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1.
Inorg Chem ; 63(22): 10194-10206, 2024 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-38767516

RESUMO

We report details on the synthesis and properties of barium praseodymium tungstate, Ba2PrWO6, a double perovskite that has not been synthesized before. Room-temperature (RT) powder X-ray diffraction identified the most probable space group (SG) as monoclinic I2/m, but it was only slightly distorted from the cubic structure. X-ray photoelectron spectroscopy confirmed that the initial (postsynthesis) material contained praseodymium in both 3+ and 4+ charge states. The former (Pr3+) disappeared after exposure to UV light at RT. Photoluminescence studies of Pr3+ revealed that Ba2PrWO6 is an insulator with a band gap exceeding 4.93 eV. Pressure-dependent Raman spectroscopy excluded the possibility of a phase transition up to 20 GPa; however, measurements between 8 and 873 K signified that there might be a change toward the lower symmetry SG below 200 K. Electron paramagnetic resonance spectra revealed the presence of interstitial oxygen which acts as a deep electron trap.

2.
Nanotechnology ; 33(3)2021 Oct 29.
Artigo em Inglês | MEDLINE | ID: mdl-34633305

RESUMO

Perovskites, garnets, monoclinic forms, and lately also oxyhydroxides doped with rare-earth ions have been drawn large attention due to their beneficial optical and photovoltaic properties. In this work, we have shown that several forms of crystals from Y-Al-O family can be synthesized using microwave driven hydrothermal technique using different pH and post-growth annealing at different temperatures. The structural and optical properties of these crystals were investigated as a function of hydrothermal crystallization conditions. For this purpose, x-ray diffraction, scanning electron microscopy, energy-dispersive x-ray spectroscopy, transmission electron microscopy, photoluminescence, and photoluminescence excitation studies were performed. All the structures have been doped with Eu3+ions which are known as a local symmetry sensor because various symmetries generate different crystal fields and thus affect their luminescence spectra. The optical properties of the obtained nanoparticles in correlation with their structure and chemical composition are discussed.

3.
Nanotechnology ; 32(24)2021 Mar 24.
Artigo em Inglês | MEDLINE | ID: mdl-33690193

RESUMO

Gd2O3:1% Er3+, 18% Yb3+,x% Mg2+(x = 0; 2.5; 4; 5; 6; 8;10; 20; 25; 50) and Gd2O3:1% Er3+, 18% Yb3+, 2,5% Mg2+,y% Li+(y = 0.5-2.5) nanoparticles were synthesized by homogenous precipitation method and calcined at 900 °C for 3 h in air atmosphere. Powder x-ray diffraction, scanning electron microscopy, cathodoluminescence, transmission electron microscopy, energy dispersive x-ray spectroscopy and photoluminescence techniques were employed to characterize the obtained nanoparticles. We observed a 8-fold increase in red luminescence for samples suspended in DMSO solution for 2.5% of Mg2+doping. The x-ray analysis shows that for the concentration of 2.5% Mg, the size of the crystallites in the NPs is the largest, which is mainly responsible for the increase in the intensity of the upconversion luminescence. But the addition of Li+ions did not improve the luminescence of the upconversion due to decreasing of crystallites size of the NPs. Synthesized nanomaterials with very effective upconverting luminescence, can act as luminescent markers inin vivoimaging. The cytotoxicity of the nanoparticles was evaluated on the 4T1 cell line for the first time.

