Semiempirical and DFT computations of the influence of Tb(III) dopant on unit cell dimensions of cerium(III) fluoride.

Several computational methods, both semiempirical and ab initio, were used to study the influence of the amount of dopant on crystal cell dimensions of CeF3 doped with Tb(3+) ions (CeF3 :Tb(3+) ). AM1, RM1, PM3, PM6, and PM7 semiempirical parameterization models were used, while the Sparkle model was used to represent the lanthanide cations in all cases. Ab initio calculations were performed by means of GGA+U/PBE projector augmented wave density functional theory. The computational results agree well with the experimental data. According to both computation and experiment, the crystal cell parameters undergo a linear decrease with increasing amount of the dopant. The computations performed using Sparkle/PM3 and DFT methods resulted in the best agreement with the experiment with the average deviation of about 1% in both cases. Typical Sparkle/PM3 computation on a 2×2×2 supercell of CeF3:Tb3+ lasted about two orders of magnitude shorter than the DFT computation concerning a unit cell of this material.

Synthesis and organic surface modification of luminescent, lanthanide-doped core/shell nanomaterials (LnF3@SiO2@NH2@organic acid) for potential bioapplications: spectroscopic, structural, and in vitro cytotoxicity evaluation.

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.

Structural, spectroscopic, and magnetic properties of Eu3+-doped GdVO4 nanocrystals synthesized by a hydrothermal method.

New interesting aspects of the spectroscopic properties, magnetism, and method of synthesis of gadolinium orthovanadates doped with Eu(3+) ions are discussed. Gd(1-x)Eu(x)VO4 (x = 0, 0.05, 0.2) bifunctional luminescent materials with complex magnetic properties were synthesized by a microwave-assisted hydrothermal method. Products were formed in situ without previous precipitation. The crystal structures and morphologies of the obtained nanomaterials were analyzed by X-ray diffraction and transmission and scanning electron microscopy. Crystallographic data were analyzed using Rietveld refinement. The products obtained were nanocrystalline with average grain sizes of 70-80 nm. The qualitative and quantitative elemental composition as well as mapping of the nanocrystals was proved using energy-dispersive X-ray spectroscopy. The spectroscopic properties of red-emitting nanophosphors were characterized by their excitation and emission spectra and luminescence decays. Magnetic measurements were performed by means of vibrating sample magnetometry. GdVO4 and Gd0.8Eu0.2VO4 exhibited paramagnetic behavior with a weak influence of antiferromagnetic couplings between rare-earth ions. In the substituted sample, an additional magnetic contribution connected with the population of low-lying excited states of europium was observed.

Hydrothermal synthesis and structural and spectroscopic properties of the new triclinic form of GdBO3:Eu3+ nanocrystals.

Triclinic Gd1-xEuxBO3 nanophosphors have been prepared by a hydrothermal method without using additional coreagents and prior precipitation of precursor (in situ). The formation of the borate nanorods and their crystal structure was refined on the basis of X-ray diffraction patterns (XRD) and well confirmed using various techniques such as infrared spectroscopy (IR), Raman spectroscopy, transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDX). The new triclinic crystal structure (space group P1) for the GdBO3 nanocrystals and detailed structure parameters were determined with the help of the Rietveld analysis. The spectroscopic characteristics of the synthesized nanomaterials with different concentrations of Eu(3+) ions were defined with the use of luminescence excitation spectra as well as emission spectra and decay kinetics. The Judd-Ofelt parameters (Ω2, Ω4) and quantum efficiency, η, were also calculated for the more detailed analysis of Eu(3+) spectra in the GdBO3 host.

Generation of Pure Green Up-Conversion Luminescence in Er3+ Doped and Yb3+-Er3+ Co-Doped YVO4 Nanomaterials under 785 and 975 nm Excitation.

