808 nm driven Nd 3+

The in vivo biological applications of upconversion nanoparticles (UCNPs) prefer excitation at 700-850 nm, instead of 980 nm, due to the absorption of water. Recent approaches in constructing robust Nd3+ doped UCNPs with 808 nm excitation properties rely on a thick Nd3+ sensitized shell. However, for the very important and popular Frster resonance energy transfer (FRET)-based applications, such as photodynamic therapy (PDT) or switchable biosensors, this type of structure has restrictions resulting in a poor energy transfer. In this work, we have designed a NaYF4:Yb/Ho@NaYF4:Nd@NaYF4 core-shell-shell nanostructure. We have proven that this optimal structure balances the robustness of the upconversion emission and the FRET efficiency for FRET-based bioapplications. A proof of the concept was demonstrated for photodynamic therapy and simultaneous fluorescence imaging of HeLa cells triggered by 808 nm light, where low heating and a high PDT efficacy were achieved

Size-dependent lanthanide energy transfer amplifies upconversion luminescence quantum yields

Optical upconversion from lanthanide-doped nanoparticles is promising for a variety of applications ranging from bioimaging, optogenetics, nanothermometry, super-resolution nanoscopy and volumetric displays to solar cells. Despite remarkable progress made in enhancing upconversion to fuel these applications, achieving luminescence of upconversion nanoparticles (UCNPs) that is comparable to or higher than the bulk counterparts has been challenging due to nanoscale-induced quenching effects. Here we demonstrate a size-dependent lanthanide energy transfer effect in a conceptual design of hexagonal sodium yttrium fluoride (NaYF4) core–shell–shell NaYF4@NaYF4:Yb/Tm@NaYF4 UCNPs with depleted surface quenching. We show that precise control over the domain size (or the thickness of the middle shell doped with ytterbium (Yb) and thulium (Tm) from 1.2 to 13 nm) increases the lanthanide energy transfer efficiency (from 30.2 to 50.4%) and amplifies the upconversion quantum yield to a high value of 13.0 ± 1.3% in sub-50 nm UCNPs (excitation: 980 nm, 100 W cm−2), which is around fourfold higher than the micrometre-scale hexagonal NaYF4:Yb/Tm bulk counterparts. Spectroscopic studies and theoretical microscopic modelling reveal that long-range lanthanide energy transfer (&gt;9.5 nm) takes place and underlies the observed size-dependent phenomena. Demonstration of size-dependent lanthanide energy transfer and upconversion quantum yields at the nanoscale transforms our long-existing conceptual understanding of lanthanide energy transfer (size independence), thereby having important implications for applications of lanthanide nanophotonics and biophotonics.</p

Targeted labeling of an early-stage tumor spheroid in a chorioallantoic membrane model with upconversion nanoparticles

In vivo detection of cancer at an early-stage, i.e. smaller than 2 mm, is a challenge in biomedicine. In this work target labeling of an early-stage tumor spheroid (~500 μm) is realized for the first time in a chick embryo chorioallantoic membrane (CAM) model with monoclonal antibody functionalized upconversion nanoparticles (UCNPs-mAb).5 page(s

Near Infrared Light Sensitive Ultraviolet–Blue Nanophotoswitch for Imaging-Guided “Off–On” Therapy

Photoswitchable materials are important in broad applications. Recently appeared inorganic photoswitchable upconversion nanoparticles (PUCNPs) become a competitive candidate to surmount the widespread issue of the organic counterparts photobleaching. However, current PUCNPs follow solely Yb³⁺/Nd³⁺ cosensitizing mode, which results in complex multilayer doping patterns and imperfectness of switching in UV–blue region. In this work, we have adopted a new strategy to construct Nd³⁺ free PUCNPsNaErF₄@NaYF₄@NaYbF₄:0.5%Tm@NaYF₄. These PUCNPs demonstrate the superior property of photoswitching. A prominent UV–blue emission from Tm³⁺ is turned on upon 980 nm excitation, which can be completely turned off by 800 nm light. The quasi-monochromatic red upconversion emission upon 800 nm excitationa distinct feature of undoping NaErF₄ upconversion systemendows the PUCNPs with promising image-guided photoinduced “off–on” therapy in biomedicine. As a proof-of-concept we have demonstrated the imaging-guided photodynamic therapy (PDT) of cancer, where 800 nm excitation turns off the UV–blue emission and leaves the emission at 660 nm for imaging. Once the tumor site is targeted, excitation switching to 980 nm results in UV–blue emission and the red emission. The former is used to induce PDT, whereas the latter is to monitor the therapeutic process. Our study implies that this upconversion photoswitching material is suitable for real-time imaging and image-guided therapy under temporal and spatial control

Ultrastrong Absorption Meets Ultraweak Absorption: Unraveling the Energy-Dissipative Routes for Dye-Sensitized Upconversion Luminescence

Dye sensitization is becoming a new dimension to highly improve the upconversion luminescence (UCL) of lanthanide-doped upconversion nanoparticles (UCNPs). However, there is still a lack of general understanding of the dye–UCNPs interactions, especially the confused large mismatch between the inputs and outputs. By taking dye-sensitized NaYF₄:Yb/Er@NaYF₄:Nd UCNPs as a model system, we not only revealed the in-depth energy-dissipative process for dye-sensitized UCL but also confirmed the first ever experimental observation of the energy back transfer (EBT) in the dye-sensitized UCL. Furthermore, this energy-dissipative EBT restricted the optimal ratio of dyes to UCNP. By unearthing all of the energy loss behind the EBT, energy transfer, and energy migration processes, this paper sheds light on the further design of effective dye-sensitized nanosystems for UCL or even downconversion luminescence

Covalently Assembled NIR Nanoplatform for Simultaneous Fluorescence Imaging and Photodynamic Therapy of Cancer Cells

A highly efficient multifunctional nanoplatform for simultaneous upconversion luminescence (UCL) imaging and photodynamic therapy has been developed on the basis of selective energy transfer from multicolor luminescent NaYF₄:Yb³⁺,Er³⁺ upconversion nanoparticles (UCNPs) to photosensitizers (PS). Different from popular approaches based on electrostatic or hydrophobic interactions, over 100 photosensitizing molecules were covalently bonded to every 20 nm UCNP, which significantly strengthened the UCNP–PS linkage and reduced the probability of leakage/desorption of the PS. Over 80% UCL was transferred to PS, and the singlet oxygen production was readily detected by its feature emission at 1270 nm. Tests performed on JAR choriocarcinoma and NIH 3T3 fibroblast cells verified the efficient endocytosis and photodynamic effect of the nanoplatform with 980 nm irradiation specific to JAR cancer cells. Our work highlights the promise of using UCNPs for potential image-guided cancer photodynamic therapy

Near infrared light-driven water oxidation in a molecule-based artificial photosynthetic device using an upconversion nano-photosensitizer

We provide the first demonstration of a near infrared light driven water oxidation reaction in a molecule-based artificial photosynthetic device using an upconversion nano-photosensitizer. One very attractive advantage of this system is that using NIR light irradiation does not cause significant photodamage, a serious problem in molecular based artificial photosynthesis under visible light irradiation