Lanthanide Upconverted Luminescence for Simultaneous Contactless Optical Thermometry and Manometry-Sensing under Extreme Conditions of Pressure and Temperature.

The growing interest in the miniaturization of various devices and conducting experiments under extreme conditions of pressure and temperature causes the need for the development of small, contactless, precise, and accurate optical sensors without any electrical connections. In this work, YF3:Yb3+-Er3+ upconverting microparticles are used as a bifunctional luminescence sensor for simultaneous temperature and pressure measurements. Different changes in the properties of Er3+ green and red upconverted luminescence, after excitation of Yb3+ ions in the near-infrared at ∼975 nm, are used to calibrate pressure and/or temperature inside the hydrostatic chamber of a diamond anvil cell (DAC). For temperature sensing, changes in the relative intensities of the Er3+ green upconverted luminescence of 2H11/2 and 4S3/2 thermally coupled multiplets to the 4I15/2 ground state, whose relative populations follow a Boltzmann distribution, are calibrated. For pressure sensing, the spectral shift of the Er3+ upconverted red emission peak at ∼665 nm, between the Stark sublevels of the 4F9/2 → 4I15/2 transition, is used. Experiments performed under simultaneous extreme conditions of pressure, up to ∼8 GPa, and temperature, up to ∼473 K, confirm the possibility of remote optical pressure and temperature sensing.

Lanthanide Luminescence Enhancement of Core-Shell Magnetite-SiO2 Nanoparticles Covered with Chain-Structured Helical Eu/Tb Complexes.

Oligomeric-brush chains of helical lanthanide (Ln) complexes retain their structural and luminescent behavior after coating onto magnetic nanoparticles (MNPs) consisting of Fe3O4 covered with silicate. It is one of the type of bifunctional NPs exhibiting luminescence of Ln and superparamagnetism of Fe3O4. In comparison to a simple monolayer of complexes adsorbed on a modified surface, a layer made of luminescent chains allowed us to obtain a more intensive red/green luminescence originating from Eu3+/Tb3+ ions, and at the same time, no visible increase in particle size (compared to Fe3O4@silica particles) was observed. The luminescent properties of the Tb3+ complex were altered by MNPs; the decrease of the luminescence was not as large as expected, the excitation spectrum changed significantly, and the average luminescence lifetime was much longer at room temperature. Surprisingly, this phenomenon was not observed at 77 K and also did not occur for the Eu3+ complexes. The possibility to stack building blocks in a chain using complexes of different lanthanide ions can be used to design novel multifunctional nanosystems.

Upconverting Lanthanide Fluoride Core@Shell Nanorods for Luminescent Thermometry in the First and Second Biological Windows: ß-NaYF4:Yb3+- Er3+@SiO2 Temperature Sensor.

Upconverting core@shell type ß-NaYF4:Yb3+-Er3+@SiO2 nanorods have been obtained by a two-step synthesis process, which encompasses hydrothermal and microemulsion routes. The synthesized nanomaterial forms stable aqueous colloids and exhibits a bright dual-center emission (λex = 975 nm), i.e., upconversion luminescence of Er3+ and down-shifting emission of Yb3+, located in the first (I-BW) and the second (II-BW) biological windows of the spectral range, respectively. The intensity ratios of the emission bands of Er3+ and Yb3+ observed in the vis-near-infrared (NIR) range monotonously change with temperature, i.e., the thermalized Er3+ levels (2H11/2 → 4I15/2/4S3/2 → 4I15/2) and the nonthermally coupled Yb3+/Er3+ levels (2F5/2 → 2F7/2/4I9/2 → 4I15/2 or 4F9/2 → 4I15/2). Hence, their thermal evolutions have been correlated with temperature using the Boltzmann type distribution and second-order polynomial fits for temperature-sensing purposes, i.e., Er3+ 525/545 nm (max Sr = 1.31% K-1) and Yb3+/Er3+ 1010/810 nm (1.64% K-1) or 1010/660 nm (0.96% K-1). Additionally, a fresh chicken breast was used as a tissue imitation in the performed ex vivo experiment, showing the advantage of the use of NIR Yb3+/Er3+ bands, vs. the typically used Er3+ 525/545 nm band ratio, i.e., better penetration of the luminescence signal through the tissue in the I-BW and II-BW. Such nanomaterials can be utilized as accurate and effective, broad-range vis-NIR optical, contactless sensors of temperature.

Luminescent-Magnetic Cellulose Fibers, Modified with Lanthanide-Doped Core/Shell Nanostructures.

Novel luminescent-magnetic cellulose microfibers were prepared by a dry-wet spinning method with the use of N-methylmorpholine-N-oxide. The synthesized luminescent-magnetic core/shell type nanostructures, based on the lanthanide-doped fluorides and magnetite nanoparticles (NPs)-Fe3O4/SiO2/NH2/PAA/LnF3, were used as nanomodifiers of the fibers. Thanks to the successful incorporation of the bifunctional nanomodifiers into the cellulose structure, the functionalized fibers exhibited superior properties, that is, bright multicolor emission under UV light and strong magnetic response. By the use of the as-prepared fibers, the luminescent-magnetic thread was fabricated and used to sew and make a unique pattern in the glove material, as a proof of concept for advanced, multimodal cloths'/materials' protection against counterfeiting. The presence and uniform distribution of the modifier NPs in the polymer matrix were confirmed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray analysis (EDX). The concentration of the modifier NPs in the fibers was determined by inductively coupled plasma mass spectrometry, EDX, and magnetic measurements. The luminescence characteristics of the materials were examined by photoluminescence spectroscopy, and their magnetic field-responsive behavior was investigated by a superconducting quantum interference device.