Materials that generate pure, single-color emission are desirable in the development and manufacturing of modern optoelectronic devices. This work shows the possibility of generating pure, green up-conversion luminescence upon the excitation of Er3+-doped nanomaterials with a 785 nm NIR laser. The up-converting inorganic nanoluminophores YVO4: Er3+ and YVO4: Yb3+ and Er3+ were obtained using a hydrothermal method and subsequent calcination. The synthesized vanadate nanomaterials had a tetragonal structure and crystallized in the form of nearly spherical nanoparticles. Up-conversion emission spectra of the nanomaterials were measured using laser light sources with λex = 785 and 975 nm. Importantly, under the influence of the mentioned laser irradiation, the as-prepared samples exhibited bright green up-conversion luminescence that was visible to the naked eye. Depending on the dopant ions used and the selected excitation wavelengths, two (green) or three (green and red) bands originating from erbium ions appeared in the emission spectra. In this way, by changing the UC mechanisms, pure green luminescence of the material can be obtained. The proposed strategy, in combination with various single-doped UC nanomaterials activated with Er3+, might be beneficial for modern optoelectronics, such as light-emitting diodes with a rich color gamut for back-light display applications.

Optically active plasmonic cellulose fibers based on Au nanorods for SERS applications.

Cellulose might be a promising material for surface-enhanced Raman scattering (SERS) substrates due to its wide availability, low cost, ease of fabrication, high flexibility and low optical activity. This work shows, for the first time development of the cellulose-based substrate, that owes its SERS activity to the presence of gold nanorods in its internal structure, and not only on the surface, as it is shown elsewhere, thus ensuring superior stability of the obtained material. This flexible cellulose-based substrate exhibiting plasmonic activity, provide easy and reproducible detection of different analytes via SERS technique. The substrate was prepared by introduction of gold nanorods into the cellulose fibers matrix using an eco-friendly process based on N-Methylmorpholine-N-Oxide. Au-modified cellulose fibers were used for the detection of p-Mercaptobenzoic acid and Bovine Serum Albumin by the SERS method. The obtained results show that this substrate offers large signal enhancement of 6-orders of magnitude, and high signal reproducibility with a relative standard deviation of 8.3%. Additionally, washing tests (90 °C, 20 h) showed superior stability of the as prepared plasmonic fibers, thus proving the good reusability of the substrates and the long shelf life.

Ratiometric Upconversion Temperature Sensor Based on Cellulose Fibers Modified with Yttrium Fluoride Nanoparticles.

In this study, an optical thermometer based on regenerated cellulose fibers modified with YF3: 20% Yb3+, 2% Er3+ nanoparticles was developed. The presented sensor was fabricated by introducing YF3 nanoparticles into cellulose fibers during their formation by the so-called Lyocell process using N-methylmorpholine N-oxide as a direct solvent of cellulose. Under near-infrared excitation, the applied nanoparticles exhibited thermosensitive upconversion emission, which originated from the thermally coupled levels of Er3+ ions. The combination of cellulose fibers with upconversion nanoparticles resulted in a flexible thermometer that is resistant to environmental and electromagnetic interferences and allows precise and repeatable temperature measurements in the range of 298-362 K. The obtained fibers were used to produce a fabric that was successfully applied to determine human skin temperature, demonstrating its application potential in the field of wearable health monitoring devices and providing a promising alternative to thermometers based on conductive materials that are sensitive to electromagnetic fields.

Chemiluminescence determination of fluoroquinolones using Fenton system in the presence of terbium(iii) ions.

A simple new chemiluminescent, CL, method is described for the determination of fluoroquinolones such as: ciprofloxacin (CF), norfloxacin (NF), and ofloxacin (OF). This method is based on the measurement of terbium(iii) emission. This emission follows an energy transfer to the uncomplexed terbium(iii) ions from the excited products of fluoroquinolone oxidations. Under optimum conditions, calibration graphs were obtained for 2 × 10(-8)-2 × 10(-6) mol L(-1) of NF; 3 × 10(-8)-2 × 10(-6) mol L(-1) of CF and 4 × 10(-7)-5 × 10(-5) mol L(-1) of OF. The detection limits are 7 × 10(-9) mol L(-1) norfloxacin, 1 × 10(-8) mol L(-1) ciprofloxacin and 1.5 × 10(-7) mol L(-1) ofloxacin. The method was successfully applied to the determination of these drugs in pharmaceutical formulations.

