Local electronic transport across probe/ionic conductor interface in scanning probe microscopy.

Charge carrier transport through the probe-sample junction can have substantial consequences for outcomes of electrical and electromechanical atomic-force-microscopy (AFM) measurements. For understanding physical processes under the probe, we carried out conductive-AFM (C-AFM) measurements of local current-voltage (I-V) curves as well as their derivatives on samples of a mixed ionic-electronic conductor Li1-xMn2O4 and developed an analytical framework for the data analysis. The implemented approach discriminates between contributions the highly resistive sample surface layer and the bulk with the account of ion redistribution in the field of the probe. It was found that, with increasing probe voltage, the conductance mechanism in the surface layer transforms from Pool-Frenkel to space-charge-limited current. The surface layer significantly alters the ion dynamics in the sample bulk under the probe, which leads, in particular, to a decrease of the effective electromechanical AFM signal associated with the ionic motion in the sample. The framework can be applied for the analysis of electronic transport mechanisms across the probe/sample interface as well as to uncover the role of the charge transport in the electric field distribution, mechanical, and other responses in AFM measurements of a broad spectrum of conducting materials.

Silicon-hydroxyapatite‒glycerohydrogel as a promising biomaterial for dental applications.

Nanocomposite silicon-hydroxyapatite‒glycerohydrogel (Si-HA‒glycerohydrogel) with different hydroxyapatite (HA) contents of 0.75 and 1.75 wt.% and the same Si content (2.04 wt.%) was obtained by the sol‒gel method. Silicon tetraglycerolate in the form of glycerol solution was used as a biocompatible precursor and HА in the form of aqueous colloidal suspension - as a template and property modifier. Transmission electron microscopy was applied to demonstrate that there are nanoscale HA particles that are in the crystalline state. For the first time, using the atomic force microscopy method, the remineralizing properties of Si-HA‒glycerohydrogel were studied on human teeth extracted for orthodontic reasons. It was found that Si-HA‒glycerohydrogel containing 1.75 wt.% HA has a pronounced remineralizing effect. Immersion of tooth enamel samples in the gel for one month significantly reduces roughness and makes the enamel surface more uniform. Silicon contained in glycerolates in a biologically active and accessible form exerts an additional positive effect on the process of remineralization of tooth enamel. By the energy dispersive X-ray analysis, it was demonstrated that the tooth enamel had an increased silicon content; and the Vickers microhardness test showed greater microhardness values. The obtained data analysis allows the remineralizing Si-HA‒glycerohydrogel to be considered as a promising biomaterial for dental applications.

Low loss optical waveguides fabricated in LiTaO3 by swift heavy ion irradiation.

Optical waveguides are fabricated by irradiation of LiTaO3 with a variety of swift heavy ions that provide increasing levels of both nuclear and electronic damage rates, including C, F and Si ions, in the energy range of 15-40 MeV. A systematic study of the role of the ion fluence has been carried out in the broad range of 1e13-2e15 at/cm2. The kinetics of damage is initially of nuclear origin for the lowest fluences and stopping powers and, then, is enhanced by the electronic excitation (for F and Si ions) in synergy with the nuclear damage. Applying suitable annealing treatments, optical propagation losses values as low as 0.1 dB have been achieved. The damage rates found in LiTaO3 have been compared with those known for the reference LiNbO3 and discussed in the context of the thermal spike model.

Quantitative characterization of the ionic mobility and concentration in Li-battery cathodes via low frequency electrochemical strain microscopy.

Electrochemical strain microscopy (ESM) can provide useful information on the ionic processes in materials at the local scale. This is especially important for ever growing applications of Li-batteries whose performance is limited by the intrinsic and extrinsic degradation. However, the ESM method used so far has been only qualitative due to multiple contributions to the apparent ESM signal. In this work, we provide a viable approach for the local probing of ionic concentration and diffusion coefficients based on the frequency dependence of the ESM signal. A theoretical basis considering the dynamic behavior of ion migration and relaxation and change of ion concentration profiles under the action of the electric field of the ESM tip is developed. We argue that several parasitic contributions to the ESM signal discussed in the literature can be thus eliminated. The analysis of ESM images using the proposed approach allows a quantitative mapping of the ionic diffusion coefficients and concentration in ionic conductors. The results are validated on Li-battery cathodes (LiMn2O4) extracted from commercial Li-batteries and can provide novel possibilities for their development and further insight into the mechanisms of their degradation.

Temperature Effect on the Stability of the Polarized State Created by Local Electric Fields in Strontium Barium Niobate Single Crystals.

The stability of ferroelectric domain patterns at the nanoscale has been a topic of much interest for many years. We investigated the relaxation of the polarized state created by application of a local electric field using a conductive tip of a scanning probe microscope for the model uniaxial relaxor system SrxBa1-xNb2O6 (SBN) in its pure and Ce-doped form. The temporal relaxation of the induced PFM contrast was measured at various temperatures. The average value of the induced contrast decreases during heating for all investigated crystals. Below the freezing temperature the induced state remains stable after an initial relaxation. Above the freezing temperature the induced state is unstable and gradually decays with time. The stability of the induced state is strongly affected by the measuring conditions, so continuous scanning results in a faster decay of the poled domain. The obtained effects are attributed to a decrease of the induced polarization and backswitching of the polarized area under the action of the depolarization field.