4.
Nanotechnology ; 31(46): 465101, 2020 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-32717731

RESUMO

In photodynamic therapy (PDT), photosensitizer (PS) molecules are irradiated by light to generate reactive oxygen species (ROS), the presence of which subsequently leads to cell death. At present, the modality is limited to the treatment of skin diseases because of the low tissue penetration of visible or ultraviolet light required for producing ROS. To increase tissue penetration and extend the therapeutic possibilities of PDT to the treatment of deep-seated cancer, rare-earth doped nanoparticles capable of up-converting infrared to visible light are investigated. These up-converting nanoparticles (UCNPs) are conjugated with PS molecules to efficiently generate ROS. In this work, we employ hexagonal ß-NaYF4:Yb3 + ,Er3 + as UCNPs and Rose Bengal (RB) as PS molecules and demonstrate efficient in vitro PDT using this nanoformulation. Covalent bonding of the RB molecules is accomplished without their functionalization-an approach which is expected to increase the efficiency of ROS generation by 30%. Spectroscopic studies reveal that our approach results in UCNP surface fully covered with RB molecules. The energy transfer from UCNPs to RB is predominantly non-radiative as evidenced by luminescence lifetime measurements. As a result, ROS are generated as efficiently as under visible light illumination. The in vitro PDT is tested on murine breast 4T1 cancer cells incubated with 250 µg ml-1 of the nanoparticles and irradiated with NIR light under power density of 2 W cm-2 for 10 minutes. After 24 hours, the cell viability decreased to 33% demonstrating a very good treatment efficiency. These results are expected to simplify the protocols for preparation of the PDT agents and lead to improved therapeutic effects.


Assuntos
Érbio/farmacologia , Fluoretos/farmacologia , Fármacos Fotossensibilizantes/farmacologia , Rosa Bengala/farmacologia , Itérbio/farmacologia , Ítrio/farmacologia , Animais , Linhagem Celular Tumoral , Érbio/química , Feminino , Fluoretos/química , Neoplasias Mamárias Animais/tratamento farmacológico , Neoplasias Mamárias Experimentais/tratamento farmacológico , Camundongos , Nanopartículas/química , Fotoquimioterapia , Fármacos Fotossensibilizantes/química , Rosa Bengala/química , Itérbio/química , Ítrio/química
5.
Nanotechnology ; 31(22): 225711, 2020 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-32032002

RESUMO

The paramagnetic Y3-0.02-x Er0.02Yb x Al5O12 (x = 0.02, 0.06, 0.10, 0.12, 0.18, 0.20) nanocrystals (NCs) were synthesized by the microwave-induced solution combustion method. The XRD, TEM and SEM techniques were applied to determine the NCs' structures and sizes. The XRD patterns confirmed that the NCs have for the most part a regular structure of the Y3Al5O12 (YAG) phase. The changes of the distance between donor Yb3+ (sensitizer) and acceptor Er3+ (activator) were realized by changing the donor's concentration with a constant amount of acceptor. Under 980 nm excitation, at room temperature, the NCs exhibited strong red emission near 660 and 675 nm, and green upconversion emission at 550 nm, corresponding to the intra 4f transitions of Er3+ (4F9/2, 2H11/2, 4S3/2) â†’ Er3+ (4I15/2). The strongest emission was observed in a sample containing 18% Yb3+ ions. The red and green emission intensities are respectively about 5 and 12 times higher as compared to NCs doped with 2% of Yb3+. In order to prove that the main factor responsible for the increase of the upconversion luminescence efficiency is reduction of the distance between Yb3+ and Er3+, we examined, for the first time the influence of hydrostatic pressure on luminescence and luminescence decay time of the radiative transitions inside donor ion. The decrease of both luminescence intensity and luminescence decay times, with increasing hydrostatic pressure was observed. After applying hydrostatic pressure to samples with e.g. 2% and 6% Yb3+, the distance between the donor and acceptor decreases. However, for higher concentrations of the donor, this distance is smaller, and this leads to the effective energy transfer to Er3+ ions. With increasing pressure, the maximum intensity of near infrared emission is observed at 1029, 1038 and 1047 nm, what corresponds to 2F5/2 â†’ 2F7/2 transition of Yb3+.

