Generation and characterization of stable, highly concentrated titanium dioxide nanoparticle aerosols for rodent inhalation studies

The intensive use of nano-sized titanium dioxide (TiO₂) particles in many different applications necessitates studies on their risk assessment as there are still open questions on their safe handling and utilization. For reliable risk assessment, the interaction of TiO₂ nanoparticles (NP) with biological systems ideally needs to be investigated using physico-chemically uniform and well-characterized NP. In this article, we describe the reproducible production of TiO₂ NP aerosols using spark ignition technology. Because currently no data are available on inhaled NP in the 10?C50 nm diameter range, the emphasis was to generate NP as small as 20 nm for inhalation studies in rodents. For anticipated in vivo dosimetry analyses, TiO₂ NP were radiolabeled with ⁴⁸V by proton irradiation of the titanium electrodes of the spark generator. The dissolution rate of the ⁴⁸V label was about 1% within the first day. The highly concentrated, polydisperse TiO₂ NP aerosol (3?C6 × 10⁶ cm^?3) proved to be constant over several hours in terms of its count median mobility diameter, its geometric standard deviation, and number concentration. Extensive characterization of NP chemical composition, physical structure, morphology, and specific surface area was performed. The originally generated amorphous TiO₂ NP were converted into crystalline anatase TiO₂ NP by thermal annealing at 950 °C. Both crystalline and amorphous 20-nm TiO₂ NP were chain agglomerated/aggregated, consisting of primary particles in the range of 5 nm. Disintegration of the deposited TiO₂ NP in lung tissue was not detectable within 24 h.     

Proliferative reactive gliosis is compatible with glial metabolic support and neuronal function

Background

Trail-making tests, such as the Concept Shifting Task (CST), can be used to test the effects of treatment on cognitive performance over time in various neuropsychological disorders. However, cognitive performance in such experimental designs might improve as a result of the practice obtained during repeated testing rather than the treatment itself. The current study investigated if practice affects the accuracy and duration of performance on the repeatedly administered Concept Shifting Task modified to make it resistant to practice (mCST). The mCST was administered to 54 healthy participants twice a day, before and after a short break, for eight days. Results. The ANOVA and meta-analysis showed that there was no improvement in the mCST accuracy on the last vs. the first trial (Hedges' g = .14, p = .221) or within the session (after vs. before the break on all days; g = .01, p = .922). However, the participants performed the task faster on the last vs. the first trial (g = -.75, p < .001) and after vs. before the break on all days (g = -.12, p = .002). Conclusions. Repeated administration of the mCST does not affect the accuracy of performance on the test. However, practice might contribute to faster performance on the mCST over time and within each session.     

Optical and microstructural properties of self-assembled InAs quantum structures in silicon

The InAs quantum structures were formed in silicon by sequential ion implantation and subsequent thermal annealing. Two kinds of crystalline InAs nanostructures were successfully synthesized: nanodots (NDs) and nanopyramids (NPs). The peaks at 215 and 235 cm^?1, corresponding to the transverse optical (TO) and longitudinal optical (LO) InAs single-phonon modes, respectively, are clearly visible in the Raman spectra. Moreover, the PL band at around 1.3 µm, due to light emission from InAs NDs with an average diameter 7±2 nm, was observed. The InAs NPs were found only in samples annealed for 20 ms at temperatures ranging from 1000 up to 1200°C. The crystallinity and pyramidal shape of InAs quantum structures were confirmed by HRTEM and XRD techniques. The average size of the NPs is 50 nm base and 50 nm height, and they are oriented parallel to the Si (001) planes. The lattice parameter of the NPs increases from 6.051 to 6.055 Å with the annealing temperature increasing from 1100 to 1200°C, due to lattice relaxation. Energy dispersive spectroscopy (EDS) shows almost stoichiometric composition of the InAs NPs.     

Photo-Induced Electron Spin Polarization in Chemical and Biological Reactions: Probing Structure and Dynamics of Transient Intermediates by Multifrequency EPR Spectroscopy

In this minireview, modern multifrequency electron paramagnetic resonance (EPR) spectroscopy, in particular, at high magnetic fields, is shown to provide detailed information about structure, motional dynamics and spin chemistry of transient radicals and radical pairs occurring in photochemical reactions. Examples discussed comprise spin-polarized radicals and radical pairs in disordered systems, such as ultraviolet-irradiated quinone and ketone compounds in fluid alcohol solutions, green-light initiated electron transfer in biomimetic porphyrin?Cquinone donor?Cacceptor model systems in frozen solution, aiming at artificial photosynthesis, and red-light initiated electron transfer in natural photosynthetic reaction-center protein complexes. The transient paramagnetic states exhibit characteristic electron polarization (CIDEP) effects originating from a triplet mechanism, a radical-pair mechanism or a correlated coupled radical-pair mechanism. They contain valuable information about structure and dynamics of the short-lived reaction intermediates. Moreover, the CIDEP effects can be exploited for signal enhancement. Continuous-wave and pulsed versions of time-resolved high-field EPR spectroscopy, such as transient EPR and electron spin-echo experiments, are compared with respect to their advantages and limitations for the specific photoreaction under study. Furthermore, orientation resolving W-band pulsed electron-electron double resonance (PELDOR) experiments on the spin-correlated coupled radical pair $ {\text{P}}_{865}^{ \cdot + } $ $ {\text{Q}}_{\text{A}}^{ \cdot - } $ in frozen solution reaction centers from the purple photosynthetic bacterium Rb. sphaeroides reveal details of distance and orientation of the pair partners in their charge-separated transient state. The results are compared with those of the ground-state P₈₆₅Q_A. In conjunction with Q-band proton electron-nuclear double resonance (ENDOR) experiments the W-band PELDOR results provide decisive evidence that the local structure of the Q_A binding site does not change under photoreduction of the quinone??in agreement with earlier FTIR studies. The examples given demonstrate that multifrequency EPR experiments on disordered systems add heavily to the capabilities of ??classical?? spectroscopic and diffraction techniques for determining structure?Cdynamics?Cfunction relations of biochemical processes, since short-lived intermediates can be observed in real time while staying in their working states at biologically relevant time scales.     