On the contribution of the phagocytosis and the solubilization to the iron oxide nanoparticles retention in and elimination from lungs under long-term inhalation exposure.

The aim of our study was to test a hypothesis according to which the pulmonary clearance vs. retention of metal oxide nanoparticles (NPs) is controlled not only by physiological mechanisms but also by their solubilization which in some cases may even prevail. Airborne Fe2O3 NPs with the mean diameter of 14±4nm produced by sparking from 99.99% pure iron rods were fed into a nose-only exposure tower. Rats were exposed to these NPs for 4h a day, 5days a week during 3, 6 or 10 months at the mean concentration of 1.14±0.01mg/m(3). NPs collected from the air exhausted from the exposure tower proved insoluble in water but dissolved markedly in the cell free broncho-alveolar lavage fluid supernatant and in the sterile bovine blood serum. The Fe2O3 content of the lungs and lung-associated lymph nodes was measured by the Electron Paramagnetic Resonance (EPR) spectroscopy. We found a relatively low but significant pulmonary accumulation of Fe2O3, gradually increasing with time. Besides, we obtained TEM-images of nanoparticles within alveolocytes and the myelin sheaths of brain fibers associated with ultrastructural damage. We have developed a multicompartmental system model describing the toxicokinetics of inhaled nanoparticles after their deposition in the lower airways as a process controlled by their (a) high ability to penetrate through the alveolar membrane; (b) active endocytosis; (c) in vivo dissolution. To conclude, both experimental data and the identification of the system model confirmed our initial hypothesis and demonstrated that, as concerns iron oxide NPs of the dimensions used, the dissolution-depending mechanisms proved to be dominant.

[Combined subchronic toxicity of nickel and manganese oxides nanoparticles, and its decrease due to bioprotectors complex].

Stable suspensions of NiO and/or Mn304 nanoparticles with average diameter 16,7?8,2 nm and 18,4?5,4 nm respectively, obtained via laser ablation of the metals with 99,99% purification in deionized water, were injected intraperitoneally into rats in dose of 0,5 mg or 0,25 mg three times per week up to 18 times separately or in various dose combinations. A group of rats received combined injections of nanoparticles in the highest dose or merely water with oral <> containing pectin, vitamins A, C and E, glutamate, glycine, N-acetylcysteine, selenium, iodine and polyunsaturated fatty acids of omega-3 class. Intoxication development was assessed through multiple functional parameters and histologic changes in liver, spleen, kidneys and brain. Nickel and manganese accumulation in these organs was measured-via various methods. Both types of metallic oxide nanoparticles appeared to be hazardous for body, but Mn304 caused more harm according to major nonspecific toxicity manifestations. Moreover, they caused more intense injury to caudate nucleus and hippocamp neurons - that can be considered as an experimental model of manganese parkinsonism. Mathematic analysis based on response pattern revealed ambiguity of the combined toxicity type, depending on the effects assessed and on its level. Due to the bioprotector complex, organic and systemic toxicity and genotoxicity of Mn304 and NiO nanoparticles combined were diminished.

[Increasing resistance against hazardous effects of metals-containing nanoparticles as a prospective approach to health risks management].

Extremely high toxicity of metal-containing nanoparticles necessitates search of methods to increase body resistance against its harmful effects. The authors' experiments summarized in the article demonstrated that some combinations of certain biologically active substances selected according to sound theoretic background and prescribed in harmless doses can significantly decrease integral and specific manifestations of organ and system toxicity and even genotoxicity of such nanoparticles. Further development of this research direction should be recommended for practical implementation.

Nonlinear Raman-Nath diffraction of femtosecond laser pulses in a 2D nonlinear photonic crystal.

We study second-harmonic generation (SHG) of femtosecond laser pulses in a rectangular two-dimensional nonlinear photonic crystal (NLPC). Multiple SH beams were observed in the vicinity of the propagation direction of the fundamental beam. It has been verified that the angular positions of these beams obey the conditions of nonlinear Raman-Nath diffraction (NRND). The measured SH spectra of specific NRND orders consist of narrow peaks that experience a high-frequency spectral shift as the order grows. We derive an analytical expression for the process studied and find the theoretical results to be in good agreement with the experimental data. We estimate the enhancement factor of nonlinear Raman-Nath diffraction in 2D NLPC to be 70.

Nonlinear Raman-Nath diffraction of femtosecond laser pulses.

We study the nonlinear Raman-Nath diffraction (NRND) of femtosecond laser pulses in a 1D periodic nonlinear photonic structure. The calculated second-harmonic spectra represent frequency combs for different orders of transverse phase matching. These frequency combs are in close analogy with the well-known spectral Maker fringes observed in single crystals. The spectral intensity of the second harmonic experiences a redshift with a propagation angle, which is opposite the case of Cerenkov nonlinear diffraction. We analyze how NRND is affected by the group-velocity mismatch between fundamental and second-harmonic pulses and by the parameters of the structure. Our experimental results prove the theoretical predictions.