Search Results (7)

In this paper, we report on the solvothermal preparation and detailed characterization of pristine and intentionally doped zirconium dioxide (ZrO₂) nanocrystals (NCs, ~5 nm) with Eu³⁺ or Ti⁴⁺/Eu³⁺ ions using alkoxide precursors. The results indicated that the ZrO₂ NCs were dominantly of a tetragonal phase (t-ZrO₂) with a small proportion of monoclinic ZrO₂ (m-ZrO₂). The high purity of t-ZrO₂ NCs could be synthesized with more Eu³⁺ doping. It was found that the as-obtained ZrO₂ NCs contain some naturally present Ti⁴⁺ ions originating from precursors, but were being overlooked commonly, and some carbon impurities produced during synthesis. These species showed distinct photoluminescence (PL) properties. At least two types of Eu³⁺, located at low- and high-symmetry sites (probably sevenfold and eightfold oxygen coordination), respectively, were demonstrated to build into the lattice structure of t-ZrO₂ NCs together. The cationic dopants were illustrated to be distributed non-randomly over the sites normally occupied by Zr, while Ti impurities preferentially occupied the sites near the low-symmetry site of Eu³⁺, yielding efficient energy transfer from the titanate groups to the neighboring Eu³⁺. Luminescence nanothermometry could measure temperature in a non-contact and remote way and could find great potentials in micro/nano-electronics, integrated photonics, and biomedicine. On the basis of the dual-emitting combination strategy involving the white broadband CT (Ti³⁺→O⁻) emissions of the titanate groups and red sharp Eu³⁺ emissions, t-ZrO₂:Eu³⁺ nanophosphors were demonstrated to be ratiometric self-referencing optical thermometric materials, with a working range of 130–230 K and a maxima of relative sensitivity of ~1.9% K⁻¹ at 230 K. Full article

Multifunctional nano-objects containing a magnetic heater and a temperature emissive sensor in the same nanoparticle have recently emerged as promising tools towards personalized nanomedicine permitting hyperthermia-assisted treatment under local temperature control. However, a fine control of nano-systems’ morphology permitting the synthesis of a single magnetic core with controlled position of the sensor presents a main challenge. We report here the design of new iron oxide core–silica shell nano-objects containing luminescent Tb³⁺/Eu³⁺-(acetylacetonate) moieties covalently anchored to the silica surface, which act as a promising heater/thermometer system. They present a single magnetic core and a controlled thickness of the silica shell, permitting a uniform spatial distribution of the emissive nanothermometer relative to the heat source. These nanoparticles exhibit the Tb³⁺ and Eu³⁺ characteristic emissions and suitable magnetic properties that make them efficient as a nanoheater with a Ln³⁺-based emissive self-referencing temperature sensor covalently coupled to it. Heating capacity under an alternating current magnetic field was demonstrated by thermal imaging. This system offers a new strategy permitting a rapid heating of a solution under an applied magnetic field and a local self-referencing temperature sensing with excellent thermal sensitivity (1.64%·K⁻¹ (at 40 °C)) in the range 25–70 °C, good photostability, and reproducibility after several heating cycles. Full article

The incorporation of oleic acid and oleylamine, acting as organic surfactant coatings for a novel solvothermal synthesis procedure, resulted in the formation of monoclinic KLu(WO₄)₂ nanocrystals. The formation of this crystalline phase was confirmed structurally from X-ray powder diffraction patterns and Raman vibrational modes, and thermally by differential thermal analysis. The transmission electron microscopy images confirm the nanodimensional size (~12 nm and ~16 nm for microwave-assisted and conventional autoclave solvothermal synthesis) of the particles and no agglomeration, contrary to the traditional modified sol-gel Pechini methodology. Upon doping with holmium (III) and thulium (III) lanthanide ions, these nanocrystals can generate simultaneously photoluminescence and heat, acting as nanothermometers and as photothermal agents in the third biological window, i.e., self-assessed photothermal agents, upon excitation with 808 nm near infrared, lying in the first biological window. The emissions of these nanocrystals, regardless of the solvothermal synthetic methodology applied to synthesize them, are located at 1.45 μm, 1.8 μm and 1.96 μm, attributed to the ³H₄ → ³F₄ and ³F₄ → ³H₆ electronic transition of Tm³⁺ and ⁵I₇ → ⁵I₈ electronic transition of Ho³⁺, respectively. The self-assessing properties of these nanocrystals are studied as a function of their size and shape and compared to the ones prepared by the modified sol-gel Pechini methodology, revealing that the small nanocrystals obtained by the hydrothermal methods have the ability to generate heat more efficiently, but their capacity to sense temperature is not as good as that of the nanoparticles prepared by the modified sol-gel Pechnini method, revealing that the synthesis method influences the performance of these self-assessed photothermal agents. The self-assessing ability of these nanocrystals in the third biological window is proven via an ex-vivo experiment, achieving thermal knowledge and heat generation at a maximum penetration depth of 2 mm. Full article

