Present technological demands in disparate areas, such as microfluidics and nanofluidics, microelectronics and nanoelectronics, photonics and biomedicine, among others, have reached to a development such that conventional contact thermal probes are not accomplished anymore to perform accurate measurements with submicrometric spatial resolution. The development of novel noncontact thermal probes is, then, mandatory, contributing to an expansionary epoch of luminescence thermometry. Luminescence thermometry based on trivalent lanthanide ions has become very popular since 2010 due to the unique versatility, stability, and narrow emission band profiles of the ions that cover the entire electromagnetic spectrum with relatively high emission quantum yields. Here, a perspective overview on the field is given from the beginnings in the 1950s until the most recent cutting‐edge examples. The current movement toward usage of the technique as a new tool for thermal imaging, early tumor detection, and as a tool for unveiling the properties of the thermometers themselves or of their local neighborhoods is also summarized.
In the past decade, noninvasive luminescent thermometry has become popular due to the limitations of traditional contact thermometers to operate at scales below 100 μm, as required by current demands in disparate areas. Generally, the calibration procedure requires an independent measurement of the temperature to convert the thermometric parameter (usually an intensity ratio) to temperature. A new calibration procedure is necessary whenever the thermometer operates in a different medium. However, recording multiple calibrations is a time-consuming task, and not always possible to perform, e.g., in living cells and in electronic devices. Typically, a unique calibration relation is assumed to be valid, independent of the medium, which is a bottleneck of the secondary luminescent thermometers developed up to now. Here we report a straightforward method to predict the temperature calibration curve of any upconverting thermometer based on two thermally coupled electronic levels independently of the medium, demonstrating that these systems are intrinsically primary thermometers. SrF2:Yb/Er powder and water suspended nanoparticles were used as an illustrative example.
Luminescence thermal sensing and deep-tissue imaging using nanomaterials operating within the first biological window (ca. 700-980 nm) are of great interest, prompted by the ever-growing demands in the fields of nanotechnology and nanomedicine. Here, we show that (Gd1-xNdx)2O3 (x = 0.009, 0.024 and 0.049) nanorods exhibit one of the highest thermal sensitivity and temperature uncertainty reported so far (1.75 ± 0.04% K(-1) and 0.14 ± 0.05 K, respectively) for a nanothermometer operating in the first transparent near infrared window at temperatures in the physiological range. This sensitivity value is achieved using a common R928 photomultiplier tube that allows defining the thermometric parameter as the integrated intensity ratio between the (4)F5/2 → (4)I9/2 and (4)F3/2 → (4)I9/2 transitions (with an energy difference between the barycentres of the two transitions >1000 cm(-1)). Moreover, the measured sensitivity is one order of magnitude higher than the values reported so far for Nd(3+)-based nanothermometers enlarging, therefore, the potential of using Nd(3+) ions in luminescence thermal sensing and deep-tissue imaging.
A facile coprecipitation reaction between Ce(3+), Gd(3+), Tb(3+), and F(-) ions, in the presence of glycerine as a capping agent, led to the formation of ultrafine, nanocrystalline CeF3:Tb(3+) 5%, Gd(3+) 5% (LnF3). The as-prepared fluoride nanoparticles were successfully coated with an amine modified silica shell. Subsequently, the obtained LnF3@SiO2@NH2 nanostructures were conjugated with 4-ethoxybenzoic acid in order to prove the possibility of organic modification and obtain a new functional nanomaterial. All of the nanophosphors synthesized exhibited intense green luminescence under UV light irradiation. Based on TEM (transmission electron microscopy) measurements, the diameters of the cores (≈12 nm) and core/shell particles (≈50 nm) were determined. To evaluate the cytotoxic activity of the nanomaterials obtained, their effect on human erythrocytes was investigated. LnF3 nanoparticles were bound to the erythrocyte membrane, without inducing any cytotoxic effects. After coating with silica, the nanoparticles revealed significant cytotoxicity. However, further functionalization of the nanomaterial with -NH2 groups as well as conjugation with 4-ethoxybenzoic acid entailed a decrease in cytotoxicity of the core/shell nanoparticles.
Plasmonic nanostructures concentrate light and heat within a small volume at the nanoscale, offering potential applications in nanotechnology and biomedicine (e.g., hyperthermia). However, the precise quantification of the actual temperature rise in the vicinity of such nanosystems poses considerable challenges. Here, we present a new heater–thermometer nanoplatform capable of measuring the plasmon‐induced local temperature increase of Au nanorods via the ratiometric upconversion of (Gd,Yb,Er)2O3 nanothermometers upon 980 nm laser excitation (up to 102.0 W cm−2). The local temperature rise, 302–548 K (maximum temperature sensitivity 1.22 % K−1, uncertainty 0.32 K and repeatability >99 %), is assessed using Boltzmann's distribution of the Er3+ 2H11/2→4I15/2/ 4S3/2→4I15/2 intensity ratio. The nanoplatforms are biocompatible with MG‐63 and A549 cells and were mapped within the former using hyperspectral imaging, opening up an avenue to monitor the cellular uptake of Ln3+‐based nanoplatforms.
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