Simultaneous Second Harmonic Generation and Multiphoton Excited Photoluminescence in Samarium-Doped BaTiO3 Nanoparticles Functionalized with Poly(ethylene glycol).

In this work, samarium-doped BaTiO3 (BT:Sm) nanoparticles (NPs) were prepared and coated with poly(ethylene glycol) (PEG) to investigate their optical characteristics and compatibility with biological systems. The structure, particle morphology, optical properties, and biological compatibility of the NPs were assessed. The results demonstrated the formation of BT:Sm and [(BT:Sm)-PEG]. The relative intensities and positions of peaks in the X-ray diffraction (XRD) are consistent with an average crystallite size of ∼75 nm. The Raman spectra showed that Sm doping produced the typical tetragonal peaks at around 306 and 715 cm-1, and Fourier transform infrared (FTIR) spectroscopy showed that the PEGylation process was effective. Also, our investigation demonstrates the potential of these NPs as very temperature-sensitive nanosensors with a resolution exceeding 0.5 °C, which is achievable through optical excitation. We also analyze their emission properties. Finally, we present a study related with the mitochondrial activity of naked and PEG-coated NPs. The results indicate that neither naked nor PEG-coated NPs exhibit changes in mitochondrial metabolism, as indicated by quantitative cell viability and morphological visualization. The PEG-coated NPs prevented the formation of aggregates in cell culture compared to naked NPs, demonstrating the significance of PEG as a stabilizing agent.

The use of energy looping between Tm3+ and Er3+ ions to obtain an intense upconversion under the 1208 nm radiation and its use in temperature sensing.

The upconversion phenomenon allows for the emission of nanoparticles (NPs) under excitation with near-infrared (NIR) light. Such property is demanded in biology and medicine to detect or treat diseases such as tumours. The transparency of biological systems for NIR light is limited to three spectral ranges, called biological windows. However, the most frequently used excitation laser to obtain upconversion is out of these ranges, with a wavelength of around 975 nm. In this article, we show an alternative - Tm3+/Er3+-doped NPs that can convert 1208 nm excitation radiation, which is in the range of the 2nd biological window, to visible light within the 1st biological window. The spectroscopic properties of the core@shell NaYF4:Tm3+@NaYF4 and NaYF4:Er3+,Tm3+@NaYF4 NPs revealed a complex mechanism responsible for the observed upconversion. To explain emission in the studied NPs, we propose an energy looping mechanism: a sequence of ground state absorption, energy transfers and cross-relaxation (CR) processes between Tm3+ ions. Next, the excited Tm3+ ions transfer the absorbed energy to Er3+ ions, which results in green, red and NIR emission at 526, 546, 660, 698, 802 and 982 nm. The ratio between these bands is temperature-dependent and can be used in remote optical thermometers with high relative temperature sensitivity, up to 2.37%/°C at 57 °C. The excitation and emission properties of the studied NPs fall within 1st and 2nd biological windows, making them promising candidates for studies in biological systems.