Evolution of the structure of MSnO3 (M = Ba, Sr) perovskites during hydrothermal synthesis and their photocatalytic activity.

The synthesis of barium and strontium stannates in the process of decomposition of hydrothermally obtained precursors has been investigated. It was found that endothermic weight loss during the synthesis of barium stannate occurs in two stages, whereas during the synthesis of strontium stannate it occurs in one stage. From the summary of the results of thermogravimetric analysis, X-ray diffraction, and Mössbauer spectroscopy, the composition and local structure of X-ray amorphous phases are proposed. It is shown that the improvement of the crystal structure of the perovskite phases of MSnO3 (M = Ba, Sr) and the symmetry of the local environment of 119Sn continues up to high temperatures (1250-1500 °C) and is associated with the elimination of defects in the anion sublattice. The photocatalytic activity of hydrothermal phases MSn(OH)6 and their thermolysis products has been studied and was found not to be directly related to the specific surface area of the photocatalysts. The degradation of rhodamine B (RhB) occurs during the "dark" stages of catalysis due to the interaction of the dye with reactive oxygen species (mainly singlet oxygen). At the first stage, the decomposition of the RhB photochromic system is observed, whereas at the final stage of bleaching the dye is deethylated.

Role of the Eu3+ Distribution on the Properties of ß-Ca3(PO4)2 Phosphors: Structural, Luminescent, and 151Eu Mössbauer Spectroscopy Study of Ca9.5-1.5xMgEux(PO4)7.

The series of ß-Ca3(PO4)2-type phosphors Ca9.5-1.5xMgEux(PO4)7 were synthesized by a solid-state route. Observation of the proper Eu3+ ion distribution in the Ca9.5Mg(PO4)7 host matrix was made by a direct method using 151Eu Mössbauer spectroscopy in combination with X-ray analysis and dielectric and luminescent spectroscopy. The photoluminescence properties were studied in detail. The samples exhibit an exceptionally narrow-band red emission according to the dominant 5D0 → 7F2 transition and fulfill the industrial requirements for high-energy-efficiency red phosphors. The contribution of Eu3+ ions in different crystal sites to the luminescent properties is discussed in detail. The difference of the excitation of Eu3+ in the M1 and M2 sites was revealed by photoluminescence excitation spectra in accordance with structure refinement. The temperature dependence of the luminescence intensity was studied. Different tendencies in the thermal behavior of emission lines allow one to consider the studied compounds as phosphors suitable for luminescence thermometry. The measured quantum yield for Ca9.5-1.5xMgEux(PO4)7 shows excellent results and reaches 63%.

Common and rare iron, sulfur, and zinc minerals in technogenically contaminated hydromorphic soil from Southern Russia.

Soils formed after the desiccation of Lake Atamanskoe, which has served as a reservoir for liquid industrial waste from the city of Kamensk-Shakhtinsky during a long time, were studied. These soils differ from zonal soils by a strong contamination with zinc and sulfur. Preliminary studies showed that Fe compounds fix a significant part of zinc. This requires to study S, Zn, and Fe minerals. In this work, Mössbauer spectroscopy was used for the identification of iron compounds and scanning electron microscopy was used for the microanalysis of these and other minerals. To facilitate the identification of Fe minerals, brown iron ocher was removed from a contaminated soil sample and analyzed. From electron microscopy and Mössbauer spectroscopy data, ocher contained hydrogoethite with a high content of sorption water and schwertmannite (a rare mineral, probably found in Russia for the first time). The chemical composition of this schwertmannite better corresponds to the Cashion-Murad model than to the Bigham model. Particles of partially oxidized magnetite and wustite enriched with zinc were revealed under electron microscope. Siderite with partial substitution of Fe2+ by Zn2+ was detected. Thus, contaminated hydromorphic soil contains both common minerals (illite, goethite, hematite, gypsum) and rare minerals (schwertmannite, Zn siderite, partially oxidized magnetite and wustite enriched with zinc).

Low toxic maghemite nanoparticles for theranostic applications.

BACKGROUND: Iron oxide nanoparticles have numerous and versatile biological properties, ranging from direct and immediate biochemical effects to prolonged influences on tissues. Most applications have strict requirements with respect to the chemical and physical properties of such agents. Therefore, developing rational design methods of synthesis of iron oxide nanoparticles remains of vital importance in nanobiomedicine. METHODS: Low toxic superparamagnetic iron oxide nanoparticles (SPIONs) for theranostic applications in oncology having spherical shape and maghemite structure were produced using the fast microwave synthesis technique and were fully characterized by several complementary methods (transmission electron microscopy [TEM], X-ray diffraction [XRD], dynamic light scattering [DLS], X-ray photoelectron spectroscopy [XPS], X-ray absorption near edge structure [XANES], Mossbauer spectroscopy, and HeLa cells toxicity testing). RESULTS: TEM showed that the majority of the obtained nanoparticles were almost spherical and did not exceed 20 nm in diameter. The averaged DLS hydrodynamic size was found to be ~33 nm, while that of nanocrystallites estimated by XRD was16 nm. Both XRD and XPS studies evidenced the maghemite (γ-Fe2O3) atomic and electronic structure of the synthesized nanoparticles. The XANES data analysis demonstrated the structure of the nanoparticles being similar to that of macroscopic maghemite. The Mossbauer spectroscopy revealed the γ-Fe2O3 phase of the nanoparticles and vibration magnetometry study showed that reactive oxygen species in HeLa cells are generated both in the cytoplasm and the nucleus. CONCLUSION: Quasispherical Fe3+ SPIONs having the maghemite structure with the average size of 16 nm obtained by using the fast microwave synthesis technique are expected to be of great value for theranostic applications in oncology and multimodal anticancer therapy.

Dielectric and Mössbauer studies of ferroelectric and magnetic phase transitions in A-site and B-site substituted multiferroic PbFe0.5Nb0.5O3.

In the present study, we diluted either A- or B- sublattice of perovskite multiferroic PbFe(0.5)Nb(0.5)O(3) (PFN) and studied the changes of the magnetic and ferroelectric phase transition temperatures and dielectric properties caused by such dilution. Dielectric studies of PFN single crystals show that, in contrast to the commonly adopted view, the ferroelectric phase transition in PFN is non-diffused and the relaxor-like behavior usually observed in ceramic samples has an extrinsic nature. A-site substitutions (Ba, Ca) lead to the smearing of the permittivity-temperature maximum, lowering its maximum temperature, T(m) and inducing relaxor behavior. B-site diluting of PFN by Ti increases T(m) and only slightly affects the permittivity maximum diffuseness. Both A-site and B-site substitutions in PFN lead to lowering of its Neel temperature, T(N). However, above a certain compositional threshold, fast lowering of T(N) stops and a new magnetic state with comparatively high (~50K) transition temperature becomes stable in a rather wide compositional range.

Dielectric and piezoelectric properties of PbFe1/2Nb1/2O3-PbTiO3 ceramics from the morphotropic phase boundary compositional range.

Dielectric, X-ray, and piezoelectric studies of highly-resistive Li-doped (1-x)PbFe(1/2)Nb(1/2)O(3)-(x)PbTiO(3) (PFN-xPT) ceramics from the 0 ≤ x ≤ 0.2 range fabricated by solid-state synthesis and usual sintering have been carried out. Distinct anomalies of dielectric and piezoelectric parameters, corresponding to the transition between rhombohedral (monoclinic) and tetragonal ferroelectric phases, have been observed in pure PFN and PFN-xPT compositions with PbTiO(3) content up to 8 mol.%. The x,T-phase diagram of the PFN-xPT solid solution system has been constructed using these data.