6.
Inorg Chem ; 57(21): 13115-13127, 2018 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-30351065

RESUMO

Ca9R(VO4)7 (R = rare earth) multicomponent oxides of a whitlockite-related structure are under consideration for applications in optoelectronics. In this work, the Czochralski-grown Ca9R(VO4)7 crystals were investigated as a function of pressure by powder X-ray diffraction and single-crystal Raman spectroscopy. The diffraction experiments were performed at the ALBA synchrotron under pressures ranging up to 9.22(5), 10.7(1), and 8.55(5) GPa for R = La, Nd, and Gd, respectively, to determine the third order equation of state (EOS) parameters. Fitting of the Birch-Murnaghan EOS provided the isothermal bulk moduli K0 = 63(4), 63(2), and 61(5) GPa for these three orthovanadates. These values are apparently lower than that reported for structurally related tricalcium vanadate Ca3(VO4)2. The compressibility anisotropy was observed; the lattice is markedly stiffer in [001] than in [100] direction. For Ca9Nd(VO4)7, the variation of the diffractograms just above 10 GPa provides an indication on the beginning of amorphization process; during pressure release the whitlockite-like structure is recovered. Raman spectroscopy measurements for single crystals of the above-mentioned rare-earth vanadates and Ca9Y(VO4)7 were performed (the maximum pressures achieved were 16.3(1), 21.2(1), 15.3(1), and 18.6(1) GPa for R = Y, La, Nd, and Gd, respectively). These measurements reveal a partially reversible phase transition interpreted as amorphization, with an onset at the pressure of ∼9-10 GPa, characterized by broadening of the peaks and their shift to lower energies.

7.
Nanotechnology ; 29(2): 025702, 2018 01 12.
Artigo em Inglês | MEDLINE | ID: mdl-29130898

RESUMO

Nanostructures as color-tunable luminescent markers have become major, promising tools for bioimaging and biosensing. In this paper separated molybdate/Gd2O3 doped rare earth ions (erbium, Er3+ and ytterbium, Yb3+) core-shell nanoparticles (NPs), were fabricated by a one-step homogeneous precipitation process. Emission properties were studied by cathodo- and photoluminescence. Scanning electron and transmission electron microscopes were used to visualize and determine the size and shape of the NPs. Spherical NPs were obtained. Their core-shell structures were confirmed by x-ray diffraction and energy-dispersive x-ray spectroscopy measurements. We postulated that the molybdate rich core is formed due to high segregation coefficient of the Mo ion during the precipitation. The calcination process resulted in crystallization of δ/ξ (core/shell) NP doped Er and Yb ions, where δ-gadolinium molybdates and ξ-molybdates or gadolinium oxide. We confirmed two different upconversion mechanisms. In the presence of molybdenum ions, in the core of the NPs, Yb3+-[Formula: see text] (∣2F7/2, 3T2〉) dimers were formed. As a result of a two 980 nm photon absorption by the dimer, we observed enhanced green luminescence in the upconversion process. However, for the shell formed by the Gd2O3:Er, Yb NPs (without the Mo ions), the typical energy transfer upconversion takes place, which results in red luminescence. We demonstrated that the NPs were transported into cytosol of the HeLa and astrocytes cells by endocytosis. The core-shell NPs are sensitive sensors for the environment prevailing inside (shorter luminescence decay) and outside (longer luminescence decay) of the tested cells. The toxicity of the NPs was examined using MTT assay.


Assuntos
Érbio/química , Gadolínio/química , Substâncias Luminescentes/química , Molibdênio/química , Nanopartículas/química , Imagem Óptica/métodos , Itérbio/química , Astrócitos/citologia , Células HeLa , Humanos , Medições Luminescentes/métodos , Microscopia Confocal/métodos , Nanopartículas/ultraestrutura , Nanotecnologia/métodos
8.
J Chem Phys ; 141(1): 014705, 2014 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-25005301

RESUMO

α-SrSi2O2N2 is one of the recently studied oxonitridosilicates applicable in optoelectronics, in particular in white LEDs. Its elastic properties remain unknown. A survey of literature shows that, up to now, nine oxonitridosilicate materials have been identified. For most of these compounds, doped with rare earths and manganese, a luminescence has been reported at a wavelength characteristic for the given material; all together cover a broad spectral range. The present study focuses on the elastic properties of one of these oxonitridosilicates, the Eu-doped triclinic α-SrSi2O2N2. High-pressure powder diffraction experiments are used in order to experimentally determine, for the first time, the equation of state of this compound. The in situ experiment was performed for pressures ranging up to 9.65 GPa, for Eu-doped α-SrSi2O2N2 sample mounted in a diamond anvil cell ascertaining the hydrostatic compression conditions. The obtained experimental variation of volume of the triclinic unit cell of α-SrSi2O2N2:Eu with rising pressure served for determination of the Birch-Murnaghan equation of state. The determined above quoted bulk modulus is 103(5) GPa, its first derivative is 4.5(1.1). The above quoted bulk modulus value is found to be comparable to that of earlier reported oxynitrides of different composition.