Structural and spectroscopic properties of LaOF:Eu3+ nanocrystals prepared by the sol-gel Pechini method.

A new method was used to obtain Eu(3+)-doped LaOF nanocrystals. The obtained nanocrystals were synthesized for the first time using a modified Pechini sol-gel method. The products were analyzed by X-ray powder diffraction and the Rietveld method. Optimal conditions for the synthesis were found. Luminescent properties of the tetragonal and rhombohedral LaOF:Eu(3+) nanocrystals were investigated by collecting excitation and luminescence spectra. The most effective dopant concentrations in both hosts were found. Luminescent lifetimes were also measured. The time-resolved luminescent traces showed both a growth and a decay, which pointed to energy transfer processes between Eu(3+) ions in the LaOF host. In order to explain these phenomena, an adequate mechanism has been proposed. Intensity parameters Ω(2), Ω(4) and quantum efficiencies were calculated using the Judd-Ofelt theory, allowing for an extensive study of the luminescent properties of Eu(3+) ion in the LaOF matrix.

New Multicolor Tungstate-Molybdate Microphosphors as an Alternative to LED Components.

Due to the ongoing need to create phosphors with the appropriate emission color for the production of light emitting diodes, we decided to synthesize a series of multicolour microphosphors with tunable visible emissions, depending on the composition of dopant ions. In this work, we investigated the structure, morphology, and luminescent properties of new molybdate-tungstate phosphors co-doped with Tb3+ and Eu3+ ions. The conventional high temperature solid state method was used to prepare a series of CaMoyW1-yO4:Eu3+x/Tb3+1-x materials. In order to obtain phosphors with the most promising luminescent properties, the experiment was planned by taking into account the different composition of the matrix and the concentration of the particular dopant ions (Eu3+x/Tb3+1-x, x = 0.001, 0.003, 0.005, 0.007, 0.009). As a result, luminescent materials were obtained with a pure tetragonal crystal structure, the space group of I41/a, confirmed by X-ray diffraction (XRD). The size and shape of the particles obtained from the materials were analyzed based on scanning electron microscopy images. Luminescence spectroscopy (excitation and emission spectra, decay lifetimes) was utilized to characterize the luminescence properties of the as-prepared phosphors. The color change of the emission from green-yellow to orange-red was confirmed using the 1931 Comission Internationale de l'Eclairage (CIE) chromaticity coordinates and color correlated temperature (CCT).

Improving performance of luminescent nanothermometers based on non-thermally and thermally coupled levels of lanthanides by modulating laser power.

This work sheds light on the pump power impact on the performance of luminescent thermometers, which is often underestimated by researchers. An up-converting, inorganic nanoluminophore, YVO4:Yb3+,Er3+ (nanothermometer) was synthesized using the hydrothermal method and a subsequent calcination. This nanomaterial appears as a white powder composed of small nanoparticles (≈20 nm), exhibiting a very intense, green upconverted luminescence (λex = 975 nm), visible to the naked eye. Its emission spectrum consists of four Er3+ bands (500-850 nm) and one Yb3+ band (>900 nm). The obtained compound exhibits temperature-dependent luminescence properties, hence it is used as an optical nanosensor of temperature. The determined band intensity ratios of the non-thermally coupled levels (non-TCLs) of Yb3+/Er3+ and thermally coupled levels (TCLs) of Er3+ are correlated with temperature, and they are used for ratiometric sensing of temperature. The effects of the pump (NIR laser) power on the luminescence properties of the material, including band intensity ratios, absolute and relative sensitivities and temperature resolution are analysed. It was pointed out that the applied laser power has a huge impact on the values of the aforementioned thermometric parameters, and manipulating the laser power can significantly improve the performance of optical nanothermometers.

Ligand-Sensitised LaF3 :Eu3+ and SrF2 :Eu3+ Nanoparticles and in Vitro Haemocompatiblity Studies.

