Less is more: dimensionality reduction as a general strategy for more precise luminescence thermometry.

Thermal resolution (also referred to as temperature uncertainty) establishes the minimum discernible temperature change sensed by luminescent thermometers and is a key figure of merit to rank them. Much has been done to minimize its value via probe optimization and correction of readout artifacts, but little effort was put into a better exploitation of calibration datasets. In this context, this work aims at providing a new perspective on the definition of luminescence-based thermometric parameters using dimensionality reduction techniques that emerged in the last years. The application of linear (Principal Component Analysis) and non-linear (t-distributed Stochastic Neighbor Embedding) transformations to the calibration datasets obtained from rare-earth nanoparticles and semiconductor nanocrystals resulted in an improvement in thermal resolution compared to the more classical intensity-based and ratiometric approaches. This, in turn, enabled precise monitoring of temperature changes smaller than 0.1 °C. The methods here presented allow choosing superior thermometric parameters compared to the more classical ones, pushing the performance of luminescent thermometers close to the experimentally achievable limits.

Unveiling in Vivo Subcutaneous Thermal Dynamics by Infrared Luminescent Nanothermometers.

The recent development of core/shell engineering of rare earth doped luminescent nanoparticles has ushered a new era in fluorescence thermal biosensing, allowing for the performance of minimally invasive experiments, not only in living cells but also in more challenging small animal models. Here, the potential use of active-core/active-shell Nd(3+)- and Yb(3+)-doped nanoparticles as subcutaneous thermal probes has been evaluated. These temperature nanoprobes operate in the infrared transparency window of biological tissues, enabling deep temperature sensing into animal bodies thanks to the temperature dependence of their emission spectra that leads to a ratiometric temperature readout. The ability of active-core/active-shell Nd(3+)- and Yb(3+)-doped nanoparticles for unveiling fundamental tissue properties in in vivo conditions was demonstrated by subcutaneous thermal relaxation monitoring through the injected core/shell nanoparticles. The reported results evidence the potential of infrared luminescence nanothermometry as a diagnosis tool at the small animal level.

Light emission of a polyfluorene derivative containing complexed europium ions.

The photophysical properties of a new alternating copolymer containing fluorene, terpyridine, and complexed sites with trivalent europium (Eu(3+)) ions (LaPPS66Eu) were investigated, using the non-complexed backbone (LaPPS66) and a low molecular weight compound of similar chemical structure of the ligand/Eu(3+) site (LaPPS66M) as a model compound. The analogous gadolinium complex (LaPPS66Gd) was also synthesized to determine the triplet state of the complex. (1)H and (13)C nuclear magnetic resonance (NMR) analysis, Fourier transform infrared (FT-IR) spectroscopy, inductively coupled plasma optical emission spectroscopy (ICP-OES), elemental analyses, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) characterized the chemical structure and thermal properties of the synthesized materials. A level of Eu(3+) insertion of 37% (molar basis) in the polymer backbone was achieved. The photoluminescence studies were performed in the solid state showing the occurrence of polymer-to-Eu(3+) energy transfer brought about by the spectral overlap between the absorption spectra of the Eu(3+) complex and the emission of the polymer backbone. A detailed theoretical photoluminescence study performed using time-dependent DFT (TD-DFT) calculations and the recently developed LUMPAC luminescence package is also presented. The high accuracy of the theoretical calculations was achieved on comparison with the experimental values. Aiming at a deeper level of understanding of the photoluminescence process, the ligand-to-Eu(3+) intramolecular energy transfer and back-transfer rates were predicted. The complexed materials showed a dominant pathway involving the energy transfer between the triplet of the dbm (dibenzoylmethane) ligand and the (5)D1 and (5)D0 Eu(3+) levels.