9.
Sci Rep ; 14(1): 15793, 2024 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-38982197

RESUMO

Crystals of YGa3(BO3)4, YAl3(BO3)4, EuGa3(BO3)4 and EuAl3(BO3)4 with copper alloy were studied by electron paramagnetic resonance and X-ray diffraction analysis. The lattice parameters and coordinates of copper-doped boron atoms were determined. The study of EPR spectra showed that copper is in the divalent state and replaces aluminum ions with C2 node symmetry. In YAl3(BO3)4:Cu crystals, a ligand structure exists due to the interaction of copper electrons with yttrium nuclei. The parameters of the spin Hamiltonian describing the behavior of the Cu2+ spectrum have been determined. The deviation of the Z-axis spectra from the C3 axis by 54(1)° is due to Jahn-Teller vibronic interaction and monoclinic distortion. In the EuGa3(BO3)4 crystal, a new spectrum 2 was found, which also belongs to divalent copper but is observed at an excited state 31 cm-1 away from the ground state. Above 70 K, an isotropic EPR line with a width of 450 Gs, g = 2.1, appears and exists up to room temperature.

10.
Artigo em Inglês | MEDLINE | ID: mdl-39462263

RESUMO

Nickel orthovanadate is a promising material with potential applications in energy storage and photocatalytic devices. The crystal structure of Ni3V2O8 at 299 (3) K and 1323 (8) K was studied using X-ray powder diffraction. The sample was a single-phase orthorhombic kagome-staircase-Ni3(VO4)2-type structure (space group Cmca) at both temperatures. The phase purity and morphology was studied using energy-dispersive X-ray spectroscopy and scanning electron microscopy. The refined unit-cell parameters at 299 (3) K are a = 5.93384 (4) Å, b = 11.38318 (7) Šand c = 8.23818 (5) Å, and at 1323 (8) K are a = 6.02077 (7) Å, b = 11.48838 (7) Šand c = 8.32611 (9) Å. The obtained results indicate thermal expansion anisotropy, with a largest expansivity along a. Variations in Ni-O and V-O bonds with temperature are observed. The variation in the Ni-O bond is about one order higher in magnitude than that of the V-O bond, signifying the high rigidity of V-O bonds. The unit-cell size variations with rising effective ionic volume of the divalent A ion in the A3B2O8 family [A = Ni, Mg, Zn, Co, Mn (experimental data) and also A = Cu, Cd (theoretical data), B = V or As] are analyzed. Based on experimental and theoretical data, trends within the family are observed and the unit-cell size for reported solid solution of nickel (87%) and copper (13%) mixture in (Ni1-xCux)3V2O8 are predicted. Predictions are also provided for some hypothetical A3B2O8 ternary compound and solid solutions.

11.
Dalton Trans ; 53(36): 15070-15082, 2024 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-39206724

RESUMO

Crystals of Ca10.5-xTMx(VO4)7 (TM = Co, Cu), belonging to the whitlockite family, were synthesized by solid-state reaction and studied as a function of the TM content (x) for the first time. The structure was refined at ambient conditions and at high temperatures up to 1200 K using the Rietveld method. The unit cell size significantly decreases with increasing TM content up to the solubility limit, xlim, which is 0.78(3) for TM = Co and 0.75(4) for TM = Cu. Occupancy factors show a preference for the M5 site by Co/Cu. The unit cell size varies smoothly with temperature, while the axial ratio exhibits nonlinear behaviour above approximately 800 K. The thermal expansion coefficient was determined from 300-1100 K. Atomic arrangement modifications at higher temperatures are indicated by changes in the axial ratio, the thermal expansion coefficient, and the reduction of fractional TM occupancy at the M5 site at specific temperatures.