Luminescent Ln3+ -doped nanoparticles (NPs) functionalised with the desired organic ligand molecules for haemocompatibility studies were obtained in a one-pot synthesis. Chelated aromatic organic ligands such as isophthalic acid, terephthalic acid, ibuprofen, aspirin, 1,2,4,5-benzenetetracarboxylic acid, 2,6-pyridine dicarboxylic acid and adenosine were applied for surface functionalisation. The modification of the nanoparticles is based on the donor-acceptor character of the ligand-nanoparticle system, which is an alternative to covalent functionalisation by peptide bonding as presented in our recent report. The aromatic groups of selected ligands absorb UV light and transfer their excited-state energy to the dopant Eu3+ ions in LaF3 and SrF2 NPs. Herein, we discuss the structural and spectroscopic characterisation of the NPs and the results of haemocompatibility studies. Flow cytometry analysis of the nanoparticles' membrane-binding is also presented.

UV-Vis-NIR absorption spectra of lanthanide oxides and fluorides.

The absorption characteristics of lanthanide-based functional materials are of key importance for many scientists and engineers, e.g. in luminescence studies, bioimaging, optical heating/cooling, Raman spectroscopy, and industrial applications such as new light sources, optical sensors, labeling and tracing techniques, etc. Here we show the absorption spectra of solid, optically active lanthanide fluorides (CeF3, PrF3, NdF3, SmF3, EuF3, GdF3, TbF3, DyF3, HoF3, ErF3, TmF3, and YbF3) and oxides (CeO2, Pr6O11, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, and Yb2O3), measured in the UV-Vis-NIR range, from 200 to 2500 nm. The spectra were measured in diffused-reflectance mode using a spherical integrator. We assigned energy levels (2S+1LJ) of lanthanide ions(iii), i.e. intraconfigurational 4f-4f transitions to the observed absorption bands. In order to clearly distinguish the 4f → 4f transitions, we also pointed out other absorption bands commonly observed in the measured spectra, such as intrinsic absorption of the matrices, interconfigurational 4f → 5d and charge transfer transitions, artificial bands from absorbed water (present in most materials) and a quartz holder.

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.

3,5-Dihydroxy Benzoic Acid-Capped CaF2:Tb3+ Nanocrystals as Luminescent Probes for the WO4 2- Ion in Aqueous Solution.

We report a facile and effective luminescence method for the determination of the WO4 2- ion in aqueous medium at initial pH = 6.3. This is achieved using 3,5-dihydroxybenzoic acid-capped CaF2:Tb3+ (5%) nanocrystals (NCs) as a luminescent probe. This is accomplished based on the energy transfer luminescence from the WO4 2- ion to the Tb3+ ion in small-size CaF2:Tb3+ NCs. Hydroxyl groups on the surface ligand helps in binding the tungstate ion to the surface of the NCs. With the gradual addition of the WO4 2- ion, the intensity of the Tb3+ excitation and emission spectra significantly increased. The linear range of the detection was from 1 to 10 µM for the WO4 2- ion (R 2 = 0.99). The calculated detection limit was 0.4 µM (by applying the 3σ/K criterion).

Luminescent Nanothermometer Operating at Very High Temperature-Sensing up to 1000 K with Upconverting Nanoparticles (Yb3+/Tm3+).

