Lanthanide-doped upconversion nanoparticles (UCNPs) are capable of converting near-infra-red excitation into visible and ultraviolet emission. Their unique optical properties have advanced a broad range of applications, such as fluorescent microscopy, deep-tissue bioimaging, nanomedicine, optogenetics, security labelling and volumetric display. However, the constraint of concentration quenching on upconversion luminescence has hampered the nanoscience community to develop bright UCNPs with a large number of dopants. This review surveys recent advances in developing highly doped UCNPs, highlights the strategies that bypass the concentration quenching effect, and discusses new optical properties as well as emerging applications enabled by these nanoparticles.
Lanthanide doped nanoparticles (Ln:NPs) hold promise as novel luminescent probes for numerous applications in nanobiophotonics. Despite excellent photostability, narrowband photoluminescence, efficient anti-Stokes emission and long luminescence lifetimes, which are needed to meet the requirements of multiplexed and background free detection at prolonged observation times, concern about their toxicity is still an issue for both in vivo and in vitro applications. Similar to other chemicals or pharmaceuticals, the very same properties that are desirable and potentially useful from a biomedical perspective can also give rise to unexpected and hazardous toxicities. In engineered bionanomaterials, the potentially harmful effects may originate not only from their chemical composition but also from their small size. The latter property enables the nanoparticles to bypass the biological barriers, thus allowing deep tissue penetration and the accumulation of the nanoparticles in a number of organs. In addition, nanoparticles are known to possess high surface chemical reactivity as well as a large surface-to-volume ratio, which may seriously affect their biocompatibility. Herein we survey the underlying mechanisms of nanotoxicity and provide an overview on the nanotoxicity of lanthanides and of upconverting nanoparticles.
Luminescence nanothermometry requires standardization for reliable and quantitative evaluation.
Avalanche phenomena leverage steeply nonlinear dynamics to generate disproportionately high responses from small perturbations and are found in a multitude of events and materials 1 , enabling technologies including optical phase-conjugate imaging, 2 infrared quantum counting, 3 and efficient upconverted lasing 4-6 . However, the photon avalanching (PA) mechanism underlying these optical innovations has been observed only in bulk materials and aggregates 6,7 , and typically at cryogenic temperatures 5-8 , limiting its utility and impact in many applications. Here, we report the realization of PA at room temperature in single nanostructures -small, Tm 3+ -doped upconverting nanocrystals -and demonstrate their use in superresolution imaging at wavelengths that fall within near-infrared (NIR) spectral windows of maximal biological transparency. Avalanching nanoparticles (ANPs) can be pumped by either continuous-wave or pulsed lasers and exhibit all of the defining features of PA. These hallmarks include clear excitation power thresholds, exceptionally long rise time at threshold, and a dominant excited-state absorption that is >13,000 times larger than ground-state absorption. Beyond the avalanching threshold, ANP emission scales nonlinearly with the 26 th power of pump intensity, resulting from induced positive optical feedback in each nanocrystal. This enables the experimental realization of photon-avalanche single-beam superresolution imaging (PASSI) 7 , achieving sub-70 nm spatial resolution using only simple scanning confocal microscopy and before any computational analysis. Pairing their steep nonlinearity with existing superresolution techniques and computational methods 9-11 , ANPs allow for imaging with higher resolution and at ca. 100-fold lower excitation intensities than is possible with other probes. The low PA threshold and exceptional photostability of ANPs also suggest their utility in a diverse array of applications 7 including subwavelength bioimaging 7,12,13 , IR detection, temperature [14][15][16] and pressure 17 transduction, neuromorphic computing 18 , and quantum optics 19,20 . Main
We report that non-contact optical temperature sensing can be achieved with the use of heavily Nd(3+) doped NaYF(4) nanoparticles. The temperature evaluation can be realized either by monitoring the absolute luminescence intensity or by measuring the intensity ratio of the two Stark components of the (4)F(3/2) multiplet in the Nd(3+) ions.
Förster resonance energy transfer (FRET) between nanoparticles of up-conversion lanthanide phosphor as donors and quantum dots as acceptors is demonstrated. Fluoride (NaYF4) nanocrystals (ca. 30 nm size) codoped with the Er3+ and Yb3+ ions were synthesized with a high-pressure solvothermal microwave assisted technique and dispersed in organic solvent. Up-converted luminescence from the rare-earth ions doped into fluoride nanomatrix was achieved with optical pumping in NIR (976 nm) region. The green erbium upconversion emission at 540 nm is efficiently quenched by quantum dots (QDs) leading to color change of the mixture for different relative concentrations. Simultaneously, orange emission from quantum dots appears due to energy transfer from Er3+/Yb3+:NPs donors to QDs acceptors. The concomitant decrease of the average lifetime of donor emission at 540 nm (from ∼153 to ∼130 μs) indicates that the excitation of CdSe QDs occurs not only through reabsorption but also through Förster Resonance Energy Transfer. Acceptor luminescence lifetime mimics that of the donor and reaches hundreds of microseconds. The Förster radius (R 0) was calculated to be short (∼15 Å), mostly due to low quantum yield of the multilevel emitting donor. This short-range interaction proves that in our system the FRET occurs mostly through Er3+ ions proximate to the surface, resulting in efficiency of energy transfer equal to η = 14.8%.
The current frontier in nanomaterials engineering is to intentionally design and fabricate heterogeneous nanoparticles with desirable morphology and composition, and to integrate multiple functionalities through highly controlled epitaxial growth. Here we show that heterogeneous doping of Nd ions following a core-shell design already allows three optical functions, namely efficient (η > 72%) light-to-heat conversion, bright NIR emission, and sensitive (S > 0.1% K) localized temperature quantification, to be built within a single ca. 25 nm nanoparticle. Importantly, all these optical functions operate within the transparent biological window of the NIR spectral region (λ ∼ 800 nm, λ ∼ 860 nm), in which light scattering and absorption by tissues and water are minimal. We find NaNdF as a core is efficient in absorbing and converting 808 nm light to heat, while NaYF:1%Nd as a shell is a temperature sensor based on the ratio-metric luminescence reading but an intermediate inert spacer shell, e.g. NaYF, is necessary to insulate the heat convertor and thermometer by preventing the possible Nd-Nd energy relaxation. Moreover, we notice that while temperature sensitivity and luminescence intensity are optically stable, increased excitation intensity to generate heat above room temperature may saturate the sensing capacity of temperature feedback. We therefore propose a dual beam photoexcitation scheme as a solution for possible light-induced hyperthermia treatment.
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