12.
Nanotechnology ; 24(23): 235702, 2013 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-23669145

RESUMO

An effective, simple and practically useful method to incorporate fluorescent nanoparticles inside live biological cells was developed. The internalization time and concentration dependence of a frequently used liposomal transfection factor (Lipofectamine 2000) was studied. A user friendly, one-step technique to obtain water and organic solvent soluble Er(3+) and Yb(3+) doped NaYF4 nanoparticles coated with polyvinylpyrrolidone was obtained. Structural analysis of the nanoparticles confirmed the formation of nanocrystals of the desired sizes and spectral properties. The internalization of NaYF4 nanoparticles in HeLa cervical cancer cells was determined at different nanoparticle concentrations and for incubation periods from 3 to 24 h. The images revealed a redistribution of nanoparticles inside the cell, which increases with incubation time and concentration levels, and depends on the presence of the transfection factor. The study identifies, for the first time, factors responsible for an effective endocytosis of the up-converting nanoparticles to HeLa cells. Thus, the method could be applied to investigate a wide range of future 'smart' theranostic agents. Nanoparticles incorporated into the liposomes appear to be very promising fluorescent probes for imaging real-time cellular dynamics.


Assuntos
Endocitose , Érbio/metabolismo , Fluoretos/metabolismo , Nanopartículas/química , Itérbio/metabolismo , Ítrio/metabolismo , Células HeLa , Humanos , Luminescência , Microscopia Confocal , Nanopartículas/ultraestrutura , Tamanho da Partícula , Espectrometria de Fluorescência , Coloração e Rotulagem , Difração de Raios X
13.
ACS Omega ; 8(48): 45834-45843, 2023 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-38075762

RESUMO

The nanohardness and Young's modulus of Pb1-xCdxTe single crystals prepared by the self-selecting vapor growth (SSVG) method and thick, MBE-grown layers with a total Cd content of up to 7% metal atoms were studied using the nanoindentation technique; the nanohardness and Young's modulus were calculated by the Oliver and Pharr method. Significant hardening of SSVG crystals with increasing number of Cd atoms replacing Pb atoms in the formed solid solution was observed, and low anisotropy of the nanohardness and Young's modulus were found. The CdTe solubility limit in the solid solution grown using an MBE equal to 2.1% was demonstrated; even for the significantly higher total Cd concentration in the layer, the possible presence of precipitates was not detected. Significant differences were found for both the energy of elastic crystal deformation and Young's modulus determined for samples grown using the two methods. An increase in nanohardness with an increase in the number of Cd atoms outside the cation sublattice was shown. The different ratios of hardening mechanisms acting simultaneously in the analyzed crystals in various ranges of Cd concentrations were demonstrated and discussed. The observed effects were attributed to the much higher concentration of point defects in MBE-grown layers than in SSVG crystals, in particular, the interstitial Cd-Te vacancy complexes effectively hampering nucleation and propagation of dislocations in the former case.

14.
Nanomedicine (Lond) ; 18(3): 233-258, 2023 02.
Artigo em Inglês | MEDLINE | ID: mdl-37078419

RESUMO

Background: Modern medicine requires intensive research to find new diagnostic and therapeutic solutions. Recently, upconverting nanoparticles (UCNPs) doped with lanthanide ions have attracted significant attention. Methods: The efficient internalization of UCNPs by cells was confirmed, and their precise cellular localization was determined by electron microscopy and confocal studies. Results: UCNPs colocalized only with specific organelles, such as early endosomes, late endosomes and lysosomes. Furthermore, experiments with chemical inhibitors confirmed the involvement of endocytosis in UCNPs internalization and helped select several mechanisms involved in internalization. Exposure to selected UCNPs concentrations did not show significant cytotoxicity, induction of oxidative stress or ultrastructural changes in cells. Conclusion: This study suggests that UCNPs offer new diagnostic options for biomedical infrared imaging.


