TY - JOUR

T1 - Influence of Stabilizing Ion Content on the Structure, Photoluminescence and Biological Properties of Zr1–xEuxO2–0.5x Nanoparticles

AU - Bugrov, Alexander N.

AU - Smyslov, Ruslan Yu.

AU - Zavialova , Anastasia Yu.

AU - Kopitsa , Gennady P.

AU - Khamova, Tamara V.

AU - Kirilenko, Demid A.

AU - Kolesnikov, Ilya E.

AU - Pankin, Dmitrii V.

AU - Baigildin, Vadim A.

AU - Licitra, Christophe

N1 - Publisher Copyright: © 2020 by the authors. Licensee MDPI, Basel, Switzerland.

PY - 2020/11/15

Y1 - 2020/11/15

N2 - Quasi-spherical nanoparticles of ZrO2 containing EuO1.5 from 2 to 15 mol.% were synthesized from the chlorides of the corresponding metals under hydrothermal conditions. The structural changes of Zr1–xEuxO2–0.5x (x = 0.02 ÷ 0.15) nanoparticles depending on the content of europium (III) ions were studied using the complementary methods (X-ray diffraction, electron microdiffraction, Raman and photoluminescence spectroscopy). It was shown that increasing the Eu3+ concentration in the Zr1–xEuxO2–0.5x nanoparticles leads to a transition from the equilibrium monoclinic zirconia phase to metastable tetragonal and cubic polymorphic modifications. In this case, the size of the nanoparticles decreases from 11.5 nm to 9 nm; the specific surface area grows from 80.2 to 111.3 m2/g, and the electrokinetic potential increases monotonously from −8.7 to 16.3 mV. The evolution of the phase composition of Zr1–xEuxO2-0.5x nanoparticles from monoclinic to tetragonal/cubic allomorphs with an increase in the molar fraction of stabilizer ions was correlated with changes in the sublevel structure of 5D0 → 7F2 and 5D0 → 7F4 optical transitions for Eu3+ in the luminescence spectra. Besides, for the nanoparticles obtained by hydrothermal synthesis from chlorides, the quantum efficiency does not exceed 3%. According to the M.T.T. assay, as a result of three-day human fibroblast cultivation in the aqueous dispersion of Zr1–xEuxO2–0.5x (x = 0.02 ÷ 0.15) nanoparticles, the proliferation activity of the cells is maintained, indicating that they do not have cytotoxic properties. Such nanoparticles can be used in organic–inorganic composites for medical applications in order to strengthen the polymer scaffolds and visualize changes in their structure within time.

AB - Quasi-spherical nanoparticles of ZrO2 containing EuO1.5 from 2 to 15 mol.% were synthesized from the chlorides of the corresponding metals under hydrothermal conditions. The structural changes of Zr1–xEuxO2–0.5x (x = 0.02 ÷ 0.15) nanoparticles depending on the content of europium (III) ions were studied using the complementary methods (X-ray diffraction, electron microdiffraction, Raman and photoluminescence spectroscopy). It was shown that increasing the Eu3+ concentration in the Zr1–xEuxO2–0.5x nanoparticles leads to a transition from the equilibrium monoclinic zirconia phase to metastable tetragonal and cubic polymorphic modifications. In this case, the size of the nanoparticles decreases from 11.5 nm to 9 nm; the specific surface area grows from 80.2 to 111.3 m2/g, and the electrokinetic potential increases monotonously from −8.7 to 16.3 mV. The evolution of the phase composition of Zr1–xEuxO2-0.5x nanoparticles from monoclinic to tetragonal/cubic allomorphs with an increase in the molar fraction of stabilizer ions was correlated with changes in the sublevel structure of 5D0 → 7F2 and 5D0 → 7F4 optical transitions for Eu3+ in the luminescence spectra. Besides, for the nanoparticles obtained by hydrothermal synthesis from chlorides, the quantum efficiency does not exceed 3%. According to the M.T.T. assay, as a result of three-day human fibroblast cultivation in the aqueous dispersion of Zr1–xEuxO2–0.5x (x = 0.02 ÷ 0.15) nanoparticles, the proliferation activity of the cells is maintained, indicating that they do not have cytotoxic properties. Such nanoparticles can be used in organic–inorganic composites for medical applications in order to strengthen the polymer scaffolds and visualize changes in their structure within time.

KW - hydrothermal synthesis

KW - zirconia

KW - Rare-earth ions

KW - phase composition

KW - photoluminescence

KW - cytotoxicity

KW - Zirconia

KW - Hydrothermal synthesis

KW - Phase composition

KW - Photoluminescence

KW - Cytotoxicity

KW - rare-earth ions

KW - ZIRCONIA

KW - EU3+

KW - X-RAY-ABSORPTION

KW - EUROPIUM

KW - ZRO2

KW - PHASE-TRANSFORMATION

KW - PHOSPHORS

KW - EMISSION

KW - VARIABLE CONCENTRATION

KW - MICRO-RAMAN

UR - http://www.scopus.com/inward/record.url?scp=85096061337&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/6e990607-37ab-32f9-8c61-e43b12de1433/

U2 - 10.3390/cryst10111038

DO - 10.3390/cryst10111038

M3 - Article

VL - 10

SP - 1

EP - 19

JO - Crystals

JF - Crystals

SN - 2073-4352

IS - 11

M1 - 1038

ER -