and the results confirmed that the laser-induced local overheating effect is greatly minimized.

Active center engineering at atomic level is a grand challenge for catalyst design and optimization in many industrial catalytic processes. Exploring new strategies to delicately tailor the structures of active centers and bonding modes of surface reactive intermediates for nanocatalysts is crucial to high-efficiency nanocatalysis that bridges heterogeneous and homogeneous catalysis. Here we demonstrate a robust approach to tune the CO oxidation activity over CeO2 nanowires (NWs) through the modulation of the local structure and surface state around Ln(Ce)' defect centers by doping other lanthanides (Ln), based on the continuous variation of the ionic radius of lanthanide dopants caused by the lanthanide contraction. Homogeneously doped (110)-oriented CeO2:Ln NWs with no residual capping agents were synthesized by controlling the redox chemistry of Ce(III)/Ce(IV) in a mild hydrothermal process. The CO oxidation reactivity over CeO2:Ln NWs was dependent on the Ln dopants, and the reactivity reached the maximum in turnover rates over Nd-doped samples. On the basis of the results obtained from combined experimentations and density functional theory simulations, the decisive factors of the modulation effect along the lanthanide dopant series were deduced as surface oxygen release capability and the bonding configuration of the surface adsorbed species (i.e., carbonates and bicarbonates) formed during catalytic process, which resulted in the existence of an optimal doping effect from the lanthanide with moderate ionic radius.

Upconversion emissions from rare-earth nanoparticles have attracted much interest as potential biolabels, for which small particle size and high emission intensity are both desired. Herein we report a facile way to achieve NaYF(4):Yb,Er@CaF(2) nanoparticles (NPs) with a small size (10-13 nm) and highly enhanced (ca. 300 times) upconversion emission compared with the pristine NPs. The CaF(2) shell protects the rare-earth ions from leaking, when the nanoparticles are exposed to buffer solution, and ensures biological safety for the potential bioprobe applications. With the upconversion emission from NaYF(4):Yb,Er@CaF(2) NPs, HeLa cells were imaged with low background interference.