Assuntos
Elementos da Série dos Lantanídeos , Nanopartículas , Distribuição Tecidual , Elementos da Série dos Lantanídeos/química , Diagnóstico por Imagem , Nanopartículas/química
15.
Dalton Trans ; 50(41): 14762-14773, 2021 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-34590656

RESUMO

The whitlockite-related materials have attracted researchers' attention because of their potential application in various fields, especially in optoelectronics. In the present work, the structure of novel whitlockite-related oxides Ca10TM0.5(VO4)7 (TM = Co, Cu) is studied at room and high temperatures, using X-ray powder diffraction. These compounds form by fractional substitution of divalent transition metal atoms into the Ca3(VO4)2 lattice. Rietveld refinements provided the structural details. The lattice parameters are a = 10.78074(6) Å, c = 37.8196(2) Å, and V = 3806.67(4) Å3 for Ca10Co0.5(VO4)7 and a = 10.78710(7) Å, c = 37.8997(3) Å, and V = 3819.23(4) Å3 for Ca10Cu0.5(VO4)7. Structure refinement results show that among the five available sites (M1-M5), the M2+ ions select the M5 site. This finding is confirmed by analysis of interatomic distances: due to the difference in size between TM and Ca ions sharing the M5 site, the M5-O distance shortens by about 5.0% for Ca10Co0.5(VO4)7 and 2.7% for Ca10Cu0.5(VO4)7 with respect to the unsubstituted parent compound, Ca3(VO4)2. The observed trends in the crystallographic properties of the studied crystals are in line with those of previously reported structurally related phosphates, Ca10.5-xMx(PO4)7 (M = Mg or divalent transition metal). Moreover, the observed tendency for occupation of M5 by small divalent ions follows the earlier theoretical results. For cobalt and copper substituted orthovanadate and orthophosphate whitlockite related materials, a linear variation in the unit cell size is demonstrated. The common equation for evaluation of volume is applicable to the substitution of the two transition metals in orthovanadate and orthophosphate whitlockite related materials. Thermal expansion is investigated for both compounds. The variations of the lattice parameters and the thermal expansion coefficient with temperature are determined in the 300-810 K range. The lattice parameter, a, expands by 0.80% for Ca10Co0.5(VO4)7 and 0.74% for Ca10Cu0.5(VO4)7 in this range. The lattice parameter, c, enlarges by about 0.70% for both samples. In the studied temperature range, the volume thermal expansion coefficient of Ca10Co0.5(VO4)7 increases from 37.2 to 44.8 MK-1 and for Ca10Cu0.5(VO4)7, it increases from 35.1 to 45.2 MK-1; the observed expansion anisotropy is smaller than those of other related compounds.

16.
Materials (Basel) ; 14(10)2021 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-34065578

RESUMO

Copper nitride shows various properties that depend on the structure of the material and is influenced by the change in technical parameters. In the present work, Cu-N layers were synthesized using the pulsed magnetron sputtering method. The synthesis was performed under different operating conditions: direct current (DC) or alternating current (AC) power supply, and various atmospheres: pure Ar and a mixture of Ar + N2. The structural properties of the deposited layers were characterized by X-ray diffraction measurements, and Raman spectroscopy and scanning electron microscopy have been performed. Optical properties were also evaluated. The obtained layers showed tightly packed columnar grain features. The kinetics of the layer growth in the AC mode was lower than that observed in the DC mode, and the layers were thinner and more fine-grained. The copper nitride layers were characterized by the one-phase and two-phase polycrystalline structure of the Cu3N phase with the preferred growth orientation (100). The lattice constant oscillates between 3.808 and 3.815 Å for one-phase and has a value of 3.828 Å for a two-phase structure. Phase composition results were correlated with Raman spectroscopy measurements. Raman spectra exhibited a broad, diffused, and intense signal of Cu3N phase, with Raman shift located at 628-635 cm-1. Studies on optical properties showed that the energy gap ranged from 2.17 to 2.47 eV. The results showed that controlling technical parameters gives a possibility to optimize the structure and phase composition of deposited layers. The reported changes were discussed and attributed to the properties of the material layers and technology method.