Study of the oxygen incorporation and diffusion in Sr(Ti0.65Fe0.35)O3 ceramics

For applications in high temperature fast conductometric gas sensors and oxygen membranes, several mixed conductors show promising features. In particular, acceptor-doped strontium titanate (STO) has been widely investigated for an application as a fast conductometric oxygen sensor. By a B-site substitution with 35% iron, the resulting ceramic solid solution SrTi_0.65Fe_0.35O₃ (STF35) exhibits a temperature-independent conductivity, an ideal prerequisite for a gas sensor.In the presented study, the oxygen tracer exchange behavior and the tracer diffusion of dense ceramic STF35 bulks have been investigated in the temperature range between 600 and 900 °C by means of ¹⁸O₂ tracer exchange experiments and subsequent secondary ion mass spectrometry (SIMS), resulting in the determination of k* and D* values, respectively.Furthermore, by coating the samples with a thin alkaline earth metal oxide layer (CaO), a significantly enhanced oxygen surface exchange reaction was observed. These findings are in good agreement with previous results on STO single crystals.     

Thermal stability of the cubic phase in Ba0.5Sr0.5Co0.8Fe0.2O3 - δ (BSCF)1

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 - δ (BSCF) is a material with excellent oxygen ionic and electronic transport properties reported by many research groups. In its cubic phase, this mixed ionic-electronic conducting (MIEC) perovskite is a promising candidate for oxygen permeation membranes. For this application, its long-term stability under operating conditions (especially temperature and oxygen partial pressure) is of crucial importance.The present work is focused on the thermal stability of the BSCF cubic phase in the targeted temperature range for applications (700…900 °C) in light of previous studies in literature reporting a reversible transition to a hexagonal phase somewhere below 900 °C.To this end, single phase cubic BSCF powders were annealed at different temperatures over varying periods of time. Phase composition was subsequently analysed by X-ray diffractometry (XRD) in order to determine both the temperature limit and the time-scale for the formation of the hexagonal phase. Additionally, the long-term behaviour of the electrical conductivity was examined on bulk samples at 700 °C, 800 °C and 900 °C over several hundreds of hours, showing a prolonged decrease at 800 °C. The decrease in electrical conductivity at this temperature was also examined on bulk samples with different grain sizes, showing a more pronounced decrease the smaller the average grain size.Coexistence of both phases (cubic and hexagonal) could also be shown for 700 °C, however with a different phase equilibrium than at 800 °C.     

Model reduction of porous-media problems using proper orthogonal decomposition

In the context of finite-element simulations of porous media, computing time and numerical effort is an important issue because the number of degrees of freedom of such coupled problems can become very large. Following this, model reduction plays an important role. A broad variety of materials exhibit a porous microstructure. In order to evaluate the overall response of these materials, a macroscopic continuum-mechanical modelling approach is used. Therefore, the complex inner structure of porous media is regarded in a multi-phasic and multi-component manner by means of the well-founded Theory of Porous Media (TPM). The mechanical behaviour of porous media is solved using the Finite-Element Method (FEM). The basic idea of model reduction is to transform a high dimensional system, in terms of the system's degrees of freedom, to a low dimensional subspace to minimise the computational effort while maintaining the accuracy of the solution. The method of proper orthogonal decomposition (POD) can be seen as a method to approximate a given data set with a low dimensional subspace. Furthermore, the POD method is independent of the type of the model and can be used for nonlinear systems as well as for systems of second order. In several applications, such as consolidation problems of partially saturated soils, commonly occurring motion sequences can be found, which can be used as typical “snapshots” of the system. Therefore, the application of the POD method to the simulation of porous media is discussed in the present contribution. Investigated computations of a biphasic standard problem show that the POD method reduces the numerical effort to solve the linearised system of equations in each iteration step. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

An inverse problem for infinitely divisible moving average random fields

Statistical Inference for Stochastic Processes - Given a low frequency sample of an infinitely divisible moving average random field $${int _{mathbb {R}^d} f(x-t)varLambda (dx); t in mathbb...