NIR-II Responsive Upconversion Nanoprobe with Simultaneously Enhanced Single-Band Red Luminescence and Phase/Size Control for Bioimaging and Photodynamic Therapy

Abstract

Lanthanide based upconversion (UC) nanoprobes have emerged as promising agents for biological applications. Extending the excitation light to the second near-infrared (NIR-II), instead of the traditional 980/808 nm light, and realizing NIR-II responsive single-band red UC emission is highly demanded for bioimaging application, which has not yet been explored. Here, a new type of NIR-II (1532 nm) light responsive UC nanoparticles (UCNPs) with enhanced single-band red UC emission and controllable phase and size is designed by introducing Er³⁺ as sensitizer and utilizing Mn²⁺ as energy manipulator. Through tuning the content of Mn²⁺ in NaLnF₄ :Er/Mn, the crystal phase, size, and emitting color are readily controlled, and the red-to-green (R/G) ratio is significantly increased from ≈20 to ≈300, leading to NIR-II responsive single band red emission via efficient energy transfer between Er³⁺ and Mn²⁺ . In addition, the single band red emitting intensity can be further improved by coating shell to avoid the surface quenching effect. More importantly, NIR-II light activated red UC bioimaging and photodynamic therapy through loading photosensitizer of zinc phthalocyanine are successfully achieved for the first time. These findings provide a new strategy of designing NIR-II light responsive single-band red emissive UCNPs for biomedical applications.

Keywords: Er 3+ sensitization; NIR-II responsive photon upconversion; NIR-II responsive photodynamic therapy; energy transfer; single band red emission.