17.
Acta Crystallogr B Struct Sci Cryst Eng Mater ; 77(Pt 3): 339-346, 2021 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-34096515

RESUMO

The structures of polycrystalline Ca3RE2(BO3)4 (RE = La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Y; space group Pnma) orthoborates were determined using powder X-ray diffraction. Trends in the unit-cell dimensions and yet unreported trends in other structural properties (interatomic distances and the fractional occupation of three Ca/RE sites) for these compounds are demonstrated as a function of RE ionic radius. The unit-cell volume and a unit-cell parameter present a linear dependence, while the b and c unit-cell parameters change in a nonlinear manner. For the whole series, the RE atoms are present at all three cationic sites (labelled as M1, M2 and M3), but the fractional occupancies depend on the RE ionic radius. The small rare-earth atoms tend to enter mainly the M3 site; for the larger rare earths, the occupancy of this site decreases sharply. The occupancy of the M1 site by RE atoms is around 0.5 and tends to increase with increasing RE ionic radius. The M2 site is the least preferentially occupied by RE ions, but the occupancy discernibly increases with rising radius as well. These findings are assembled with properties of isostructural strontium and barium borates, allowing prediction of occupancy schemes for not yet investigated compounds from the A3RE2(BO3)4 (A = Ca, Ba, Sr).

18.
Nanoscale ; 13(16): 7685-7693, 2021 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-33928952

RESUMO

The Dzyaloshinskii-Moriya interaction (DMI) manifesting in asymmetric layered ferromagnetic films gives rise to non-colinear spin structures stabilizing magnetization configurations with nontrivial topology. In this work magnetization reversal, magnetic domain alignment, and strength of DMI are related to the crystalline structure of W/Co/Pt multilayers grown by molecular beam epitaxy. The applied growth method enables the fabrication of layered systems with higher crystalline quality than commonly applied sputtering techniques. A relatively high value of the D coefficient was determined from the aligned magnetic domain stripe structure, substantially exceeding 2 mJ m-2. The highest value of DMI strength Deff = 2.64 mJ m-2 and surface DMI parameter DS = 1.83 pJ m-1 have been observed for a repetition number equal to 10. The experimental results correlate exactly with those obtained from the micromagnetic modelling and density functional theory calculations performed for the well-defined layered stacks. This high value of DMI strength originates from the additive contributions of the interfacial atomic Co layers at the two types of interfaces.

19.
Nanoscale ; 12(39): 20300-20307, 2020 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-33001125

RESUMO

Lanthanide-doped nanoparticles enable conversion of near-infrared photons to visible ones. This property is envisioned as a basis of a broad range of applications: from optoelectronics, via energy conversion, to bio-sensing and phototherapy. The spectrum of applications can be extended if magnetooptical properties of lanthanide dopants are well understood. However, at present, there are many conflicting reports on the influence of the magnetic field on the upconverted luminescence. In this work, we resolve this discrepancy by performing a comprehensive study of ß-NaYF4:Er3+,Yb3+ nanoparticles. Crucially, we show that the magnetic field impacts the luminescence only via a Zeeman-driven detuning between the excitation laser and the absorption transition. On the other hand, the energy transfer and multiphonon relaxation rates are unaffected. We propose a phenomenological model, which qualitatively reproduces the experimental results. The presented results are expected to lead to design of novel, dual-mode opto-magnetic upconverting nanomaterials.

20.
J Phys Chem C Nanomater Interfaces ; 124(12): 6871-6883, 2020 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-32952770

RESUMO

Magnetic nanoparticles of Fe3O4 doped by different amounts of Y3+ (0, 0.1, 1, and 10%) ions were designed to obtain maximum heating efficiency in magnetic hyperthermia for cancer treatment. Single-phase formation was evident by X-ray diffraction measurements. An improved magnetization value was obtained for the Fe3O4 sample with 1% Y3+ doping. The specific absorption rate (SAR) and intrinsic loss of power (ILP) values for prepared colloids were obtained in water. The best results were estimated for Fe3O4 with 0.1% Y3+ ions (SAR = 194 W/g and ILP = 1.85 nHm2/kg for a magnetic field of 16 kA/m with the frequency of 413 kHz). The excellent biocompatibility with low cell cytotoxicity of Fe3O4:Y nanoparticles was observed. Immediately after magnetic hyperthermia treatment with Fe3O4:0.1%Y, a decrease in 4T1 cells' viability was observed (77% for 35 µg/mL and 68% for 100 µg/mL). These results suggest that nanoparticles of Fe3O4 doped by Y3+ ions are suitable for biomedical applications, especially for hyperthermia treatment.

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