Lanthanide-based luminescent nanothermometers play a crucial role in optical temperature determination. However, because of the strong thermal quenching of the luminescence, as well as the deterioration of their sensitivity and resolution with temperature elevation, they can operate in a relatively low-temperature range, usually from cryogenic to ≈800 K. In this work, we show how to overcome these limitations and monitor very high-temperature values, with high sensitivity (≈2.1% K-1) and good thermal resolution (≈1.4 K) at around 1000 K. As an optical probe of temperature, we chose upconverting Yb3+-Tm3+ codoped YVO4 nanoparticles. For ratiometric sensing in the low-temperature range, we used the relative intensities of the Tm3+ emissions associated with the 3F2,3 and 3H4 thermally coupled levels, that is, 3F2,3 → 3H6/3H4 → 3H6 (700/800 nm) band intensity ratio. In order to improve sensitivity and resolution in the high-temperature range, we used the 940/800 nm band intensity ratio of the nonthermally coupled levels of Yb3+ (2F5/2 → 2F7/2) and Tm3+ (3H4 → 3H6). These NIR bands are very intense, even at extreme temperature values, and their intensity ratio changes significantly, allowing accurate temperature sensing with high thermal and spatial resolutions. The results presented in this work may be particularly important for industrial applications, such as metallurgy, catalysis, high-temperature synthesis, materials processing and engineering, and so forth, which require rapid, contactless temperature monitoring at extreme conditions.

Surface Modification of Luminescent LnIII Fluoride Core-Shell Nanoparticles with Acetylsalicylic acid (Aspirin): Synthesis, Spectroscopic and in Vitro Hemocompatibility Studies.

Luminescent lanthanide fluoride core-shell (LaF3 :Tb3+ ,Ce3+ @SiO2 -NH2 ) nanoparticles, with acetylsalicylic acid (aspirin) coated on the surface have been obtained. The synthesized products, which combine the potential located in the silica shell with the luminescent activity of the core, were characterized in detail with the use of luminescence spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and transmission electron microscopy (TEM) methods. The in vitro effects of the modified luminescent nanoparticles on human red blood cell (RBC) membrane permeability, RBC shape, and sedimentation rate were investigated to assess the hemocompatibility of the obtained compounds. This study demonstrates that LaF3 : Tb3+ 5 %, Ce3+ 10 %@SiO2 -NH2 nanoparticles with acetylsalicylic acid (aspirin) coated on the surface are very good precursors for multifunctional drug-delivery systems or bio-imaging probes that can be used safely in potential biomedical applications.

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.

Modification of cellulose fibers with inorganic luminescent nanoparticles based on lanthanide(III) ions.

This article presents synthesis and properties of the fibers modified with luminescent, inorganic nanoparticles doped with lanthanide(III) ions, i.e. LaF3:Ce3+, Gd3+, Eu3+; CeF3:Tb3+ and CePO4:Tb3+. The fibers with luminescent properties were prepared via so called Lyocell process. This method involves dissolving cellulose in aqueous solution of N-methylmorpholine-N-oxide (NMMO) and a subsequent spinning of the fibers, using a dry-wet method. Thanks to the successful incorporation of the modifier nanoparticles (NPs) into the cellulose matrices, the fibers exhibited bright, multicolor emission upon UV irradiation and good mechanical properties, which allowed further textile processing. This type of fibers, as well as the as-prepared textiles/fabric can be used as an anti-counterfeiting agent for clothes and documents protection.

Optical Pressure Sensor Based on the Emission and Excitation Band Width (fwhm) and Luminescence Shift of Ce3+-Doped Fluorapatite-High-Pressure Sensing.

A novel, contactless optical sensor of pressure based on the luminescence red-shift and bandwidth (full width at half-maximum, fwhm) of the Ce3+-doped fluorapatite-Y6Ba4(SiO4)6F2 powder has been successfully synthesized via a facile solid-state method. The obtained material exhibits a bright blue emission under UV light excitation. It was characterized using powder X-ray diffraction, scanning electron microscopy and luminescence spectroscopy, including high-pressure measurements of excitation and emission spectra, up to above ∼30 GPa. Compression of the material resulted in a significant red-shift of the allowed 4f → 5d and 5d → 4f transitions of Ce3+ in the excitation and emission spectra, respectively. The pressure-induced monotonic shift of the emission band, as well as changes in the excitation/emission band widths, have been correlated with pressure for sensing purposes. The material exhibits a high pressure sensitivity (dλ/d P ≈ 0.63 nm/GPa) and outstanding signal intensity at high-pressure conditions (∼90% of the initial intensity at around 20 GPa) with minimal pressure-induced quenching of luminescence.