Dual-light emitting Yb³⁺,Er³⁺-codoped α-La(IO₃)₃ nanocrystals, known to exhibit both second harmonic signal and photoluminescence (PL), are evaluated as optical nanoprobes and thermal sensors using both conventional microscopes and a more sophisticated micro-PL setup. When loaded in cortical and hippocampal neurons for a few hours at a concentration of 0.01 mg/mL, a visible PL signal arising from the nanocrystals can be clearly detected using an epifluorescent conventional microscope, enabling to localize the nanocrystals along the stained neurons and to record PL variation with temperature of 0.5% K⁻¹. No signal of cytotoxicity, associated with the presence of nanocrystals, is observed during the few hours of the experiment. Alternatively, a micro-PL setup can be used to discriminate the different PL lines. From ratiometric PL measurements, a relative thermal sensitivity of 1.2% K⁻¹ was measured. Full article

The bifunctional possibilities of Tm,Yb:GdVO₄@SiO₂ core-shell nanoparticles for temperature sensing by using the near-infrared (NIR)-excited upconversion emissions in the first biological window, and biolabeling through the visible emissions they generate, were investigated. The two emission lines located at 700 and 800 nm, that arise from the thermally coupled ³F_2,3 and ³H₄ energy levels of Tm³⁺, were used to develop a luminescent thermometer, operating through the Fluorescence Intensity Ratio (FIR) technique, with a very high thermal relative sensitivity. Moreover, since the inert shell surrounding the luminescent active core allows for dispersal of the nanoparticles in water and biological compatible fluids, we investigated the penetration depth that can be realized in biological tissues with their emissions in the NIR range, achieving a value of 0.8 mm when excited at powers of 50 mW. After their internalization in HeLa cells, a low toxicity was observed and the potentiality for biolabelling in the visible range was demonstrated, which facilitated the identification of the location of the nanoparticles inside the cells, and the temperature determination. Full article

Herein, a novel synthesis method of colloidal GdPO₄:Mn²⁺,Eu³⁺ nanoparticles for luminescent nanothermometry is proposed. XRD, TEM, DLS, and zeta potential measurements confirmed the crystallographic purity and reproducible morphology of the obtained nanoparticles. The spectroscopic properties of GdPO₄:Mn²⁺,Eu³⁺ with different amounts of Mn²⁺ and Eu³⁺ were analyzed in a physiological temperature range. It was found that GdPO₄:1%Eu³⁺,10%Mn²⁺ nanoparticles revealed extraordinary performance for noncontact temperature sensing with relative sensitivity S_R = 8.88%/°C at 32 °C. Furthermore, the biocompatibility and safety of GdPO₄:15%Mn²⁺,1%Eu³⁺ was confirmed by cytotoxicity studies. These results indicated that colloidal GdPO₄ doped with Mn²⁺ and Eu³⁺ is a very promising candidate as a luminescent nanothermometer for in vitro applications. Full article

In this work the influence of the Ga³⁺ concentration on the luminescent properties and the abilities of the Y₃Al_5−xGa_xO₁₂: V nanocrystals to noncontact temperature sensing were investigated. It was shown that the increase of the Ga³⁺ amount enables enhancement of V⁴⁺ emission intensity in respect to the V³⁺ and V⁵⁺ and thus modify the color of emission. The introduction of Ga³⁺ ions provides the appearance of the crystallographic sites, suitable for V⁴⁺ occupation. Consequently, the increase of V⁴⁺ amount facilitates V⁵⁺ → V⁴⁺ interionic energy transfer throughout the shortening of the distance between interacting ions. The opposite thermal dependence of V⁴⁺ and V⁵⁺ emission intensities enables to create the bandshape luminescent thermometr of the highest relative sensitivity of V-based luminescent thermometers reported up to date (S_max, 2.64%/°C, for Y₃Al₂Ga₃O₁₂ at 0 °C). An approach of tuning the performance of Y₃Al_5−xGa_xO₁₂: V nanocrystals to luminescent temperature sensing, including the spectral response, maximal relative sensitivity and usable temperature range, by the Ga³⁺ doping was presented and discussed. Full article