Solvothermal synthesis derived Co-Ga codoped ZnO diluted magnetic degenerated semiconductor nanocrystals

Authors kindly acknowledge to the Estonian Research Council ( PUT1096 , IUT2-25 , PUT735 ), the Estonian Centre of Excellence in Research project “Advanced materials and high-technology devices for sustainable energetics, sensorics and nanoelectronics (TK141), and the financial support of HZB. We are grateful to the staff of BESSY II for the assistance and co-operation during the synchrotron-based measurements.Here we are reporting solvothermal synthesis derived diluted magnetic and plasmonic Co-Ga co-doped ZnO nanocrystals with high magnetization values (from 1.02 to 4.88 emu/g) at room temperature. Co-Ga co-doped ZnO nanocrystals show up to 2 fold increase in saturation magnetization compared to Co doped ZnO nanocrystals at the same Co concentration, with the observed room temperature magnetization higher than previously reported values for multifunctional magnetic and plasmonic nanocrystals, and the effect of Ga suggesting some role of the correspondingly introduced itinerant charge. While at the lowest Ga content the nanoparticles appear homogeneously doped, we note that already a moderate Ga content of several percent triggers a fraction of Co to segregate in metallic form in the bulk of the nanoparticles. However, the amount of segregated Co is not sufficient to account for the total effect, whereas a dominating contribution to the observed magnetism has to be related to itinerant charge mediated exchange interactions.Eesti Teadusagentuur IUT2-25,PUT1096,PUT735; Estonian Centre of Excellence in Research TK141; HZB; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

In vitro response of mesenchymal stem cells to biomimetic hydroxyapatite substrates: a new strategy to assess the effect of ion exchange

Biomaterials can interact with cells directly, that is, by direct contact of the cells with the material surface, or indirectly, through soluble species that can be released to or uptaken from the surrounding fluids. However, it is difficult to characterise the relevance of this fluid-mediated interaction separately from the topography and composition of the substrate, because they are coupled variables. These fluid-mediated interactions are amplified in the case of highly reactive calcium phosphates (CaPs) such as biomimetic calcium deficient hydroxyapatite (CDHA), particularly in static in vitro cultures. The present work proposes a strategy to decouple the effect of ion exchange from topographical features by adjusting the volume ratio between the cell culture medium and biomaterial (VCM/VB). Increasing this ratio allowed mitigating the drastic ionic exchanges associated to the compositional changes experienced by the material exposed to the cell culture medium. This strategy was validated using rat mesenchymal stem cells (rMSCs) cultured on CDHA and beta-tricalcium phosphate (ß-TCP) discs using different VCM/VB ratios. Whereas in the case of ß-TCP the cell response was not affected by this ratio, a significant effect on cell adhesion and proliferation was found for the more reactive CDHA. The ionic exchange, produced by CDHA at low VCM/VB, altered cell adhesion due to the reduced number of focal adhesions, caused cell shrinkage and further rMCSs apoptosis. This was mitigated when using a high VCM/VB, which attenuated the changes of calcium and phosphate concentrations in the cell culture medium, resulting in rMSCs spreading and a viability over time. Moreover, rMSCs showed an earlier expression of osteogenic genes on CDHA compared to sintered ß-TCP when extracellular calcium fluctuations were reduced. Statement of Significance Fluid mediated interactions play a significant role in the bioactivity of calcium phosphates. Ionic exchange is amplified in the case of biomimetic hydroxyapatite, which makes the in vitro characterisation of cell-material interactions especially challenging. The present work proposes a novel and simple strategy to explore the mechanisms of interaction of biomimetic and sintered calcium phosphates with mesenchymal stem cells. The effects of topography and ion exchange are analysed separately by modifying the volume ratio between cell culture medium and biomaterial. High ionic fluctuations interfered in the maturation of focal adhesions, hampering cell adhesion and leading to increased apoptosis and reduced proliferation rate.Peer Reviewe

In vitro response of mesenchymal stem cells to biomimetic hydroxyapatite substrates: a new strategy to assess the effect of ion exchange

Biomaterials can interact with cells directly, that is, by direct contact of the cells with the material surface, or indirectly, through soluble species that can be released to or uptaken from the surrounding fluids. However, it is difficult to characterise the relevance of this fluid-mediated interaction separately from the topography and composition of the substrate, because they are coupled variables. These fluid-mediated interactions are amplified in the case of highly reactive calcium phosphates (CaPs) such as biomimetic calcium deficient hydroxyapatite (CDHA), particularly in static in vitro cultures. The present work proposes a strategy to decouple the effect of ion exchange from topographical features by adjusting the volume ratio between the cell culture medium and biomaterial (VCM/VB). Increasing this ratio allowed mitigating the drastic ionic exchanges associated to the compositional changes experienced by the material exposed to the cell culture medium. This strategy was validated using rat mesenchymal stem cells (rMSCs) cultured on CDHA and beta-tricalcium phosphate (ß-TCP) discs using different VCM/VB ratios. Whereas in the case of ß-TCP the cell response was not affected by this ratio, a significant effect on cell adhesion and proliferation was found for the more reactive CDHA. The ionic exchange, produced by CDHA at low VCM/VB, altered cell adhesion due to the reduced number of focal adhesions, caused cell shrinkage and further rMCSs apoptosis. This was mitigated when using a high VCM/VB, which attenuated the changes of calcium and phosphate concentrations in the cell culture medium, resulting in rMSCs spreading and a viability over time. Moreover, rMSCs showed an earlier expression of osteogenic genes on CDHA compared to sintered ß-TCP when extracellular calcium fluctuations were reduced. Statement of Significance Fluid mediated interactions play a significant role in the bioactivity of calcium phosphates. Ionic exchange is amplified in the case of biomimetic hydroxyapatite, which makes the in vitro characterisation of cell-material interactions especially challenging. The present work proposes a novel and simple strategy to explore the mechanisms of interaction of biomimetic and sintered calcium phosphates with mesenchymal stem cells. The effects of topography and ion exchange are analysed separately by modifying the volume ratio between cell culture medium and biomaterial. High ionic fluctuations interfered in the maturation of focal adhesions, hampering cell adhesion and leading to increased apoptosis and reduced proliferation rate.Peer Reviewe

A Straightforward and “Green” Solvothermal Synthesis of Al Doped Zinc Oxide Plasmonic Nanocrystals and Piezoresistive Elastomer Nanocomposite

Plasmonic oxide nanocrystals hold great promise in a wide range of applications, for which the availability of scalable and “green” synthesis methods is prerequisite, whereas until recently an excellent response has been demonstrated only for samples prepared through intricate synthesis paths. We report here a simple ethanol solvothermal synthesis route of Al doped ZnO plasmonic nanocrystals (Zn1xAlxO) at doping levels of x up to 0.15. The obtained Al doped ZnO samples consisted of nanoparticles and short nanorods with a diameter of around 10 nm at x ¼ 0.15 doping level while reaching aspect ratio levels of 50 for lower doping levels. Detailed structural studies using powder X-ray diffraction Rietveld refinement, X-ray absorption and photoelectron spectroscopies show that all samples maintain the structure of the phase-pure zincite with the space group P63mc. The resulting powders exhibit strong infrared absorption while remaining largely transparent for visible light, enabling the preparation of transparent colloidal dispersions. Furthermore, as a test of applicability in a practical device, the nanocrystals were used to prepare transparent piezoresistive Zn0.925Al0.075O–polydimethylsiloxane composites. The prepared sensor material exhibits excellent repeatable and reproducible piezoresistive behaviour

Photocatalytic Activity of Anatase–Nickel Ferrite Heterostructures

The simple co-precipitation route was used to couple commercial TiO2 anatase nanopowder with nickel ferrite (NiFe2O4). The morphology and the crystalline structure of composite nanoparticles were characterised by TEM, N2 adsorption-desorption, XRD and Rietveld refinement, XPS and XAS. The optical and magnetic properties were investigated. After co-precipitation NiFe2O4 nanoparticles, composed of spinel ferrite crystal phase, were formed on the surface of TiO2 anatase nanopowder. The TiO2/NiFe2O4 composite oxide demonstrated large specific surface area, high visible light absorption efficiency and efficient charge carrier separation, compared to pristine anatase TiO2 or pristine NiFe2O4, representatively. The obtained TiO2/NiFe2O4 composite oxides, with different nickel ferrite contents (5, 10, 25, 50 and 75 wt%) showed decent visible light photocatalytic efficiency, up to three times higher than pure anatase or pure NiFe2O4. However, TiO2/NiFe2O4 composite oxides did not demonstrate high magnetic properties